Styrenic block copolymer based hot-melt adhesives, their use for disposable soft goods, and tackifying resins contained therein

• US 6,103,814 A
• Filed: 04/10/1997
• Issued: 08/15/2000
• Est. Priority Date: 04/15/1996
• Status: Expired due to Fees

• Current Assignee: Eastman Chemical Resins, Inc. (Eastman Chemical Company)
• Original Assignee: Hercules Incorporated (Ashland Global Holdings, Inc.)
• Inventors: Simons, Johannes Cornelis M., vanDrongelen, Jan
• Primary Examiner(s): Warzel, Mark L.
• Application Number:
  US08/843,684
• Time in Patent Office: 1,223 Days
• Field of Search: 525/98, 524/481, 524/483, 524/484, 524/490, 524/491, 524/505, 524/270, 524/499, 526/935, 585/365, 585/502, 585/507, 585/525, 585/532
• US Class Current: 524/505
• CPC Class Codes: A61F 13/539 characterised by the connection of the absorbent layers with each other or with the outer layers
• CPC Class Codes: A61F 2013/53908 with adhesive
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C09J 153/02 Vinyl aromatic monomers and conjugated dienes

Abstract

Disclosed are hot-melt adhesive compositions suitable for the manufacture of soft goods. They have a melt viscosity of 60,000 mPa.s or less at a temperature of 120° C. and include: (a) 50 to 150 parts by weight of a styrenic block copolymer or mixtures and/or modified and/or hydrogenated derivatives thereof; (b) 20 to 450 parts by weight of a tackifying resin which, when incorporated into a reference composition, leads to the following properties:

a tan δ value of 3.5 or less, wherein tan δ is defined as the ratio between the loss modulus and the storage modulus of said composition and

an elastic retention on spandex fibers (300%) or natural latex rubber (200%) after 4 h at 40° C. of 70% or more; and

a crossover temperature of 95° C. or less.

Further disclosed are novel partially hydrogenated hydrocarbon resins which are useful as tackifying resins and have the following properties: (a) a R&B softening point (R&B) of 50° C. to 150° C.; (b) a mixed methylcyclohexane aniline cloudpoint (MMAP) of 10° C. to 75° C.; (c) a Di-Acetone Alcohol cloudpoint (DACP) of 35° C. or less; (d) a molecular weight (Mz) of 10,000 Dalton or less; and (e) a UV absorbance at 268 nm ranging from 2.0 to 5.0.

Claims

1. A hot-melt adhesive composition which comprises:

(a) about 50 to about 150 parts by weight of a styrenic block copolymer;

(b) about 20 to about 450 parts by weight of a tackifying resin which, when incorporated into a reference composition consisting of 100 parts by weight of a styrene-isoprene-styrene copolymer having a styrene content of about 20 to 30% by weight, 250 parts by weight of said tackifying resin, 50 parts by weight of a paraffinic/napthenic (70/30 weight/weight) extender oil and 2 parts by weight of a stabilizer consisting essentially of pentaerythrityl-tetrakis[3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate], leads to the following properties of said reference composition;

a melt viscosity of about 60,000 mPa.s or less at a temperature of about 120°

C.;

a tan δ

value of about 3.5 or less, wherein tan δ

is defined as the ratio between the loss modulus (G") and the storage modulus (G'"'"') of said composition;

an elastic retention on natural latex rubber (200%) after 4 h at about 40°

C. of about 70% or more; and

a crossover temperature between G'"'"' and G" (tan δ

=1) of about 95°

C. or less,

wherein G" and G'"'"' of said composition are determined on a Rheometrics Mechanical Spectrometer (RDS-II) using 8 mm circular shaped parallel plates with a 2 mm gap distance over a temperature range from about -60°

C. up to about 140°

C. and a frequency of 10 radians/sec.

2. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring and Ball (R&

B) softening point of about 50°

C. to about 150°

C., and is a resin or resin mixture selected from the group consisting of natural, dimerized and polymerized rosins.

3. The hot-melt adhesive composition of claim 2 wherein the tackifying resin is hydrogenated or hydrotreated.

4. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring &

Bell softenting point of about 50°

C. to about 150°

C., and is a resin or resin mixture selected from the group consisting of polyterpene resins.

