Releasable adhesive for attachments of substrates and joints

• US 6,858,667 B1
• Filed: 11/20/2000
• Issued: 02/22/2005
• Est. Priority Date: 11/24/1999
• Status: Expired due to Fees

• Current Assignee: HELLA KG Hueck & Co.
• Original Assignee: HELLA KG Hueck & Co.
• Inventors: Rohrberg, Simone, Temme, Ulrich, Flerlage, Horst, Schmidt, Stephan
• Primary Examiner(s): Cain, Edward J.
• Application Number:
  US09/715,138
• Time in Patent Office: 1,555 Days
• Field of Search: 524/504
• US Class Current: 524/504
• CPC Class Codes: B29C 65/4815 Hot melt adhesives, e.g. thermoplastic adhesives
• CPC Class Codes: B29C 65/76 Making non-permanent or releasable joints
• CPC Class Codes: B29C 66/1162 Single bevel to bevel joints, e.g. mitre joints
• CPC Class Codes: B29C 66/54 Joining several hollow-preforms, e.g. half-shells, to form hollow articles, e.g. for making balls, containers; Joining several hollow-preforms, e.g. half-cylinders, to form tubular articles
• CPC Class Codes: B29C 66/71 characterised by the composition of the plastics material of the parts to be joined welding bar compositions B29C65/125
• CPC Class Codes: B29C 66/7392 characterised by the material of at least one of the parts being a thermoplastic
• CPC Class Codes: B29C 66/7394 characterised by the material of at least one of the parts being a thermoset
• CPC Class Codes: B29K 2023/083 EVA, i.e. ethylene vinyl acetate copolymer
• CPC Class Codes: B29K 2023/12 PP, i.e. polypropylene
• CPC Class Codes: B29K 2033/12 Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• CPC Class Codes: B29K 2069/00 Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
• CPC Class Codes: B29L 2031/3055 Cars
• CPC Class Codes: B29L 2031/747 Lightning equipment
• CPC Class Codes: C08F 255/00 Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 287/00 Macromolecular compounds obtained by polymerising monomers on to block polymers
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C09J 151/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: C09J 153/02 Vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C09J 153/025 modified

Abstract

A hot-melt adhesive contains a non-pressure-sensitive adhesive that is fluid at application temperatures and that is removable, residue-free, by peeling at small peel angles. The adhesive contains additives selected from the group consisting of fillers, stabilizers, dyes, carbon black, and moisture absorbents. The adhesive also containing the following: a) thermoplastic elastomers that may be grafted, b) grafted and poly-α-olefins, c) polyisobutylene or a softening oil, d) adhesive resin, and e) end block resin.

Claims

1. A hot-melt adhesive comprising a non-pressure-sensitive adhesive that is fluid at application temperatures and that is removable, residue-free, by peeling at small peel angles, wherein said adhesive contains additives selected from the group consisting of fillers, stabilizers, dyes, carbon black, and moisture absorbents, said adhesive also containing the following:

a) thermoplastic elastomers that may be grafted,

b) grafted poly-α

-olefins,

c) polyisobutylene or a softening oil,

d) adhesive resin, and

e) end block resin,

wherein the adhesive has a tear resistance greater than 800%.

2. The adhesive according to claim 1, wherein the thermoplastic elastomers are styrenes selected from the group consisting of SBS, SIS, SEBS, SEPS, block polystyrene-(block poly(ethylene-butylene)), and block polystyrene-(block poly(ethylene-butylene)) having 1 to 10 block styrene units per molecule, which optionally are modified with block polyisoprene or block butadiene units;

elastomer alloys selected from the group consisting of EPDM/PP, NR/PP, EVA/PVDC and NBR/PP;

polyurethane;

polyether esters or polyamides.

3. The adhesive according to claim 1, wherein the poly-α

-olefins are at least partially grafted, and the poly-α

-olefins are selected from amorphous poly-α

-olefins, monopolymers, copolymers, or terpolymers of monomers of ethylene, propylene, 1-butene, 1-pentene, or 1-hexene, or from a poly-α

-olefin of the general formula (I);

where

m=0 to 15, and

n=5 to 50,000.

4. The adhesive according to claim 3, wherein the poly-α

-olefins are semicrystalline, and the poly-α

-olefins comprise at least one of polyethylene, polypropylene, or poly-1-butene, which have high tacticity in the crystalline regions.

