CA1335122C - Hot melt adhesive composition - Google Patents
Hot melt adhesive compositionInfo
- Publication number
- CA1335122C CA1335122C CA000607274A CA607274A CA1335122C CA 1335122 C CA1335122 C CA 1335122C CA 000607274 A CA000607274 A CA 000607274A CA 607274 A CA607274 A CA 607274A CA 1335122 C CA1335122 C CA 1335122C
- Authority
- CA
- Canada
- Prior art keywords
- hot melt
- polymer
- cyclohexane dimethanol
- melt adhesive
- adhesive composition
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
- C09D5/037—Rheology improving agents, e.g. flow control agents
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Abstract
An adhesive composition comprising a polymer, a tackifier, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate is disclosed. The composition, which contains from 5 to 40% by weight of 1,4-cyclohexane dimethanol dibenzoate, is particularly useful as a hot melt adhesive. Compared to prior art compositions, the compositions of the invention require a lower amount of heat to change from their solid to their liquid phase and provide faster set times without adversely affecting open times.
Description
- 1 - 1 335~ 22 HOT MELT ADHESIVE COMPOSITION
BACKGROUND OF THE INVENTION
Hot melt adhesive compositions are typically thermoplastic materials which are solid at room temperature. When heated to a liquid or molten form, the hot melt adhesive can be applied to a first substrate. The hot melt adhesive can then join the first substrate together with a second substrate as the hot melt adhesive cools back to a solid.
Hot melt adhesives are generally composed of three components: (1) a polymer; (2) a tackifier; and (3) a wax.
The polymer provides strength and adhesive characteristics. The tackifier allows the polymer to be more adhesive by improving wetting during the application. The tackifier is typically necessary in preferred compositions. The wax reduces the overall viscosity of the adhesive, thereby allowing the adhesive to liquify for a hot melt application at lower temperatures. The wax also controls the set time of the system--i.e. the time required to solidify the adhesive once the first and second substrates are compressed together.
Other components such as plasticizers are used in the formulation of hot melt adhesives for various applications. Plasticizers reduce the overall viscosity of the adhesive and promote flexibility and wetting. Typical types of plasticizers used are phthalates, glycolates, polybutenes, and mineral oil.
See "Adhesive Bonding", Chap. 8 Hot-melt Adhesives, by Thomas Flanagan, at p. 8-3, published by MacMillan.
Waxes can adversely affect the adhesion characteristics of the polymer. In addition, waxes are not compatible with polymers with high vinyl acetate contents. Thus, plasticizers are used in some - 2 - ~ ~3~
applications instead of waxes. Examples of plasticizers are given in U.S. Patent No. 4,745,026, such as dicyclohexyl phthalate.
of particular importance is the change in heat, i.e. ~ H, as the hot melt adhesive changes from one phase to another. The lower the rA H, the less heat is required to convert the solid adhesive to the liquid phase. ~ H is proportional to melt down rate, i.e., the rate of melt down of the adhesive from a solid phase to the liquid phase. Adhesives that melt down to a liquid phase quickly and easily can be used in faster manufacturing applications than adhesives with slower melt down rates. Therefore the lower the A H, and the faster the melt down rate, the easier the adhesive is to work with in manufacturing applications. See 1988 Hot Melt, "Thermal Analyses as a Predictor of Performance", by Ernest F. Eastman, published in 1988 TAPPI Conference Papers. ~ H values can be readily determined using Differential Scanning Calorimeters (Perkin-Elmer).
Another major factor in hot melt adhesive compositions is compatibility -- i.e. the degree of solubility of one component in another. The greater the compatibility, the more uniform and homogeneous the adhesive, and the better the bond the adhesive will provide. The closer the solubility parameters of different components are to each other, the greater the compatibility. See "Some Factors Affecting the Solubility of Polymers", by P.A. Small, J. Appl. Chem., 3, February 1953 (which teaches how to predict solubility parameters).
Compatibility is related to cloud point temperature. Cloud point temperature is the temperature at which a component begins to solidify or "cloud up" as it cools from a clear liquid phase to the solid phase. For example, for waxes, the cloud point 3 l 335~ 22 is usually the melting point of the wax. Generally, the lower the cloud point temperature, the greater the compatibility. See "Adhesives and Coatings Manual" by National Distillers and Chemical Corporation (1983).
As previously mentioned, set time is the time required to solidify the adhesive once the first and second substrates are compressed together. Fast set times are desirable in most manufacturing applications.
Generally, the higher the melting point, the crystallinity, and the viscosity, the faster the set time. Id. Open time is the time during which the adhesive is applied to the first substrate and remains sufficiently molten to effect a bond between the first and second substrates. Long open times are desirable in most manufacturing applications. Generally, the lower the melting point, the crystallinity, and the viscosity, the longer the open time. Id.
Thus, it is desirable to have a highly crystalline adhesive component that has both high-melting-point and low-melting-point characteristics.
The primary objective of the present invention is to provide a hot melt adhesive composition containing 1,4-cyclohexane dimethanol dibenzoate as a unique component. The physical properties of 1,4-cyclohexane dimethanol dibenzoate indicate that it would be an improvement over existing hot melt adhesive components such as dicyclohexyl phthalate. More specifically, 1,4-cyclohexane dimethanol dibenzoate provides shorter set times than dicyclohexyl phthalate without adversely affecting open times.
In addition, 1,4-cyclohexane dimethanol dibenzoate has a slightly lower A H than dicyclohexyl phthalate. Although other solid benzoates may have a lower /~H than 1,4-cyclohexane dimethanol dibenzoate, they tend to super cool. During the cool down cycle, these other solid benzoates that super cool remain ~ 4 ~ 1 3 3 5 ~ 2 2 liquid in the system and act as liquid plasticizers would act, i.e., resulting in longer open times and adversely affecting set times. 1-4,cyclohexane dimethanol dibenzoate is highly crystalline and does not super cool.
Furthermore, the 1,4-cyclohexane dimethanol dibenzoate would be very useful as a polyester hot melt modifier. The crystalline nature of the 1,4-cyclohexane dimethanol dibenzoate would contribute lo significantly to the properties of a polyester hot melt (e.g., faster set time, improved viscosity reduction, etc.). Further, the polyester hot melts containing the 1,4-cyclohexane dimethanol dibenzoate would be useful in applications not now possible without it.
Polyesters are generally not compatible with waxes and are not easily modified by waxes. U.S. Patents Nos.
BACKGROUND OF THE INVENTION
Hot melt adhesive compositions are typically thermoplastic materials which are solid at room temperature. When heated to a liquid or molten form, the hot melt adhesive can be applied to a first substrate. The hot melt adhesive can then join the first substrate together with a second substrate as the hot melt adhesive cools back to a solid.
Hot melt adhesives are generally composed of three components: (1) a polymer; (2) a tackifier; and (3) a wax.
The polymer provides strength and adhesive characteristics. The tackifier allows the polymer to be more adhesive by improving wetting during the application. The tackifier is typically necessary in preferred compositions. The wax reduces the overall viscosity of the adhesive, thereby allowing the adhesive to liquify for a hot melt application at lower temperatures. The wax also controls the set time of the system--i.e. the time required to solidify the adhesive once the first and second substrates are compressed together.
Other components such as plasticizers are used in the formulation of hot melt adhesives for various applications. Plasticizers reduce the overall viscosity of the adhesive and promote flexibility and wetting. Typical types of plasticizers used are phthalates, glycolates, polybutenes, and mineral oil.
See "Adhesive Bonding", Chap. 8 Hot-melt Adhesives, by Thomas Flanagan, at p. 8-3, published by MacMillan.
Waxes can adversely affect the adhesion characteristics of the polymer. In addition, waxes are not compatible with polymers with high vinyl acetate contents. Thus, plasticizers are used in some - 2 - ~ ~3~
applications instead of waxes. Examples of plasticizers are given in U.S. Patent No. 4,745,026, such as dicyclohexyl phthalate.
of particular importance is the change in heat, i.e. ~ H, as the hot melt adhesive changes from one phase to another. The lower the rA H, the less heat is required to convert the solid adhesive to the liquid phase. ~ H is proportional to melt down rate, i.e., the rate of melt down of the adhesive from a solid phase to the liquid phase. Adhesives that melt down to a liquid phase quickly and easily can be used in faster manufacturing applications than adhesives with slower melt down rates. Therefore the lower the A H, and the faster the melt down rate, the easier the adhesive is to work with in manufacturing applications. See 1988 Hot Melt, "Thermal Analyses as a Predictor of Performance", by Ernest F. Eastman, published in 1988 TAPPI Conference Papers. ~ H values can be readily determined using Differential Scanning Calorimeters (Perkin-Elmer).
