CN103517957A - Rosin esters for non-wovens - Google Patents
Rosin esters for non-wovens Download PDFInfo
- Publication number
- CN103517957A CN103517957A CN201180070558.1A CN201180070558A CN103517957A CN 103517957 A CN103517957 A CN 103517957A CN 201180070558 A CN201180070558 A CN 201180070558A CN 103517957 A CN103517957 A CN 103517957A
- Authority
- CN
- China
- Prior art keywords
- rosin ester
- rosin
- tetramethylolmethane
- less
- respect
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
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 product that the present invention relates to rosin ester, the product being made by rosin ester or comprise rosin ester, and the method for preparing and use these rosin esters or product.In yet another aspect, the present invention relates to can be used for the rosin ester in application of nonwovens, the nonwoven products being made by rosin ester and/or the nonwoven products that comprises rosin ester, and the method for preparing and use these rosin esters and product.Even in one aspect of the method, they the present invention relates to there is suitable color, colour stability and/or smell so that can be used for the rosin ester in application of nonwovens, the nonwoven products being made by rosin ester and/or the nonwoven products that comprises rosin ester, and the method for preparing and use these rosin esters and product.
Background technology
At present, rosin ester can not be accepted for non-woven tackiness agent industry.As a nonrestrictive example, the use of the tackiness agent using as structure disposable infant diaper.In most cases, 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 adhesive 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 for the low smell of non-woven tackiness agent.
The GC with Headspace of (Princeton laboratories) in laboratory, Princeton-MS research shows, has a large amount of compositions with fetor in rosin ester.With some species of being low to moderate in the chemical species of these stenches that the level that almost can not detect exists, be low-molecular-weight aldehyde and carboxylic acid.Soon the other work completing in Princeton after described head space research shows, the smell that the rosin ester being made by cyclohexanedimethanol (CHDM, cyclohexane dlmethanol) and corresponding hotmelt tool are significantly improved.Yet problem is that CHDM base rosin ester has too low softening temperature (SP) to such an extent as to cannot effectively be applied in most of hotmelts.Technique center, Princeton Mass Spectrum Laboratory report (Princeton Technology Center Mass Spectrometry Laboratory Reports) referring in February, 1998 and issue on April 5th, 1996.
The U.S. Patent No. 4,302,371 of authorizing Matsuo etc. on November 24th, 1981 discloses a kind of stable rosin ester and pressure sensitive adhesive and the hot-melt composition based on them.Preparation has compared with the method for this stable rosin ester of high softening-point and comprises and make rosin generation disproportionation reaction purifying, by resulting purifying through the rosin of disproportionation reaction and poly-hydroxy type alcohol esterification more than trivalent to obtain having the rosin ester of the softening temperature (according to around-France and ball method) of 65 ℃ to 140 ℃.Resulting rosin ester has good thermotolerance and ageing resistance and high softening temperature, and is suitable as the tackifier of contact adhesive composition and hot-melt composition.
On April 29th, 1986, authorize Johnson, the U.S. Patent No. 4,585,584 of Jr. etc. discloses a kind of method of rosin ester for the preparation of having the color of improvement.The toll oil rosin ester of the tetramethylolmethane of preparing in the situation that gac exists has improved more shallow color.
The U.S. Patent No. 4,643,848 of authorizing Thomas etc. on February 17th, 1987 discloses a kind of rosin ester preparation of modification.Disclose when amount with considerably less is used, what phospho acid (also referred to as Hypophosporous Acid, 50) had been accelerated rosin and unsaturated dibasic acid as catalyzer reacts to be formed for subsequently the modified rosin with the esterification of poly-hydroxy type alcohol.According to the method for this invention, in the situation that phospho acid exist, rosin and unsaturated dibasic acid are as maleic anhydride or the fumaric acid thermotonus at approximately 180 ℃ to approximately 220 ℃.When subsequently modified rosin being carried out to esterification, rosin ester shows color, softening temperature and the viscosity (in particular solution) of improvement.
The U.S. Patent No. 4,657,703 of authorizing Durkee on April 14th, 1987 discloses a kind of method of improving the color of toll oil rosin ester.The described method of improving the color of toll oil rosin ester comprises following sequential steps: (a) in the situation that lewis acid catalyst exists, heat and stir toll oil rosin to form mixture, (b) distill this mixture so that a kind of toll oil rosin overhead product to be provided, and (c) in the situation that phenol sulfide compound exists by described toll oil rosin overhead product and polyvalent alcohol esterification esterification.The toll oil rosin ester of the improvement making thus can be used for manufacturing various products, as paper and textiles sizing material, softening agent, paint, varnish, hotmelt and pressure sensitive adhesive for polyolefin film.
On November 10th, 1992, authorize Johnson, the U.S. Patent No. 5,162,496 of Jr. discloses a kind of method for the preparation of light-colored rosin esters.The esterification of rosin and poly-hydroxy type alcohol is accelerated and mediated to the catalyzed combination of phosphorous acid ester and phenol sulfide, obtains having many advantageous feature in particular as the esterified rosin of the advantageous feature of the tackifier of hotmelt.
