CN103517957B - Rosin esters for non-wovens - Google Patents
Rosin esters for non-wovens Download PDFInfo
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- CN103517957B CN103517957B CN201180070558.1A CN201180070558A CN103517957B CN 103517957 B CN103517957 B CN 103517957B CN 201180070558 A CN201180070558 A CN 201180070558A CN 103517957 B CN103517957 B CN 103517957B
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- rosin
- rosin ester
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- tetramethylolmethane
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to rosin esters having suitable color, color stability and/or odor to make them useful for non-woven applications, non-woven products made from and/or comprising rosin esters, and methods of making and using such rosin esters and products.
Description
Related application data
Inapplicable.
Technical field
The present invention relates to rosin ester, the product obtained by rosin ester or comprise the product of rosin ester, and preparation and use the method for these rosin esters or product.In yet another aspect, the present invention relates to the rosin ester that can be used in application of nonwovens, the nonwoven products obtained by rosin ester and/or comprise the nonwoven products of rosin ester, and preparation and use the method for these rosin esters and product.Even in one aspect of the method, the present invention relates to and there is suitable color, colour stability and/or smell with the rosin ester making them can be used in application of nonwovens, the nonwoven products obtained by rosin ester and/or comprise the nonwoven products of rosin ester, and preparation and use the method for these rosin esters and product.
Background technology
At present, rosin ester can not be accepted in non-woven tackiness agent industry.Such as, as the use constructing the tackiness agent that disposable infant diaper uses.For the utilization in application of nonwovens by the most generally accepted be hydrogenated hydrocarbon resins base tackifier.
Although for why rosin ester can not be accepted for having a lot of reasons in non-woven tackiness agent application, but chief reason is at present, past and present toll oil rosin base rosin ester had not both had color, colour stability, again not used for the low smell of non-woven tackiness agent.
A kind of stable rosin ester and pressure sensitive adhesive and the hot-melt composition based on them is disclosed in the U.S. Patent No. 4,302,371 of authorizing Matsuo etc. on November 24th, 1981.Preparation has to comprise compared with the method for this stable rosin ester of high softening-point makes rosin generation disproportionation reaction and purifying, by poly-hydroxy type alcohol the esterification more than rosin through disproportionation reaction of obtained purifying and trivalent to obtain the rosin ester of the softening temperature (according to around-France and ball) with 65 DEG C to 140 DEG C.The rosin ester obtained has excellent thermotolerance and ageing resistance and high softening temperature, and is suitable as the tackifier of contact adhesive composition and hot-melt composition.
Authorize Johnson on April 29th, 1986, the U.S. Patent No. 4,585,584 of Jr. etc. discloses a kind of method of rosin ester of color for the preparation of having improvement.The toll oil rosin ester depositing the tetramethylolmethane prepared in case at gac has the more shallow color of improvement.
A kind of rosin ester preparation of modification is disclosed in the U.S. Patent No. 4,643,848 of authorizing Thomas etc. on February 17th, 1987.Disclose when using with considerably less amount, phospho acid (also referred to as Hypophosporous Acid, 50) accelerate rosin and unsaturated dibasic acid reaction as catalyzer with formed for subsequently with the modified rosin of the esterification of poly-hydroxy type alcohol.According to the method for this invention, deposit in case at phospho acid, rosin and unsaturated dibasic acid are if maleic anhydride or fumaric acid are the thermotonus of about 180 DEG C to about 220 DEG C.When carrying out esterification to modified rosin subsequently, rosin ester shows the color of improvement, softening temperature and viscosity (in particular solution).
The U.S. Patent No. 4,657,703 of authorizing Durkee on April 14th, 1987 discloses a kind of method improving the color of toll oil rosin ester.The described method improving the color of toll oil rosin ester comprises following sequential steps: (a) deposits at lewis acid catalyst and heat and stir toll oil rosin in case to form mixture, b () distills this mixture to provide a kind of toll oil rosin overhead product, and (c) when phenolic curing compounds exists by described toll oil rosin overhead product and polyhydric alcohol esterification.The toll oil rosin ester of improvement obtained thus can be used for manufacturing various product, as paper and textiles sizing material, softening agent, paint, varnish, hotmelt and pressure sensitive adhesive for polyolefin film.
Authorize Johnson on November 10th, 1992, the U.S. Patent No. 5,162,496 of Jr. discloses a kind of method for the preparation of light-colored rosin esters.The catalyzed combination of phosphorous acid ester and phenol sulfide is accelerated and has been mediated the esterification of rosin and poly-hydroxy type alcohol, obtains having the esterified rosin of many advantageous feature in particular as the advantageous feature of the tackifier of hotmelt.
The esterification of rosin is disclosed in the U.S. Patent No. 5,504,152 of authorizing Schluenz etc. on April 2nd, 1996.Deposit make rosin contact to prepare rosin ester with polyvalent alcohol under enzymatic synthesis condition in case for rosin and the method for polyhydric alcohol being included in Bleachability mixture, described Bleachability mixture comprises alkaline earth hypophosphite and Hypophosporous Acid, 50, preferably also comprises machine sulfide.Described method can produce the rosin ester of the color with the gardner color number (Gardner neat) being less than about 5.Preferred Bleachability mixture comprises the alkaline earth hypophosphite of about 0.01% to about 0.10% and the active Hypophosporous Acid, 50 of about 0.10% to about 0.15%, and wherein said amount is based on the weight of rosin.Most preferred alkaline earth hypophosphite is calcium propionate.Specification sheets also describes the method being prepared tackiness agent by rosin ester.