Another major factor in hot melt adhesive compositions is compatibility -- i.e. the degree of solubility of one component in another. The greater the compatibility, the more uniform and homogeneous the adhesive, and the better the bond the adhesive will provide. The closer the solubility parameters of different components are to each other, the greater the compatibility. See "Some Factors Affecting the Solubility of Polymers", by P.A. Small, J. Appl. Chem., 3, February 1953 (which teaches how to predict solubility parameters).
Compatibility is related to cloud point temperature. Cloud point temperature is the temperature at which a component begins to solidify or "cloud up" as it cools from a clear liquid phase to the solid phase. For example, for waxes, the cloud point 3 l 335~ 22 is usually the melting point of the wax. Generally, the lower the cloud point temperature, the greater the compatibility. See "Adhesives and Coatings Manual" by National Distillers and Chemical Corporation (1983).
As previously mentioned, set time is the time required to solidify the adhesive once the first and second substrates are compressed together. Fast set times are desirable in most manufacturing applications.
Generally, the higher the melting point, the crystallinity, and the viscosity, the faster the set time. Id. Open time is the time during which the adhesive is applied to the first substrate and remains sufficiently molten to effect a bond between the first and second substrates. Long open times are desirable in most manufacturing applications. Generally, the lower the melting point, the crystallinity, and the viscosity, the longer the open time. Id.
Thus, it is desirable to have a highly crystalline adhesive component that has both high-melting-point and low-melting-point characteristics.
The primary objective of the present invention is to provide a hot melt adhesive composition containing 1,4-cyclohexane dimethanol dibenzoate as a unique component. The physical properties of 1,4-cyclohexane dimethanol dibenzoate indicate that it would be an improvement over existing hot melt adhesive components such as dicyclohexyl phthalate. More specifically, 1,4-cyclohexane dimethanol dibenzoate provides shorter set times than dicyclohexyl phthalate without adversely affecting open times.
In addition, 1,4-cyclohexane dimethanol dibenzoate has a slightly lower A H than dicyclohexyl phthalate. Although other solid benzoates may have a lower /~H than 1,4-cyclohexane dimethanol dibenzoate, they tend to super cool. During the cool down cycle, these other solid benzoates that super cool remain ~ 4 ~ 1 3 3 5 ~ 2 2 liquid in the system and act as liquid plasticizers would act, i.e., resulting in longer open times and adversely affecting set times. 1-4,cyclohexane dimethanol dibenzoate is highly crystalline and does not super cool.
Furthermore, the 1,4-cyclohexane dimethanol dibenzoate would be very useful as a polyester hot melt modifier. The crystalline nature of the 1,4-cyclohexane dimethanol dibenzoate would contribute lo significantly to the properties of a polyester hot melt (e.g., faster set time, improved viscosity reduction, etc.). Further, the polyester hot melts containing the 1,4-cyclohexane dimethanol dibenzoate would be useful in applications not now possible without it.
Polyesters are generally not compatible with waxes and are not easily modified by waxes. U.S. Patents Nos.
4,172,824 and 4,340,526 teach that certain benzoates are of use in polyester hot melts. However, the cited benzoates are limited in nature due to their tendency to super cool. The 1,4-cyclohexane dimethanol dibenzoate is an improvement over these prior art benzoates.
The use of polyesters comprising 1,4-cyclohexane dimethanol as a hot melt adhesive when blended with certain monomeric ester plasticizers is taught in U.S.
Patent No. 4,340,526. However, this patent does not teach the use of 1,4 - cyclohexane dimethanol dibenzoate as a plasticizer in a hot melt adhesive composition.
1 335 ~ 22 SUMMARY OF THE INVENTION
It has now been discovered that a hot melt adhesive composition comprising a polymer, a tackifier, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate works well as a hot melt adhesive. More particularly, it has been discovered that a hot melt adhesive composition comprising ethylene vinyl acetate as the polymer, a tackifier, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate is a suitable hot melt adhesive.
In the present invention, the adhesive comprises a range of about 5-40% parts by weight of 1,4-cyclohexane dimethanol dibenzoate.
More preferably, the adhesive comprises a range of about 25-35%
parts by weight of 1,4-cyclohexane dimethanol dibenzoate. Most preferably, the adhesive comprises about 30% parts by weight of 1,4-cyclohexane dimethanol dibenzoate.
It has also been discovered that a hot melt adhesive compo~ition comprising a polymer, a tacki~ier, a wax, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate is suitable as a hot melt adhesive. In such a composition, the adhesive comprises a range of about 5-40% parts by weight of 1,4-cyclohexane dimethanol dibenzoate. More preferably, this adhesivecomprises a range of about 8-25% parts by weight of 1,4-cyclohexane dimethanol dibenzoate. Most preferably, the adhesive comprises about 16.6% parts by weight of 1,4-cyclohexane dimethanol dibenzoate.
Thus, according to one aspect, the invention provides an adhesive composition comprising a polymer, a tackifier, and a plasticizing amount in the range of about 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
1 3~5 1 22 5a 61368-844 According to another aspect, the invention provides a hot melt adhesive composition comprising a polymer, a tackifier, and a plasticizing amount in the range of about 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to still another aspect, the invention provides a latex composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to yet another aspect, the invention provides a powdered coating composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to another aspect, the invention provides a heat reactive thermal delayed tack composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to still another aspect, the invention provides a thermoplastic composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
In addition, based on solubility parameters, it isanticipated that 1,4-cyclohexane dimethanol dibenzoate would work well in hot melt adhesive formulations having other polymers, such as polyvinyl acetate, ethylene/vinyl acetate copolymer, block copolymers (styrene-isoprene-styrene, styrene-butadiene-styrene, styrene-isobutalene-styrene).
r - 6 - I 33 51 2~
polyvinyl chloride, polyvinyl chloride/polyvinyl acetate, polyurethanes, polyesters and polyamides.
Specifically, the solubility parameter of 1,4-cyclohexane dimethanol dibenzoate is about 8Ø
Comparison of this value with, for example, those listed on p. 76 of the P.A. Small article cited above, indicates that 1,4-cyclohexane dimethanol dibenzoate is compatible with many different polymers.
For example, it is known that glycerol tribenzoate functions very well in polyester hot melt applications. Since 1,4-cyclohexane dimethanol dibenzoate has a similar solubility parameter as glycerol tribenzoate, it would be expected that 1,4-cyclohexane dimethanol dibenzoate would also work well in polyester hot melt applications. It is expected that 1,4-cyclohexane dimethanol dibenzoate is advantageous over glycerol tribenzoate in that 1,4-cyclohexane dimethanol dibenzoate has a significantly higher melting point resulting in faster set times without adversely affecting open times.
Furthermore, it has been discovered that compared to prior art compositions, 1,4-cyclohexane dimethanol dibenzoate requires a lower amount of heat to change from its solid to its liquid phase, and provides faster set times without adversely affecting open times.
1,4-cyclohexane dimethanol dibenzoate has the following structure wherein the dimethanol dibenzoate groups can be cis or trans and the cyclohexane ring can have either a chair or boat configuration:
O ~ ~ O
~ C- O - C ~C ~ 1' ~~
~ 7 ~ ~ 33~ 1 ~2 The following examples of the present invention demonstrate the advantages of the present invention over the prior art.
Examples The Differential Scanning Calorimeter ("DSC") curves for 1, 4-cyclohexane dimethanol dibenzoate are depicted in Figure 1 of the drawings. The curve shown is binodal and shows that this molecule has both high melting point and low melting point characteristics.
The sharpness of the primary curve demonstrates that 1,4-cyclohexane dimethanol dibenzoate is highly crystalline. Because of the binodal curve, the melting point is at two different temperatures, namely about 123C at the primary curve and about 80 C at the secondary curve. The ~H is about 8.85 mcal/mg.
In the drawings, Figure 2 is th~e DSC curve for a ethylene vinyl acetate compound Elvax~250 made by E.I.
duPont de Nemours Company, having a melt Index of 22-28 and comprising 28% vinyl acetate. Figure 3 is the DSC
curve for paraffin wax.
Figure 4 is the DSC curve for microcrystalline wax.
Figure 5 is the DSC curve for dicyclohexyl phthalate.
Figure 6 is the DSC curve for triphenyl phosphate.
Figure 7 is the DSC curve for glycerol tribenzoate.
Figure 8 is the DSC curve for neopentyl benzoate.
Figure 9 is the DSC curve for pentaerythritol tetrabenzoate.