The U.S. Patent No. 5,504,152 of authorizing Schluenz etc. on April 2nd, 1996 discloses the esterification of rosin.For the method for rosin and polyvalent alcohol esterification being included in the situation that bleaching property mixture exists, make rosin under enzymatic synthesis condition, contact to prepare rosin ester with polyvalent alcohol, described bleaching mixture comprises alkaline earth hypophosphite and Hypophosporous Acid, 50, preferably also comprises machine sulfide.Described method can be produced the rosin ester of the color with the gardner color number (Gardner neat) that is less than approximately 5.Preferred bleaching property mixture comprises approximately 0.01% to approximately 0.10% alkaline earth hypophosphite and approximately 0.10% to approximately 0.15% active Hypophosporous Acid, 50, the weight of wherein said amount based on rosin.Most preferred alkaline earth hypophosphite is calcium propionate.Specification sheets has also been described the method for 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 light color, colour stable and preparation method thereof.The rosin ester of light color and colour stable is by (making the poly-hydroxy type alcohol rosin excessive with equivalent react to prepare in the situation that single ethyl (3,5-, bis--tertiary butyl-4-hydroxy benzyl) phosphonic acids calcium exists two.When phospho acid are joined in reaction mixture, make the rosin ester of light color and colour stable, and no matter whether equivalent is excessive for rosin or polyvalent alcohol, but preferably rosin is that equivalent is excessive.Preferably comprise phenol sulfide compound (as Vultac.RTM2) and two (single ethyl (3,5-bis--tertiary butyl-4-hydroxy benzyl) phosphonic acids calcium, and drop to approximately and with incremental manner, add phospho acid after 100 at the acid number of rosin and poly-hydroxy type alcohol reaction mixture.Preferably that excessive rosin is separated with product mixture in approximately 275 ℃.
The U.S. Patent No. 5,969,092 of authorizing Karvo on October 19th, 1999 discloses the preparation of the toll oil rosin ester with low odor level.This preparation method with the toll oil rosin ester of low odor level comprises makes toll oil rosin and polyvalent alcohol esterification to form the esterif iotacation step of the product that contains toll oil rosin ester, and this product is evaporated to 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 at the condenser of this near surface, on condenser, the component that is 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 be light color and colour stable, can be by making rosin and containing two organic compound reactions that separate each other above the hydroxyl of at least 4 carbon atoms and make.Suitably select esterifying catalyst and antioxidant, rosin ester can be used as tackifier, and can be mixed with binder composition.Described binder composition will further comprise suitable binder polymer.
The WO2007092250 announcing on August 16th, 2007 and U.S.'s communique 20070179277 (all belonging to Anthony Dallavia) of announcing on August 2nd, 2007 disclose the have low look rosin ester and preparation method thereof of (low color).For the preparation of the method for light-colored rosin esters resin (be preferably based on appropriate you rosin), in the situation that be less than the sour functional organic compounds of 10 % by weight and exist and carry out, and avoided using the needs of the excessive polyvalent alcohol hydroxyl of the excessive sylvic acid of stoichiometry or stoichiometry.The method allows to use lower look or darker toll oil rosin in the preparation of low look rosin ester.
All patents, application and the publication quoted are in this manual hereby incorporated by.
Yet, although there is above-mentioned advantage, still exist in the art to rosin ester, from the needs of the product of rosin ester and the method for manufacture and these resins of use and product.
The another kind also existing need to be the alternative tackiness agent of having found at the acceptable tackifier based on hydrogenated hydrocarbon resins of application of nonwovens.
Another also existence in the art need to be to have for for example 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 need to be that the tackifier for EVA packaging adhesive of the viscosity stability of increase are provided for tackiness agent.
In the art, also still be there are to needs in the novel tackifier for than using hydrogenated hydrocarbon resins base tackifier to have the pressure sensitive adhesive with low look (PSA) of lower cost.
Also have, in the art, to for provide the novel tackifier of bookbinding adhesive of the viscosity stability of improvement also still to have 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 be realized or not reach one or more object in following target.
An object of the present invention is to provide the method for rosin ester, the 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 of 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 that are used to EVA packaging adhesive that viscosity stability is provided.
Another object of the present invention is to provide for having than the tackifier for pressure sensitive adhesive (PSA) with low look that use the cost that hydrogenated hydrocarbon resins base tackifier are low.
