EP0521079A1 - Hot melt adhesive compositions - Google Patents
Hot melt adhesive compositionsInfo
- 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- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims description 30
- 239000004831 Hot glue Substances 0.000 title claims description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005977 Ethylene Substances 0.000 claims abstract description 3
- 238000009472 formulation Methods 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 claims 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims 1
- 150000003505 terpenes Chemical class 0.000 claims 1
- 235000007586 terpenes Nutrition 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 239000004840 adhesive resin Substances 0.000 abstract 1
- 229920006223 adhesive resin Polymers 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- -1 unsaturated ethylene ester Chemical class 0.000 abstract 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 241001643597 Evas Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SEBVBMQGOVGVAR-UHFFFAOYSA-N ethene;ethenyl acetate;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C.CC(=O)OC=C SEBVBMQGOVGVAR-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010691 naphtenic oil Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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
Claims
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)
| 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, resin composition for hot melt adhesion, 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 |
| WO2018217748A1 (en) | 2017-05-22 | 2018-11-29 | H.B. Fuller Company | Hot melt adhesive composition |
Family Cites Families (4)
| 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 |
-
1990
- 1990-03-23 GB GB909006548A patent/GB9006548D0/en active Pending
-
1991
- 1991-03-21 WO PCT/EP1991/000576 patent/WO1991014750A1/en not_active Ceased
- 1991-03-21 EP EP91906870A patent/EP0521079A1/en not_active Withdrawn
- 1991-03-21 JP JP91506803A patent/JPH05505638A/en active Pending
Non-Patent Citations (1)
| 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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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19920919 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT NL |
|
| 17Q | First examination report despatched |
Effective date: 19940125 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19960624 |