The U.S. Patent No. 5,830,992 of authorizing Whalen on November 3rd, 1998 discloses rosin ester that is light, colour stable and preparation method thereof.Light color and the rosin ester of colour stable are by (single ethyl (3,5-, bis--tertiary butyl-4-hydroxy benzyl) phosphonic acids calcium is deposited and made poly-hydroxy type alcohol and the excessive rosin of equivalent react to prepare in case two.When phospho acid are joined in reaction mixture, obtained light color and the rosin ester of colour stable, and no matter rosin or polyvalent alcohol whether equivalent is excessive, but preferably rosin is that equivalent is excessive.Preferably comprise phenolic curing compounds (as Vultac.RTM2) and two (single ethyl (3,5-bis--tertiary butyl-4-hydroxy benzyl) phosphonic acids calcium, and drop at the acid number of rosin and poly-hydroxy type alcohol reaction mixture and about incrementally add phospho acid after 100.Preferably excessive rosin is separated in about 275 DEG C with product mixture.
The preparation of the toll oil rosin ester with low odor level is disclosed in the U.S. Patent No. 5,969,092 of authorizing Karvo on October 19th, 1999.This preparation method with the toll oil rosin ester of low odor level comprises makes toll oil rosin and polyhydric alcohol to form the esterif iotacation step of the product containing toll oil rosin ester, and this product is evaporated from this product, remove odour-producing component and other volatile constituent, this evaporation is carried out in short path evaporator (short-path evaporator), described vaporizer comprises water surface of evaporation and the condenser at this near surface, on condenser, the component being vaporized to be removed will be condensed, so reclaim the toll oil rosin ester with low odor level from vaporizer.
The U.S. Patent No. 6,562,888 of authorizing Frihart etc. on May 13rd, 2003 discloses light rosin ester and binder composition.These rosin esters are light color and colour stable, can obtain by making rosin with the organic compound reaction of the hydroxyl containing two or more at least 4 carbon atoms spaced from one another.Suitably select esterifying catalyst and antioxidant, rosin ester can be used as tackifier, and can be mixed with binder composition.Described binder composition will comprise suitable binder polymer further.
On August 16th, 2007 announce WO2007092250 and on August 2nd, 2007 announce U.S. publication 20070179277 (all belonging to Anthony Dallavia) disclose rosin ester with low look (low color) and preparation method thereof.Method (being preferably based on appropriate that rosin) for the preparation of light-colored rosin esters resin is deposited at the sour functional organic compounds being less than 10 % by weight and is carried out in case, and avoids the needs to using the sylvic acid of stoichiometric excess or the polyol hydroxyls of stoichiometric excess.The method allows to use lower look or darker toll oil rosin in the preparation of low look rosin ester.
The all patent quoted in this manual, application and publication are hereby incorporated by.
But, although have above-mentioned advantage, still exist in the art rosin ester, needs from the product of rosin ester and the method for manufacture and these resins of use and product.
It is found the alternative tackiness agent at the acceptable tackifier based on hydrogenated hydrocarbon resins of application of nonwovens that the another kind also existed needs.
Another needs also existed in the art have for such as application of nonwovens and the rosin ester of stark suitable color, colour stability and/or smell.
In the art, still there are other needs to tackifier.
In the art another needs to be for tackiness agent provides the tackifier for EVA packaging adhesive of the viscosity stability of increase.
In the art, also still needs are existed to the new tackifier for having the pressure sensitive adhesive with low look (PSA) of lower cost than use hydrogenated hydrocarbon resins base tackifier.
Further, in the art, to for providing the new tackifier of the bookbinding adhesive of the viscosity stability of improvement also still to there are needs with low cost.
For a person skilled in the art, after this specification sheets of reading comprises its accompanying drawing and claim, these and other demands in this area will become clear.
Summary of the invention
Various embodiment of the present invention can realize or not reach one or more object in following target.
An object of the present invention is to provide the method for rosin ester, product from rosin ester, manufacture and these resin esters of use and product.
Another object of the present invention is to provide the alternative tackiness agent finding acceptable hydrogenated hydrocarbon resins base tackifier in application of nonwovens.
Another object of the present invention is to provide the rosin ester with suitable color, colour stability and/or smell.
Another object of the present invention is to provide tackifier.
Another object of the present invention is to provide the tackifier for this tackiness agent for providing viscosity stability for EVA packaging adhesive.
Another object of the present invention is to provide the tackifier for pressure sensitive adhesive (PSA) with low look for having the cost lower than use hydrogenated hydrocarbon resins base tackifier.
Another object of the present invention is to provide the tackifier for bookbinding adhesive of the viscosity stability for providing low look and improvement with low cost.
For a person skilled in the art, after this specification sheets of reading comprises its accompanying drawing and claim, these and other objects in this area will become clear.
According to an embodiment of the invention, provide the method preparing rosin ester.Any one or more steps during described method can comprise the following steps with random order: the rosin making to have PAN isomer contacts the rosin providing PAN number to be less than 45 with disproportionation reaction reagent, thus provides the rosin through disproportionation reaction; Make the described rosin through disproportionation reaction contact to be reduced further by described PAN number with addition reaction reagent, thus the rosin through addition reaction is provided; And/or make the described rosin through addition reaction contact to form rosin ester with poly-hydroxy type polyvalent alcohol.
According to another implementation of the invention, the method preparing rosin ester is additionally provided.Any one or more steps during described method can comprise the following steps with random order: the rosin making PAN number be less than 45 contacts with addition reaction reagent to reduce described PAN number further, thus provides the rosin through addition reaction; And/or make the described rosin through addition reaction contact to form rosin ester with poly-hydroxy type polyvalent alcohol.
