CA2256705A1 - Adhesive applicator crayon - Google Patents
Adhesive applicator crayon Download PDFInfo
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- CA2256705A1 CA2256705A1 CA002256705A CA2256705A CA2256705A1 CA 2256705 A1 CA2256705 A1 CA 2256705A1 CA 002256705 A CA002256705 A CA 002256705A CA 2256705 A CA2256705 A CA 2256705A CA 2256705 A1 CA2256705 A1 CA 2256705A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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Abstract
Adhesive compositions exhibiting fast cure time in solid form, e.g. in the form of an applicator crayon or glue stick. The adhesive exhibiting polymer of the composition is based on a mixture of critical amounts of high molecular weight polyvinylpyrrolidone polymer, with a lower molecular weight polyvinylpyrrolidone polymer, with water, an organic solvent, and a salt of a long-chain fatty acid, e.g. sodium stearate. Color indicators and other optional ingredients, e.g. mildewcide, can be included.
Description
CA 022~670~ l998-ll-26 WO 98/47953 PCT/U~;97/06713 ADHESIVF, APPLICATOR CRAYON
Bark~;round of the Invention 1. Field of the Invention Fast setting adhesive formulations in an easy applicator form are desirable for office, school and home consumers. The present invention provides a polyvinylpyrrolidone (hereinafter "PVP")-based composition in solid form, e.g. glue stick or crayon, which is easy to apply, bonds faster and is safe to use. The adhesive bonds porous substrates to which they are applied.
such as paper. fabrics, polystryene foam, wood and similar porous substrate materials.
Bark~;round of the Invention 1. Field of the Invention Fast setting adhesive formulations in an easy applicator form are desirable for office, school and home consumers. The present invention provides a polyvinylpyrrolidone (hereinafter "PVP")-based composition in solid form, e.g. glue stick or crayon, which is easy to apply, bonds faster and is safe to use. The adhesive bonds porous substrates to which they are applied.
such as paper. fabrics, polystryene foam, wood and similar porous substrate materials.
2. Description of the Related Art U.S. Patent 3,576,776, issued in 1971, contains a disclosure of an invention for adhesive applicator crayons comprising a shape-giving base consisting of a gel-forming salt, a liquid, and an adhesive component. Among the adhesives are listed salts of various acids, arnides, and N-alkyl substituted amides including polyvinylpyrrolidone. The disclosure of U.S. patent 3,576,776 was said to be an improvement over known adhesive applicator crayons prepared from rubber, resins and waxes, which required that surface layers must be rubbed off from such crayons under relatively high pressure in order to carry out the spreading of the adhesive.
Later solid adhesive compositions, such as those disclosed in U.S. Patents 4,073,756 and 4,075,830, were said to avoid the problem inherent in the crayons of U.S. Patent 3,576,776, the long time it took to produce the adhesive composition and the high viscosity of the adhesive composition (e.g.
CA 022~670~ 1998-ll-26 higher than 150,000 cps) which made it difficult to fill the adhesive composition in containers.
The later patents thus used water soluble or water dispersible polymers having adhesive properties in combination with N-fatty acid acy}ated amino acids or salts thereof and water, or a mixture of water and one or more organic solvent(s) and/or plasticizer(s). The water dispersible or water soluble polymers having adhesive properties listed, arnong others, homopolymers or copolymers having a carboxyl group or a carboxylic anhydride group? where the proportions of the carboxyl and/or carboxylic anhydride group containing monomer is preferably about 30 to 100 mol %.
These, and other prior art formulations (the entire disclosures of all of which are herein incorporated by reference), were still slow to exhibit adhesive properties when dispensed, i.e. slow to e~hibit paper tear when applied to bond paper.
Among other properties, the present invention provides strong final bonds and a pH generally in the range of about 8.5 to about 9.~.
However. in the embodiments of the invention where a color indicator is used, the hue or intensity of the color is enhanced by having a pH more alkaline than the range given above, e.g. up to a pH of about 11, e.g. 10.9 - 11.1.
Object of the Invention It is thus an object of the invention to provide new adhesive compositions e~hibiting fast adhesive properties (e.g. fast initial tear of paper) and strong final bonds.
CA 022~670~ 1998-ll-26 It is a further object of the invention to provide adhesive compositions in the form of solids at ambient conditions, i.e. glue sticks or applicator crayons which exhibit fast adhesive properties when applied to a substrate and suitable for bonding paper, fabric, polystyrene foam and similar materials.
It is a still further object of the invention to provide bonded substrates, such as paper, fabric, and similar porous materials, bonded with the adhesive compositions of the invention.
Summary of the Invention Water-based solid adhesive crayons which contain water in a mixture comprising a relatively low molecular weight (all references to "molecular weight" in this Specification, claims and Abstract are intended to mean "weight average molecular weight" unless otherwise design~ted) water dispersible or water soluble polymer, e.g. polyvinylpyrrolidone polvmer, i.e.
a molecular weight below about 1,300,000, and a critical amount of a relatively high molecular weight water dispersible or water soluble polymer, e.g. polyvinylpyrollidone polymer, i.e. a molecular weight above 1,300,000.
By critical arnounts is meant sufficient amounts of the high molecular weight (polyvinylpyrollidone) polymer to impart 1.) a fast film-forming or setting property, 2.) a strong final bonding property, and 3.) an additional firmness to the crayon adhesive to reduce "crumbling" when pressure is applied to the crayon, while keeping the water content of the adhesive at 50 weight percent, or more, to ensure easy spreading and performance during use and after storage. Optional ingredients include a plasticizer for the (polyvinylpyrollidone) polymers to impart a degree of flexibility to the dry CA 022~670~ 1998-ll-26 WO 98/47953 PCT/US97tO6713 adhesive film, a preservative to protect the adhesive from attack by microorp~ni~m~, a long chain fatty acid salt to impart a solid gel property to the adhesive, and a color indicator for the purpose of indicating when an applied film of adhesive has dried.
This composition may be formulated so as to exhibit physical properties of a solid, e.g. it may be formulated so as to be suitable for application in the forrn of a crayon or glue stick to porous substrates to be bonded. The composition is preferably formulated so as to be satisfactorily extruded from and retracted into a container, exhibit good spreadability without being "runny" or dispensing excessive adhesive to a substrate nor so firm that the crayon or adhesive stick "crumbles" due to the requirement to exert excessive pressure during application of the crayon/stick to a substrate to effect adequate spreading of the adhesive on the substrate.
It is also within the purview of the invention to provide substrates bonded with the forrnulations of the invention.