T~e- ~
-8- 133~2 TA~3LE I
Table I is a summary of data taken from Figure 1 for the plasticizer of the present invention, 1,4-cyclohexane dimethanol dibenzoate and Figures 3-9 for prior art plasticizers and waxes.
As shown in Table I, 1,4-cyclohexane dimethanol dibenzoate is the only adhesive component which had all the following advantageous characteristics:
Low A H, high melting point, high crystallinity as shown by the sharpness of the primary curve, and a binodal curve.
TABLE I
Sharp-Plasticizer Melting ness of Or /\ H Point Primary Binodal Wax fmcal/mg) fC) ~urve Curve 1,4-cyclohexane 8.85 80,123 extremely Yes dimethanol sharp dibenzoate Paraffin Wax 16.80 69 moderate No - Micro- 16.60 64,80 not sharp Yes crystalline Wax Dicyclohexyl 9.94 70 moderate No Phthalate Triphenyl 9.25 54 moderate No Phosphate Glycerol 4.53 73 moderate No Tribenzoate Neopentyl 5.09 54 moderate No Benzoate Pentaerythritol 6.78 103 moderate No Tetrabenæoate ~ - 9 - 1 3 3 5 1 2 2 TABLE II
Table II shows cloud point temperatures (F) and consisting of a 1:1 mixture of various polymers containing vinyl acetate and various plasticizer benzoates, including in Column 4 for plasticizer 1, mixtures containing the adhesive component of the present invention, 1,4-cyclohexane dimethanol dibenzoate.
Table II shows that when the plasticizer 1,4-cyclohexane dimethanol dibenzoate constitutes 50% partsby weight of the adhesive composition, it acts much like a wax. Table II also gives an estimate on the upper limits of the % plasticizer in mixture with polymers before compatibility begins to become adversely affected. Thus, in the present invention the 1,4-cyclohexane dimethanol dibenzoate in the adhesive is preferably less than 50% parts by weight.
1 33S 1 ~2 TABLE II (A) CLOUD POINT l~..~ATURE (DEGREE F)/CONSISTENCY
~ 1~1UK~ OF POLYMER AND PLASTICIZER
Ethylene Vinyl Melt Index % Vinyl Acetate Acetate Polymer of the Polymer in the Polymer 1. ELVAX 40W 48-66 40%
2. ELVAX 150 38-48 33%
3. ELVAX 150W 38-48 33%
Anti Blocking ln Additive 4. ELVAX 210 365-440 28%
5. ELVAX 250 22-28 28%
6. ELVAX 260 53-67 28%
TABLE II (B) CLOUD POINT '~ ~KATURE (n~R~ F)/CONSISTENCY
~ Xl~K~ OF POLYMER AND PLASTICIZER
Plasticizer 1 Plasticizer 2 Plasticizer 3 1:1 Mixture of dipropylene glycol ~ihen~oate and 1,4-cyclohexane diethylene dimethanol glycol Neopentyl debenzoate dibenzoate Benzoate 1. 196 degrees <160 <160 Cheesy, Smooth Smooth Plasticizer Crystallized out 2. 210 degrees <160 <160 Cheesy Smooth Smooth Plasticizer Crystallized 3. 230 degrees <160 <160 Cheesy Smooth Smooth Plasticizer Crystallized 4. 262 degrees 190 204 Cheesy Smooth Smooth Plasticizer Crystallized 5. 210 degrees 166 <160 Cheesy Smooth Smooth Plasticizer Crystallized 6. 188 degrees <160 <160 Cheesy Smooth Smooth - 12 - 1 335~ 22 TABLE II (C) CLOUD POINT TEMPER~TURE (DEGREE F)/CONSISTENCY
1:1 MIXTURE OF POLYNER AND PLASTICIZER
Plasticizer 4 Plasticizer 5 Glycerol Pentaerythritol Tribenzoate Tetrabenzoate 1. <160 260 Smooth Smooth 2. 262 >350 Smooth Smooth 3. 260 >360 Smooth Smooth 4. 260 >360 Smooth Smooth 5. 260 >360 Smooth Smooth 6. 265 >360 Smooth Not all went in ~ - 13 - 1335~2~
TABLE III
Table III shows cloud point temperatures for various polymer/plasticizer or wax mixtures. M-8880 is microcrystalline wax with a melting point of 183F and R-0855 is a paraffin wax with a melting point of 153F.
Elvax 150, as already described in Table III is an ethylene vinyl acetate polymer with a melt index of 38-48 and a 33% vinyl acetate in the polymer. Table III
demonstrates that adhesive compositions with 1,4-cyclohexane dimethanol dibenzoate and Elvax 150 had lower cloud point temperatures than similar mixtures with Elvax 150 and the M-8800 and R-0855 waxes. This data confirms that 1,4-cyclohexane dimethanol dibenzoate has greater compatibility with Elvax 150 than M-8880 and R-0855 waxes.
TABLE III
% of Polymer Cloud Polymer/ to Plasticizer Point Plasticizer or Wax or Wax Temp. F
Elvax 150/1,4-cyclohexane 75/25 134 dimethanol dibenzoate Elvax 150/1,4-cyclohexane dimethanol dibenzoate 88/12 68 Elvax 150/M-8880 50/50 184 Elvax 150/M-8880 75/25 152 Elvax 150/M-8880 88/12 150 Elvax 150/R-0855 50/50 164 Elvax 150/R-0855 75/25 150 Elvax 150/R-0855 8~/12 142 TABLE IV
Table IV shows cloud point temperatures for various polymers and other adhesive components. Elvax 250, as already described in Table II, is an ethylene vinyl acetate polymer with a melt index of 22-28 and . - 14 - l ~3~
low molecular weight, nonpolar, thermoplastic, alkylary~ hydrocarbon polymer modifier made by Hercules, Incorporated. Piccovar L60 has a density of 1.05 kg/L at 25C, and a flashpoint of 243C. Piccovar L60 has a melt viscosity of l poise at 129C, 10 poises at 97C, and 100 poises at 77C. H-100 is a tackifier and is specifically a hydrocarbon resin made by Eastman Chemical Products, Inc. under the trade name "Eastotac H-100". H-100 has a melting point >185F, and a specific gravity of 1.04. Table IV shows that M-8880 and R-0855 waxes have no lower cloud point temperatures and thus no better compatibility than 1,4-A ~ cyclohex~ne dimethanol dibenzoate in mixtures with Piccovar~60 and Elvax 250, and H-100.
In addition, Table IV shows that 1,4-cyclohexane dimethanol dibenzoate, when mixed with Elvax 250 has a lower cloud point temperature and greater compatibility than mixtures of M-8880 and R-0855 waxes with Elvax 250.
Furthermore, Table IV shows that in a mixture of Elvax 250, H-100, M-8880, and 1,4-cyclohexane dimethanol dibenzoate, as the ratio of 1, 4-cyclohexane dimethanol dibenzoate to M-8880 increases the cloud point temperature decreases, thereby indicating greater compatibility.
3~ ~r~d e - w~k . ~ - 15 ~ 1 3 3 5 1 2 2 TABLE IV
Ratio of Cloud polymer to Point - other Temp.
Polymer/Other Components components (F) Elvax 250/1,4-cyclohexane 50/50 210 dimethanol dibenzoate Elvax 250/1,4-cyclohexane 75/25 140 dimethanol dibenzoate Elvax 250/M-8880 75/25 186 Elvax 250/R-0855 75/25 168 Piccovar L60/Elvax 250/ 33/33/33 160 1,4-cyclohexane dimeth-anol dibenzoate Piccovar L60/Elvax 250/ 33/33/33 160 Piccovar L60/Elvax 250 33/33/33 160 Elvax 250/H-100/1,4-cyclohexane dimethanol dibenzoate 33/33/33 160 Elvax 250/H-100/M-8880 33/33/33 182 Elvax 250/H-100/R-0855 33/33/33 160 Elvax 250/H-100/M-8880/
1,4-cyclohexane dimeth-anol dibenzoate 33/20.5/20.5/25 178 Elvax 250/H-100/M-8880/
1,4-cyclohexane dimeth-anol dibenzoate 33/8/33/25 190 Elvax 250/H-100/M-8880/ 33/33/8/25 163 1,4-cyclohexane dimeth-anol dibenzoate ~ - 16 - 133512~
TABLE V
Table V shows tensile strength and % elongation at break date for various adhesive compositions.