Another object of the present invention is to provide for the tackifier for bookbinding adhesive of the viscosity stability of low look and improvement are provided 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 for preparing rosin ester.Any one or more steps during described method can comprise the following steps with random order: make the rosin with PAN isomer contact with disproportionation reaction reagent the rosin that provides PAN number to be less than 45, thereby the rosin through disproportionation reaction is provided; Make the described rosin through disproportionation reaction contact that with addition reaction reagent described PAN number is further reduced, thereby 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, also provide the method for preparing rosin ester.Any one or more steps during described method can comprise the following steps with random order: make PAN number be less than 45 rosin and contact further to reduce described PAN number with addition reaction reagent, thereby 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, also provide a kind of rosin ester composition, described composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
According to another embodiment of the present invention, a kind of tackiness agent that comprises rosin ester composition is also provided, described composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
According to another embodiment of the present invention, a kind of nonwoven products that comprises tackiness agent is also provided, described tackiness agent comprises rosin ester composition, and described rosin ester composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
Embodiment
In the practice of some non-limiting embodiment of the present invention, developed a kind of method synthesize there is lower smell, compared with the colour stability of weak color and/or the improvement rosin ester of (compared with prior art).The colour stability that some embodiment of rosin ester composition of the present invention is significantly improved at the temperature tool up to 150 ℃, and/or these compositions when the temperature up to 150 ℃ is aging for hotmelt provides excellent thermostability.Some of these rosin esters that obtain is applicable to using in traditional packing and pressure sensitive adhesive, and unlike traditional rosin ester, they can also be for the application of smell and color sensitivity, in non-woven tackiness agent (diaper configurations tackiness agent) or other high-end packaging adhesives.
In practice of the present invention, for providing the possible method of the RE tackiness agent of low smell to comprise the polyvalent alcohol using outside tetramethylolmethane (PE), use the mixture of polyvalent alcohol, or by using the polyvalent alcohol of one or more other types to substitute PE partly or completely in rosin ester preparation significantly to reduce the content of described PE.
Particularly, a non-limiting embodiment of the present invention provides the fumaric acid modification 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 can also provide excellent colour stability and viscosity stability while storing in the thermal stimulus warehouse condition raising.
Some embodiments of the present invention will provide the tackiness agent with low initial color and lower aging color (comparing with commercial adhesive).Some embodiments of the present invention provide and have compared viscosity variation less when aging with commercial adhesive.As a nonrestrictive example, the viscosity of the tackiness agent being made by some embodiments of rosin ester of the present invention changes after 350F is aging 96 hours as being less than 5%, 4%, 3%, 2% or 1%.
Some embodiment of the present invention can utilize part disproportionation reaction step.Be also noted that, rosin color can reduce in this step process, but final ester can be shallow singularly in color.
Should be understood that, for method and the reagent of disproportionation of gum rosin, be well-known, and can utilize any suitable disproportionation reaction method and reagent, and the present invention is not limited to any specific method or reagent.Certainly, can use one or more disproportionation reaction methods and reagent.Suitable disproportionation reaction method and the non-limitative example of reagent provide at US3, and 423,389, 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 are utilized the reagent of various phenol sulfide types.As concrete non-limitative example, ROSINOX
tM(poly--tert.-butyl phenol disulphide, can be from Arkema, and Inc. obtains), 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 disulphide polymkeric substance 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 (the 6-tertiary butyl-m-cresol) and 4/4'-thiobis (the 6-tertiary butyl-o-cresols), thiobis naphthols, 2,2'-sulfo--bis-phenol, 3,3'-sulfo--bis-phenol etc.
Ferric iodide) or sulfide (its nonrestrictive example includes, but are not limited to picture iron sulphide) other non-limitative examples of suitable disproportionation reaction reagent comprise that (its non-limitative example includes, but are not limited to: for metal (its non-limitative example includes but not limited to: palladium, nickel, platinum) or iodine or iodide.
In some embodiments, the rosin before disproportionation reaction can have approximately 50 PAN number.PAN number is the summation of the percentage ratio of the sylvic acid (it is palustric acid, abietic acid, neoabietic acid) in rosin as used herein.In some embodiments of the present invention, disproportionation reaction is approximately 20 to 25 by causing final PAN number.In some other embodiment of the present invention, disproportionation reaction is 15 to 30 by causing final PAN number.In some other embodiment of the present invention, disproportionation reaction is 10 to 40 by causing final PAN number in addition.It is 0.1,1,2,5,10,15,20,25,35,35,40 or 45 that disproportionation reaction may cause final PAN number, or is that a numerical value in any two numerical value between any two numerical value in above numerical value and/or from above numerical value is to the scope of another numerical value.
Some embodiments of the present invention represent in the rosin through disproportionation reaction that color is improved and the ester that made 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 the appropriately combined of adopting process and synthesis condition.
As well-known in the prior art, rosin ester can be used 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, for example,, described in United States Patent (USP) 2729660,3310575,3423389,3780013,4172070,4548746,4690783,4693847,4725384,4744925,4788009,5021548 and 5049652.
In general, for the preparation of the method for rosin ester of the present invention, can comprise 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 being mainly comprised of C20 condensed ring monocarboxylic acid hydrocarbon, 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 be different.