Detailed Description of the Invention The composition of matter of this invention e~hibits adhesive properties and is form~ t~d of components (A), (B), (C), and (D), wherein (A) is an aqueous vehicle, typically water or aqueous emulsions/dispersions of one or more of components (B), (C), (D) andlor any optional components; (B) is at least one water soluble or water dispersible polymer, e.g.
polyvinylpyrollidone (hereinafter "PVP") polymer exhibiting adhesive properties having a molecular weight below about 1,300,000, (C) is a salt of - a long chain fatty acid or a precursor thereof which forms a salt of a long chain CA 022~670~ 1998-ll-26 fatty acid when combined with the other components of the compositions of matter of this invention and (D) is a water soluble or water dispersible polymer, e.g. a PVP polymer having a molecular weight above about 1,300,000, preferably above about 2,000,000 most preferably of at least about 2,800,000. Suitable polymers for component (B) include homopolymers or copolymers of the types identified in U.S. Patents 4,073,756 or 4,954,544, although PVP is particularly preferred. Although higher molecular weight polymers of component (D) can be of the same type of polymer as component (B), it is preferred that the high molecular weight polymer be PVP.
When it is desirable, certain optional ingredients may be included in the composition of matter of the invention, e.g. a mildewcide and/or fungicide, solvents for the adhesive exhibiting polymeric components, e.g. alcohols, such as glycerol or polyglycols for PVP, pigments and/or dyes to impart a permanent color, and/or a color indicator, such as phenolphthalein or thymolphthalein, for indicating when the applied film is dried.
Generally, the components of the invention may be combined over a wide range. However, in order to forrnulate the composition of matter in solid form, e.g. suitable for use, as an adhesive applicator stick or crayon, it is preferable that the composition contain not less than about 50% nor more than about 80% (all % in this application are by weight unless otherwise noted) by weight of component (A) (wherein (A) is water). If (A) is an aqueous formulation cont~ining one or more components (B)-(D), or having optional components. the arnount of (A) can be adjusted so as to be greater than, or lesser than, the amounts indicated. Although it is preferable that the CA 022~670~ l998-ll-26 composition contain not less than about 50%, preferably not less than about 60% of component (A) (where (A) is water) this amount can be adjusted lower, e.g. 45% or less though not exhibiting the most preferred properties of the adhesive stick of the invention. The presence of plasticizers, solvents or mixtures thereof for the water dispersible polymers may also decrease the requirements for component (A) to be present in an amount of not less than 50%, because such plasticizers/solvents enhance the spreadability properties.
As with the case of the maximum content of component (A), when (A) is an aqueous forrnulation containing one or more of components (B)-(D), or any optional components, the amount of (A) will be adjusted accordingly.
Component (B) is at least one polymer exhibiting a&esive properties, preferably a polyvinylpyrrolidone (PVP) of relatively low molecular weight?
e.g. below about 1,300,000. PVP polymers are commercially available in several viscosity grades, ranging from very low to very high molecular weight.
This range, coupled with solubility in water, aqueous and organic solvent systems and its non-toxic character, give PVP great flexibility in the compositions and applicator solid forrns of the present invention.
Commercially available PVP suitable for use in this invention as components (B) or (D) are available from GAF Chemicals Corporation, International Specialty Products, of Wayne, N.J., U.S .A., under the tradenames PVP K-90 and PVP K-120, each having an off-white powder appearance.
PVP K-90 has a viscosity average molecular weight of 630,000 (perforrned at 25 ~C, in H,O, using Mark Houwink constants of K = 1.4 x 10-4 and a = 0.7), a weight average molecular weight (Wt.Avg.MW) of 1.2~0,000 (obtair~ed by CA 022~670~ 1998-11-26 low angle laser light scattering (LALLS) photometry) and a K-value of 88-100. PVP K-120 has a viscosity average molecular weight of 1,450,000 (performed under the same conditions above); a weight average molecular weight of 2,800,000 (performed by LALLS photometry as above) and a K-value of 115-125. These same polymers are also available as solutions from the same source. Other commercially available PVP in powder or solution form can be obtained from BASF Corporation of Mount Olive, N.J., U.S.A.
under the registered trademark LUVISKOL over a wide range of molecular weights. Luviskol K-90 has a weight average molecular weight of 1,200,000;
Luviskol K-80 has a weight average molecular weight of 900,000 and Luviskol K-60, K-30 and K-77 have lower molecular weights. These products are described in the Luviskol~) Polyvinylpyrollidone Polymers catalog by BASF corporation and PVP Polyvinylpyrollidone Polymers catalog by ISP
(lnt~rn~tional Specialty Products) GAF corporation, the entire disclosures of which are herein incorporated by reference.
It is to be expressly understood that the identification of the aforementioned commercially available sources of PVP polymers and/or solutions is by way of illustration only and not by way of limitation; as other commonly available sources or synthPsi7Pd polymers may be used in the invention without departing from the spirit or scope of the appended claims.
Preferablv~ in the compositions of the invention, component (B) is present in amounts of at least about 12% but not more than about 26%. More than one low molecular weight polymer can be used as component (B). When -- more than one low molecular weight adhesive-e~hibiting polymer is present~
CA 022~670~ 1998-ll-26 WO 98/47953 PCTtUS97/06713 it is preferable that the higher molecular weight polymer of such low molecular weight polymers is present in an equal or greater amount.
Component (C) is generally present from about 3% to about 10%, based on the total weight of the composition, preferably in the range of about 6% to about 8%. Component (C) is a long chain (i.e. C,5-C~6) fatty acid, preferably in the forrn of a salt with an alkali-metal or alkaline earth metal, e.g.
Li, Na K, Ca, Sr, Ba, most preferably sodium stearate. It /~nh~nc.es spreading properties when the crayon or glue stick is rubbed against a porous substrate.
Component (D) is a high molecular weight (e.g. above about a molecular weight of 1,300,000, preferably above 2,000,000, most preferably at least 2,800,000) polymer, e.g. PVP. The amount of component (D) is sufficient to impart fast setting properties, e.g. preferably in less than 20 seconds, preferably less than 15 seconds to the film applied to a porous substrate from the glue stick of the invention. However, the amount of component (D) should not be so great as to induce crumbling when pressure is applied to the glue stick upon rubbing the stick on the porous substrate. The amount of component (D) will vary with the molecular weight of the polymer, lower amounts being required with the highest molecular weights. In general, component (D) may be present in an amount of from about 0.5% to about 10%. preferably about 0.5% to about 4%. Most preferably, the arnount of component (D) is at least 0.5 wt %, preferably at least 0.7 wt %, most preferably at least about 1 wt %.
When a solvent for the water dispersible polymer, e.g. PVP, is present, - it is preferably an organic solvent. Preferably the solvent is an alcohol, more CA 022~670~ l998-ll-26 preferably an alcohol selected from the group consisting of glycerol, polyglycols, especially low molecular weight polyglycols, e.g. propylene glycol and mixtures thereof, though most preferably, glycerols and propylene glycol. Other solvents, including acids, ketone and ether alcohols, lactones, lactams, certain esters, ketones and chlorinated hydrocarbons; esters and nitroparaffins are known solvents for PVP. The solvent is present in amounts ranging from about 3% to about 8%, preferably about 3.2% to about 7%.
Plasticizers for the water soluble/dispersible polvmers may also be included in the formulations of the inventions. Low molecular weight polyethylene glycols, e.g. having a M.W. of 400 or less. are particularly good plasticizers.
The compositions of the invention can be made by mixing components (A)-(D), and any optional components, in any order. During this mixing, temperature can be elevated to 85-95~C and mixing continued with slow agitation until components (B) and (D) are completely dissolved (within about 15 minutes) and the component (C) and any optional ingredients added and mixed until dissolved completely. Alternatively, components (A) can be mixed with (C) and/or any optional components and then mixed with the polymer components (B) and (D). Still further components (A), (B) and (D) can be mixed, or components (B) and (D) can be in solution/dispersion form, before being mixed with any other component. The resulting composition can be extruded directly into glue stick containers or drawn off into drums for storage to be reheated and used at a future date.
..... ... . . _ .. . . .
CA 022~670~ 1998-ll-26 When an optional component for controlling microorg~ni~m.~ is added, it may take the form of a mildewcide and/or fungicide. Suitable substances are commercially available, such as the mildewcide sold under the trademark "DOWICIL 150" ~available from Dow Chemical Corporation, Midland, Michigan, USA) in an effective amount, e.g. as little as 0.18 wt % to 0.20 wt %.
Permanent color can be imparted to the composition of the invention by including pigments and/or dyes as an optional component.
When a color indicator is added for the purpose of indicating when the film has dried, the freshly applied adhesive has a color, e.g. blue, which fades to colorless when the adhesive has dried, e.g. in about ~-15 seconds. When the color indicator is present in combination with a permanent color, the color will change from the as applied to dried adhesive, rather than fade to colorless.
As suitable indicators can be used phenolphtalein (chemical name 3,3-bis(4-hydroxyphenyl)- 1-(3 ~)-isobenzofuranone) orthymolphthalein (chemical name 3 ,3 -bisL4-hydroxy-2-methyl-5-( 1 -methylethyl)phenyl]- 1-(3 H)-isobenzofuranone. These indicators are commerically available such as phenolphthalein and its alkyl derivatives. The indicators are present in an effective amount to indicate a change between a color and colorless phase and generally are present in an amount of not more than 2 wt % preferably from about 0.01 to about 0.5 wt %. As mentioned hereinabove, higher alkalinity enhances the intensity of these indicators to impart a stronger hue to the color exhibited.
CA 02256705 1998-ll-26 I I
The ~vantages of the compositiorls of the invention will be illus~ted bv the followi~g E.Y~rnpies ~nd Comparative E.Y~mples. In the E.Yarnples. it c~n be seen tha~ the properties of the composition. especiallv properties of exle~sion and retr~ction of the composition from a cont~iner ~nd most importantlv its spre~ding and sertin~ chzr~cteristics. can be tailored bv proportioning the components.
:: ., . . ~ . ..... .. . . ..
W3~er 60.10 ~ ~ Firrn Cre~rnv 12 sec. Some F311ea~ Slight pVP 90 21.,0 ~-vhite resist nc_ di~cultv PVP 1'0 01.00 to in Gl,vce.ol 07.00 c:c~ension srJr~3ding.
\la Ste3r3te 07.00 r~equired Dowicil ()0.~0 addition3i ?ressure wnicn arJplied e~c_sslve dhesi-e Wa~er 60.10 '~ ~ Fimm C;e3mv 11 ,e . Slit~n~ Faliet~ iome pVp 4~) ".00 ~vhile reslstmce ~ti~lcukv PVP 1~0 00.. 0 to .n Glvcerol 07.00 c.Y~ension scrc3dinr~.
~la ite3r~e 07.00 out t~erter Do~vlc~ 0 nn ~O :han EY. ! .
I 00.00 ;10 ~-Jmolin~
W3~e oO. 10'' ~ Lcss C.earn~ ec. E3sv E ~s~ E3sicr PVP 40 '~., O lirtn ~vhilc SDre3 nn~
PVp !'!) Ol 00 th~n EY. ~u~ cYcess PG. 0/ 00 I ma' ~iuc !~a jtear3~e 07 00 ~ooiica .iuc Do~vlc;i !~0/~n ~o O ;or~ness 1 00.00 W;l~e oO.10'' ~ Fimn C,e3rn~ 4sec. E;ls~ '~s~ _ s~
pvP 40 '~, O ~vhi~e ,ore~lmn P'~P '_!) ')I JO ' :lo P G O; ~n ;~molin~
ivce-ol 0;.~0 ear3~e 1), 00 ~o~vlc~ n ~
I ~)() ~)() SUBSTITUTE SHEET (RULE 26) WO 98/47953 PCTfUS97/06713 Wl~lcr60.10 g Slightly Gearny 9-10s~ Easr Easy Ea pVP 90~. 0 so~ whuc Sr PVP 1 001.00 spre~ding P.G. Ol.;0 no Glvc~rol05~0 crumbling ~la Slel~ate O7.00 Dowlcil 150 no ~o 100.00 6 Water60.10 15 g Firm Cre3rnv 9 scc. Easv Easv Easv pVP 904 95 whj~e PVP 1 0OO. 5 spreadmg.
P.G I03.50 no GivcerDI03 50 crumDlinv ~ia Ste3rare 07 00 Dowlcil 150 no~o 100.00 7 Walcr60.10 15 v Sligh~ly Creamv 9sec. Easy E~sv Evcrso PVP 9025. 0 sott white slight PVP 12000.50 spre~ding P.G. 03.~0 r~sist3nce Glvcerol03.50 due to ~a 5~e~teO7.00 slighdv Dowicil 150 nn~o ioltersticl;
'~~ ~~ no crumbling i 8 Water60.10 ~ ~ Slightly Crearny ll sec. Easv Failed- Slight PVP 905 00 less white crumDlh~v PVP l 0OO.70 firm Glvcerol08.00 e~rLt~e06.00 Do ~ic:dcnn ~o 1 00.00 9 W~er 60.g7 F;rm E31ue when 9 sec. E3sv E3sv Easv Proovlene 3pplicd~ spre3dino Glvcoli.; Colorless no Givc:roii.ii when drv ;rumblin_ PVP 90 i 6 PVp ~-1'0O., I
Thvmol-pnthalein 0.'~
~fa S~e3ra~e 6.67 Sod ium Hvdro.Yide Pcl l~ts0 . ~ O
W3~er I De~onized~ 0 60 Dowlc:l 150 ~ !C) 1 00.~0 ComDar3- b~l Suc I Firm Whi~e S-30sec. E sv E3sv Eas tive I opaoue ioreaainq.
no crumoiing ComDara- Ross i-nYelopc ~ ~ 1 Firm Cre3mv ~ sec E3s E3s E~-tive 3 wnite inreoblng.
no ;rumDiinq ComD~r;~- Rosi r~idsu~ Firm Fucnsi~ _i iec E~sv Eas~ Els dve ~ purpie ~-oreabing.
no _rumDling SlJ~i 111 UTE SHEET (RULE 26) CA 02256705 1998-ll-26 Compa~ .~verv 7.4 g Slighay Cr~amy ~5 scc. Easy F~iied- Sprcats ovc~ Icss whirc-firrn vvhitc resistancc ~luc ~o s~ v Icss ~irm ~I~C~
Compara- jM Sco~ch 7.08 g Firm Creamy 'Oscc. Easv Easy Easv tive j whilc sprcaoing, no erumblin, Compar2- Water 60.10 ~', Verv Creamv ~tnan 15 Easv Easv Sprearls tive 6 PVP iO'25. . 0 sort white mm. wlth some P.G.' 03.50 resist2nc: i Gl,vc~rol 03.50 due to glue ~laStear te 07.00 crumbling Dowicil 150 00.~0 1 00.00 Compara- Water 60,10 22g VerY Creumy 90sec. Easv Easv Spre2ds tive 7 PVP 50'1'.55 sort white with some PVP 90 1'.55 resistance P.G.' 03.50 due to the Glvcerol03.50 giue's ~la Stearate 07.00 sortness:
Dowlcil 150 00.30 some 100 00 crumbling Compar2- Water 60.10 ~ g Slightly Crcarny '5 sec. E cv Easv Spreads tive 5 PVP 90~5. 7 0 sort white with some P.G I 03.50 resist2ncc Gl ,vceroi 03 .50 due ~o d~e Ste2r~Le 07.00 ~lue's Dowicil 150 ~n 30 sortness:
100.00 some crumbling ComDar3- W:~ter 7;.6~ '', Firm White ~ione 3~er E2sv E~sv Vervtive9 PVP ''01 00 opaquc lOmln. imoolh P G. 03.60 iDrer~din~:
Glvceroi0i.60 howevcr.
!la Ste3r~e 07.00 Ippears Dowicii !~0, 00 !5 th2~cnher 100.00 '~iU~ Is Ibsorr co ~ n the r2Der or thc amount ot ~luc ~rmsrerreb is mimm~l.
ver~ linlc it'an~ JrlCa vluc resiauc ' i elt on e iDcr ~o v ~
:~ahes~ c.
i-vcn ~w.cn :v~te .
_onlenl .~pDro:lc.-c, uDper :Imu h mh Sl '.~
.lahesl~ e uocs no~
~Drc~J
SUb~i 111 IJTE SHEET (RULE 26) . . . ~ ... . . .. ~
CA 022=,670=, 1998-11-26 W 098/47953 PCT~US97/06713 -1~
Comp~ W~ 81.~ 7~g So~ W~ min. E~ E~ Sp~
~v~ 10 PVP 120 1_00 opaqu~ 5jly P.G.' 01.63 d~~nt Glyo~l 01.63 ~umblc ~aS~ 03.~ butlos~;~
Dowicil150 ~0.70 fo~ ~d 100.00 whcn Jppl icd 'Propylene glycol 'Wt Avg.MW = 55,000 *Glue stick se~d~dl~d from the carry platform.
It c~n re~dily be seen that the compositions of matter of Ihe present inventiorL in the form of glue sticks or crayons. provide a fast set~ing, non-toxic composition suitable for adhering porous substrates.
It is to be understood that. in the specification and accompanying claims, the fo~ul~tions are considered to consist of components of two phases. e.g. Iiauids and solids. The liquid phase component is water or aqueous phase and all other components are considered solids. even though some compone~ts used in the invention may be thought of s liquids. ~he percentage of solids c n thus be c~lculated bv subtracting the percentage of liquid component from 100%. For e~cample, if the liquid phase is 70~h bv weight the solid phase is ,0% b~v wei~ht (100% - 70~~0 = ~0%). It thus can be appreciated thal Ihe formulations of the invention compnse a minor to equivalent pe.centage of solids to liquid. but vet ~re f~st settingJ strong bondforrning a&esive compositions.
ile ~he invention has been described in detail lnd ~vith reference ~o specific embodirnents the~eo~: it ~vill be aDparent to those skilled in the art that v~rious changes and modifications can be made therein without departing *orn he spirit md scope thereof.
SU~S 1 l I UTE SHEET (RULE 26)
Later solid adhesive compositions, such as those disclosed in U.S. Patents 4,073,756 and 4,075,830, were said to avoid the problem inherent in the crayons of U.S. Patent 3,576,776, the long time it took to produce the adhesive composition and the high viscosity of the adhesive composition (e.g.
CA 022~670~ 1998-ll-26 higher than 150,000 cps) which made it difficult to fill the adhesive composition in containers.
The later patents thus used water soluble or water dispersible polymers having adhesive properties in combination with N-fatty acid acy}ated amino acids or salts thereof and water, or a mixture of water and one or more organic solvent(s) and/or plasticizer(s). The water dispersible or water soluble polymers having adhesive properties listed, arnong others, homopolymers or copolymers having a carboxyl group or a carboxylic anhydride group? where the proportions of the carboxyl and/or carboxylic anhydride group containing monomer is preferably about 30 to 100 mol %.
These, and other prior art formulations (the entire disclosures of all of which are herein incorporated by reference), were still slow to exhibit adhesive properties when dispensed, i.e. slow to e~hibit paper tear when applied to bond paper.
Among other properties, the present invention provides strong final bonds and a pH generally in the range of about 8.5 to about 9.~.
However. in the embodiments of the invention where a color indicator is used, the hue or intensity of the color is enhanced by having a pH more alkaline than the range given above, e.g. up to a pH of about 11, e.g. 10.9 - 11.1.
Object of the Invention It is thus an object of the invention to provide new adhesive compositions e~hibiting fast adhesive properties (e.g. fast initial tear of paper) and strong final bonds.
CA 022~670~ 1998-ll-26 It is a further object of the invention to provide adhesive compositions in the form of solids at ambient conditions, i.e. glue sticks or applicator crayons which exhibit fast adhesive properties when applied to a substrate and suitable for bonding paper, fabric, polystyrene foam and similar materials.
It is a still further object of the invention to provide bonded substrates, such as paper, fabric, and similar porous materials, bonded with the adhesive compositions of the invention.
Summary of the Invention Water-based solid adhesive crayons which contain water in a mixture comprising a relatively low molecular weight (all references to "molecular weight" in this Specification, claims and Abstract are intended to mean "weight average molecular weight" unless otherwise design~ted) water dispersible or water soluble polymer, e.g. polyvinylpyrrolidone polvmer, i.e.
a molecular weight below about 1,300,000, and a critical amount of a relatively high molecular weight water dispersible or water soluble polymer, e.g. polyvinylpyrollidone polymer, i.e. a molecular weight above 1,300,000.
By critical arnounts is meant sufficient amounts of the high molecular weight (polyvinylpyrollidone) polymer to impart 1.) a fast film-forming or setting property, 2.) a strong final bonding property, and 3.) an additional firmness to the crayon adhesive to reduce "crumbling" when pressure is applied to the crayon, while keeping the water content of the adhesive at 50 weight percent, or more, to ensure easy spreading and performance during use and after storage. Optional ingredients include a plasticizer for the (polyvinylpyrollidone) polymers to impart a degree of flexibility to the dry CA 022~670~ 1998-ll-26 WO 98/47953 PCT/US97tO6713 adhesive film, a preservative to protect the adhesive from attack by microorp~ni~m~, a long chain fatty acid salt to impart a solid gel property to the adhesive, and a color indicator for the purpose of indicating when an applied film of adhesive has dried.
This composition may be formulated so as to exhibit physical properties of a solid, e.g. it may be formulated so as to be suitable for application in the forrn of a crayon or glue stick to porous substrates to be bonded. The composition is preferably formulated so as to be satisfactorily extruded from and retracted into a container, exhibit good spreadability without being "runny" or dispensing excessive adhesive to a substrate nor so firm that the crayon or adhesive stick "crumbles" due to the requirement to exert excessive pressure during application of the crayon/stick to a substrate to effect adequate spreading of the adhesive on the substrate.
It is also within the purview of the invention to provide substrates bonded with the forrnulations of the invention.
Detailed Description of the Invention The composition of matter of this invention e~hibits adhesive properties and is form~ t~d of components (A), (B), (C), and (D), wherein (A) is an aqueous vehicle, typically water or aqueous emulsions/dispersions of one or more of components (B), (C), (D) andlor any optional components; (B) is at least one water soluble or water dispersible polymer, e.g.
polyvinylpyrollidone (hereinafter "PVP") polymer exhibiting adhesive properties having a molecular weight below about 1,300,000, (C) is a salt of - a long chain fatty acid or a precursor thereof which forms a salt of a long chain CA 022~670~ 1998-ll-26 fatty acid when combined with the other components of the compositions of matter of this invention and (D) is a water soluble or water dispersible polymer, e.g. a PVP polymer having a molecular weight above about 1,300,000, preferably above about 2,000,000 most preferably of at least about 2,800,000. Suitable polymers for component (B) include homopolymers or copolymers of the types identified in U.S. Patents 4,073,756 or 4,954,544, although PVP is particularly preferred. Although higher molecular weight polymers of component (D) can be of the same type of polymer as component (B), it is preferred that the high molecular weight polymer be PVP.
When it is desirable, certain optional ingredients may be included in the composition of matter of the invention, e.g. a mildewcide and/or fungicide, solvents for the adhesive exhibiting polymeric components, e.g. alcohols, such as glycerol or polyglycols for PVP, pigments and/or dyes to impart a permanent color, and/or a color indicator, such as phenolphthalein or thymolphthalein, for indicating when the applied film is dried.
Generally, the components of the invention may be combined over a wide range. However, in order to forrnulate the composition of matter in solid form, e.g. suitable for use, as an adhesive applicator stick or crayon, it is preferable that the composition contain not less than about 50% nor more than about 80% (all % in this application are by weight unless otherwise noted) by weight of component (A) (wherein (A) is water). If (A) is an aqueous formulation cont~ining one or more components (B)-(D), or having optional components. the arnount of (A) can be adjusted so as to be greater than, or lesser than, the amounts indicated. Although it is preferable that the CA 022~670~ l998-ll-26 composition contain not less than about 50%, preferably not less than about 60% of component (A) (where (A) is water) this amount can be adjusted lower, e.g. 45% or less though not exhibiting the most preferred properties of the adhesive stick of the invention. The presence of plasticizers, solvents or mixtures thereof for the water dispersible polymers may also decrease the requirements for component (A) to be present in an amount of not less than 50%, because such plasticizers/solvents enhance the spreadability properties.
As with the case of the maximum content of component (A), when (A) is an aqueous forrnulation containing one or more of components (B)-(D), or any optional components, the amount of (A) will be adjusted accordingly.
Component (B) is at least one polymer exhibiting a&esive properties, preferably a polyvinylpyrrolidone (PVP) of relatively low molecular weight?
e.g. below about 1,300,000. PVP polymers are commercially available in several viscosity grades, ranging from very low to very high molecular weight.
This range, coupled with solubility in water, aqueous and organic solvent systems and its non-toxic character, give PVP great flexibility in the compositions and applicator solid forrns of the present invention.
Commercially available PVP suitable for use in this invention as components (B) or (D) are available from GAF Chemicals Corporation, International Specialty Products, of Wayne, N.J., U.S .A., under the tradenames PVP K-90 and PVP K-120, each having an off-white powder appearance.
PVP K-90 has a viscosity average molecular weight of 630,000 (perforrned at 25 ~C, in H,O, using Mark Houwink constants of K = 1.4 x 10-4 and a = 0.7), a weight average molecular weight (Wt.Avg.MW) of 1.2~0,000 (obtair~ed by CA 022~670~ 1998-11-26 low angle laser light scattering (LALLS) photometry) and a K-value of 88-100. PVP K-120 has a viscosity average molecular weight of 1,450,000 (performed under the same conditions above); a weight average molecular weight of 2,800,000 (performed by LALLS photometry as above) and a K-value of 115-125. These same polymers are also available as solutions from the same source. Other commercially available PVP in powder or solution form can be obtained from BASF Corporation of Mount Olive, N.J., U.S.A.
under the registered trademark LUVISKOL over a wide range of molecular weights. Luviskol K-90 has a weight average molecular weight of 1,200,000;
Luviskol K-80 has a weight average molecular weight of 900,000 and Luviskol K-60, K-30 and K-77 have lower molecular weights. These products are described in the Luviskol~) Polyvinylpyrollidone Polymers catalog by BASF corporation and PVP Polyvinylpyrollidone Polymers catalog by ISP
(lnt~rn~tional Specialty Products) GAF corporation, the entire disclosures of which are herein incorporated by reference.
It is to be expressly understood that the identification of the aforementioned commercially available sources of PVP polymers and/or solutions is by way of illustration only and not by way of limitation; as other commonly available sources or synthPsi7Pd polymers may be used in the invention without departing from the spirit or scope of the appended claims.
Preferablv~ in the compositions of the invention, component (B) is present in amounts of at least about 12% but not more than about 26%. More than one low molecular weight polymer can be used as component (B). When -- more than one low molecular weight adhesive-e~hibiting polymer is present~
CA 022~670~ 1998-ll-26 WO 98/47953 PCTtUS97/06713 it is preferable that the higher molecular weight polymer of such low molecular weight polymers is present in an equal or greater amount.
Component (C) is generally present from about 3% to about 10%, based on the total weight of the composition, preferably in the range of about 6% to about 8%. Component (C) is a long chain (i.e. C,5-C~6) fatty acid, preferably in the forrn of a salt with an alkali-metal or alkaline earth metal, e.g.
Li, Na K, Ca, Sr, Ba, most preferably sodium stearate. It /~nh~nc.es spreading properties when the crayon or glue stick is rubbed against a porous substrate.
Component (D) is a high molecular weight (e.g. above about a molecular weight of 1,300,000, preferably above 2,000,000, most preferably at least 2,800,000) polymer, e.g. PVP. The amount of component (D) is sufficient to impart fast setting properties, e.g. preferably in less than 20 seconds, preferably less than 15 seconds to the film applied to a porous substrate from the glue stick of the invention. However, the amount of component (D) should not be so great as to induce crumbling when pressure is applied to the glue stick upon rubbing the stick on the porous substrate. The amount of component (D) will vary with the molecular weight of the polymer, lower amounts being required with the highest molecular weights. In general, component (D) may be present in an amount of from about 0.5% to about 10%. preferably about 0.5% to about 4%. Most preferably, the arnount of component (D) is at least 0.5 wt %, preferably at least 0.7 wt %, most preferably at least about 1 wt %.
When a solvent for the water dispersible polymer, e.g. PVP, is present, - it is preferably an organic solvent. Preferably the solvent is an alcohol, more CA 022~670~ l998-ll-26 preferably an alcohol selected from the group consisting of glycerol, polyglycols, especially low molecular weight polyglycols, e.g. propylene glycol and mixtures thereof, though most preferably, glycerols and propylene glycol. Other solvents, including acids, ketone and ether alcohols, lactones, lactams, certain esters, ketones and chlorinated hydrocarbons; esters and nitroparaffins are known solvents for PVP. The solvent is present in amounts ranging from about 3% to about 8%, preferably about 3.2% to about 7%.
Plasticizers for the water soluble/dispersible polvmers may also be included in the formulations of the inventions. Low molecular weight polyethylene glycols, e.g. having a M.W. of 400 or less. are particularly good plasticizers.
The compositions of the invention can be made by mixing components (A)-(D), and any optional components, in any order. During this mixing, temperature can be elevated to 85-95~C and mixing continued with slow agitation until components (B) and (D) are completely dissolved (within about 15 minutes) and the component (C) and any optional ingredients added and mixed until dissolved completely. Alternatively, components (A) can be mixed with (C) and/or any optional components and then mixed with the polymer components (B) and (D). Still further components (A), (B) and (D) can be mixed, or components (B) and (D) can be in solution/dispersion form, before being mixed with any other component. The resulting composition can be extruded directly into glue stick containers or drawn off into drums for storage to be reheated and used at a future date.
..... ... . . _ .. . . .
CA 022~670~ 1998-ll-26 When an optional component for controlling microorg~ni~m.~ is added, it may take the form of a mildewcide and/or fungicide. Suitable substances are commercially available, such as the mildewcide sold under the trademark "DOWICIL 150" ~available from Dow Chemical Corporation, Midland, Michigan, USA) in an effective amount, e.g. as little as 0.18 wt % to 0.20 wt %.
Permanent color can be imparted to the composition of the invention by including pigments and/or dyes as an optional component.
When a color indicator is added for the purpose of indicating when the film has dried, the freshly applied adhesive has a color, e.g. blue, which fades to colorless when the adhesive has dried, e.g. in about ~-15 seconds. When the color indicator is present in combination with a permanent color, the color will change from the as applied to dried adhesive, rather than fade to colorless.
As suitable indicators can be used phenolphtalein (chemical name 3,3-bis(4-hydroxyphenyl)- 1-(3 ~)-isobenzofuranone) orthymolphthalein (chemical name 3 ,3 -bisL4-hydroxy-2-methyl-5-( 1 -methylethyl)phenyl]- 1-(3 H)-isobenzofuranone. These indicators are commerically available such as phenolphthalein and its alkyl derivatives. The indicators are present in an effective amount to indicate a change between a color and colorless phase and generally are present in an amount of not more than 2 wt % preferably from about 0.01 to about 0.5 wt %. As mentioned hereinabove, higher alkalinity enhances the intensity of these indicators to impart a stronger hue to the color exhibited.
CA 02256705 1998-ll-26 I I
The ~vantages of the compositiorls of the invention will be illus~ted bv the followi~g E.Y~rnpies ~nd Comparative E.Y~mples. In the E.Yarnples. it c~n be seen tha~ the properties of the composition. especiallv properties of exle~sion and retr~ction of the composition from a cont~iner ~nd most importantlv its spre~ding and sertin~ chzr~cteristics. can be tailored bv proportioning the components.
:: ., . . ~ . ..... .. . . ..
W3~er 60.10 ~ ~ Firrn Cre~rnv 12 sec. Some F311ea~ Slight pVP 90 21.,0 ~-vhite resist nc_ di~cultv PVP 1'0 01.00 to in Gl,vce.ol 07.00 c:c~ension srJr~3ding.
\la Ste3r3te 07.00 r~equired Dowicil ()0.~0 addition3i ?ressure wnicn arJplied e~c_sslve dhesi-e Wa~er 60.10 '~ ~ Fimm C;e3mv 11 ,e . Slit~n~ Faliet~ iome pVp 4~) ".00 ~vhile reslstmce ~ti~lcukv PVP 1~0 00.. 0 to .n Glvcerol 07.00 c.Y~ension scrc3dinr~.
~la ite3r~e 07.00 out t~erter Do~vlc~ 0 nn ~O :han EY. ! .
I 00.00 ;10 ~-Jmolin~
W3~e oO. 10'' ~ Lcss C.earn~ ec. E3sv E ~s~ E3sicr PVP 40 '~., O lirtn ~vhilc SDre3 nn~
PVp !'!) Ol 00 th~n EY. ~u~ cYcess PG. 0/ 00 I ma' ~iuc !~a jtear3~e 07 00 ~ooiica .iuc Do~vlc;i !~0/~n ~o O ;or~ness 1 00.00 W;l~e oO.10'' ~ Fimn C,e3rn~ 4sec. E;ls~ '~s~ _ s~
pvP 40 '~, O ~vhi~e ,ore~lmn P'~P '_!) ')I JO ' :lo P G O; ~n ;~molin~
ivce-ol 0;.~0 ear3~e 1), 00 ~o~vlc~ n ~
I ~)() ~)() SUBSTITUTE SHEET (RULE 26) WO 98/47953 PCTfUS97/06713 Wl~lcr60.10 g Slightly Gearny 9-10s~ Easr Easy Ea pVP 90~. 0 so~ whuc Sr PVP 1 001.00 spre~ding P.G. Ol.;0 no Glvc~rol05~0 crumbling ~la Slel~ate O7.00 Dowlcil 150 no ~o 100.00 6 Water60.10 15 g Firm Cre3rnv 9 scc. Easv Easv Easv pVP 904 95 whj~e PVP 1 0OO. 5 spreadmg.
P.G I03.50 no GivcerDI03 50 crumDlinv ~ia Ste3rare 07 00 Dowlcil 150 no~o 100.00 7 Walcr60.10 15 v Sligh~ly Creamv 9sec. Easy E~sv Evcrso PVP 9025. 0 sott white slight PVP 12000.50 spre~ding P.G. 03.~0 r~sist3nce Glvcerol03.50 due to ~a 5~e~teO7.00 slighdv Dowicil 150 nn~o ioltersticl;
'~~ ~~ no crumbling i 8 Water60.10 ~ ~ Slightly Crearny ll sec. Easv Failed- Slight PVP 905 00 less white crumDlh~v PVP l 0OO.70 firm Glvcerol08.00 e~rLt~e06.00 Do ~ic:dcnn ~o 1 00.00 9 W~er 60.g7 F;rm E31ue when 9 sec. E3sv E3sv Easv Proovlene 3pplicd~ spre3dino Glvcoli.; Colorless no Givc:roii.ii when drv ;rumblin_ PVP 90 i 6 PVp ~-1'0O., I
Thvmol-pnthalein 0.'~
~fa S~e3ra~e 6.67 Sod ium Hvdro.Yide Pcl l~ts0 . ~ O
W3~er I De~onized~ 0 60 Dowlc:l 150 ~ !C) 1 00.~0 ComDar3- b~l Suc I Firm Whi~e S-30sec. E sv E3sv Eas tive I opaoue ioreaainq.
no crumoiing ComDara- Ross i-nYelopc ~ ~ 1 Firm Cre3mv ~ sec E3s E3s E~-tive 3 wnite inreoblng.
no ;rumDiinq ComD~r;~- Rosi r~idsu~ Firm Fucnsi~ _i iec E~sv Eas~ Els dve ~ purpie ~-oreabing.
no _rumDling SlJ~i 111 UTE SHEET (RULE 26) CA 02256705 1998-ll-26 Compa~ .~verv 7.4 g Slighay Cr~amy ~5 scc. Easy F~iied- Sprcats ovc~ Icss whirc-firrn vvhitc resistancc ~luc ~o s~ v Icss ~irm ~I~C~
Compara- jM Sco~ch 7.08 g Firm Creamy 'Oscc. Easv Easy Easv tive j whilc sprcaoing, no erumblin, Compar2- Water 60.10 ~', Verv Creamv ~tnan 15 Easv Easv Sprearls tive 6 PVP iO'25. . 0 sort white mm. wlth some P.G.' 03.50 resist2nc: i Gl,vc~rol 03.50 due to glue ~laStear te 07.00 crumbling Dowicil 150 00.~0 1 00.00 Compara- Water 60,10 22g VerY Creumy 90sec. Easv Easv Spre2ds tive 7 PVP 50'1'.55 sort white with some PVP 90 1'.55 resistance P.G.' 03.50 due to the Glvcerol03.50 giue's ~la Stearate 07.00 sortness:
Dowlcil 150 00.30 some 100 00 crumbling Compar2- Water 60.10 ~ g Slightly Crcarny '5 sec. E cv Easv Spreads tive 5 PVP 90~5. 7 0 sort white with some P.G I 03.50 resist2ncc Gl ,vceroi 03 .50 due ~o d~e Ste2r~Le 07.00 ~lue's Dowicil 150 ~n 30 sortness:
100.00 some crumbling ComDar3- W:~ter 7;.6~ '', Firm White ~ione 3~er E2sv E~sv Vervtive9 PVP ''01 00 opaquc lOmln. imoolh P G. 03.60 iDrer~din~:
Glvceroi0i.60 howevcr.
!la Ste3r~e 07.00 Ippears Dowicii !~0, 00 !5 th2~cnher 100.00 '~iU~ Is Ibsorr co ~ n the r2Der or thc amount ot ~luc ~rmsrerreb is mimm~l.
ver~ linlc it'an~ JrlCa vluc resiauc ' i elt on e iDcr ~o v ~
:~ahes~ c.
i-vcn ~w.cn :v~te .
_onlenl .~pDro:lc.-c, uDper :Imu h mh Sl '.~
.lahesl~ e uocs no~
~Drc~J
SUb~i 111 IJTE SHEET (RULE 26) . . . ~ ... . . .. ~
CA 022=,670=, 1998-11-26 W 098/47953 PCT~US97/06713 -1~
Comp~ W~ 81.~ 7~g So~ W~ min. E~ E~ Sp~
~v~ 10 PVP 120 1_00 opaqu~ 5jly P.G.' 01.63 d~~nt Glyo~l 01.63 ~umblc ~aS~ 03.~ butlos~;~
Dowicil150 ~0.70 fo~ ~d 100.00 whcn Jppl icd 'Propylene glycol 'Wt Avg.MW = 55,000 *Glue stick se~d~dl~d from the carry platform.
It c~n re~dily be seen that the compositions of matter of Ihe present inventiorL in the form of glue sticks or crayons. provide a fast set~ing, non-toxic composition suitable for adhering porous substrates.
It is to be understood that. in the specification and accompanying claims, the fo~ul~tions are considered to consist of components of two phases. e.g. Iiauids and solids. The liquid phase component is water or aqueous phase and all other components are considered solids. even though some compone~ts used in the invention may be thought of s liquids. ~he percentage of solids c n thus be c~lculated bv subtracting the percentage of liquid component from 100%. For e~cample, if the liquid phase is 70~h bv weight the solid phase is ,0% b~v wei~ht (100% - 70~~0 = ~0%). It thus can be appreciated thal Ihe formulations of the invention compnse a minor to equivalent pe.centage of solids to liquid. but vet ~re f~st settingJ strong bondforrning a&esive compositions.
ile ~he invention has been described in detail lnd ~vith reference ~o specific embodirnents the~eo~: it ~vill be aDparent to those skilled in the art that v~rious changes and modifications can be made therein without departing *orn he spirit md scope thereof.
SU~S 1 l I UTE SHEET (RULE 26)
Claims (22)
1 . A composition of matter comprising a mixture of the following components (A)-(D):
(A) about 45% to about 80% by weight water;
(B) about 12% to about 26% by weight of at least one water soluble or water dispersible polymer exhibiting adhesive properties, said polymer having a molecular weight of less than about 1,300,000;
(C) a long-chain fatty acid. or a salt of a long-chain fatty acid. in an amount of from about 3% to about 10%; and (D) a high molecular weight water soluble or water dispersible polymer, said high molecular weight polymer having a molecular weight of at least 1,300,000 and being present in an amount sufficient to impart fast film forming and strong final bonding property to the composition.
(A) about 45% to about 80% by weight water;
(B) about 12% to about 26% by weight of at least one water soluble or water dispersible polymer exhibiting adhesive properties, said polymer having a molecular weight of less than about 1,300,000;
(C) a long-chain fatty acid. or a salt of a long-chain fatty acid. in an amount of from about 3% to about 10%; and (D) a high molecular weight water soluble or water dispersible polymer, said high molecular weight polymer having a molecular weight of at least 1,300,000 and being present in an amount sufficient to impart fast film forming and strong final bonding property to the composition.
2. The composition of claim 1 wherein the component (B) is at least one polyvinylpyrrolidone polymer.
3. The composition of claim 1 wherein component (B) comprises at least two polyvinylpyrrolidone polymers, the polymers having different molecular weights.
4. The composition of claim 3 wherein the weight ratio of the polyvinylpyrrolidone of lower molecular weight to the polyvinylpyrrolidone of greater molecular weight is not greater than about 1:1.
5. The composition of claim 1 wherein component (D) is present in an amount of from about 0.5 to about 4% by weight.
6. The composition of claim 1 wherein component (C) is sodium stearate.
7. The composition of claim 1 further comprising a component selected from the group consisting of glycerol, propylene glycol and mixtures thereof.
8. The composition of claim 1 further including a color indicator.
9. An adhesive crayon comprising the composition of claim 1 in solid form.
10. An adhesive crayon according to claim 9 wherein the water content is at least 50% by weight.
11. Porous substrates adhered by an adhesive formulation of claim
12. The porous substrates of claim 11 wherein the porous substrate is selected from the group consisting of paper, wood, fabric and polystyrene foam.
13. A composition of matter in solid form at ambient conditions comprising:
(A) from about 45% to about 80% by weight of water;
(B) from about 12% to about 26% of at least one polyvinylpyrrolidone polymer of molecular weight less than about 1,300,000.
(C) from about 3% to about 10% of a long chain fatty acid or salt thereof; and (D) from about 0.5% to about 4% of a polyvinylpyrrolidone polymer having a molecular weight in the range of from about 1,300,000 to about 2,800,000.
(A) from about 45% to about 80% by weight of water;
(B) from about 12% to about 26% of at least one polyvinylpyrrolidone polymer of molecular weight less than about 1,300,000.
(C) from about 3% to about 10% of a long chain fatty acid or salt thereof; and (D) from about 0.5% to about 4% of a polyvinylpyrrolidone polymer having a molecular weight in the range of from about 1,300,000 to about 2,800,000.
14. The composition of claim 13 wherein component (A) is present in an amount of at least 50% by weight.
15. The composition of claim 13 further comprising an effective amount of a mildecide.
16. The composition of claim 13 further comprising a color indicator in an amount of from about 0.01% to 0.5% by weight.
17. Porous substrates adhered by an adhesive formulation of claim 13.
18. The porous substrates of claim 16 wherein the porous substrate is selected from the group consisting of paper, wood, fabric and polystyrene foam.
19. The composition of claim 13 further comprising at least one component selected from the group consisting of solvents, plasticizers and mixtures thereof.
20. The composition of claim 13 wherein component (C) is sodium stearate.
21. The composition of claim 13 further comprising a color indicator selected from the group consisting of phenolphthalein and thymolphthalein.
22. An adhesive crayon comprising the composition according to claim 13 in solid form wherein the solid phase is from about 30% to about 50% by weight.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1997/006713 WO1998047953A1 (en) | 1997-04-23 | 1997-04-23 | Adhesive applicator crayon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2256705A1 true CA2256705A1 (en) | 1998-10-29 |
Family
ID=22260769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002256705A Abandoned CA2256705A1 (en) | 1997-04-23 | 1997-04-23 | Adhesive applicator crayon |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2738597A (en) |
| CA (1) | CA2256705A1 (en) |
| WO (1) | WO1998047953A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004019181A1 (en) * | 2004-04-16 | 2005-12-08 | Basf Ag | Process for the preparation of aqueous polyvinyllactam dispersions |
| US8691340B2 (en) | 2008-12-31 | 2014-04-08 | Apinee, Inc. | Preservation of wood, compositions and methods thereof |
| US9878464B1 (en) | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
| KR102266300B1 (en) * | 2019-07-16 | 2021-06-17 | 주식회사 문교오엔에스 | Crayons containing polyvinylpyrrolidone |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL132208C (en) * | 1968-02-01 | |||
| DE2054503C2 (en) * | 1970-11-05 | 1982-12-09 | Lingner + Fischer GmbH, 7580 Bühl | Pen for applying glue to documents |
| US4073756A (en) * | 1976-04-26 | 1978-02-14 | Konishi Co., Ltd. | Solid adhesive compositions |
| US4075830A (en) * | 1976-04-26 | 1978-02-28 | Konishi Co., Ltd. | Solid adhesive compositions |
| US4325851A (en) * | 1980-10-24 | 1982-04-20 | Herman Colon | Water-activatable hot-melt adhesives |
-
1997
- 1997-04-23 WO PCT/US1997/006713 patent/WO1998047953A1/en active Application Filing
- 1997-04-23 AU AU27385/97A patent/AU2738597A/en not_active Abandoned
- 1997-04-23 CA CA002256705A patent/CA2256705A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998047953A1 (en) | 1998-10-29 |
| AU2738597A (en) | 1998-11-13 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |