EP0521079A1 - Hot melt adhesive compositions - Google Patents

Hot melt adhesive compositions

Info

Publication number
EP0521079A1
EP0521079A1 EP91906870A EP91906870A EP0521079A1 EP 0521079 A1 EP0521079 A1 EP 0521079A1 EP 91906870 A EP91906870 A EP 91906870A EP 91906870 A EP91906870 A EP 91906870A EP 0521079 A1 EP0521079 A1 EP 0521079A1
Authority
EP
European Patent Office
Prior art keywords
polymer
weight
formulation according
hot melt
derived
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.)
Withdrawn
Application number
EP91906870A
Other languages
German (de)
French (fr)
Inventor
Michel Louis Faissat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents 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 Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0521079A1 publication Critical patent/EP0521079A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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

Definitions

  • the invention relates to hot melt adhesive compositions for use especially but not exclusively in sanitary (diaper) end uses.
  • medium melt index ethylene vinylacetate polymers in hot melt adhesive blends is known from EP-A-78122.
  • a range of vinyl acetate contents of from 11 to 40 % is used together with a high melt index of from 700 to 10000.
  • a range of different transfer agents is disclosed for use providing the high melt index.
  • EP-A-271254 disclosed hot melt formulations including ethylene vinyl acetate acrylic acid terpolymers having a melt viscosity of from 3000 mPa.s to 7000 mPa.s. at a temperature of 190-.C.
  • the terpolymers may contain from 5 to 20 wt% of vinylacetate.
  • AU 2995689 discloses the use of an ethylene vinylacetate copolymer having a melt index from 700 to 10000 and from 5 to 40 wt% of VA with less than 10 alkyl branches per 1000 backbone C-atoms as asphalt modifier.
  • a melt index from 700 to 10000 and from 5 to 40 wt% of VA with less than 10 alkyl branches per 1000 backbone C-atoms as asphalt modifier.
  • VA ethylene vinylacetate copolymer having a melt index from 700 to 10000 and from 5 to 40 wt% of VA with less than 10 alkyl branches per 1000 backbone C-atoms as asphalt modifier.
  • the invention provides a hot melt adhesive composition including
  • the polymer may be a co- or terpolymer with additional functional groups. It is preferred that the polymer is an EVA copolymer. It is further preferred to have an ester derived content of from 25 wt%, especially from 30 wt% up to 35 wt % so as to obtain a flexible formulation with good compatibility characteristics.
  • the ester may also be methyl acrylate or is homologues or methacrylate equivalents. It is preferred that the melt index is from 200 to 1000 and especially from 300 to 800.
  • the polymer may be made by the process described in EP-A-78122 but preferably using an aldehyde, particularly acetaldehyde, as a chain transfer agent for increasing the
  • the tackifiers are preferably compatible hydrogenated, low colour tackifiers.
  • Advantageously hydrogenated petroleum resins are used derived from a C5/C6 olefin or diolefin feed stream and a C9 aromatic compound containing feed stream by thermal or catalytic (Friedel-Crafts) polymerisation. It is preferred, in order that compatibility can be optimised to provide a resin having an aromaticity of from 0 to 50 % preferably from 10 to 40 wt%. With good compatability high tackifier amounts can be incorporated preferably from 35 to 65 wt%.
  • the tackifiers have a Mn of from 200 to 1300 and a Mw/Mn of from 11 to 25 as determined by GPC.
  • the oils and waxes are used optionally to lower the viscosity of the overall formulation to a level suitable for application. As these ingredients reduce generally reduce tack they are used in minimal amounts.
  • the oils may be naphthenic oils, polybutenes, liquid resins, paraffinic oils etc.
  • the overall viscosity of the formulation is preferably from 300 to 15000 mPa.s at 180°C. Amounts of the ingredients and melt indices are selected so as to produce the desired viscosity.
  • MI EVA'S were prepared using acetaldehyde as the transfer agent. Properties of the products are listed below in Table 1.
  • the MI was determined according to ASTM 1238D using condition E i.e. a load of 2,1 kg at 190 - ⁇ C
  • the number of alkyl branches per 1000 C backbone atoms is less than 10 as determined by proton NMR.
  • Runs 3, 6, 7, 10 are not according to the invention and are for comparative purpose.
  • Cloud point (degC) 115 105 145 >200 170 190 >200 170 110 135
  • T-peel PE/N C multiline (g/cm) at 23 degC 2.25 1.40 0.6 0.8 0.7 0.5 0.2 0.4 jerking at 40 degC 0.5 0.5 0.2 - 0.15 0.3 0.45 0.5 0.4
  • Formulation of the invention shows superior heat resistance as measured with hot shear shaft test and similar adhesive properties at lower HMA blend viscosity than formulation using regular EVAs.
  • Runs 1, 4 and 8 are not according to the invention and are for comparative purposes
  • the invention permits formulations to be prepared which are in many ways competitive with formulations based on propylene/butene copolymer and regular EVAs.
  • the formulation of the invention of superior compatibility, lower cloud point, better adhesive performance as measured with T-peel test, of higher tensile strength, and secant modulus, good elongation and higher heat resistance, obtained at lower HMA blend viscosity.