Gum resin, wood rosin, toll oil rosin and other rosin itself can directly be used in the method for the invention, or can before using in the method for the invention, carry out other processing.For example, rosin material can be subject to distillation, disproportionation, hydrogenation or polymerization in use before present method, or some combined treatment of these processing and/or other processing.
Poly-hydroxy type polyvalent alcohol, is also known as polyvalent alcohol sometimes, as the other reactant adopting 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 be utilized the combination of two or more polyvalent alcohols of above-mentioned polyvalent alcohol.As a non-limitative example, some embodiments can be used two or more the combination in glycerol, tetramethylolmethane and TriMethylolPropane(TMP).
Some embodiments of the present invention will be utilized the polyvalent alcohol combination of tetramethylolmethane and at least 1,2,3,4,5 kind or more kinds of other polyvalent alcohols, and a nonrestrictive example of described polyvalent alcohol combination comprises at least one in (TMP) in tetramethylolmethane and glycerol or TriMethylolPropane(TMP).The mixture that combination can be used as tetramethylolmethane and other polyvalent alcohols adds, or combination can be added by the tetramethylolmethane mode that then other polyvalent alcohols add in turn, or first adds described a kind of or more kinds of polyvalent alcohol and then add tetramethylolmethane.Therefore, some embodiments of the present invention can adopt tetramethylolmethane then at least 1,2,3,4, the addition manner in turn of 5 kind or more kinds of other polyvalent alcohols, its nonrestrictive example comprise tetramethylolmethane then glycerol, tetramethylolmethane then TriMethylolPropane(TMP), tetramethylolmethane then glycerol more then TriMethylolPropane(TMP), tetramethylolmethane then TriMethylolPropane(TMP) then then glycerol or tetramethylolmethane are the mixtures of glycerol and TriMethylolPropane(TMP) again.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 will adopt the combination of glycerol and/or TriMethylolPropane(TMP) and at least 1,2,3,4,5 kind or more kinds of other polyvalent alcohols.The mixture that this combination can be used as glycerol and/or TriMethylolPropane(TMP) and other polyvalent alcohols adds, or this combination can be added by glycerol and/or the TriMethylolPropane(TMP) mode that then other polyvalent alcohols add in turn, or by described a kind of or more kinds of other polyvalent alcohols then the mode of glycerol add.Therefore, some embodiments of the present invention can adopt glycerol and/or TriMethylolPropane(TMP), at least 1,2,3,4,5 kind or more kinds of other polyvalent alcohol mode that then glycerol is added in turn to add, and its nonrestrictive example comprises then tetramethylolmethane, TriMethylolPropane(TMP) tetramethylolmethane or glycerol and TriMethylolPropane(TMP) (together with add or add in turn) tetramethylolmethane then then of glycerol.
Polyvalent alcohol mentioned above combination can comprise the tetramethylolmethane (gross weight of the polyvalent alcohol based in this combination) that is 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 a numerical value in any two numerical value from above-mentioned numerical value to the weight percent of another numerical value.
The amount of the alcohol adopting in esterification step can change widely.Yet in general, the amount based on rosin, adopts the poly-hydroxy type polyvalent alcohol at least about equivalent, its upper limit is generally to exceed approximately 50% of this equivalent.
In some 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 some embodiments of the present invention, after disproportionation reaction step, in rosin, can exist enough PAN isomer to react with addition reaction reagent with permission.In some embodiments, may need enough low PAN isomer, because exist in some cases too many unreacted PAN acid isomer body (being no matter the acid that dissociates or the acid of esterification) can cause oxidative stability poor when storing in final rosin ester, this may cause poor colour stability and poor smell.The suitable PAN number of the rosin of pending addition reaction (, PAN number before addition reaction) non-limitative example comprises 0.1,1,2,5,10,15,20,25,35,35,40 or 45, or is that a numerical value in any two numerical value between any two numerical value in above numerical value and/or from above numerical value is to the scope of another 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, can adopt the level that further reduces the PAN colophony isomerization body staying after disproportionation reaction in addition reaction step.In some embodiments, addition reaction step may increase molecular weight and the softening temperature of rosin ester.In some embodiments, this can allow with the ester of lower smell can be provided for example but glycerol or TMP replace tetramethylolmethane (PE) to other polyvalent alcohols can also with the softening temperature lower than PE ester.As a nonrestrictive example, the glycerine ester of fumaric acid adduction can have and the similar softening temperature of PE ester, and can still can have stronger scale resistance and lower smell for similar purposes.In some embodiments, part disproportionation reaction step 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, our smell group judges when with the comparison of normal business PE rosin ester.
In some embodiments, the weight percent of the addition reaction reagent using 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 the scope between in above-mentioned weight percent any two or in any two weight percents one is in another scope.As a nonrestrictive example, approximately 2% to 2.8% the fumaric acid level that accounts for preparation is increased to approximately 1200 to 1600 dalton (comparing with approximately 900 to 1000 dalton of PE rosin ester) by the weight-average molecular weight Mw of resulting rosin ester.For some embodiments, 2.4% to 2.8% fumaric acid may be favourable.