Tensile strength was determined pursuant to ASTM D638-64T. Table V shows that in specific formulations, 1,4-cyclohexane dimethanol dibenzoate outperforms dicyclohexyl phthalate in terms of tensile strength and % elongation at break. Specifically, Table V shows formulas A.2 and A.8 have greater tensile strength than corresponding formulas B.2 and B.8. Table V also shows that formula C.1. has greater tensile strength and %
elongation at break than corresponding formula D.l, and that C.4 has greater tensile strength than corresponding formula D.4.
~ - 17 - 1 335 ~ 22 TABLE V -- A
Parts by Weight 1,4-cyclo-h~YAn~ Tensile % Elonga-Elvax M-8880 dimethanol strength tion No. 250 H-100 wax dibenzoate (psi) at break 4 75 - 25 _ 514 . 28 6 30 30 - 30 69 lo 9 30 15 15 30 172 lo - 18 - ~ 3351 22 TABLE V -- B
Parts bY Weiqht Dicyclo- Tensile % Elonga-ElvaxM-8880 hexyl strength tion No. 250 H-100 wax phthalate (psi) at break l 100 - - - 847 400 TABLE V -- C
Parts by Wei~ht 1,4-cyclo-h~Y~n~ Tensile % Elonga-Elvax Piccovar M-8880 dimethanol strength tion No. 250 L-60 wax dibenzoate (psi) at break TABLE V -- D
Parts by Weiqht dicyclo- Tensile % Elonga-Elvax Piccovar M-8880 hexyl strength tion No. 250 L-60 wax Dhthalate f~si) at break ~ - 21 - 1 3351 22 TAB~E VI
Table VI shows cloud point temperatures for various adhesive compositions. Table VI shows that certain formulations having 1,4-cyclohexane dimethanol dibenzoate has the same cloud point temperatures and thus, the same compatibility as those of corresponding formulations containing dicyclohexyl phthalate.
Specifically, A.10. through A. 13. has the same cloud point temperatures, and thus, the same compatibility as corresponding formulations B.10 through B. 13.
. - 22 - ~ 335 ~ 22 TABLE VI -- A
Parts by Weight 1,4-cyclo- Temper-hexane ature Elvax Piccovar M-8880 dimethanol (Degree No. 250 H-100 r~-6o wax ~ib~n~oate F
- 30 30 - <160 11 30 - 30 - 30 <160 12 30 - 30 15 15 <160 13 30 - 15 15 30 <160 -TABLE VI -- B
Parts by Weiqht Cloud Point Temper-dicyclo- ature Elvax Piccovar M-8880 hexyl (Degree No. 250 H-100 T.-60 wax phthalate F
1 75 - - - 25 ~160 2 75 _ _ 25 _ 186 3 50 - - - 50 <160 6 30 30 - - 30 <160 7 30 30 - 15 15 <160 8 30 15 - 15 30 <160 9 30 - - 30 30 <160 - 30 30 - <160 11 30 - 30 - 30 <160 12 30 - 30 15 15 <160 13 30 - 15 15 30 <160 14 30 - - 30 30 <160 . - 24 - ~ 3351 22 TABLE VII
Table VII shows temperature and viscosity data for various adhesive compositions. Table VII shows that as l,4-cyclohexane dime~hanol dibenzoate is substituted for tackifier H-100, the viscosity of the composition is dramatically reduced. Viscosity was determined using a Brookfield RVT Viscometer and Thermosel.
-~ ~ - 25 TABLE VII
Ratio of Parts by Weiqht Adhesive Components 1,4-cyclo- Tempera-hPYAne ture Elvax M-8880 dimethanol (Degree Viscosity No.250 wax H-100 ~ih~n~oate F ) (cps) l. 1 1 1 - 250 1250 10 2. 1 _ 1 1 300 950 3. 1 1 - 1 250 S25 4. 1 .5 1 .5 250 1600 5. 1 .5 .5 1 250 soo - ~ - 26 - 1335~22 TABLE VIII
Table VIII shows set times and open times for two adhesive compositions, one containing 1,4-cyclohexane dimethanol dibenzoate and the other containing dicyclohexyl phthalate. This data shows that adhesive compositions with l,4-cyclohexane dimethanol dibenzoate has faster set times and the same open time as a corresponding adhesive composition containing dicyclohexyl phthalate. Open times were determined pursuant to ASTM D4497-85. Set times were determined by the following test:
The adhesive and a drawdown bar were heated to 350F. A 1.5 inch by 10 inch strip of 40 lb. Kraft paper was glued to a 40 lb. Kraft paper substrate using the drawdown bar to administer a 10 mil thick film and press the strip to the substrate. Immediately after application, the strip was peeled away from the substrate. The time at which 50% of the paper fiber tore was taken as the set time.
- 27 - 13351~2 TABLE VIII (A) Ratio Of Parts By Weight of Adhesive Components 1,4-cyclo-h~Y~n~ dicyclo-Elvax M-8880 dimethanol hexyl No. 250 wax H-100 dibenzoate phthalate 1. 1 1 1 ~ --2. 1 - 1 1 -3.
4. 1 .5 1 .5 5. 1 .5 .5 6. 1 .5 1 .5 7. 1 .5 1 n 5 TABLE VIII (B) Ratio Of Parts By Weight of Adhesive Components Set Temp. Open Set Open (Degree Viscosity Time Time No. F ) (cps) (sec) (sec) 1. 250 1250 2. 250 2650 3. 250 525 4. 250 1600 5. 250 goo 6. 250 2200 7. 250 1600 - 29 - t335122 TABLE IX
Table IX shows the cloud point temperatures and viscosity at specific temperatures for compositions containing 1,4-cyclohexane dimethanol dibenzoate. This table shows that 1,4-cyclohexane dimethanol dibenzoate r~ works well as an adhesive component with polymers other than ethylene vinyl acetate. Kraton~D1107 is made by Shell Chemical Corporation. Macromelt~ 239 is made by Henkel Corporation. Viscosity was determined using a Brookfield RVT Visometer and Thermosel.
~ Tr~ k ~ 335 ~ 22 TABLE IX (A) Parts by Parts Weight 1,4-by cyclohPYAne Type of Weight dimethanol No. Polymer Polymer Polywer dibenzoate 1. Kraton Styrene-D1107 Isoprene- 75 25 Styrene Block Copolymer 2. Macromelt 75 25 Polyamide - 31 - l 335 1 22 T~BLE IX ~B) Cloud Point Temp. Temp.
(Degree Viscosity (Degree No. F ) (cps) F
1. 160 9500 350 120 Too viscous to be measureable 2. <140 - -<140 ==
- 32 - ~ 3 3 5 1 2 2 Figure 10 shows curves of thermal viscosity versus temperature for various adhesive compositions.
Figure 10 demonstrates the effect 1,4-cyclohexanol dimethanol dibenzoate has in decreasing the thermal viscosity of adhesive compositions. Thermal viscosity was determined using a Brookfield RVT Viscometer and Thermosel.
~ 33 _ 1335122 Formulations Ratio Of Parts By Wei~ht of Adhesive Components 1,4-cyclo-heY~n~ Dicyclo-Formu- Elvax M-8880 dimethanol hexyl lation 250 wax H-lQQ ~ih~n~oate phthalate B 1 .5 .5 1 -c D 1 .5 1 .5 E
' ~ - 34 - 1335122 Figure 11 shows curves of thermal viscosity versus temperature for two different adhesive compositions, one containing 1,4-cyclohexane dimethanol dibenzoate and one containing dicyclohexyl phthalate.
Figure 11 demonstrates that at a specific temperature, the composition containing 1,4-cyclohexane dimethanol dibenzoate has a lower thermal viscosity than the composition containing dicyclohexyl phthalate.
Thermal viscosity was determined using a Brookfield RVT
Viscometer and Thermosel.
_ 35 _ ~ 335 1 22 Formulations Ratio Of Parts BY Weiqht Of Adhesive Components 1,4 cyclo-h~Y~ne Formu- Elvax M-8880 dimethanol Dicyclohexyl lation 25 Wax H-100 dibenzoate phthalate A 1 .5 1 .5 B 1 .5 1 - .5 - 36 - l 335 ~ 22 Othe~ Applications and Summary Other components besides a polymer, a tackifier, and 1,4-cyclohexane dimethanol dibenzoate can be added to the adhesive compositions of the present invention.
It is expected that 1,4-cyclohexane dimethanol dibenzoate can be used in many other applications besides hot melt adhesive compositions. For example, it is believed that 1,4-cyclohexane dimethanol dibenzoate would work well in latex applications, powdered coating applications, and in heat reactive thermal delayed tack applications. In addition, it is expected that 1,4-cyclohexane dimethanol dibenzoate would work well as a thermoplastic process aid.