According to another implementation of the invention, additionally provide a kind of rosin ester composition, described composition has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
According to another embodiment of the present invention, additionally provide a kind of tackiness agent comprising rosin ester composition, described composition has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
According to another embodiment of the present invention, additionally provide a kind of nonwoven products comprising tackiness agent, described tackiness agent comprises rosin ester composition, and described rosin ester composition has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
Embodiment
In the practice of some non-limiting embodiment of the present invention, develop a kind of method to synthesize there is lower smell, rosin ester compared with the colour stability (compared with prior art) of weak color and/or improvement.The colour stability that some embodiment of rosin ester composition of the present invention is significantly improved at the temperature tool up to 150 DEG C, and/or these compositions are that hotmelt provides excellent thermostability when the aging at temperature up to 150 DEG C.Some of these rosin esters obtained is applicable to being used in traditional packaging and pressure sensitive adhesive, and unlike traditional rosin ester, they can also be used for the application of smell and Color-sensitive, as in non-woven tackiness agent (diaper configurations tackiness agent) or other high-end packaging adhesives.
In the practice of the invention, possible method for the RE tackiness agent providing low smell comprises the polyvalent alcohol used outside tetramethylolmethane (PE), use the mixture of polyvalent alcohol, or substitute PE partly or completely in rosin ester preparation significantly to reduce the content of described PE by the polyvalent alcohol of one or more other types of use.
Specifically, a non-limiting embodiment of the present invention provides the fumaric acid modified ester based on polyol component (it may be the blend of polyvalent alcohol, and a nonrestrictive example of this blend comprises glycerol and PE).Some embodiments in these embodiments can provide more shallow color and lower smell (with business SYLVALITE
tMrosin ester is compared), and aging or excellent colour stability and viscosity stability can also be provided when storing in the thermal stimulus warehouse condition raised.
Some embodiments of the present invention will provide the tackiness agent with low initial color and lower aging color (compared with commercial adhesive).Some embodiments of the present invention provide viscosity B coefficent less when aging compared with commercial adhesive.As a nonrestrictive example, the viscosity B coefficent of the tackiness agent obtained by some embodiments of rosin ester of the present invention after 350F is aging 96 hours for being less than 5%, 4%, 3%, 2% or 1%.
Some embodiment of the present invention can utilize partial disproportionation reactions steps.It is further observed that rosin color can reduce in this step process, but final ester can be shallow singularly in color.
Should be understood that, be well-known for the method for disproportionation of gum rosin and reagent, and any suitable disproportionation reaction method and reagent can be utilized, and the present invention is not limited to any specific method or reagent.Certainly, one or more disproportionation reaction method and reagent can be used.Suitable disproportionation reaction method and the non-limitative example of reagent are provided in US3,423, and 389, US4,302,371 and US4,657,703, its full content is introduced by reference to mode at this.
Disproportionation reaction reagent may be divided into some classes.Some embodiments of the present invention utilize the reagent of various phenol sulfide type.As concrete non-limitative example, ROSINOX
tM(poly-tert.-butyl phenol disulphide can obtain from Arkema, Inc.), LOWINOX
tMtBM-6 (4,4'-thiobis (the 2-tertiary butyl-5-methylphenol, can obtain from Chemtura), ETHANOX
tM323 (nonylphenol disulphide oligopolymer can obtain from Albemarle Corp.) and/or VULTAC
tM2 (amyl phenol disulfide polymer can obtain from Sovereign Chemical Co.).
Other non-limitative example of suitable disproportionation reaction reagent generally comprises thiobis naphthols.Suitable nonrestrictive example includes but not limited to: 2,2'-thiobisphenol, 3,3'-thiobisphenol, 4,4'-thiobis (Resorcinol) and t, t'-thiobis (pyrogallol), 4,4'-thiobis (6-tert-butyl-m-cresol) and 4/4'-thiobis (the 6-tertiary butyl-o-cresols), thiobis naphthols, 2,2'-sulfo-s-bis-phenol, 3,3'-sulfo-s-bis-phenol etc.
Other non-limitative examples of suitable disproportionation reaction reagent comprise metal (its non-limitative example includes but not limited to: palladium, nickel, platinum) or iodine or iodide (its non-limitative example includes, but are not limited to: ferric iodide) or sulfide (its nonrestrictive example includes, but are not limited to picture iron sulphide).
In some embodiments, the rosin before disproportionation reaction can have the PAN number of about 50.PAN number as used herein is the summation of the percentage ratio of sylvic acid (it is palustric acid, abietic acid, neoabietic acid) in rosin.In certain embodiments of the present invention, disproportionation reaction will cause final PAN number to be about 20 to 25.In some other embodiment of the present invention, disproportionation reaction is 15 to 30 by causing final PAN number.In addition in some other embodiment of the present invention, disproportionation reaction is 10 to 40 by causing final PAN number.Disproportionation reaction may cause final PAN number to be 0.1,1,2,5,10,15,20,25,35,35,40 or 45, or is to the scope of another numerical value between any two numerical value in above numerical value and/or from a numerical value in any two numerical value above numerical value.
Some embodiments of the present invention represent color perfecting in the rosin through disproportionation reaction and the ester obtained by described rosin shows the scale resistance of improvement, and find that fumaric acid adduction glycerol/pentaerythritol ester can show smell and the colour stability of improvement.Some embodiment of the present invention can provide the light-colored rosin esters of suitable low smell, and this rosin ester can be suitable in non-woven fabric tackiness agent by adopting the appropriately combined of technique and synthesis condition.