5. The hot-melt adhesive composition of claim 4 wherein the tackifying resin is hydrogenated or hydrotreated.

6. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring &

Bell softenting point of about 50°

C. to about 150°

C., and is a resin or resin mixture selected from the group consisting of copolymers and terpolymers of natural terpenes.

7. The hot-melt adhesive composition of claim 6 wherein the tackifying resin is hydrogenated or hydrotreated.

8. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring and Ball softening point of about 50°

C. to about 150°

C., and is a resin or resin mixture selected from the group consisting of polar terpene resins.

9. The hot-melt adhesive composition of claim 8 wherein the tackifying resin is hydrogenated or hydrotreated.

10. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring &

Bell softenting point of about 50°

C. to about 150°

C., and is a resin or resin mixture comprising aliphatic petroleum hydrocarbon resins.

11. The hot-melt adhesive composition of claim 10 wherein the tackifying resin is hydrogenated or hydrotreated.

12. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring &

Bell softenting point of about 50°

C. to about 150°

C., and is a resin or resin mixture comprising aromatic petroleum hydrocarbon resins.

13. The hot-melt adhesive composition of claim 12 wherein the tackifying resin is hydrogenated or hydrotreated.

14. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring &

Bell softenting point of about 50°

C. to about 150°

C., and is a resin or resin mixture comprising aliphatic/aromatic petroleum derived hydrocarbon resins.

15. The hot-melt adhesive composition of claim 14 wherein the tackifying resin is hydrogenated or hydrotreated.

16. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) has a Ring and Ball softening point of about 50°

C. to about 150°

C., and is a resin or resin mixture comprising polar aliphatic and/or aromatic petroleum hydrocarbon resins.

17. The hot-melt adhesive composition of claim 16 wherein the tackifying resin is hydrogenated or hydrotreated.

18. The hot-melt adhesive composition of claim 1 wherein the tackifying resin (b) is a partially hydrogenated aromatic hydrocarbon resin having the following properties:

(i) a Ring &

Bell softening point of about 50°

C. to about 150°

C.;

(ii) a mixed methylcyclohexane aniline cloudpoint (MMAP) of about 10°

C. to about 75°

C.;

(iii) a Di-Acetone Alcohol cloudpoint (DACP) of about 35°

C. or less;

(iv) a z-average molecular weight (Mz) of about 10,000 Dalton or less; and

(v) a UV absorbance at 268 nm (UV alpha) ranging from about 2.0 to about 5.0.

19. The hot-melt adhesive composition of claim 18 wherein the tackifying resin (b) is a partially hydrogenated aromatic C9 hydrocarbon resin having the following properties:

space="preserve" listing-type="tabular">______________________________________ Ring and Ball softening point (°

C.) 100 ±

5°

C. MMAP (°

C.) 52 ±

5°

C. DACP (°

C.) 2 ±

5°

C. UV-alpha 268 nm 2.9 ±

0.2 Mz (Dalton) 1,500 ±

30. ______________________________________

20. The hot-melt adhesive composition of claim 1 characterized in that the styrenic block copolymer (a) is selected from

(a'"'"') copolymers wherein the respective monomeric moieties are arranged in an alternating sequence having the general sequence of A-B-A or A-B-A-B-A.-B-;

and/or

(a") teleblock copolymers wherein at least three branches radially extend outwardly from a central hub, and wherein each of the branches have terminal blocks "A" and an elastomeric segment "B" in the center;

wherein "A" represents a non-elastomeric block selected from the group consisting of polystyrene, homopolymers or copolymers of vinyl monomers, alpha olefins, alkylene oxides, acetals and urethanes and "B" represents an unvulcanized elastomeric block selected from the group consisting of isoprene, butadiene, vinyl isoprene or vinyl butadiene, and hydrogenated versions thereof.

21. The hot-melt adhesive composition of claim 20 wherein the tackifying resin (b) is a partially hydrogenated aromatic hydrocarbon resin having the following properties:

(i) a Ring &

Bell softening point of about 50°

C. to about 150°

C.;

(ii) a mixed methylcyclohexane aniline cloudpoint (MMAP) of about 10°

C. to about 75°

C.;

(iii) a Di-Acetone Alcohol cloudpoint (DACP) of about 35°

C. or less;

(iv) a z-average molecular weight (Mz) of about 10,000 Dalton or less; and

(v) a UV absorbance at 268 nm (UV alpha) ranging from about 2.0 to about 5.0.