Some embodiments of rosin ester can show and compare the odor intensity having reduced with PE rosin ester.As some non-limitative examples, the odor intensity of some embodiment of rosin ester (it adopts the PE that is less than 100%) relative intensity having (with respect to the rosin ester that adopts 100% PE) is equal to or less than the PE that adopts 100% rosin ester 80%, 75%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, or in the scope between in above-mentioned relative intensity any two or in any two relative intensities one is in 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 as the tackifying resin in hotmelt and for example, as low look used in printing (high gloss magazine, advertisement and company's annual report), the binder resin in chromatography varnish.
Embodiment
Result shown in the following examples and table 1-6 below illustrates advantage of the present invention by various types of tests of carrying out on rosin ester of the present invention and the result of evaluation.
General following the carrying out of embodiment:
At nitrogen, 180 ℃, in 2 liters of three-necked bottles, melt the toll oil rosin (SYLVAROS of the light color (gardner color number is 3.2) of 600g
tMr type S).
The ROSINOX that adds wherein 3.53g
tMdisproportionation reaction reagent, by the mixture of gained be heated to 275 ℃ 2 hours, with nitrogen gas stream slowly, by reactor, use syringe pump with 3.9 mls/hour, to add distilled water in flask simultaneously.
Next, flask is cooled to 180 ℃ and add the fumaric acid of 19.77g (total reinforced 2.8%), by the mixture of gained be heated to 220 ℃ 1 hour, be then cooled to 180 ℃.
Now, add tetramethylolmethane and then add glycerol, and temperature is elevated to 250 ℃.
Once reach 250 ℃, add that three of 1.06g-(nonyl phenyl) phosphite (or ester) (TNPP).
After 1 hour, cool the temperature to 180 ℃ and spend the night (13 hours).
Morning, be heated to 250 ℃ 2 hours.
Reactor sample has the softening temperature of 85.2 ℃, and acid number is 24.5, and gardner color number is 2.
Reactant is heated to 275 ℃, and uses nitrogen bubble 4 hours.
Then reactant is cooling, and add 50% the KOH aqueous solution of 0.14g, the Irganox of 0.99g
tM1010 and the Irganox of 0.35g
tM565.The resin of 200 ℃ is poured in pot cooling.
Final analysis: softening temperature is 98.3 ℃, acid number is 4.9, gardner color number is 2+.
The smell group assessment of 5 of rosin ester of the present invention non-limitative examples and business rosin ester SYLVALITE in the time of 50 ℃
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, each resin that takes 25g is put into the wide-necked bottle of 8 ounces.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 of three sealings is placed in to the baking oven that is preheating to (49+/-2 ℃) by random sequence.
4, wide-necked bottle is put on to coding, make trial body do not know each sample identity.
5, by sample balance 2 hours in baking oven.
6, our at least 5 bit test persons of smell group (they are having experience aspect 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 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, rather than the characteristic of smell.
8, at smell, evaluate gap, shake gently sealed sample sets, and put back to baking box minimum 30 minutes.
9, after being evaluated by 5 to 8 smell evaluation members, the odor intensity value of each sample is averaged to calculating.The intensity of calculating each sample is with respect to the ratio of standard specimen and report (standard specimen=1.0) together with raw data.
Specifically, sample D and E fumaric acid content the highest, (" SYLVALITE
tMrosin ester does not have).Without being limited by theory, applicant's supposition, this surprising situation may be to reduce one of relevant factor with smell.A nonrestrictive hypothesis is, the colophony isomerization precursor reactant of the preferential and tool activity of fumaric acid, and it may also produce relevant with smell.
Table 1. odor intensity is (relative with the good addition reaction level of fumaric acid
In 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 are coincide with the early stage supposition of the offending smell that the tetramethylolmethane impurity producing during high temperature esterification reaction process or degradation production cause final ester.Therefore, this shows, for some embodiments, if use PE, should keep lower level so that the smell of resulting rosin ester is minimum.
Table 2. odor intensity and tetramethylolmethane level
Embodiment 3
Table 3 shows the high oxidation resistance voltinism that method comprises some embodiment of the present invention of disproportionation reaction step.150 ℃ in air 24 hours, tackifying resin of the present invention, particularly favourable formulation C and D, show the colour-darkening of wanting much less than contrast.Although all embodiments differ, establish a capital like this, 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. improves from oxidative stability of the present invention and color
DSC=dsc.In oxidisability DSC, sample heats until sample oxidation (as shown in its heat release) at 128 ℃ at the oxygen pressure of 550psi.
EVA=ethylene vinyl acetate copolymer.