As is well known in the art, rosin ester can use rosin, catalyzer, SYNTHETIC OPTICAL WHITNER, poly-hydroxy type polyvalent alcohol (also referred to as being polyvalent alcohol), stablizer and/or antioxidant to prepare.Described catalyzer, stablizer and/or SYNTHETIC OPTICAL WHITNER are known as described in this area, such as, described in United States Patent (USP) 2729660,3310575,3423389,3780013,4172070,4548746,4690783,4693847,4725384,4744925,4788009,5021548 and 5049652.
In general, can comprise for the preparation of the method for rosin ester of the present invention rosin preferred molten rosin is contacted with polyvalent alcohol.
The suitable example of operable rosin can include but not limited in the method for the invention: gum resin, wood rosin or toll oil rosin or their random subset or mixture.Preferred rosin is toll oil rosin.In some embodiments, toll oil rosin can be the isomer mixture primarily of C20 condensed ring monocarboxylic acid hydrocarbon composition, and it can be typically levopimaric acid, abietic acid, pimaric acid, dehydroabietic acid.In the present invention, the amount of rosin used can depend on final application and different.
Gum resin, wood rosin, toll oil rosin and other rosin itself can be directly used in method of the present invention, or can carry out other process before use in the method for the invention.Such as, rosin material can be subject to distillation, disproportionation, hydrogenation or polymerization before being used in present method, or some combined treatment of these process and/or other process.
Poly-hydroxy type polyvalent alcohol, is also referred to as polyvalent alcohol sometimes, as the other reactant adopted in present method, is also well-known.The example of such compound is ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1,3-PD, glycerol, tetramethylolmethane, Dipentaerythritol, tripentaerythritol, trimethylolethane, TriMethylolPropane(TMP), mannitol and Sorbitol Powder.Some embodiments of the present invention can utilize the combination of two or more polyvalent alcohols of above-mentioned polyvalent alcohol.As a non-limitative example, some embodiments can use the combination of two or more in glycerol, tetramethylolmethane and TriMethylolPropane(TMP).
Some embodiments of the present invention by utilize tetramethylolmethane and at least 1,2,3,4,5 kind or more polyhydric alcohol conjugate of planting other polyvalent alcohol, a nonrestrictive example of described polyhydric alcohol conjugate comprises at least one in tetramethylolmethane and glycerol or TriMethylolPropane(TMP) in (TMP).Combination can be added as the mixture of tetramethylolmethane and other polyvalent alcohols, or combination can be added by the tetramethylolmethane mode that then other polyvalent alcohols add in turn, or first adds described one or then more kinds of polyvalent alcohol adds tetramethylolmethane.Therefore, some embodiments of the present invention can adopt tetramethylolmethane then at least 1,2,3,4,5 kind or more addition manner in turn of planting other polyvalent alcohol, its nonrestrictive example comprise tetramethylolmethane then glycerol, tetramethylolmethane then TriMethylolPropane(TMP), tetramethylolmethane then glycerol subsequently TriMethylolPropane(TMP), tetramethylolmethane then TriMethylolPropane(TMP) subsequently then glycerol or tetramethylolmethane are the mixtures of glycerol and TriMethylolPropane(TMP).Some embodiments of the present invention can adopt the mode of adding following mixture: the mixture of the mixture of the mixture of tetramethylolmethane and glycerol, tetramethylolmethane and TriMethylolPropane(TMP), tetramethylolmethane and glycerol and TriMethylolPropane(TMP).
Some embodiment of the present invention by adopt glycerol and/or TriMethylolPropane(TMP) and at least 1,2,3,4, the combination of 5 kind or more other polyvalent alcohol of kind.This combination can be added as the mixture of glycerol and/or TriMethylolPropane(TMP) and other polyvalent alcohols, or this combination can be added by glycerol and/or the TriMethylolPropane(TMP) mode that then other polyvalent alcohols add in turn, or add by the mode of described other polyvalent alcohols a kind of or more kinds of then glycerol.Therefore, some embodiments of the present invention can adopt glycerol and/or TriMethylolPropane(TMP), at least 1,2,3,4,5 kind or more plant other polyvalent alcohol mode that then glycerol is added in turn and add, its nonrestrictive example comprises glycerol then tetramethylolmethane, TriMethylolPropane(TMP) then tetramethylolmethane or glycerol and TriMethylolPropane(TMP) (together with add or add in turn) then tetramethylolmethane.
Polyhydric alcohol conjugate mentioned above can comprise the tetramethylolmethane (gross weight based on the polyvalent alcohol in this combination) being equal to or less than following weight percent: 0,0.001,0.01,0.1,1,2,3,4,5,6,7,8,9,10,15,17.5,20 or any two numerical value in above-mentioned numerical value between weight percent and/or from a numerical value in any two numerical value above-mentioned numerical value to the weight percent of another numerical value.
The amount of the alcohol adopted in esterification step can change widely.But in general, based on the amount of rosin, adopt the poly-hydroxy type polyvalent alcohol at least about equivalent, its upper limit is generally exceed this equivalent about 50%.
In certain embodiments of the present invention, rosin can carry out addition reaction step before alcohol being shunk to (contracting).In some embodiments, addition reaction reagent can be selected as by Diels-Alder reaction (Diels-Alder reaction) or alkene reaction (Ene reaction) the most easily and the PAN isomerization reaction of rosin.The non-limitative example of suitable addition reaction reagent includes but not limited to that unsaturated carboxylic acid or their equivalent are as acid anhydrides.
