WO1999025785A1 - Adhesif thermofusible a base d'un copolymere de l'ethylene et d'un (meth)acrylate d'alkyle - Google Patents
Adhesif thermofusible a base d'un copolymere de l'ethylene et d'un (meth)acrylate d'alkyle Download PDFInfo
- Publication number
- WO1999025785A1 WO1999025785A1 PCT/FR1998/002409 FR9802409W WO9925785A1 WO 1999025785 A1 WO1999025785 A1 WO 1999025785A1 FR 9802409 W FR9802409 W FR 9802409W WO 9925785 A1 WO9925785 A1 WO 9925785A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive
- acrylate
- copolymer
- meth
- tack
- Prior art date
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
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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 present invention relates to a hot-melt adhesive based on a copolymer of ethylene and an alkyl (meth) acrylate.
- Hotmelt are thermoplastic materials which are solid at room temperature and which, when heated, become viscous liquids. These viscous liquids are applied to a first substrate and then covered with a second surface. By cooling, an adhesion is obtained between the substrate and the second surface.
- the open time is the period during which the adhesive which has been applied to a substrate which is at room temperature remains tacky, that is to say the time interval during which the second surface can be applied and by cooling to obtain adhesion between the substrate and the second surface.
- HMA hot melt adhesives
- Adhesives with infinite open time are required for self-adhesive labels or adhesive tapes used at room temperature. Depending on the nature of the adhesive, more or less strong adhesions can be obtained, for example peeling off and re-sticking the label. Bonding is carried out by pressure at room temperature. The adhesive is deposited on the substrate (for example label or tape) when hot.
- HMPSA hot melt pressure sensitive adhesives
- the present invention relates to these two types of hot-melt adhesives, that is to say HMA and HMPSA.
- the HMPSAs are preferably based on block copolymers SIS (styrene-isoprene-styrene) but also SBS (styrene-butadiene-styrene).
- ethylene- (meth) acrylate copolymers the alkyl group having at least 5 carbon atoms and advantageously 6 to 24 carbon atoms, make it possible to prepare HMPSA adhesives with properties essentially similar to those based on SIS or SBS while having better loop tack, better finger tack, better peel level than ethylene butyl acrylate copolymers.
- the heavy (meth) acrylates of the 2-ethylhexyl acrylate type provide better resistance at low temperature by comparison with butyl or ethyl acrylate.
- they are applicable at low temperature (COOL MELT), for example between 130 and 1 50.
- the present invention is therefore a hot-melt adhesive comprising:
- the adhesives of the HMPSA type are deposited hot (in fusion) on a substrate such as for example a paper tape, in polyamide, or polyolefinic or polyester substrate; by cooling, an adhesive face is obtained at room temperature.
- a substrate such as for example a paper tape, in polyamide, or polyolefinic or polyester substrate
- This adhesive side can be protected before use by a silicone paper or the other side of the substrate (winding of an adhesive tape on itself).
- the loop tack test is the FINAT FTM 9 test described in the FINAT technical manual, Laan Copes Van Cattenbubch 79, NL 2585 EW LA HAYE (1 995) (HMPSA).
- the tack is defined as being the force required to take off a loop of PET (Polyethylene terephthalate) coated with HMPSA, of which a determined surface has been previously brought into contact with a stainless steel plate.
- the HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 * 400) mm 2 .
- the thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 .
- the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH (relative humidity).
- the self-adhesive tape is applied using a standard 2 kg standard roller.
- the test is carried out using a dynamometer, at a traction speed of 300 mm / min in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
- the loop-tack is quantified by the value of the maximum force.
- the result of the loop tack measurement test is given in N / cm. The type of rupture must also be mentioned.
- the rupture is undecided and one can observe on the same test tube the two types of ruptures described above.
- FTM8 The creep resistance is determined by the FTM8 test (FINAT Manual already cited) (HMPSA).
- the creep test measures the capacity of an HMPSA to resist a static force of 1 kgf at a given temperature (at room temperature in the examples of the present invention).
- the static shear resistance is defined by the time necessary to separate by parallel vertical sliding an area of (25 x 25) mm 2 coated with HMPSA, of a flat stainless steel plate.
- the HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 x 400) mm 2 .
- the thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 .
- the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
- the self-adhesive tape is applied using a standard 2 kg standard roller. The result of the creep test is given in minutes. The type of rupture must also be mentioned.
- FTM1 The adhesion to steel is determined by the FTM1 test (FINAT Manual already mentioned) (HMPSA). This test quantifies the adhesive power. The latter is defined as the force required to remove a PET strip coated with HMPSA from a stainless steel plate.
- the HMPSA is coated between 140 ° C and 180 ° C on a PET strip of (25 * 400) mm 2 .
- the thickness being constant, the grammage is between 18 g / m 2 and 22 g / m 2 .
- the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
- the self-adhesive tape is applied using a standard 2 kg standard roller. The adhesion strength is measured 20 minutes after application.