5. The adhesive according to claim 3 or 4, wherein the poly-α

-olefins are randomly grafted with olefinically unsaturated compounds, which are selected from the group consisting of maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and compounds of the general formula (II);

where

R₁ represents the following groups;

where

Z is hydrogen, a methyl group, or a phenyl group, and

X is —

(—

CH₂—

)₁—

or

where

Y is a hydrolyzable group,

m 0,1, or 2,

n is 0, 1, or 2, and

1 is 1, 2, 3, 4, 5, or 6;

or

where

k is 0, 1, or 2,

R₂ is hydrogen or methyl,

R₃ is an R₁ group, hydrogen, or methyl, and

R₄ is hydrogen or methyl.

6. An adhesive according to claim 1, wherein the quantity of grafted poly-α

-olefins is 0 to 100% by weight, relative to the total content of poly-α

-olefins.

7. The adhesive according to claim 1, wherein the thermoplastic elastomers are randomly grafted with olefinically unsaturated compounds that are selected from maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, or compounds of the general formula (II):

where

R₁ represents the following groups;

where

Z is hydrogen, a methyl group, or a phenyl group, and

X is —

(—

CH₂—

)₁—

or

where

Y is a hydrolyzable group,

m 0,1, or 2,

n is 0, 1, or 2, and

1 is 1, 2, 3, 4, 5, or 6;

or

where

k is 0, 1, or 2,

R₂ is hydrogen or methyl,

R₃ is an R₁ group, hydrogen, or methyl, and

R₄ is hydrogen or methyl.

8. The adhesive according to claim 1, wherein the percentage of grafted thermoplastic elastomers, relative to the total content of the thermoplastic elastomers, is 0 to 100% by weight.

9. The adhesive according to claim 1, wherein the adhesive resins are selected from polymeric monomers of the petrochemical C₅ to C₉ distillation fractions, which are not hydrated partially hydrated, or completely hydrated, natural rosin resins, modified natural rosin resins, terpene resins, polyterpene resins of β

-pinene, α

-pinene, and/or δ

-limonene;

resins obtained by copolymerization of terpene with monomers from the C₅ to C₉ fraction from petroleum distillation, or terpene-phenol resins.

10. The adhesive according to claim 1, wherein the polyisobutylenes are at least one selected from the group consisting of homopolymers of isobutylene of average molecular weight in the range of 20,000 to 5,000,000 g×

mol<sup>−

1</sup> (determined by gel permeation chromatography), copolymers of isobutylene and a conjugated diene in quantities of 0.3 to 4.5 mol % (relative to said copolymer), and terpolymers of isobutylene, divinylbenzene in quantities of 0.01 to 4.5 mol %.

11. The adhesive according to claim 1, wherein the polyisobutylenes or softening oils are at least one selected from the group consisting of polyisobutylenes, oligomers or polymers of isobutylene or 1-butene, and modified naphthalene- or paraffin-based oils recovered from petroleum distillation with an average molecular weight in the range of 200 to 20,000 g×

mol<sup>−

1</sup> (determined using gel permeation chromatography).

12. The adhesive according to claim 1, wherein said adhesive contains:

f) 0 to 80% by weight, or 15 to 70% by weight of polyisoprene, polybutadiene, grafted polyisoprene or polybutadiene.

13. The adhesive according to claim 1, wherein said adhesive contains:

g) 0 to 50% by weight, preferably 0 to 40% by weight, fillers; and

h) 0 to 25% by weight, preferably 0 to 10% by weight, aromatic resins and/or stabilizers.

14. The adhesive according to claim 13, wherein the fillers are inorganic fillers selected from the group consisting of calcium carbonate, calcium hydroxide, calcium oxide, dolomite, titanium dioxide, zinc oxide, silicon oxide, barium sulfate, and manganese dioxide;

or the fillers are an organic filler which is preferably carbon black.

15. The adhesive according to claim 13, wherein the stabilizers are selected from the group consisting of epoxides, sterically hindered phenols, amines, thioesters, phosphites, triazinetriazoles, piperidinetriazoles and benzotriazoles.

16. The adhesive according to claim 1, wherein said adhesives contain adhesives comprising at least one of epoxy resins, silicones, polysulfides, polyurethanes, polyureas, or acrylates.

17. An adhesive method which comprises:

attaching glass-like substrates to thermoplastic or duroplastic plastic substrates using the adhesive set forth in claim 1.

18. The method according to claim 17, wherein the glass-like plastic substrates are selected from polymethyl methacrylate, polycarbonate, or cycloolefin copolymer, or said plastic substrates comprise polypropylene.

19. The method according to claim 17 or 18, wherein light disks or headlight lenses are releasably attached to lamp housings of automobile lights or automobile headlights.

20. In automobile lights or automobile headlights comprising light disks or headlight lenses, preferably having a scratch-resistant finish, composed of a glass-like plastic substrate, and lamp housings composed of a thermoplastic or duroplastic plastic substrate, wherein said light disks or headlight lenses and lamp housings are attached to the adhesive of claim 1.