The foregoing detailed description of the invention has been made in general terms and with respect to several preferred embodiments. Many of the specific preferred materials, temperatures, and methods stated herein may be varied by persons skilled in the art without departing from the spirit and scope of this invention. Accordingly, the invention resides solely in the claims hereinafter appended.
The use of polyesters comprising 1,4-cyclohexane dimethanol as a hot melt adhesive when blended with certain monomeric ester plasticizers is taught in U.S.
Patent No. 4,340,526. However, this patent does not teach the use of 1,4 - cyclohexane dimethanol dibenzoate as a plasticizer in a hot melt adhesive composition.
1 335 ~ 22 SUMMARY OF THE INVENTION
It has now been discovered that a hot melt adhesive composition comprising a polymer, a tackifier, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate works well as a hot melt adhesive. More particularly, it has been discovered that a hot melt adhesive composition comprising ethylene vinyl acetate as the polymer, a tackifier, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate is a suitable hot melt adhesive.
In the present invention, the adhesive comprises a range of about 5-40% parts by weight of 1,4-cyclohexane dimethanol dibenzoate.
More preferably, the adhesive comprises a range of about 25-35%
parts by weight of 1,4-cyclohexane dimethanol dibenzoate. Most preferably, the adhesive comprises about 30% parts by weight of 1,4-cyclohexane dimethanol dibenzoate.
It has also been discovered that a hot melt adhesive compo~ition comprising a polymer, a tacki~ier, a wax, and a plasticizing amount of 1,4-cyclohexane dimethanol dibenzoate is suitable as a hot melt adhesive. In such a composition, the adhesive comprises a range of about 5-40% parts by weight of 1,4-cyclohexane dimethanol dibenzoate. More preferably, this adhesivecomprises a range of about 8-25% parts by weight of 1,4-cyclohexane dimethanol dibenzoate. Most preferably, the adhesive comprises about 16.6% parts by weight of 1,4-cyclohexane dimethanol dibenzoate.
Thus, according to one aspect, the invention provides an adhesive composition comprising a polymer, a tackifier, and a plasticizing amount in the range of about 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
1 3~5 1 22 5a 61368-844 According to another aspect, the invention provides a hot melt adhesive composition comprising a polymer, a tackifier, and a plasticizing amount in the range of about 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to still another aspect, the invention provides a latex composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to yet another aspect, the invention provides a powdered coating composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to another aspect, the invention provides a heat reactive thermal delayed tack composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
According to still another aspect, the invention provides a thermoplastic composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
In addition, based on solubility parameters, it isanticipated that 1,4-cyclohexane dimethanol dibenzoate would work well in hot melt adhesive formulations having other polymers, such as polyvinyl acetate, ethylene/vinyl acetate copolymer, block copolymers (styrene-isoprene-styrene, styrene-butadiene-styrene, styrene-isobutalene-styrene).
r - 6 - I 33 51 2~
polyvinyl chloride, polyvinyl chloride/polyvinyl acetate, polyurethanes, polyesters and polyamides.
Specifically, the solubility parameter of 1,4-cyclohexane dimethanol dibenzoate is about 8Ø
Comparison of this value with, for example, those listed on p. 76 of the P.A. Small article cited above, indicates that 1,4-cyclohexane dimethanol dibenzoate is compatible with many different polymers.
For example, it is known that glycerol tribenzoate functions very well in polyester hot melt applications. Since 1,4-cyclohexane dimethanol dibenzoate has a similar solubility parameter as glycerol tribenzoate, it would be expected that 1,4-cyclohexane dimethanol dibenzoate would also work well in polyester hot melt applications. It is expected that 1,4-cyclohexane dimethanol dibenzoate is advantageous over glycerol tribenzoate in that 1,4-cyclohexane dimethanol dibenzoate has a significantly higher melting point resulting in faster set times without adversely affecting open times.
Furthermore, it has been discovered that compared to prior art compositions, 1,4-cyclohexane dimethanol dibenzoate requires a lower amount of heat to change from its solid to its liquid phase, and provides faster set times without adversely affecting open times.
1,4-cyclohexane dimethanol dibenzoate has the following structure wherein the dimethanol dibenzoate groups can be cis or trans and the cyclohexane ring can have either a chair or boat configuration:
O ~ ~ O
~ C- O - C ~C ~ 1' ~~
~ 7 ~ ~ 33~ 1 ~2 The following examples of the present invention demonstrate the advantages of the present invention over the prior art.
Examples The Differential Scanning Calorimeter ("DSC") curves for 1, 4-cyclohexane dimethanol dibenzoate are depicted in Figure 1 of the drawings. The curve shown is binodal and shows that this molecule has both high melting point and low melting point characteristics.
The sharpness of the primary curve demonstrates that 1,4-cyclohexane dimethanol dibenzoate is highly crystalline. Because of the binodal curve, the melting point is at two different temperatures, namely about 123C at the primary curve and about 80 C at the secondary curve. The ~H is about 8.85 mcal/mg.
In the drawings, Figure 2 is th~e DSC curve for a ethylene vinyl acetate compound Elvax~250 made by E.I.
duPont de Nemours Company, having a melt Index of 22-28 and comprising 28% vinyl acetate. Figure 3 is the DSC
curve for paraffin wax.
Figure 4 is the DSC curve for microcrystalline wax.
Figure 5 is the DSC curve for dicyclohexyl phthalate.
Figure 6 is the DSC curve for triphenyl phosphate.
Figure 7 is the DSC curve for glycerol tribenzoate.
Figure 8 is the DSC curve for neopentyl benzoate.
Figure 9 is the DSC curve for pentaerythritol tetrabenzoate.
T~e- ~
-8- 133~2 TA~3LE I
Table I is a summary of data taken from Figure 1 for the plasticizer of the present invention, 1,4-cyclohexane dimethanol dibenzoate and Figures 3-9 for prior art plasticizers and waxes.
As shown in Table I, 1,4-cyclohexane dimethanol dibenzoate is the only adhesive component which had all the following advantageous characteristics:
Low A H, high melting point, high crystallinity as shown by the sharpness of the primary curve, and a binodal curve.
TABLE I
Sharp-Plasticizer Melting ness of Or /\ H Point Primary Binodal Wax fmcal/mg) fC) ~urve Curve 1,4-cyclohexane 8.85 80,123 extremely Yes dimethanol sharp dibenzoate Paraffin Wax 16.80 69 moderate No - Micro- 16.60 64,80 not sharp Yes crystalline Wax Dicyclohexyl 9.94 70 moderate No Phthalate Triphenyl 9.25 54 moderate No Phosphate Glycerol 4.53 73 moderate No Tribenzoate Neopentyl 5.09 54 moderate No Benzoate Pentaerythritol 6.78 103 moderate No Tetrabenæoate ~ - 9 - 1 3 3 5 1 2 2 TABLE II
Table II shows cloud point temperatures (F) and consisting of a 1:1 mixture of various polymers containing vinyl acetate and various plasticizer benzoates, including in Column 4 for plasticizer 1, mixtures containing the adhesive component of the present invention, 1,4-cyclohexane dimethanol dibenzoate.
Table II shows that when the plasticizer 1,4-cyclohexane dimethanol dibenzoate constitutes 50% partsby weight of the adhesive composition, it acts much like a wax. Table II also gives an estimate on the upper limits of the % plasticizer in mixture with polymers before compatibility begins to become adversely affected. Thus, in the present invention the 1,4-cyclohexane dimethanol dibenzoate in the adhesive is preferably less than 50% parts by weight.
1 33S 1 ~2 TABLE II (A) CLOUD POINT l~..~ATURE (DEGREE F)/CONSISTENCY
~ 1~1UK~ OF POLYMER AND PLASTICIZER
Ethylene Vinyl Melt Index % Vinyl Acetate Acetate Polymer of the Polymer in the Polymer 1. ELVAX 40W 48-66 40%
2. ELVAX 150 38-48 33%
3. ELVAX 150W 38-48 33%
Anti Blocking ln Additive 4. ELVAX 210 365-440 28%
5. ELVAX 250 22-28 28%
6. ELVAX 260 53-67 28%
TABLE II (B) CLOUD POINT '~ ~KATURE (n~R~ F)/CONSISTENCY
~ Xl~K~ OF POLYMER AND PLASTICIZER
Plasticizer 1 Plasticizer 2 Plasticizer 3 1:1 Mixture of dipropylene glycol ~ihen~oate and 1,4-cyclohexane diethylene dimethanol glycol Neopentyl debenzoate dibenzoate Benzoate 1. 196 degrees <160 <160 Cheesy, Smooth Smooth Plasticizer Crystallized out 2. 210 degrees <160 <160 Cheesy Smooth Smooth Plasticizer Crystallized 3. 230 degrees <160 <160 Cheesy Smooth Smooth Plasticizer Crystallized 4. 262 degrees 190 204 Cheesy Smooth Smooth Plasticizer Crystallized 5. 210 degrees 166 <160 Cheesy Smooth Smooth Plasticizer Crystallized 6. 188 degrees <160 <160 Cheesy Smooth Smooth - 12 - 1 335~ 22 TABLE II (C) CLOUD POINT TEMPER~TURE (DEGREE F)/CONSISTENCY
1:1 MIXTURE OF POLYNER AND PLASTICIZER
Plasticizer 4 Plasticizer 5 Glycerol Pentaerythritol Tribenzoate Tetrabenzoate 1. <160 260 Smooth Smooth 2. 262 >350 Smooth Smooth 3. 260 >360 Smooth Smooth 4. 260 >360 Smooth Smooth 5. 260 >360 Smooth Smooth 6. 265 >360 Smooth Not all went in ~ - 13 - 1335~2~
TABLE III
Table III shows cloud point temperatures for various polymer/plasticizer or wax mixtures. M-8880 is microcrystalline wax with a melting point of 183F and R-0855 is a paraffin wax with a melting point of 153F.
Elvax 150, as already described in Table III is an ethylene vinyl acetate polymer with a melt index of 38-48 and a 33% vinyl acetate in the polymer. Table III
demonstrates that adhesive compositions with 1,4-cyclohexane dimethanol dibenzoate and Elvax 150 had lower cloud point temperatures than similar mixtures with Elvax 150 and the M-8800 and R-0855 waxes. This data confirms that 1,4-cyclohexane dimethanol dibenzoate has greater compatibility with Elvax 150 than M-8880 and R-0855 waxes.
TABLE III
% of Polymer Cloud Polymer/ to Plasticizer Point Plasticizer or Wax or Wax Temp. F
Elvax 150/1,4-cyclohexane 75/25 134 dimethanol dibenzoate Elvax 150/1,4-cyclohexane dimethanol dibenzoate 88/12 68 Elvax 150/M-8880 50/50 184 Elvax 150/M-8880 75/25 152 Elvax 150/M-8880 88/12 150 Elvax 150/R-0855 50/50 164 Elvax 150/R-0855 75/25 150 Elvax 150/R-0855 8~/12 142 TABLE IV
Table IV shows cloud point temperatures for various polymers and other adhesive components. Elvax 250, as already described in Table II, is an ethylene vinyl acetate polymer with a melt index of 22-28 and . - 14 - l ~3~
low molecular weight, nonpolar, thermoplastic, alkylary~ hydrocarbon polymer modifier made by Hercules, Incorporated. Piccovar L60 has a density of 1.05 kg/L at 25C, and a flashpoint of 243C. Piccovar L60 has a melt viscosity of l poise at 129C, 10 poises at 97C, and 100 poises at 77C. H-100 is a tackifier and is specifically a hydrocarbon resin made by Eastman Chemical Products, Inc. under the trade name "Eastotac H-100". H-100 has a melting point >185F, and a specific gravity of 1.04. Table IV shows that M-8880 and R-0855 waxes have no lower cloud point temperatures and thus no better compatibility than 1,4-A ~ cyclohex~ne dimethanol dibenzoate in mixtures with Piccovar~60 and Elvax 250, and H-100.
In addition, Table IV shows that 1,4-cyclohexane dimethanol dibenzoate, when mixed with Elvax 250 has a lower cloud point temperature and greater compatibility than mixtures of M-8880 and R-0855 waxes with Elvax 250.
Furthermore, Table IV shows that in a mixture of Elvax 250, H-100, M-8880, and 1,4-cyclohexane dimethanol dibenzoate, as the ratio of 1, 4-cyclohexane dimethanol dibenzoate to M-8880 increases the cloud point temperature decreases, thereby indicating greater compatibility.
3~ ~r~d e - w~k . ~ - 15 ~ 1 3 3 5 1 2 2 TABLE IV
Ratio of Cloud polymer to Point - other Temp.
Polymer/Other Components components (F) Elvax 250/1,4-cyclohexane 50/50 210 dimethanol dibenzoate Elvax 250/1,4-cyclohexane 75/25 140 dimethanol dibenzoate Elvax 250/M-8880 75/25 186 Elvax 250/R-0855 75/25 168 Piccovar L60/Elvax 250/ 33/33/33 160 1,4-cyclohexane dimeth-anol dibenzoate Piccovar L60/Elvax 250/ 33/33/33 160 Piccovar L60/Elvax 250 33/33/33 160 Elvax 250/H-100/1,4-cyclohexane dimethanol dibenzoate 33/33/33 160 Elvax 250/H-100/M-8880 33/33/33 182 Elvax 250/H-100/R-0855 33/33/33 160 Elvax 250/H-100/M-8880/
1,4-cyclohexane dimeth-anol dibenzoate 33/20.5/20.5/25 178 Elvax 250/H-100/M-8880/
1,4-cyclohexane dimeth-anol dibenzoate 33/8/33/25 190 Elvax 250/H-100/M-8880/ 33/33/8/25 163 1,4-cyclohexane dimeth-anol dibenzoate ~ - 16 - 133512~
TABLE V
Table V shows tensile strength and % elongation at break date for various adhesive compositions.
Tensile strength was determined pursuant to ASTM D638-64T. Table V shows that in specific formulations, 1,4-cyclohexane dimethanol dibenzoate outperforms dicyclohexyl phthalate in terms of tensile strength and % elongation at break. Specifically, Table V shows formulas A.2 and A.8 have greater tensile strength than corresponding formulas B.2 and B.8. Table V also shows that formula C.1. has greater tensile strength and %
elongation at break than corresponding formula D.l, and that C.4 has greater tensile strength than corresponding formula D.4.
~ - 17 - 1 335 ~ 22 TABLE V -- A
Parts by Weight 1,4-cyclo-h~YAn~ Tensile % Elonga-Elvax M-8880 dimethanol strength tion No. 250 H-100 wax dibenzoate (psi) at break 4 75 - 25 _ 514 . 28 6 30 30 - 30 69 lo 9 30 15 15 30 172 lo - 18 - ~ 3351 22 TABLE V -- B
Parts bY Weiqht Dicyclo- Tensile % Elonga-ElvaxM-8880 hexyl strength tion No. 250 H-100 wax phthalate (psi) at break l 100 - - - 847 400 TABLE V -- C
Parts by Wei~ht 1,4-cyclo-h~Y~n~ Tensile % Elonga-Elvax Piccovar M-8880 dimethanol strength tion No. 250 L-60 wax dibenzoate (psi) at break TABLE V -- D
Parts by Weiqht dicyclo- Tensile % Elonga-Elvax Piccovar M-8880 hexyl strength tion No. 250 L-60 wax Dhthalate f~si) at break ~ - 21 - 1 3351 22 TAB~E VI
Table VI shows cloud point temperatures for various adhesive compositions. Table VI shows that certain formulations having 1,4-cyclohexane dimethanol dibenzoate has the same cloud point temperatures and thus, the same compatibility as those of corresponding formulations containing dicyclohexyl phthalate.
Specifically, A.10. through A. 13. has the same cloud point temperatures, and thus, the same compatibility as corresponding formulations B.10 through B. 13.
. - 22 - ~ 335 ~ 22 TABLE VI -- A
Parts by Weight 1,4-cyclo- Temper-hexane ature Elvax Piccovar M-8880 dimethanol (Degree No. 250 H-100 r~-6o wax ~ib~n~oate F
- 30 30 - <160 11 30 - 30 - 30 <160 12 30 - 30 15 15 <160 13 30 - 15 15 30 <160 -TABLE VI -- B
Parts by Weiqht Cloud Point Temper-dicyclo- ature Elvax Piccovar M-8880 hexyl (Degree No. 250 H-100 T.-60 wax phthalate F
1 75 - - - 25 ~160 2 75 _ _ 25 _ 186 3 50 - - - 50 <160 6 30 30 - - 30 <160 7 30 30 - 15 15 <160 8 30 15 - 15 30 <160 9 30 - - 30 30 <160 - 30 30 - <160 11 30 - 30 - 30 <160 12 30 - 30 15 15 <160 13 30 - 15 15 30 <160 14 30 - - 30 30 <160 . - 24 - ~ 3351 22 TABLE VII
Table VII shows temperature and viscosity data for various adhesive compositions. Table VII shows that as l,4-cyclohexane dime~hanol dibenzoate is substituted for tackifier H-100, the viscosity of the composition is dramatically reduced. Viscosity was determined using a Brookfield RVT Viscometer and Thermosel.