- the test is carried out using a dynamometer, under a 180 ° peeling angle, at a speed of 300 mm / min in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
- the cloud point is determined as follows: the glue is heated to 175 ° C., then a drop is placed on the bulb of a thermometer
- ASTM ASTM then the temperature at which the haze appears during cooling is noted. A value below 50 ° C or 60 ° C indicates good compatibility between the constituents of the hot melt.
- SAFT shear adhesion failure temperature
- the SAFT test (ASTM D 4498) measures the capacity of a hot-melt adhesive to resist a static force of 0.5 kg (or 0.25 kg), under the effect of a regular rise in temperature of 0.4 ° C / min .
- the SAFT is defined by the temperature at which one can observe a separation, by parallel vertical sliding of an area of (25 x 25) mm 2 coated with HMPSA, of a flat stainless steel plate.
- the hot-melt adhesive is coated between 140 ° C and 180 ° C on a PET strip of (25 x 400) mm 2 .
- the thickness being constant, the grammage is between 1 8 g / m 2 and 22 g / m 2 .
- the test strips must be conditioned at least four hours before the test in an air-conditioned room at (23 ⁇ 2) ° C, (50 ⁇ 5)% RH.
- the self-adhesive tape is applied using a standard 2 kg standard roller.
- the SAFT result is given in ° C. The type of rupture must be mentioned.
- PET Polyethylene terephthalate
- the copolymer (A) ethylene- (meth) acrylate is such that the alkyl group contains at least 5 carbon atoms.
- the Applicant has indeed discovered that alkyls having at least 5 carbon atoms give tack to HMPSA and good properties at low temperature to HMA.
- the alkyl can be linear, branched or cyclic. Advantageously, it comprises 6 to 24 carbon atoms.
- alkyl (meth) acrylates mention may be made of 2-ethylhexyl (meth) acrylate and octyl acrylate.
- the (meth) acrylate content is advantageously at most
- the melt index can be between 0, 1 and 1000 and is preferably at least 200 (in g / 10 min according to ASTMD 1 238-73 conditions E at 190 ° C under a load of 2, 1 6 kg).
- (A) can be a mixture of two copolymers (A-]) and (A2) of different MFIs.
- ) has an MFI less than 10 and (A2) has an MFI greater than 10.
- ) is between 1 and 3 and the MFI of (A2) is between 50 and 400 .
- the adhesives of the invention contain one or more tackifying resins, at least one wax, optionally fillers and / or stabilizers.
- the adhesives of the invention contain one or more tackifying resins, one or more plasticizers and optionally stabilizers.
- Suitable tackifying resins are, for example, rosin, rosin esters, hydrogenated rosin, polyterpenes and derivatives, aromatic or aliphatic petroleum resins, hydrogenated cyclic resins. These resins typically have a ring ball softening temperature between 25 ° C and 180 ° C and preferably between 50 ° C and 135 ° C.
- the amount of tackifying resin can be from 50 to 180 parts per 100 parts of (A) and preferably 100 to 150 parts.
- Other examples of rosin derivatives are described in
- rosin derivatives of those obtained by hydrogenation, dehydrogenation, polymerization, esterification. These derivatives can be used as such or in the form of polyol esters such as pentaerythritol, polyethylene glycol and glycerol esters.
- tackifying resin of dicyclopentadienes.
- the adhesives of the invention may contain waxes. They make it possible to adjust the fluidity, the open time and the setting time.
- the waxes can be recovered during the refining of petroleum fractions. These are, for example, waxes consisting essentially of paraffinic hydrocarbons and containing sufficient amounts of branched, cyclic and aromatic hydrocarbons to be much less crystalline than paraffins. Synthetic waxes can also be used, such as FISCHER TROPSCH waxes.
- the paraffin waxes used in the adhesives of the invention have a melting temperature above 50 ° C and preferably between 60 ° C and 70 ° C.
- the amount of wax can be between 30 and 80 parts per 100 parts of copolymer (A).
- the plasticizers which can be used in the adhesives of the invention are, for example, aromatic or naphthenic paraffinic mineral oils. They are essentially used to lower the viscosity and to provide tack.
- the amount of plasticizer can be between 10 and 30 parts per 100 parts of (A).
- plasticizer of phthalates, azelates, adipates, tricresyl phosphate and polyesters.
- the adhesives of the invention may contain fillers. Mention may be made, as examples of fillers, of silica, alumina, glass, glass beads, calcium carbonates, fibers and metal hydroxides. These fillers must not reduce the tack or the mechanical properties of the glue after its application.
- the quantity of charges can represent up to 100 parts per 100 parts of (A).
- the hot-melt adhesives of the invention are prepared by mixing in the molten state at temperatures between 130 ° C. and 200 ° C. until a homogeneous mixture is obtained.
- the mixing time can be of the order of 30 minutes to 3 hours.