In certain embodiments of the present invention, after disproportionation reaction step, enough PAN isomer can be there is to allow to react with addition reaction reagent in rosin.In some embodiments, enough low PAN isomer may be needed, oxidative stability can may be caused poor when storing because there is too many unreacted PAN acid isomer (no matter being free acid or the acid of esterification) in some cases in final rosin ester, this may cause the colour stability of difference and the smell of difference.The suitable PAN number of the rosin of pending addition reaction (namely, PAN number before addition reaction) non-limitative example comprise 0.1,1,2,5,10,15,20,25,35,35,40 or 45, or be to the scope of another numerical value between any two numerical value in above numerical value and/or from a numerical value in any two numerical value above numerical value.The non-limitative example of OK range includes but not limited to: 20 to 25,15 to 30 and 10 to 40.
The non-limitative example of suitable addition reaction reagent includes but not limited to: fumaric acid, maleic anhydride, vinylformic acid and other unsaturated acid or their equivalent are as acid anhydrides.
In some embodiments, the level of the PAN colophony isomerization body stayed after reducing disproportionation reaction further can be adopted in addition reaction step.In some embodiments, addition reaction step may increase molecular weight and the softening temperature of rosin ester.In some embodiments, but this can allow to use can provide the ester of lower smell can also have other polyhydric alcohols of the softening temperature lower than PE ester if glycerol or TMP are to replace tetramethylolmethane (PE).But as a nonrestrictive example, the glycerine ester of fumaric acid adduction can have the softening temperature similar with PE ester, and may be used for similar purposes can have stronger scale resistance and lower smell.In some embodiments, partial disproportionation reactions steps can further improve scale resistance, and can reduce the smell of final rosin ester.For some embodiments, as shown in following embodiment, the fumaric acid of higher level provides the rosin ester of lower smell, as when comparing with normal business PE rosin ester we smell group judge.
In some embodiments, the weight percent of the addition reaction reagent used can equal or higher than 0.1,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,10,20,30 % by weight of preparation, or in scope between in above-mentioned weight percent any two or in any two weight percents one to another scope.As a nonrestrictive example, the weight-average molecular weight Mw of obtained rosin ester is increased to about 1200 to 1600 dalton (compared with about 900 to 1000 dalton of PE rosin ester) by the fumaric acid level accounting for about 2% to 2.8% of preparation.For some embodiments, the fumaric acid of 2.4% to 2.8% may be favourable.
Some embodiments of rosin ester can show the odor intensity decreased compared with PE rosin ester.As some non-limitative examples, the relative intensity had (rosin ester relative to the PE of employing 100%) is equal to or less than 80%, 75%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30% of the rosin ester of the PE of employing 100% by the odor intensity of some embodiment (it adopts the PE being less than 100%) of rosin ester, or in scope between in above-mentioned relative intensity any two or in any two relative intensities one to another scope.Odor intensity is according to determining like that shown in following embodiment.
Some embodiments of rosin ester of the present invention can be used as the tackifying resin in hotmelt and be used as the binder resin in low look used in printing (such as high gloss magazine, advertisement and company Annual report), overprint varnishes.
Embodiment
The following examples and the result shown in table 1-6 below illustrate advantage of the present invention by the result of various types of test of carrying out on rosin ester of the present invention and evaluation.
Embodiment is generally following carries out:
At nitrogen, the toll oil rosin (SYLVAROS melting the light color (gardner color number is 3.2) of 600g at 180 DEG C in 2 liters of three-necked bottles
tMr type S).
Add the ROSINOX of 3.53g wherein
tMdisproportionation reaction reagent, the mixture of gained is heated to 275 DEG C 2 hours, with nitrogen gas stream slowly by reactor, use syringe pump to add distilled water with 3.9 mls/hour in flask simultaneously.
Next, flask be cooled to 180 DEG C and add the fumaric acid of 19.77g (total reinforced 2.8%), the mixture of gained is heated to 220 DEG C 1 hour, be then cooled to 180 DEG C.
Now, add tetramethylolmethane and then add glycerol, and temperature is elevated to 250 DEG C.
Once reach 250 DEG C, add three-(nonyl phenyl) phosphite (or ester) (TNPP) of 1.06g.
After 1 hour, cool the temperature to 180 DEG C spend the night (13 hours).
Morning, be heated to 250 DEG C 2 hours.
Reactor sample has the softening temperature of 85.2 DEG C, and acid number is 24.5, and gardner color number is 2.
Reactant is heated to 275 DEG C, and uses nitrogen bubble 4 hours.
Then reactant is cooled, and add the KOH aqueous solution of 50% of 0.14g, the Irganox of 0.99g
tM1010 and the Irganox of 0.35g
tM565.The resin of 200 DEG C is poured in pot and cools.
Final analysis: softening temperature is 98.3 DEG C, acid number is 4.9, and gardner color number is 2+.
The smell group assessment of 5 non-limitative examples of rosin ester of the present invention and business rosin ester SYLVALITE when 50 DEG C
tMrosin ester compares, and lower numeral odor intensity is lower.
Embodiment 1
As shown in table 1, in some embodiments of the present invention, find that smell significantly reduces.
The test method of odor intensity is summarized as follows:
1, the wide-necked bottle of 8 ounces put into by each resin taking 25g.Two wide-necked bottles are equipped with two experiment test resins, and the 3rd wide-necked bottle is equipped with standard specimen.