22. The hot-melt adhesive composition of claim 1 which further includes >

0 to about 150 parts by weight of (c) a plasticizing oil.

23. The hot-melt adhesive composition of claim 22 wherein the plasticizing oil (c) is selected from the group consisting of naphthenic/paraffinic oils, olefinic oligomers, low molecular weight polymers, vegetable and animal oils including glycerol esters of fatty acids and polymerization products thereof, liquid resins and hydrogenated versions of these compounds.

24. The hot-melt adhesive composition of claim 1 which further includes >

0 to about 4 parts by weight of (d) a stabilizer.

25. The hot-melt adhesive composition of claim 1 which further includes 100 or less parts by weight of (e) a viscosity modifying aromatic resin having the following properties:

an Ring &

Bell softening point of 50°

C. to 150°

C.;

an MMAP cloudpoint of 20°

C. or less

a DACP cloudpoint of 0°

C. or less, and

an Mz value of 15,000 Dalton or less.

26. The hot-melt adhesive composition according to claim 25 wherein the viscosity modifying aromatic resin (e) is selected from the group consisting of:

(e'"'"') aromatic petroleum hydrocarbons; and

(e") polar aromatic petroleum hydrocarbon resins, including copolymers and terpolymers of aromatic petroleum hydrocarbon resins with vinyl monomers and/or acrylic monomers, and mixtures thereof.

27. The hot-melt adhesive composition according to claim 26 wherein the viscosity modifying aromatic resin (e) is selected from the group consisting of copolymers and terpolymers of styrene, vinyl toluene and (alpha)-methyl-styrene.

28. A partially hydrogenated hydrocarbon resin having the following properties:

(a) a Ring &

Bell softening point of about 50°

C. to about 150°

C.;

(b) a mixed methylcyclohexane aniline cloudpoint (MMAP) of about 10°

C. to about 75°

C.;

(c) a Di-Acetone Alcohol cloudpoint (DACP) of about 35°

C. or less;

(d) a z-average molecular weight (Mz) of about 10,000 Dalton or less; and

(e) a UV absorbance at 268 nm ranging from about 2.0 to about 5.0.

29. The resin according to claim 28 wherein the Ring &

Bell value ranges from about 60°

C. to about 140°

C., the MMAP ranges from about 20°

C. to about 70°

C., the DACP is about 25°

C. or less;

the Mz is about 5,000 Dalton or less, and the UV absorbance at 268 nm is about 2.7 to about 3.1.

30. The resin of claim 28 wherein the R&

B value ranges from 75°

C. to 135°

C.;

the DACP is 15°

C. or less and the Mz is 3,000 Dalton or less.

31. The resin according to claim 28 which is a partially hydrogenated aromatic C9 hydrocarbon resin having the following properties:

space="preserve" listing-type="tabular">______________________________________ Ring and Ball softening point (°

C.) 100 ±

5°

C. MMAP (°

C.) 52 ±

5°

C. DACP (°

C.) 2 ±

5°

C. UV-alpha 268 nm 2.9 ±

0.2 Mz (Dalton) 1,500 ±

30%. ______________________________________

32. A process for preparing a partially hydrogenated hydrocarbon resin comprising the following steps:

(a) providing an unsaturated aromatic feedstream predominantly containing monomers having about 7 to about 10 carbon atoms;

(b) polymerizing the unsaturated aromatic feedstream through Friedel-Crafts polymerization to form a polymerized feedstream; and

(c) partially hydrogenating the polymerized feedstream to produce a partially hydrogenated hydrocarbon resin wherein the partially hydrogenated hydrocarbon resin has the following properties;

(i) a Ring and Ball softening point of about 50°

C. to about 150°

C.;

(ii) a mixed methylcyclohexane aniline cloudpoint (MMAP) of about 10°

C. to about 75°

C.;

(iii) a Di-Acetone Alcohol cloudpoint (DACP) of about 35°

C. or less;

(iv) a z-average molecular weight (Mz) of about 10,000 Dalton or less; and

(v) a UV absorbance at 268 nm ranging from about 2.0 to about 5.0.

33. The process for preparing a partially hydrogenated hydrocarbon resin of claim 32 further comprising the step of:

(d) stripping the partially hydrogenated polymerized feedstream to adjust the Ring &

Bell softening point of the partially hydrogenated hydrocarbon resin.