Abstract

Une colle à fusion comprend: (a) de 15 à 80 % en poids d'un polymère dérivé de l'éthylène et d'un ester non saturé d'éthylène, la partie dérivée de l'ester représentant de 20 à 40 % en poids du total et le polymère ayant un MI de 100 à 6000 et de 0 à 10 ramifications alkyles pour 1000 atomes de carbone de l'ossature; (b) de 20 à 70 % en poids de résine adhésive compatible; (c) de 0 à 30 % en poids d'une huile ou d'une cire compatible, les pourcentages en poids de (a), (b) et (c) étant calculés sur le poids total de la formule. On peut obtenir une meilleure résistance à la chaleur à des viscosités faibles.A fusion adhesive comprises: (a) from 15 to 80% by weight of a polymer derived from ethylene and from an unsaturated ethylene ester, the part derived from the ester representing from 20 to 40% by weight of the total and the polymer having an MI of 100 to 6000 and 0 to 10 alkyl branches per 1000 carbon atoms of the framework; (b) from 20 to 70% by weight of compatible adhesive resin; (c) from 0 to 30% by weight of a compatible oil or wax, the weight percentages of (a), (b) and (c) being calculated on the total weight of the formula. Better heat resistance can be obtained at low viscosities.

Description

Hot melt adhesive compositions.
The invention relates to hot melt adhesive compositions for use especially but not exclusively in sanitary (diaper) end uses.
Background of the invention
The use of medium melt index ethylene vinylacetate polymers in hot melt adhesive blends is known from EP-A-78122. A range of vinyl acetate contents of from 11 to 40 % is used together with a high melt index of from 700 to 10000. A range of different transfer agents is disclosed for use providing the high melt index.
EP-A-271254 disclosed hot melt formulations including ethylene vinyl acetate acrylic acid terpolymers having a melt viscosity of from 3000 mPa.s to 7000 mPa.s. at a temperature of 190-.C. The terpolymers may contain from 5 to 20 wt% of vinylacetate.
AU 2995689 discloses the use of an ethylene vinylacetate copolymer having a melt index from 700 to 10000 and from 5 to 40 wt% of VA with less than 10 alkyl branches per 1000 backbone C-atoms as asphalt modifier. There is a need for improved hot melt formulations which have a better balance fluidity cohesion strength and thermal resistance to permit spray application yet give good bond strength and endurance. It has been found that by selecting particular low branched, high VA ethylenevinylacetate polymers a good balance of properties can be provided, superior particularly in applications such as a multi-line adhesive in diaper constructions where different panels have to adhere to another.
Summary of the invention
The invention provides a hot melt adhesive composition including
(a) from 15 to 80 wt% of a polymer derived from ethylene and an ethylenically unsaturated ester, the ester derived units being from 20 to 40 wt % of the total and the polymer having an MI of from 100 to 6000 and having from 0 to 10 alkylbranches per 1000 C-atoms;
(b) from 20 to 70 wt% of a compatible tackifier resin; and
(c) from 0 to 30 wt% of a compatible oil or wax the weight percentages of (a) , (b) and (c) being calculated on the total weight of the formulation. The polymer may be a co- or terpolymer with additional functional groups. It is preferred that the polymer is an EVA copolymer. It is further preferred to have an ester derived content of from 25 wt%, especially from 30 wt% up to 35 wt % so as to obtain a flexible formulation with good compatibility characteristics. The ester may also be methyl acrylate or is homologues or methacrylate equivalents. It is preferred that the melt index is from 200 to 1000 and especially from 300 to 800.
The polymer may be made by the process described in EP-A-78122 but preferably using an aldehyde, particularly acetaldehyde, as a chain transfer agent for increasing the
MI.