2, resin-oatmeal is broken into meal to expose fresh surf zone.
3, the wide-necked bottle that three are sealed is placed in the baking oven being preheating to (49+/-2 DEG C) by random sequence.
4, wide-necked bottle is put on coding, make trial body do not know each sample identity.
5, sample is balanced 2 hours in an oven.
6, our smell group at least 5 bit test person (they have experience in news rosin ester sample) assess sample group is as follows:
7, each group member hears wide-necked bottle simply, and gives a numeral between each resin distribution 0 to 10 according to the intensity of smell.0 represents do not have smell, and 10 represent extremely strong smell.Group member can also write the description of smell, but its numerical value only reflects the intensity of smell, instead of the characteristic of smell.
8, in Odor Evaluations gap, shake sealed sample sets gently, and put back to baking box minimum 30 minutes.
9, after being evaluated by 5 to 8 smells evaluation members, the odor intensity value of each sample is averaged calculating.The intensity calculating each sample relative to standard specimen ratio and report together with raw data (standard specimen=1.0).
Specifically, sample D and E fumaric acid content the highest, (" SYLVALITE
tMrosin ester does not have).Without being limited by theory, applicant infers, this surprising situation may be reduce one of relevant factor with smell.A nonrestrictive hypothesis is, the colophony isomerization precursor reactant of the preferential and most activity of fumaric acid, it may also produce relevant with smell.
Table 1. odor intensity and fumaric acid praise addition reaction level (relative to SYLVALITE
tMthe odor intensity of rosin ester)
Embodiment 2
Table 2 shows the smell small set of data of test resin formulation, and described test resin formulation adopts constant 2% fumaric acid (FA) addition reaction and consistent processing condition, but adopts the tetramethylolmethane of different levels to replace some glycerol.These results cause the early stage supposition of the offending smell of final ester to be identical with the tetramethylolmethane impurity produced during high temperature esterification reaction process or degradation production.Therefore, this shows, for some embodiments, if use PE, lower level should be kept to make the smell of obtained rosin ester minimum.
Table 2. odor intensity and tetramethylolmethane level
Embodiment 3
Table 3 shows the high oxidation resistance that method comprises some embodiment of the present invention of disproportionation reaction step.150 DEG C 24 hours in atmosphere, tackifying resin of the present invention, particularly favourable formulation C and D, display wants the colour-darkening of much less than contrast.Establish a capital like this although all embodiments differ, at least for the embodiment of the present embodiment, disproportionation reaction provides the resin ester with more favourable performance in some cases.Therefore, depend on desired end-use, in some cases, may wish to need disproportionation reaction step.Similarly, in EVA based adhesive preparation, some embodiment of tackifying resin of the present invention shows than the better color of contrast.
Table 3. is from oxidative stability of the present invention and color perfecting
DSC=dsc.In oxidisability DSC, sample heats until sample oxidation (as shown in its heat release) at 128 DEG C at the oxygen pressure of 550psi.
EVA=ethylene vinyl acetate copolymer.
Embodiment 4
Table 4 illustrate business SIS/ hydrogenated hydrocarbon resins thickening tackiness agent and use rosin ester tackifier obtain the comparison carried out between SIS tackiness agent.For these embodiments, the tackiness agent adopting the top rosin pentaerythritol ester of commercially available acquisition (Arizona chemistry (Arizona Chemical)) to obtain shows the smell similar or stronger to commercial adhesive with the tackiness agent that some embodiment by the ester of the present invention not carrying out disproportionation reaction step obtains.But, adopt the tackiness agent be made up of the sample resins of some embodiment of the present invention to be judged as having the smell significantly lower than business SIS tackiness agent by smell group.
Table 4. uses the SIS tackiness agent of new rosin ester tackifier to compare with the smell of business SIS/ hydrocarbon resin tackiness agent
Embodiment 5
Also styrene-based-isoprene styrene (SIS) for the standard pressure sensitive binder formulation of label applications in the rosin ester C from some embodiment of the present invention is evaluated.By result and with normal business rosin ester and SYLVALITE
tMthose results that rosin ester obtains compare.Result is shown in Table 5.Although rosin ester of the present invention demonstrates lower loop tack (loop tack), its performance and business rosin ester quite or be better than business rosin ester, therefore will be expected to become acceptable tackifier for these tackiness agents on the whole.
Table 5. uses rosin ester C and business SYLVALITE
tMthe bond properties of the HMPSA label preparation based on SIS of rosin ester
Embodiment 6
Also evaluate from rosin ester C of the present invention in based on the standard hot melt packaging adhesive preparation of EVA.By the result of thermostability (color and viscosity stability) and with normal business rosin ester, i.e. SYLVALITE
tMthose results that rosin ester obtains compare.Result is shown in Table 6.The tackiness agent adopting rosin ester of the present invention to obtain shows the stability suitable with commerical prod; Therefore, rosin ester of the present invention will be expected to become acceptable tackifier for these tackiness agents.
Table 6. uses rosin ester C and business SYLVALITE
tMthe adhesion stability of the thermal capacitance packaging adhesive preparation based on EVA of rosin ester
Present disclosure is appreciated that exemplary instead of is limited the scope of claims and character.Those skilled in the art comprises the equivalent function and/or structure surrogate that use for element as described herein at research present disclosure, the equivalent function for connection as described herein is used to connect, and/or after the action of use for the equivalent function of action as described herein, will be seen that various modifications and variations.The change of any unsubstantiality all should be considered to be within the scope of appended claim.