- the usual devices for thermoplastics can be used such as extruders, cylinders, Banbury or Brabender mixers, or propeller mixers.
- SIS styrene-isoprene-styrene block copolymer containing 15% by weight of polystyrene sold by SHELL CHIMIE under the reference KRATON-D- 1,161 N.
- E-2 EHA / 3 to 8 ethylene-2-ethylhexyl acrylate (2 EHA) copolymers with characteristics:
- PERMALYN 5095 solid rosin glycerol ester (produced by HERCULES)
- CATENEX N 956 aliphatic paraffinic oil produced by SHELL
- IRGANOX 1010 phenolic antioxidant produced by CIBA
- the following tables show the properties of the HMPSAs produced with SIS (not in accordance with the invention) and according to the invention with E-2 EHA copolymers.
- the composition of the HMPSA is listed at the top of each table.
- the column E-2 EHA / 7 means that it is an HMPSA based on the copolymer E-2 EHA / 7.
- BA 40 denotes an ethylene butyl acrylate copolymer at 35% by weight of acrylate and MFI: 40 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 67 ° C.
- BA 175 denotes a copolymer of ethylene butyl acrylate at 28% by weight of acrylate and of MFI: 1,75 (in g / 10 min at 1 90 ° C under a load of 2, 1 6 kg according to ASTM D 1 238) , Tg 80 ° C.
- BA 02 denotes an ethylene butyl acrylate copolymer at 30% by weight of acrylate and of MFI: 2 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 78 ° C.
- BA 320 denotes an ethylene butyl acrylate copolymer at 35% by weight of acrylate and of MFI: 320 (in g / 10 min at 190 ° C. under a load of 2.16 kg according to ASTM D 1 238), Tg 66 ° C. Table 1
- RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate Table 2 35% (Copolymer (A) or SIS) - 40% Permalyn 5095 - 25% Catenex N956
- RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack
- RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack Table 4
- RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate * 3: Strong tack - 2: Medium tack - 1: Weak tack - 0: Zero tack
- RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate
- RA Adhesive failure - RC: Cohesive failure - RM: Adhesive mixed failure (RA): Adhesive failure with slight deposit of material on the plate
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU12412/99A AU1241299A (en) | 1997-11-14 | 1998-11-12 | Hot melt adhesive based on an ethylene copolymer and an alkyl (meth)acrylate |
CA002277787A CA2277787A1 (fr) | 1997-11-14 | 1998-11-12 | Adhesif thermofusible a base d'un copolymere de l'ethylene et d'un (meth)acrylate d'alkyle |
EP98955642A EP0953025A1 (fr) | 1997-11-14 | 1998-11-12 | Adhesif thermofusible a base d'un copolymere de l'ethylene et d'un (meth)acrylate d'alkyle |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR97/14320 | 1997-11-14 | ||
FR9714320 | 1997-11-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999025785A1 true WO1999025785A1 (fr) | 1999-05-27 |
Family
ID=9513395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1998/002409 WO1999025785A1 (fr) | 1997-11-14 | 1998-11-12 | Adhesif thermofusible a base d'un copolymere de l'ethylene et d'un (meth)acrylate d'alkyle |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0953025A1 (fr) |
AU (1) | AU1241299A (fr) |
CA (1) | CA2277787A1 (fr) |
WO (1) | WO1999025785A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2819821A1 (fr) * | 2001-01-24 | 2002-07-26 | Atofina | Utilisation d'un hma ethylene/acrylate de 2-ethylhexyle pour la fabrication d'articles tels que des emballages |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4238766A1 (fr) | 2022-03-04 | 2023-09-06 | voestalpine Automotive Components Dettingen GmbH & Co. KG | Procédé d'assemblage d'éléments de tôlerie en paquets de tôles et dispositif associé |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997012007A1 (fr) * | 1995-09-26 | 1997-04-03 | Ato Findley S.A. | Colle thermofusible auto-adhesive pour l'hygiene |
-
1998
- 1998-11-12 WO PCT/FR1998/002409 patent/WO1999025785A1/fr not_active Application Discontinuation
- 1998-11-12 CA CA002277787A patent/CA2277787A1/fr not_active Abandoned
- 1998-11-12 AU AU12412/99A patent/AU1241299A/en not_active Abandoned
- 1998-11-12 EP EP98955642A patent/EP0953025A1/fr not_active Ceased
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997012007A1 (fr) * | 1995-09-26 | 1997-04-03 | Ato Findley S.A. | Colle thermofusible auto-adhesive pour l'hygiene |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2819821A1 (fr) * | 2001-01-24 | 2002-07-26 | Atofina | Utilisation d'un hma ethylene/acrylate de 2-ethylhexyle pour la fabrication d'articles tels que des emballages |
Also Published As
Publication number | Publication date |
---|---|
EP0953025A1 (fr) | 1999-11-03 |
CA2277787A1 (fr) | 1999-05-27 |
AU1241299A (en) | 1999-06-07 |
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