The tackifiers are preferably compatible hydrogenated, low colour tackifiers. Advantageously hydrogenated petroleum resins are used derived from a C5/C6 olefin or diolefin feed stream and a C9 aromatic compound containing feed stream by thermal or catalytic (Friedel-Crafts) polymerisation. It is preferred, in order that compatibility can be optimised to provide a resin having an aromaticity of from 0 to 50 % preferably from 10 to 40 wt%. With good compatability high tackifier amounts can be incorporated preferably from 35 to 65 wt%. Preferably the tackifiers have a Mn of from 200 to 1300 and a Mw/Mn of from 11 to 25 as determined by GPC.
The oils and waxes are used optionally to lower the viscosity of the overall formulation to a level suitable for application. As these ingredients reduce generally reduce tack they are used in minimal amounts. The oils may be naphthenic oils, polybutenes, liquid resins, paraffinic oils etc.
The overall viscosity of the formulation is preferably from 300 to 15000 mPa.s at 180°C. Amounts of the ingredients and melt indices are selected so as to produce the desired viscosity.
Examples
Different MI EVA'S were prepared using acetaldehyde as the transfer agent. Properties of the products are listed below in Table 1.
Table 1 Polymer
1 2 3 4 5 6 The MI was determined according to ASTM 1238D using condition E i.e. a load of 2,1 kg at 190 -ΪC The number of alkyl branches per 1000 C backbone atoms is less than 10 as determined by proton NMR.
These polymers were made into a formulation for sanitary uses by blending with tackifier and oil and other usual ingredients such as filler and anti-oxidant stabilizer. Table 2 shows the composition and associated results.
Runs 3, 6, 7, 10 are not according to the invention and are for comparative purpose.
Apart from polymers 1 to 6, the key to the ingredients is as follows ;
E-5300 hydrogenated dicyclopentadiene resin
Escorez (RTM) Escorene (RTM) MV02528 a 25 Meltindex, 28% VA ethylene vinylacetate polymer
Vestoplast (RTM) 708 C2/C3/C4 amorphous poly-A-olefin Parapol (RTM) 2225 Polybutene polymers produced by Parapol (RMT) 1300 Exxon Chemical Primol (RTM) 352 paraffinic/naphtenic oil Irganox (RTM) 1076 antioxidant Table 2
10
Formulations
Escorez 5300 35 35 35 50 50 50 30 50 50 50
Properties 1 2 3 4 5 6 7 8 9 10
Viscosity 180 degC 3880 1515 1620 . 2945 1985 2650 3375 1460 1520 1775 (mPa.s)
Softening point 73.2 70.5 61 67.5 73 69.5 91 67.5 70 67 (degC)
Cloud point (degC) 115 105 145 >200 170 190 >200 170 110 135
Hot shear ( in/degC) 20/60 1/60 1/50 5/60 29/60 12/60 2/50 4/60 3/70 13/60
T-peel PE/N C multiline (g/cm) at 23 degC 2.25 1.40 0.6 0.8 0.7 0.5 0.2 0.4 jerking at 40 degC 0.5 0.5 0.2 - 0.15 0.3 0.45 0.5 0.4
Similar formulations can also be used advantageously for woodworking applications. Details of the composition and properties for such end-use are set out in Table 3.
Formulation of the invention shows superior heat resistance as measured with hot shear shaft test and similar adhesive properties at lower HMA blend viscosity than formulation using regular EVAs.
SUBSTITUTESHEET TABLE 3
Formulations
ECR 340 10 10 10 10 10 10 10 10 Dertopoline P 15 15 15 15 15 15 15 15 UL 40028 45 25 Polymer 1 45 Polymer 5 45 Escorene UL 15028 45 Escorene UL 8720 45 Polymer 3 45 UL 8705 45 UL 00728 CaC03 BaS04 Irganox 1076
Saft (degC) Horniflex 71 75 83 73 78 79
Linoplex 72 75 82 73 79 80
Eiche 69 75 85 71 72 75
Ageing at 180 degC
- 2 hours colour skinning %
- 25 hours colour skinning %
- 50 hours colour skinning %
Runs 1, 4 and 8 are not according to the invention and are for comparative purposes
It can be seen that the invention permits formulations to be prepared which are in many ways competitive with formulations based on propylene/butene copolymer and regular EVAs.
The formulation of the invention of superior compatibility, lower cloud point, better adhesive performance as measured with T-peel test, of higher tensile strength, and secant modulus, good elongation and higher heat resistance, obtained at lower HMA blend viscosity.