Claims (27)
1. manufacture a method for rosin ester, described method comprises:
(A) make the rosin with PAN isomer contact the rosin providing PAN number to be less than 45 with disproportionation reaction reagent, thus the rosin through disproportionation reaction is provided;
(B) make the described rosin through disproportionation reaction contact to be reduced further by described PAN number with addition reaction reagent, thus the rosin through addition reaction is provided;
(C) the described rosin through addition reaction is made to contact to form rosin ester with poly-hydroxy type polyvalent alcohol;
Wherein, described poly-hydroxy type polyvalent alcohol comprise the gross weight based on described poly-hydroxy type polyvalent alcohol be equal to or less than 20 % by weight tetramethylolmethane;
Wherein said rosin ester has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
2. method according to claim 1, wherein, described disproportionation reaction pack is containing at least one be selected from phenol sulfide, metal, iodine, iodide and sulfide, and described addition reaction reagent is selected as the PAN isomerization reaction by Diels-Alder reaction or alkene reaction with rosin.
3. method according to claim 1, wherein, described disproportionation reaction pack is containing being selected from 2,2'-thiobisphenol, 3,3'-thiobisphenol, 4,4'-thiobis (Resorcinol) and t, t'-thiobis (pyrogallol), 4,4'-thiobis (6-tert-butyl-m-cresol) and 4/4'-thiobis (the 6-tertiary butyl-o-cresols) thiobis naphthols, 2, at least one in 2'-sulfo--bis-phenol, 3,3'-sulfo-s-bis-phenol, palladium, nickel, platinum, iodine, ferric iodide, iron sulphide.
4. method according to claim 1, wherein, described addition reaction pack is containing at least one be selected from unsaturated acid and acid anhydrides.
5. method according to claim 1, wherein, described addition reaction pack is containing at least one be selected from fumaric acid and vinylformic acid.
6. method according to claim 1, wherein, described addition reaction pack is containing maleic anhydride.
7. method according to claim 1, wherein, described poly-hydroxy type polyvalent alcohol comprises at least one in the group being selected from and being made up of ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1,3-PD, glycerol, Dipentaerythritol, tripentaerythritol, trimethylolethane, TriMethylolPropane(TMP), mannitol and Sorbitol Powder.
8. method according to claim 1, wherein, described poly-hydroxy type polyvalent alcohol comprises at least one in the group being selected from and being made up of glycerol and TriMethylolPropane(TMP).
9. manufacture a method for rosin ester, described method comprises:
(A) rosin making PAN number be less than 45 contacts to reduce PAN number further with addition reaction reagent, thus provides the rosin through addition reaction;
(B) the described rosin through addition reaction is made to contact to form rosin ester with poly-hydroxy type polyvalent alcohol;
Wherein, described poly-hydroxy type polyvalent alcohol comprise the gross weight based on described poly-hydroxy type polyvalent alcohol be equal to or less than 20 % by weight tetramethylolmethane;
Wherein said rosin ester has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
10. method according to claim 9, wherein, described addition reaction reagent be selected as by by Diels-Alder reaction or alkene reaction with the PAN isomerization reaction of rosin.
11. methods according to claim 9, wherein, described addition reaction pack is containing at least one be selected from unsaturated acid and acid anhydrides.
12. methods according to claim 9, wherein, described addition reaction pack is containing at least one be selected from fumaric acid and vinylformic acid.
13. methods according to claim 9, wherein, described addition reaction pack is containing maleic anhydride.
14. methods according to claim 9, wherein, described poly-hydroxy type polyvalent alcohol comprises at least one in the group being selected from and being made up of ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1,3-PD, glycerol, Dipentaerythritol, tripentaerythritol, trimethylolethane, TriMethylolPropane(TMP), mannitol and Sorbitol Powder.
15. methods according to claim 9, wherein, described poly-hydroxy type polyvalent alcohol comprises at least one in the group being selected from and being made up of glycerol and TriMethylolPropane(TMP).
16. 1 kinds of rosin ester compositions, described composition has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%; Wherein, described composition contacts to form rosin ester to manufacture by making the rosin through addition reaction with poly-hydroxy type polyvalent alcohol, the described poly-hydroxy type polyvalent alcohol gross weight comprised based on described poly-hydroxy type polyvalent alcohol be equal to or less than 20 % by weight tetramethylolmethane; The described rosin through addition reaction contacts to reduce PAN number further to obtain with addition reaction reagent by the rosin making PAN number and be less than 45.
17. compositions according to claim 16, described composition has the odor intensity being less than 60% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
18. compositions according to claim 16, described composition has the odor intensity being less than 55% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
19. compositions according to claim 16, described composition has the odor intensity being less than 50% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
20. 1 kinds of tackiness agents comprising rosin ester composition, described rosin ester composition has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%; Wherein, described composition contacts to form rosin ester to manufacture by making the rosin through addition reaction with poly-hydroxy type polyvalent alcohol, the described poly-hydroxy type polyvalent alcohol gross weight comprised based on described poly-hydroxy type polyvalent alcohol be equal to or less than 20 % by weight tetramethylolmethane; The described rosin through addition reaction contacts to reduce PAN number further to obtain with addition reaction reagent by the rosin making PAN number and be less than 45.
21. tackiness agents according to claim 20, wherein, described composition comprises the odor intensity being less than 60% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
22. tackiness agents according to claim 20, wherein, described composition comprises the odor intensity being less than 55% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
23. tackiness agents according to claim 20, wherein, described composition comprises the odor intensity being less than 50% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%.