Embodiment 4
Table 4 is illustrated in the tackiness agent of business SIS/ hydrogenated hydrocarbon resins tackify and uses rosin ester tackifier to make the comparison of carrying out between SIS tackiness agent.For these embodiments, the tackiness agent that adopts tackiness agent that the top rosin pentaerythritol ester of commercially available acquisition (Arizona chemistry (Arizona Chemical)) makes to make with some embodiment by not carrying out the ester of the present invention of disproportionation reaction step shows the smell similar or stronger to commercial adhesive.Yet, adopt the tackiness agent of being made by the sample resins of some embodiment of the present invention to be judged as and to have than the remarkable lower smell of business SIS tackiness agent by smell group.
Table 4. is used the SIS tackiness agent of novel rosin ester tackifier and the smell comparison of business SIS/ hydrocarbon resin tackiness agent
Embodiment 5
Also at the standard pressure sensitive adhesion agent formulation for label applications of styrene-based-isoprene-vinylbenzene (SIS), the rosin ester C from some embodiment of the present invention is evaluated.By result with normal business rosin ester, be SYLVALITE
tMthose results that rosin ester obtains compare.The results are shown in table 5.Although rosin ester of the present invention demonstrates lower annular quickstick (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. is used rosin ester C and business SYLVALITE
tMthe bond properties of the HMPSA label preparation based on SIS of rosin ester
Embodiment 6
Also in the standard hot melt packaging adhesive preparation based on EVA to evaluating from rosin ester C of the present invention.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.The results are shown in table 6.The tackiness agent that adopts rosin ester of the present invention to make 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. is used 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 rather than the scope of claims and character is limited.Those skilled in the art comprises at research present disclosure equivalent function and/or the structure surrogate using for element as described herein, use the equivalent function for connection as described herein to connect, and/or after using the action of the equivalent function that is used for action as described herein, will be seen that various modifications and variations.Within the variation of any unsubstantiality all should be considered to be in the scope of appended claim.
Claims (27)
1. manufacture a method for rosin ester, described method comprises:
(A) rosin that makes to have PAN isomer contacts with disproportionation reaction reagent the rosin that provides PAN number to be less than 45, thereby the rosin through disproportionation reaction is provided;
(B) make the described rosin through disproportionation reaction contact that with addition reaction reagent described PAN number is further reduced, thereby the rosin through addition reaction is provided;
(C) make the described rosin through addition reaction contact to form rosin ester with poly-hydroxy type polyvalent alcohol.
2. method according to claim 1, wherein, described disproportionation reaction pack is containing being selected from least one in phenol sulfide, metal, iodine, iodide and sulfide, and described addition reaction reagent be selected as by Diels-Alder reaction or alkene reaction and with the PAN isomerization reaction of 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 (the 6-tertiary butyl-m-cresol) and 4/4'-thiobis (the 6-tertiary butyl-o-cresols) thiobis naphthols, 2,2'-sulfo--bis-phenol, 3, at least one in 3'-sulfo--bis-phenol, palladium, nickel, platinum, iodine, ferric iodide, iron sulphide.
4. method according to claim 1, wherein, described addition reaction pack is containing being selected from least one in fumaric acid, maleic anhydride, vinylformic acid, unsaturated acid and acid anhydrides.
5. method according to claim 1, wherein, described poly-hydroxy type polyvalent alcohol comprises the tetramethylolmethane that is less than 20 % by weight.
6. method according to claim 5, wherein, described poly-hydroxy type polyvalent alcohol comprises at least one in the group of selecting free ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1,3-PD, glycerol, tetramethylolmethane, Dipentaerythritol, tripentaerythritol, trimethylolethane, TriMethylolPropane(TMP), mannitol and Sorbitol Powder composition.
7. method according to claim 5, wherein, described poly-hydroxy type alcohol comprises at least one that select in the group that free glycerol and TriMethylolPropane(TMP) form.
8. method according to claim 1, wherein, described rosin ester has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
9. manufacture a method for rosin ester, described method comprises:
(A) make PAN number be less than 45 rosin and contact further to reduce PAN number with addition reaction reagent, thereby the rosin through addition reaction is provided;
(B) make the described rosin through addition reaction contact to form rosin ester with poly-hydroxy type polyvalent alcohol.
10. method according to claim 9, wherein, described addition reaction reagent be selected as by by Diels-Alder reaction or alkene reaction and with the PAN isomerization reaction of rosin.
11. methods according to claim 9, wherein, described addition reaction pack is containing being selected from least one in fumaric acid, maleic anhydride, vinylformic acid, unsaturated acid and acid anhydrides.
12. methods according to claim 9, wherein, described poly-hydroxy type polyvalent alcohol comprises the tetramethylolmethane that is less than 20 % by weight.
13. methods according to claim 12, wherein, described poly-hydroxy type polyvalent alcohol comprises at least one in the group of selecting free ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1,3-PD, glycerol, tetramethylolmethane, Dipentaerythritol, tripentaerythritol, trimethylolethane, TriMethylolPropane(TMP), mannitol and Sorbitol Powder composition.
14. methods according to claim 12, wherein, described poly-hydroxy type alcohol comprises at least one in the group of selecting free glycerol and TriMethylolPropane(TMP) composition.