Claims

1. A hot melt adhesive composition including
(a) from 15 to 80 wt% of a polymer derived from ethylene and an ethylenically unsaturated ester, the ester derived units being from 20 to 40 wt% of the total and the polymer having an MI from 100 to 6000 and having from 0 to 10 alkyl branches per 1000 backbone C-atoms.
(b) from 20 to 70 wt% of a compatible tackifier resin; and
(c) from 0 to 30 wt% of a compatible oil or wax the weight percentages of (a) , (b) and (c) being calculated on the total weight of the formulation.
2. A formulation according to claim 1 or claim 2 in which the polymer is present in an amount of from 25 to 60 wt%.
SUBSTITUTESHEET 3. A formulation according to any of the preceding claims in which the tackifier is a hydrogenated or non-hydrogenated petroleum resin derived from catalytic or thermal polymerisation of dicyclopentadiene, its isomers, olefins such as 2-methyl butene; 1,2 methylbutene-2 cyclopentadiene 1,
3; C9 such as indene, vinyltoluene; aromatics such as styrene, terpenes such alpha-pinene, delta-3-carene said resin having an aromaticity of from 0 to 50%.
4. A formulation according to claim 4 in which the tackifier is present in an amount of from 20 to 70% preferably from 35 to 65 wt%.
5'. A formulation according to any of the preceding claims having a viscosity of from 200 to 20000 mPa.s at 180 e , preferably from 500 to 10000 mPa.s.
SUBSTITUTESHEET
EP91906870A 1990-03-23 1991-03-21 Hot melt adhesive compositions Withdrawn EP0521079A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909006548A GB9006548D0 (en) 1990-03-23 1990-03-23 Hot melt adhesive compositions
GB9006548 1990-03-23

Publications (1)

Publication Number Publication Date
EP0521079A1 true EP0521079A1 (en) 1993-01-07

Family

ID=10673136

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91906870A Withdrawn EP0521079A1 (en) 1990-03-23 1991-03-21 Hot melt adhesive compositions

Country Status (4)

Country Link
EP (1) EP0521079A1 (en)
JP (1) JPH05505638A (en)
GB (1) GB9006548D0 (en)
WO (1) WO1991014750A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX9206208A (en) * 1991-10-29 1993-04-01 E I Du Pont De Neumors And Com THERMOPLASTIC COMPOSITIONS WITH HIGH LOAD PROPORTION, USEFUL AS ADHESIVE PRE-LAYERS FOR CARPETS
US5331033A (en) * 1993-02-23 1994-07-19 National Starch And Chemical Investment Holding Corporation Hot melt adhesive
US5500472A (en) * 1995-02-17 1996-03-19 National Starch And Chemical Investment Holding Corporation Low application temperature hot melt adhesive
JPH0925371A (en) * 1995-07-12 1997-01-28 Sumitomo Chem Co Ltd Resin composition, hot melt adhesive resin composition, and laminate
US6568399B1 (en) 1999-04-26 2003-05-27 National Starch And Chemical Investment Holding Corporation Low application temperature hot melt adhesive for cigarette preparation
JP5382344B2 (en) * 2008-12-27 2014-01-08 荒川化学工業株式会社 Solar cell encapsulant sheet
CA3061335C (en) 2017-05-22 2021-11-30 H.B. Fuller Company Hot melt adhesive composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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
US4497941A (en) * 1981-10-16 1985-02-05 Exxon Research & Engineering Co. Ethylene copolymers for hot melt systems
US4874804A (en) * 1987-06-19 1989-10-17 National Starch And Chemical Corporation Hot melt adhesives based on ethylene-n-butyl acrylate
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9114750A1 *

Also Published As

Publication number Publication date
WO1991014750A1 (en) 1991-10-03
GB9006548D0 (en) 1990-05-23
JPH05505638A (en) 1993-08-19

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