24. 1 kinds of nonwoven products comprising tackiness agent, described tackiness agent comprises rosin ester composition, and described rosin ester composition has the odor intensity being less than 80% for the comparison rosin ester that obtains relative to the tetramethylolmethane by 100%; Wherein, described composition contacts to form rosin ester to manufacture by making the rosin through addition reaction with poly-hydroxy type polyvalent alcohol, the described poly-hydroxy type polyvalent alcohol gross weight comprised based on described poly-hydroxy type polyvalent alcohol be equal to or less than 20 % by weight tetramethylolmethane; The described rosin through addition reaction contacts to reduce PAN number further to obtain with addition reaction reagent by the rosin making PAN number and be less than 45.
25. products according to claim 24, wherein, are less than 60% for the comparison rosin ester that described odor intensity is obtained relative to the tetramethylolmethane by 100%.
26. products according to claim 24, wherein, are less than 55% for the comparison rosin ester that described odor intensity is obtained relative to the tetramethylolmethane by 100%.
27. products according to claim 24, wherein, are less than 50% for the comparison rosin ester that described odor intensity is obtained relative to the tetramethylolmethane by 100%.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2011/031884 WO2012141675A1 (en) | 2011-04-11 | 2011-04-11 | Rosin esters for non-wovens |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103517957A CN103517957A (en) | 2014-01-15 |
| CN103517957B true CN103517957B (en) | 2015-06-10 |
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|---|---|---|---|
| CN201180070558.1A Expired - Fee Related CN103517957B (en) | 2011-04-11 | 2011-04-11 | Rosin esters for non-wovens |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2697322A4 (en) |
| JP (1) | JP2014517091A (en) |
| KR (1) | KR20140022059A (en) |
| CN (1) | CN103517957B (en) |
| AU (1) | AU2011365712A1 (en) |
| BR (1) | BR112013026297A2 (en) |
| CA (1) | CA2833114A1 (en) |
| RU (1) | RU2569081C2 (en) |
| WO (1) | WO2012141675A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6040686B2 (en) * | 2012-09-28 | 2016-12-07 | 星光Pmc株式会社 | Rosin polyhydric alcohol ester resin, ink emulsification suitability improver, varnish for offset printing ink and ink composition for offset printing |
| CN103436174B (en) * | 2013-08-27 | 2015-03-18 | 广西梧州松脂股份有限公司 | Preparation method of rosin glycerin ester |
| EP3049475B1 (en) * | 2013-09-27 | 2018-01-10 | Arizona Chemical Company, LLC | Compositions containing ethylene polymers |
| US10011740B2 (en) * | 2013-09-27 | 2018-07-03 | Kraton Chemical, Llc | Rosin esters and compositions thereof |
| CN104559794B (en) * | 2013-12-16 | 2017-05-10 | 广西梧州日成林产化工股份有限公司 | Preparation method of alcohol soluble acrylic rosin resin |
| CN106103634B (en) * | 2014-03-12 | 2019-01-18 | 荒川化学工业株式会社 | Pressure sensitive adhesive compositions and acrylic pressure-sensitive adhesivee adhesive composition |
| CN106170517B (en) * | 2014-03-28 | 2019-05-28 | 荒川化学工业株式会社 | Tackifying resin, pressure sensitive adhesive compositions, thermotropic pressure sensitive adhesive tackifying resin, thermotropic pressure sensitive adhesive compound |
| KR101582952B1 (en) * | 2014-04-16 | 2016-01-06 | 주식회사 아이티엠반도체 | Package of battery protection circuits and battery pack |
| WO2016109206A2 (en) * | 2014-12-31 | 2016-07-07 | Arizona Chemical Company, Llc | Rosin-containing materials and methods of making thereof |
| CN104694015B (en) * | 2015-03-18 | 2017-01-11 | 桂林兴松林化有限责任公司 | Preparation method of light-color glycerol ester of rosin |
| JP6821647B2 (en) | 2015-03-26 | 2021-01-27 | アリゾナ ケミカル カンパニー エルエルシーＡｒｉｚｏｎａ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ， Ｌｌｃ | Composition containing rosin ester and ethylene polymer |
| KR102040268B1 (en) * | 2015-07-10 | 2019-11-04 | 재단법인 한국화학융합시험연구원 | Anti-cutting and anti-chipping agent for rubber and preparation method thereof |
| JP6996077B2 (en) * | 2015-12-28 | 2022-01-17 | 荒川化学工業株式会社 | Adhesive-imparting resin, adhesive / adhesive, hot melt adhesive |
| TWI731094B (en) * | 2016-06-16 | 2021-06-21 | 日商荒川化學工業股份有限公司 | Tackifying resin, tackifying resin emulsion, water-based adhesive composition, polychloroprene latex-based adhesive composition |
| WO2019210036A1 (en) * | 2018-04-26 | 2019-10-31 | Ingevity South Carolina, Llc | Carboxylic acid adducted rosin polyol ester with fatty acid functionality and methods of producing the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2833114A1 (en) | 2012-10-18 |
| EP2697322A4 (en) | 2015-08-05 |
| KR20140022059A (en) | 2014-02-21 |
| WO2012141675A1 (en) | 2012-10-18 |
| RU2013145603A (en) | 2015-05-20 |
| AU2011365712A1 (en) | 2013-10-31 |
| JP2014517091A (en) | 2014-07-17 |
| BR112013026297A2 (en) | 2017-06-06 |
| EP2697322A1 (en) | 2014-02-19 |
| RU2569081C2 (en) | 2015-11-20 |
| CN103517957A (en) | 2014-01-15 |
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