-~ ~ - 25 TABLE VII
Ratio of Parts by Weiqht Adhesive Components 1,4-cyclo- Tempera-hPYAne ture Elvax M-8880 dimethanol (Degree Viscosity No.250 wax H-100 ~ih~n~oate F ) (cps) l. 1 1 1 - 250 1250 10 2. 1 _ 1 1 300 950 3. 1 1 - 1 250 S25 4. 1 .5 1 .5 250 1600 5. 1 .5 .5 1 250 soo - ~ - 26 - 1335~22 TABLE VIII
Table VIII shows set times and open times for two adhesive compositions, one containing 1,4-cyclohexane dimethanol dibenzoate and the other containing dicyclohexyl phthalate. This data shows that adhesive compositions with l,4-cyclohexane dimethanol dibenzoate has faster set times and the same open time as a corresponding adhesive composition containing dicyclohexyl phthalate. Open times were determined pursuant to ASTM D4497-85. Set times were determined by the following test:
The adhesive and a drawdown bar were heated to 350F. A 1.5 inch by 10 inch strip of 40 lb. Kraft paper was glued to a 40 lb. Kraft paper substrate using the drawdown bar to administer a 10 mil thick film and press the strip to the substrate. Immediately after application, the strip was peeled away from the substrate. The time at which 50% of the paper fiber tore was taken as the set time.
- 27 - 13351~2 TABLE VIII (A) Ratio Of Parts By Weight of Adhesive Components 1,4-cyclo-h~Y~n~ dicyclo-Elvax M-8880 dimethanol hexyl No. 250 wax H-100 dibenzoate phthalate 1. 1 1 1 ~ --2. 1 - 1 1 -3.
4. 1 .5 1 .5 5. 1 .5 .5 6. 1 .5 1 .5 7. 1 .5 1 n 5 TABLE VIII (B) Ratio Of Parts By Weight of Adhesive Components Set Temp. Open Set Open (Degree Viscosity Time Time No. F ) (cps) (sec) (sec) 1. 250 1250 2. 250 2650 3. 250 525 4. 250 1600 5. 250 goo 6. 250 2200 7. 250 1600 - 29 - t335122 TABLE IX
Table IX shows the cloud point temperatures and viscosity at specific temperatures for compositions containing 1,4-cyclohexane dimethanol dibenzoate. This table shows that 1,4-cyclohexane dimethanol dibenzoate r~ works well as an adhesive component with polymers other than ethylene vinyl acetate. Kraton~D1107 is made by Shell Chemical Corporation. Macromelt~ 239 is made by Henkel Corporation. Viscosity was determined using a Brookfield RVT Visometer and Thermosel.
~ Tr~ k ~ 335 ~ 22 TABLE IX (A) Parts by Parts Weight 1,4-by cyclohPYAne Type of Weight dimethanol No. Polymer Polymer Polywer dibenzoate 1. Kraton Styrene-D1107 Isoprene- 75 25 Styrene Block Copolymer 2. Macromelt 75 25 Polyamide - 31 - l 335 1 22 T~BLE IX ~B) Cloud Point Temp. Temp.
(Degree Viscosity (Degree No. F ) (cps) F
1. 160 9500 350 120 Too viscous to be measureable 2. <140 - -<140 ==
- 32 - ~ 3 3 5 1 2 2 Figure 10 shows curves of thermal viscosity versus temperature for various adhesive compositions.
Figure 10 demonstrates the effect 1,4-cyclohexanol dimethanol dibenzoate has in decreasing the thermal viscosity of adhesive compositions. Thermal viscosity was determined using a Brookfield RVT Viscometer and Thermosel.
~ 33 _ 1335122 Formulations Ratio Of Parts By Wei~ht of Adhesive Components 1,4-cyclo-heY~n~ Dicyclo-Formu- Elvax M-8880 dimethanol hexyl lation 250 wax H-lQQ ~ih~n~oate phthalate B 1 .5 .5 1 -c D 1 .5 1 .5 E
' ~ - 34 - 1335122 Figure 11 shows curves of thermal viscosity versus temperature for two different adhesive compositions, one containing 1,4-cyclohexane dimethanol dibenzoate and one containing dicyclohexyl phthalate.
Figure 11 demonstrates that at a specific temperature, the composition containing 1,4-cyclohexane dimethanol dibenzoate has a lower thermal viscosity than the composition containing dicyclohexyl phthalate.
Thermal viscosity was determined using a Brookfield RVT
Viscometer and Thermosel.
_ 35 _ ~ 335 1 22 Formulations Ratio Of Parts BY Weiqht Of Adhesive Components 1,4 cyclo-h~Y~ne Formu- Elvax M-8880 dimethanol Dicyclohexyl lation 25 Wax H-100 dibenzoate phthalate A 1 .5 1 .5 B 1 .5 1 - .5 - 36 - l 335 ~ 22 Othe~ Applications and Summary Other components besides a polymer, a tackifier, and 1,4-cyclohexane dimethanol dibenzoate can be added to the adhesive compositions of the present invention.
It is expected that 1,4-cyclohexane dimethanol dibenzoate can be used in many other applications besides hot melt adhesive compositions. For example, it is believed that 1,4-cyclohexane dimethanol dibenzoate would work well in latex applications, powdered coating applications, and in heat reactive thermal delayed tack applications. In addition, it is expected that 1,4-cyclohexane dimethanol dibenzoate would work well as a thermoplastic process aid.
The foregoing detailed description of the invention has been made in general terms and with respect to several preferred embodiments. Many of the specific preferred materials, temperatures, and methods stated herein may be varied by persons skilled in the art without departing from the spirit and scope of this invention. Accordingly, the invention resides solely in the claims hereinafter appended.
Claims (21)
1. An adhesive composition comprising a polymer, a tackifier, and a plasticizing amount in the range of about 5-40%
by weight 1,4-cyclohexane dimethanol dibenzoate.
by weight 1,4-cyclohexane dimethanol dibenzoate.
2. A hot melt adhesive composition comprising a polymer, a tackifier, and a plasticizing amount in the range of about 5-40%
by weight 1,4-cyclohexane dimethanol dibenzoate.
by weight 1,4-cyclohexane dimethanol dibenzoate.
3. A hot melt adhesive composition as in Claim 2 wherein the composition comprises a range of about 25-35% by weight, 1,4-cyclohexane dimethanol dibenzoate.
4. A hot melt adhesive composition as in Claim 2 wherein the composition comprises about 30% by weight 1,4-cyclohexane dimethanol dibenzoate.
5. A hot melt adhesive composition as in Claim 2 wherein the polymer is ethylene vinyl acetate.
6. A hot melt adhesive composition as in Claim 2 wherein the polymer is polyvinyl acetate.
7. A hot melt adhesive composition as in Claim 2 wherein the polymer is ethylene/vinyl acetate copolymer.
8. A hot melt adhesive composition as in Claim 2 wherein the polymer is a block copolymer.
9. A hot melt adhesive composition as in Claim 8 wherein the block copolymer is styrene-isoprene-styrene.
10. A hot melt adhesive composition as in Claim 8 wherein the block copolymer is styrene-butadiene-styrene.
11. A hot melt adhesive composition as in Claim 8 wherein the block copolymer is styrene-isobutylene-styrene.
12. A hot melt adhesive composition as in Claim 2 wherein the polymer is polyvinyl chloride.
13. A hot melt adhesive composition as in Claim 2 wherein the polymer is polyvinyl chloride/polyvinyl acetate.
14. A hot melt adhesive composition as in Claim 2 wherein the polymer is polyurethane.
15. A hot melt adhesive composition as in Claim 2 wherein the polymer is polyester.
16. A hot melt adhesive composition as in Claim 2 wherein the polymer is polyamide.
17. An adhesive composition as in Claims 1 or 2 which includes a wax.
18. A latex composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
19. A powdered coating composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
20. A heat reactive thermal delayed tack composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
21. A thermoplastic composition comprising a polymer and a plasticizing amount in the range of 5-40% by weight 1,4-cyclohexane dimethanol dibenzoate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US227,705 | 1988-08-03 | ||
| US07/227,705 US5026756A (en) | 1988-08-03 | 1988-08-03 | Hot melt adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335122C true CA1335122C (en) | 1995-04-04 |
Family
ID=22854140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000607274A Expired - Lifetime CA1335122C (en) | 1988-08-03 | 1989-08-02 | Hot melt adhesive composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5026756A (en) |
| EP (1) | EP0427792B1 (en) |
| JP (1) | JP2605156B2 (en) |
| AU (1) | AU4221289A (en) |
| CA (1) | CA1335122C (en) |
| DE (1) | DE68914994T2 (en) |
| WO (1) | WO1990001525A1 (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1335138C (en) * | 1988-05-04 | 1995-04-04 | Dennis D. Hansen | Hot-melt adhesive that has good open time at room temperature and can form creep-resistant bonds |
| US5627229A (en) * | 1992-07-25 | 1997-05-06 | H.B. Fuller Licensing & Financing, Inc. | Hot melt adhesive having controlled property change |
| US5853864A (en) * | 1988-06-30 | 1998-12-29 | H. B. Fuller Licensing & Financing Inc. | Composite article resistant to moisture-induced debonding |
| EP0367058A3 (en) * | 1988-11-04 | 1991-03-27 | Giovanni Pasini | New composition for dynamicofunctional impressions |
| CA2010280C (en) * | 1989-07-25 | 1998-10-06 | William L. Bunnelle | Hot melt adhesive having controlled property change |
| JPH0757865B2 (en) * | 1990-10-05 | 1995-06-21 | 日本ゼオン株式会社 | Adhesive composition |
| US5256717A (en) * | 1990-12-19 | 1993-10-26 | National Starch And Chemical Investment Holding Corporation | Hot melt adhesives useful in temporary bonding operations |
| US5401792A (en) * | 1993-11-10 | 1995-03-28 | Minnesota Mining And Manufacturing Company | Sprayable thermoplastic compositions |
| US5582873A (en) * | 1994-08-04 | 1996-12-10 | Carol M. Botsolas | Acid scavenger stabilized halogen containing organic polymers and method for processing |
| US5739188A (en) * | 1994-10-14 | 1998-04-14 | Desai; Nirav | Thermoplastic polymer compositions with improved processability and method of processing |
| CA2200015A1 (en) * | 1996-03-15 | 1997-09-15 | Susan T. Oeltjen | Polyamide adhesives having improved bookbinding characteristics |
| US5945375A (en) * | 1997-03-31 | 1999-08-31 | Kimberly-Clark Worldwide, Inc. | Thermal dye diffusion coating and substrate |
| BR9809370A (en) | 1997-05-02 | 2000-07-04 | Eastman Chem Co | Coated substrate comprising a coating and a substrate, and processes for coating a particulate adhesive composition and for providing block anti-forming properties to a particulate adhesive composition |
| US6281166B1 (en) | 1998-02-20 | 2001-08-28 | Kimberly-Clark Worldwide | Thermal dye diffusion coating and substrate |
| US6428878B1 (en) | 1999-03-18 | 2002-08-06 | Kimberly-Clark Worldwide, Inc. | Heat transfer material having a fusible coating containing cyclohexane dimethanol dibenzoate thereon |
| WO2002100454A1 (en) * | 2001-06-11 | 2002-12-19 | Boston Scientific Limited | COMPOSITE ePTFE/TEXTILE PROSTHESIS |
| US7013818B2 (en) | 2001-10-18 | 2006-03-21 | Guangdong Esquel Textiles Co. Ltd. | Wrinkle free garment and method of manufacture |
| US8003725B2 (en) | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| US7998579B2 (en) | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
| WO2004014997A2 (en) | 2002-08-12 | 2004-02-19 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
| US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
| WO2007011541A1 (en) | 2005-07-15 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
| JP4798494B2 (en) * | 2006-04-07 | 2011-10-19 | 富士電機株式会社 | Electrophotographic photoreceptor and method for producing the same |
| US20090142981A1 (en) * | 2007-12-03 | 2009-06-04 | Velsicol Chemical Corporation | Novel Compositions Comprising Structural Isomers Of 1,4-Cyclohexanedimethanol Dibenzoate and Polymer Compositions Containing Same |
| US20120015176A1 (en) * | 2008-03-24 | 2012-01-19 | Riebel Michael J | Biolaminate composite assembly and related method |
| US8283400B2 (en) * | 2008-06-09 | 2012-10-09 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
| US8431642B2 (en) * | 2008-06-09 | 2013-04-30 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
| US8242198B2 (en) * | 2008-06-09 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
| KR101419062B1 (en) * | 2008-09-11 | 2014-07-11 | 에스케이종합화학 주식회사 | New plasticizer for polyvinylchloride resin |
| GB0904378D0 (en) | 2009-03-13 | 2009-04-29 | Innovia Films Ltd | Delayed-tack material |
| EP2435526A4 (en) * | 2009-05-29 | 2012-10-31 | Exxonmobil Chem Patents Inc | Polyolefin adhesive compositions and method of making thereof |
| US8329795B2 (en) * | 2009-07-07 | 2012-12-11 | Exxonmobil Research And Engineering Company | Oil based polyols or diacids esterified with oxo-acids or oxo-alcohols for producing plasticizers |
| KR102018187B1 (en) * | 2012-05-04 | 2019-09-04 | 에스케이이노베이션 주식회사 | Composition of the hot-melt adhesive having low viscosity |
| US20160075855A1 (en) * | 2014-09-16 | 2016-03-17 | Eastman Chemical Company | Polymeric compositions with improved noise suppression |
| DE102018118105A1 (en) | 2018-07-26 | 2020-01-30 | Clariant Plastics & Coatings Ltd | Thermoplastic molding compounds |
| JP6621126B1 (en) * | 2018-09-25 | 2019-12-18 | 積水フーラー株式会社 | Hot melt coating agent for electronic circuit mounting boards |
| EP3854365B1 (en) | 2020-01-27 | 2023-07-19 | The Procter & Gamble Company | Absorbent articles comprising a sbc based hotmelt adhesive |
| EP4096917A1 (en) | 2020-01-27 | 2022-12-07 | The Procter & Gamble Company | Absorbent articles with high toughness adhesive |
| EP4097188A1 (en) | 2020-01-27 | 2022-12-07 | Clariant International Ltd | Thermoplastic moulding materials with improved property profile |
| EP4317349A1 (en) | 2022-08-05 | 2024-02-07 | Henkel AG & Co. KGaA | Hot melt adhesive composition for secured paper packaging |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615106A (en) * | 1969-04-04 | 1971-10-26 | Nat Starch Chem Corp | Manufacture of hard covered books |
| DE2533729B2 (en) * | 1975-07-28 | 1979-12-13 | Kufner Textilwerke Kg, 8000 Muenchen | Hot melt adhesive powder and process for their manufacture |
| US4284671A (en) * | 1979-05-11 | 1981-08-18 | Clopay Corporation | Polyester compositions for gas and moisture barrier materials |
| US4431760A (en) * | 1980-05-15 | 1984-02-14 | Standard Oil Company | Esters as processing aids for maleic anhydride resins |
| DE3229656A1 (en) * | 1982-08-09 | 1984-02-09 | Henkel KGaA, 4000 Düsseldorf | ADHESIVE PRE-GEL PLASTIC |
| US4745026A (en) * | 1986-03-03 | 1988-05-17 | Mitsubishi Paper Mills, Ltd. | Thermal delayed tack sheets |
| US4767813A (en) * | 1987-03-23 | 1988-08-30 | Polysar Financial Services S.A. | High solids PSA Compounds |
-
1988
- 1988-08-03 US US07/227,705 patent/US5026756A/en not_active Expired - Lifetime
-
1989
- 1989-07-27 DE DE68914994T patent/DE68914994T2/en not_active Expired - Lifetime
- 1989-07-27 AU AU42212/89A patent/AU4221289A/en not_active Abandoned
- 1989-07-27 JP JP1509664A patent/JP2605156B2/en not_active Expired - Fee Related
- 1989-07-27 WO PCT/US1989/003247 patent/WO1990001525A1/en active IP Right Grant
- 1989-07-27 EP EP89910353A patent/EP0427792B1/en not_active Expired - Lifetime
- 1989-08-02 CA CA000607274A patent/CA1335122C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE68914994D1 (en) | 1994-06-01 |
| US5026756A (en) | 1991-06-25 |
| DE68914994T2 (en) | 1994-10-06 |
| JP2605156B2 (en) | 1997-04-30 |
| AU4221289A (en) | 1990-03-05 |
| JPH04501279A (en) | 1992-03-05 |
| EP0427792A1 (en) | 1991-05-22 |
| EP0427792B1 (en) | 1994-04-27 |
| WO1990001525A1 (en) | 1990-02-22 |
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| Date | Code | Title | Description |
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| MKLC | Lapsed (correction) |