15. methods according to claim 9, wherein, described rosin ester has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
16. 1 kinds of rosin ester compositions, described composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
17. compositions according to claim 16, described composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 60% odor intensity.
18. compositions according to claim 16, described composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 55% odor intensity.
19. compositions according to claim 16, described composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 50% odor intensity.
20. 1 kinds of tackiness agents that comprise rosin ester composition, described rosin ester composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
21. tackiness agents according to claim 20, wherein, described composition comprises for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 60% odor intensity.
22. tackiness agents according to claim 20, wherein, described composition comprises for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 55% odor intensity.
23. tackiness agents according to claim 20, wherein, described composition comprises for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 50% odor intensity.
24. 1 kinds of nonwoven products that comprise tackiness agent, described tackiness agent comprises rosin ester composition, and described rosin ester composition has for the comparison rosin ester making with respect to the tetramethylolmethane by 100% and is less than 80% odor intensity.
25. products according to claim 24, wherein, are less than 60% for the comparison rosin ester that described odor intensity makes with respect 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 makes with respect 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 makes with respect 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 true CN103517957A (en) | 2014-01-15 |
| CN103517957B CN103517957B (en) | 2015-06-10 |
Family
ID=47009591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103634A (en) * | 2014-03-12 | 2016-11-09 | 荒川化学工业株式会社 | Pressure sensitive adhesive compositions and acrylic pressure-sensitive adhesivee adhesive composition |
Families Citing this family (14)
| 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 |
| JP6416236B2 (en) | 2013-09-27 | 2018-10-31 | アリゾナ・ケミカル・カンパニー・エルエルシー | Composition comprising ethylene polymer |
| KR102366374B1 (en) * | 2013-09-27 | 2022-02-23 | 크라톤 케미칼, 엘엘씨 | 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 |
| WO2015147298A1 (en) * | 2014-03-28 | 2015-10-01 | 荒川化学工業株式会社 | Tackifier resin, pressure sensitive adhesive composition including same, tackifier resin for hot-melt pressure sensitive adhesive, hot-melt pressure sensitive adhesive composition, styrene-conjugated diene block copolymer-based pressure sensitive adhesive composition, and styrene-conjugated diene block copolymer-based hot-melt pressure sensitive adhesive composition |
| 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 |
| CN107980051A (en) * | 2015-03-26 | 2018-05-01 | 亚利桑那化学品有限责任公司 | Contain rosin ester and polyvinyl composition |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2980629A (en) * | 1957-09-13 | 1961-04-18 | Hercules Powder Co Ltd | Gel-free rosin soap and method of preparing same |
| US4447354A (en) * | 1983-03-21 | 1984-05-08 | Arizona Chemical Company | Method for making oxidation-stable, light-colored glycerol ester of modified rosin |
| US5395920A (en) * | 1991-12-21 | 1995-03-07 | Arakawa Kagaku Kogyp Kabushiki Kaisha | Process for preparing rosin and colorless rosin comprising disproportionation and dehydrogenation |
| US5541246A (en) * | 1994-10-24 | 1996-07-30 | Arizona Chemical Company | Repulpable hot melt adhesives |
| CN1197097A (en) * | 1997-04-18 | 1998-10-28 | 阿里佐纳化学公司 | Preparation of tall oil rosin ester with low odor level |
| US6172174B1 (en) * | 1998-05-08 | 2001-01-09 | Westvaco Corporation | Phenolic rosin resin compositions |
| US20080221546A1 (en) * | 2007-03-05 | 2008-09-11 | Quinn Thomas H | Novel disposable diaper construction and adhesive |
| CN101264454A (en) * | 2008-03-21 | 2008-09-17 | 广州英科新材料有限公司 | Composite catalyst and its application in preparing light-colored rosin esters |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377334A (en) * | 1966-09-16 | 1968-04-09 | Arizona Chem | Disproportionation of rosin |
| JPS559605A (en) * | 1978-06-23 | 1980-01-23 | Arakawa Chem Ind Co Ltd | Preparation of rosin ester having high softening point and improved stability |
| JPH064954B2 (en) * | 1986-04-21 | 1994-01-19 | 荒川化学工業株式会社 | Neutral papermaking sizing method |
| US4842691A (en) * | 1986-03-19 | 1989-06-27 | Arakawa Chemical Industries, Ltd. | Sizing agents in neutral range and sizing methods using the same |
| JP2548033B2 (en) * | 1989-03-22 | 1996-10-30 | ハリマ化成株式会社 | Rosin derivative, production method thereof, hot melt adhesive composition and production method thereof |
| SE9203499L (en) * | 1992-11-20 | 1994-05-21 | Eka Nobel Ab | Rosin derivative as surfactant |
| US6562888B1 (en) * | 1998-07-27 | 2003-05-13 | Arizona Chemical Company | Light-colored rosin esters and adhesive compositions |
| JP2003119230A (en) * | 2001-10-09 | 2003-04-23 | Toyo Ink Mfg Co Ltd | Curable composition, curable ink, method of printing by using it, and printed matter obtained by using it |
| US20050113499A1 (en) * | 2002-02-13 | 2005-05-26 | Thomas Tamcke | Low-emission aqueous dispersion adhesive |
| WO2007092250A2 (en) * | 2006-02-02 | 2007-08-16 | Hexion Specialty Chemicals Inc. | Rosin ester with low color and process for preparing same |
-
2011
- 2011-04-11 EP EP11863683.6A patent/EP2697322A4/en not_active Withdrawn
- 2011-04-11 JP JP2014505109A patent/JP2014517091A/en active Pending
- 2011-04-11 RU RU2013145603/05A patent/RU2569081C2/en not_active IP Right Cessation
- 2011-04-11 WO PCT/US2011/031884 patent/WO2012141675A1/en active Application Filing
- 2011-04-11 KR KR1020137029360A patent/KR20140022059A/en not_active Application Discontinuation
- 2011-04-11 CA CA2833114A patent/CA2833114A1/en not_active Abandoned
- 2011-04-11 AU AU2011365712A patent/AU2011365712A1/en not_active Abandoned
- 2011-04-11 CN CN201180070558.1A patent/CN103517957B/en not_active Expired - Fee Related
- 2011-04-11 BR BR112013026297A patent/BR112013026297A2/en not_active IP Right Cessation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2980629A (en) * | 1957-09-13 | 1961-04-18 | Hercules Powder Co Ltd | Gel-free rosin soap and method of preparing same |
| US4447354A (en) * | 1983-03-21 | 1984-05-08 | Arizona Chemical Company | Method for making oxidation-stable, light-colored glycerol ester of modified rosin |
| US5395920A (en) * | 1991-12-21 | 1995-03-07 | Arakawa Kagaku Kogyp Kabushiki Kaisha | Process for preparing rosin and colorless rosin comprising disproportionation and dehydrogenation |
| US5541246A (en) * | 1994-10-24 | 1996-07-30 | Arizona Chemical Company | Repulpable hot melt adhesives |
| CN1197097A (en) * | 1997-04-18 | 1998-10-28 | 阿里佐纳化学公司 | Preparation of tall oil rosin ester with low odor level |
| US6172174B1 (en) * | 1998-05-08 | 2001-01-09 | Westvaco Corporation | Phenolic rosin resin compositions |
| US20080221546A1 (en) * | 2007-03-05 | 2008-09-11 | Quinn Thomas H | Novel disposable diaper construction and adhesive |
| CN101264454A (en) * | 2008-03-21 | 2008-09-17 | 广州英科新材料有限公司 | Composite catalyst and its application in preparing light-colored rosin esters |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106103634A (en) * | 2014-03-12 | 2016-11-09 | 荒川化学工业株式会社 | Pressure sensitive adhesive compositions and acrylic pressure-sensitive adhesivee adhesive composition |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2833114A1 (en) | 2012-10-18 |
| BR112013026297A2 (en) | 2017-06-06 |
| RU2569081C2 (en) | 2015-11-20 |
| JP2014517091A (en) | 2014-07-17 |
| KR20140022059A (en) | 2014-02-21 |
| EP2697322A1 (en) | 2014-02-19 |
| RU2013145603A (en) | 2015-05-20 |
| WO2012141675A1 (en) | 2012-10-18 |
| EP2697322A4 (en) | 2015-08-05 |
| AU2011365712A1 (en) | 2013-10-31 |
| CN103517957B (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103517957B (en) | Rosin esters for non-wovens | |
| US20110213120A1 (en) | Rosin esters for non-woven applications, methods of making and using and products therefrom | |
| EP1144526B1 (en) | Light-colored rosin esters and adhesive compositions | |
| EP0583419B1 (en) | Acid-modified polyhydric alcohol rosin ester tackifiers and hot melt adhesive compositions containing those tackifiers | |
| AU2005212206B2 (en) | Tackifier dispersion | |
| US10011740B2 (en) | Rosin esters and compositions thereof | |
| US9940852B2 (en) | Rosin esters and compositions thereof | |
| AU780249B2 (en) | Polyester tackifier and adhesive composition | |
| CN107980051A (en) | Contain rosin ester and polyvinyl composition | |
| CN105722910B (en) | Include polyvinyl composition | |
| CA1247290A (en) | Petroleum resins | |
| US9023929B2 (en) | Tackifier dispersion | |
| CZ409497A3 (en) | Disperse adhesives based on resins, process of their preparation and their use | |
| EP2890747B1 (en) | Process for production of rosin resin, product obtained by said process and use thereof | |
| CN106366931A (en) | Preparing method for rosin glycerin ester for oil paint | |
| JPH0198676A (en) | Pressure-sensitive adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150610 Termination date: 20170411 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |