WO1998047953A1 - Adhesive applicator crayon - Google Patents

Adhesive applicator crayon Download PDF

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Publication number
WO1998047953A1
WO1998047953A1 PCT/US1997/006713 US9706713W WO9847953A1 WO 1998047953 A1 WO1998047953 A1 WO 1998047953A1 US 9706713 W US9706713 W US 9706713W WO 9847953 A1 WO9847953 A1 WO 9847953A1
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WO
WIPO (PCT)
Prior art keywords
composition
molecular weight
weight
component
adhesive
Prior art date
Application number
PCT/US1997/006713
Other languages
French (fr)
Inventor
Peter Spiros Columbus
John Anderson
Original Assignee
Elmer's Products, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Elmer's Products, Inc. filed Critical Elmer's Products, Inc.
Priority to AU27385/97A priority Critical patent/AU2738597A/en
Priority to US08/973,215 priority patent/US6066689A/en
Priority to CA002256705A priority patent/CA2256705A1/en
Priority to PCT/US1997/006713 priority patent/WO1998047953A1/en
Publication of WO1998047953A1 publication Critical patent/WO1998047953A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the present invention is desirable for office, school and home consumers.
  • PVP polyvinylpyrrolidone
  • an invention for adhesive applicator crayons comprising a shape-giving base
  • the adhesives are listed salts of various acids, amides, and N-alkyl substituted
  • crayons prepared from rubber, resins and waxes, which required that surface
  • the adhesive composition and the high viscosity of the adhesive composition e.g. higher than 150,000 cps which made it difficult to fill the adhesive composition in containers.
  • arnino acids or salts thereof and water, or a mixture of water and one or more
  • copolymers having a carboxyl group or a carboxylic anhydride group, where
  • monomer is preferably about 30 to 100 mol %.
  • the present invention provides strong
  • 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.
  • compositions exhibiting fast adhesive properties e.g. fast initial tear of paper
  • crayons which exhibit fast adhesive properties when applied to a substrate
  • compositions of the invention are provided.
  • Water-based solid adhesive crayons which contain water in a mixture
  • dispersible or water soluble polymer e.g. polyvinylpyrrolidone polymer, i.e. a molecular weight below about 1,300,000, and a critical amount of a
  • polyvinylpyrollidone polymer i.e. a molecular weight above 1,300,000.
  • critical amounts sufficient amounts of the high molecular weight
  • Optional ingredients include a plasticizer for the
  • polyvinylpyrollidone polymers to impart a degree of flexibility to the dry adhesive film, a preservative to protect the adhesive from attack by
  • microorganisms a long chain fatty acid salt to impart a solid gel property to
  • 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
  • composition is preferably formulated so as to be satisfactorily
  • composition of matter of this invention exhibits adhesive
  • components (B), (C), (D) and/or any optional components; (B) is at least one water soluble or water dispersible polymer, e.g.
  • PVP polyvinylpyrollidone
  • (C) is a salt of a long chain fatty acid or a precursor thereof which forms a salt of a long chain fatty acid when combined with the other components of the compositions of
  • polymer e.g. a PVP polymer having a molecular weight above about
  • Suitable polymers for component (B) include homopolymers or
  • polymers of component (D) can be of the same type of polymer as component
  • the high molecular weight polymer be PVP.
  • 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
  • a color indicator such as phenolphthalein or
  • thymolphthalein for indicating when the applied film is dried.
  • the components of the invention may be combined over a
  • composition contain not less than about 50% nor more than
  • component (A) (wherein (A) is water). If (A) is an aqueous formulation containing one or more components (B)-(D), or having optional components, the amount of (A) can be adjusted so as to be greater than, or lesser than, the amounts indicated. Although it is preferable that the composition contain not less than about 50%, preferably not less than about
  • mixtures thereof for the water dispersible polymers may also decrease the
  • aqueous formulation containing one or more of components (B)-(D), or any
  • the amount of (A) will be adjusted accordingly.
  • Component (B) is at least one polymer exhibiting adhesive properties
  • PVP polyvinylpyrrolidone
  • PVP polymers are commercially available in
  • compositions and applicator solid forms of the present invention are compositions and applicator solid forms of the present invention.
  • 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 (performed at
  • PVP K-120 has a viscosity average molecular weight of 1,450,000
  • 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.
  • 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).
  • molecular weight polymers is present in an equal or greater amount.
  • Component (C) is generally present from about 3% to about 10%,
  • Component (C) is a long chain (i.e. C 15 -C 26 ) fatty acid
  • Li, Na, K, Ca, Sr, Ba most preferably sodium stearate. It enhances spreading
  • Component (D) is a high molecular weight (e.g. above about a
  • component (D) is at least 2,800,000 polymer, e.g. PVP.
  • the amount of component (D) is
  • component (D) should not be so great as to induce crumbling when pressure
  • component (D) will vary with the molecular weight of the polymer
  • component (D) may be present in an amount of from about 0.5% to about
  • the amount of component (D) is at least 0.5 wt %, preferably at least 0.7 wt %, most
  • the solvent is an alcohol, more 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
  • esters certain esters, ketones and chlorinated hydrocarbons; esters and
  • nitroparaffins are known solvents for PVP.
  • the solvent is present in amounts
  • Plasticizers for the water soluble/dispersible polymers may also be used.
  • polyethylene glycols e.g. having a M.W. of 400 or less, are particularly good
  • compositions of the invention can be made by mixing components
  • temperature can be elevated to 85-95 °C and mixing continued with slow
  • components (A) can be
  • components (B) and (D) can be mixed, or components (B) and (D) can be in solution/dispersion form,
  • the resulting composition can be extruded directly into glue stick containers or drawn off into drums for
  • an optional component for controlling microorganisms it may take the form of a mildewcide and/or fungicide. Suitable substances are commercially available, such as the mildewcide sold under the trademark
  • Permanent color can be imparted to the composition of the invention by including pigments and/or dyes as an optional component.
  • the freshly applied adhesive has a color, e.g. blue, which fades
  • phenolphtalein chemical name 3,3- bis(4-hydroxyphenyl)- 1 -(3H)-isobenzofuranone
  • thymolphthalein chemical name 3,3- bis(4-hydroxyphenyl)- 1 -(3H)-isobenzofuranone
  • i ts spreading and setting characteristics can be ta i lored by proportioning the components.
  • the liquid phase component is water or
  • liquid component from 100%.
  • the liquid phase is 70% by
  • formulations of the invention comprise a minor to

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

ADHESIVE APPLICATOR CRAYON
Background 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, amides, 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. 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 acylated
arnino 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, among 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 exhibit 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 9.5.
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 exhibiting fast adhesive properties (e.g. fast initial tear of paper)
and strong final bonds. 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 designated) water
dispersible or water soluble polymer, e.g. polyvinylpyrrolidone polymer, 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 amounts 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 adhesive film, a preservative to protect the adhesive from attack by
microorganisms, 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 form 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 formulations of the invention.
Detailed Description of the Invention
The composition of matter of this invention exhibits adhesive
properties and is formulated 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) and/or 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 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 formulate 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 containing one or more components (B)-(D), or having optional components, the amount of (A) can be adjusted so as to be greater than, or lesser than, the amounts indicated. Although it is preferable that the 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 formulation 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 adhesive 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 forms 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 (performed at
25 °C, in H20, using Mark Houwink constants of K = 1.4 x 10"4 and a = 0.7), a weight average molecular weight (Wt.Avg.MW) of 1,280,000 (obtained by 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 Re¬
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
(International 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 synthesized polymers may be used in the
invention without departing from the spirit or scope of the appended claims.
Preferably, 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-exhibiting polymer is present, 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. C15-C26) fatty acid,
preferably in the form of a salt with an alkali-metal or alkaline earth metal, e.g.
Li, Na, K, Ca, Sr, Ba, most preferably sodium stearate. It enhances 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 amount 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 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 polymers 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. When an optional component for controlling microorganisms 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 9-15 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 -(3H)-isobenzofuranone) orthymolphthalein (chemical
name 3,3-bis[4-hydroxy-2-methyl-5-(l-methylethyl)phenyl]-l-(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. -11-
The advantages of the compositions of the invenuon will be illustrated
by the follo mg Examples and Comparative Examples. In the Examples,
can be seen that the properties of the composition, especially properties of
extension and retraction of the composition from a container and most
importantly its spreading and setting characteristics, can be tailored by proportioning the components.
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
'Propylene glycol
2 tAvg.M = 55,000
*Glue stick separated from the carry platform.
It can readily be seen that the compositions of matter of the present
invention, in the form of glue sticks or crayons, provide a fast setting, non-
toxic composition suitable for adhering porous substrates.
It is to be understood that, in die specification and accompanying
claims, the formulations are considered to consist of components of two
phases, e.g. liquids and solids. The liquid phase component is water or
aqueous phase and all other components are considered solids, even though
some components used in the invention may be thought of as liquids. The
percentage of solids can thus be calculated by subtracting me percentage of
liquid component from 100%. For example, if the liquid phase is 70% by
weight the solid phase is 30% by weight (100% - 70% = 30%). It thus can be
appreciated that the formulations of the invention comprise a minor to
equivalent percentage of solids to liquid, but yet are fast setting, strong bond
forming adhesive compositions.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

We Claim:
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.
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
1.
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.
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.
PCT/US1997/006713 1997-04-23 1997-04-23 Adhesive applicator crayon WO1998047953A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU27385/97A AU2738597A (en) 1997-04-23 1997-04-23 Adhesive applicator crayon
US08/973,215 US6066689A (en) 1997-04-23 1997-04-23 Adhesive applicator crayon
CA002256705A CA2256705A1 (en) 1997-04-23 1997-04-23 Adhesive applicator crayon
PCT/US1997/006713 WO1998047953A1 (en) 1997-04-23 1997-04-23 Adhesive applicator crayon

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)

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WO1998047953A1 true WO1998047953A1 (en) 1998-10-29

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AU (1) AU2738597A (en)
CA (1) CA2256705A1 (en)
WO (1) WO1998047953A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005100416A1 (en) * 2004-04-16 2005-10-27 Basf Aktiengesellschaft Method for producing 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
KR20210009065A (en) * 2019-07-16 2021-01-26 주식회사 문교오엔에스 Crayons containing polyvinylpyrrolidone

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576776A (en) * 1968-02-01 1971-04-27 Henkel & Cie Gmbh Adhesive applicator crayons
US3787345A (en) * 1970-11-05 1974-01-22 Fischer Gmbh Uhu Werk Stick for the application of adhesive to substrates
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576776A (en) * 1968-02-01 1971-04-27 Henkel & Cie Gmbh Adhesive applicator crayons
US3787345A (en) * 1970-11-05 1974-01-22 Fischer Gmbh Uhu Werk Stick for the application of adhesive to substrates
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005100416A1 (en) * 2004-04-16 2005-10-27 Basf Aktiengesellschaft Method for producing aqueous polyvinyllactam dispersions
US8691340B2 (en) 2008-12-31 2014-04-08 Apinee, Inc. Preservation of wood, compositions and methods thereof
US9314938B2 (en) 2008-12-31 2016-04-19 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
KR20210009065A (en) * 2019-07-16 2021-01-26 주식회사 문교오엔에스 Crayons containing polyvinylpyrrolidone
KR102266300B1 (en) 2019-07-16 2021-06-17 주식회사 문교오엔에스 Crayons containing polyvinylpyrrolidone

Also Published As

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AU2738597A (en) 1998-11-13
CA2256705A1 (en) 1998-10-29

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