Granted Patent B2

US 9,580,632 · App. 14/647,183 · Granted Feb 28, 2017

Abstract

Claims (69)

1. An adhesive composition for a protective film on a painting, comprising:

100 weight parts of block copolymer having the formula of S-EB-S or (S-EB)nX; and

1 to 20 weight parts of a polar tackifier resin compound,

wherein the adhesive composition is substantially free of a plasticizer oil,

wherein each S of the formula is independently a polymer block of predominantly styrene, EB is a hydrogenated polymer block of predominantly butadiene, n is an integer equal to or greater than 2, and X is the residue of a coupling agent,

wherein the block copolymer includes 13 to 21 wt % of poly(styrene) content,

wherein the EB block of the block copolymer has hydrogenation degree of at least 80%,

wherein the poly(butadiene) block precursor of the block copolymer has a vinyl content in the range of from 60 to 85 mol %,

wherein the polar tackifier resin compound has a solubility parameter (SP value) of 8.2 to 9.2 calculated by the Small method using Hoy's constant,

wherein the polar tackifier resin compound is selected from the group consisting of terpene resin, terpene phenol resin, hydrogenated terpene resin, aromatic-modified terpene resin, and aliphatic cyclic partially saturated hydrocarbon compounds, and

wherein the tackifier resin compound has a softening point equal to or greater than 110° C. as determined by the Ring and Ball method (ASTM E-28).

2. The adhesive composition according to claim 1 , comprising 1 to 15 weight parts of the tackifier resin compound.

3. The adhesive composition according to claim 2 , comprising 1 to 10 weight parts of the tackifier resin compound.

4. The adhesive composition according to claim 1 , wherein the SP value of the polar tackifier resin compound is in the range of 8.5 to 9.1.

5. The adhesive composition according to claim 4 , wherein the SP value of the polar tackifier resin compound is in the range of 8.8 to 9.1.

6. The adhesive composition according to claim 1 , comprising 1 to 5 weight parts of the tackifier resin compound.

7. The adhesive composition according to claim 1 , wherein the tackifier resin compound has a softening point equal to or greater than 130° C.

8. The adhesive composition according to any one of claims 1 to 7 , wherein the tackifier resin compound is cyclic.

9. The adhesive composition according to claim 8 , wherein the tackifier resin compound has an aromatic moiety.

10. The adhesive composition according to claim 9 , wherein the tackifier resin A compound is selected from the group consisting of terpene resin, terpene phenol resin, hydrogenated terpene resin, and aromatic-modified terpene resin.

11. The adhesive composition according to claim 1 , wherein the tackifier resin compound is terpene phenol resin.

12. The adhesive composition according to claim 1 , wherein the tackifier resin compound is an aliphatic cyclic partially-saturated hydrocarbon compound.

13. The adhesive composition according to claim 1 , wherein the block copolymer has poly(styrene) end block content of 13 to 21 wt %.

14. The adhesive composition according to claim 1 , wherein the block copolymer has a nominal molecular weight of equal to or greater than 100,000 g/mol as styrene equivalent peak molecular weight according to ASTM 3536.

15. The adhesive composition according to claim 1 , wherein the poly(styrene) end block of the block copolymer has a molecular weight of equal to or greater than 5,000 g/mol as styrene equivalent peak molecular weight according to ASTM 3536.

16. The adhesive composition according to claim 15 , wherein the poly(styrene) end block of the block copolymer has a molecular weight of 5,000 to 12,000 g/mol as styrene equivalent peak molecular weight according to ASTM 3536.

17. The adhesive composition according to claim 1 , wherein the coupling efficiency of the block copolymer is equal to or more than 95%.

18. The adhesive composition according to claim 1 , further comprising up to 5 weight parts of an antioxidant.

19. A protective film configured to stick on a painting, comprising:

a base material; and

the adhesive composition according to claim 1 .

20. A protective film configured to stick on a painting, comprising:

a base layer; and

an adhesive layer including an adhesive composition, the adhesive composition including:

100 weight parts of block copolymer having the formula of S-EB-S or (S-EB)nX; and

1 to 20 weight parts of a polar tackifier resin compound,

wherein the adhesive composition is substantially free of a plasticizer oil,

wherein each S of the formula is independently a polymer block of predominantly styrene, EB is a hydrogenated polymer block of predominantly butadiene, n is an integer equal to or greater than 2, and X is the residue of a coupling agent,

wherein the block copolymer includes 13 to 21 wt % of poly(styrene) content,

wherein the EB block of the block copolymer has hydrogenation degree of at least 80%,

wherein the poly(butadiene) block precursor of the block copolymer has a vinyl content in the range of from 60 to 85 mol %,

wherein the polar tackifier resin compound has a solubility parameter (SP value) of 8.2 to 9.2 calculated by the Small method using Hoy's constant,

wherein the polar tackifier resin compound is selected from the group consisting of terpene resin, terpene phenol resin, hydrogenated terpene resin, aromatic-modified terpene resin, and aliphatic cyclic partially saturated hydrocarbon compounds, and

wherein the tackifier resin compound has a softening point equal to or greater than 110° C. as determined by the Ring and Ball method (ASTM E-28).

21. The protective film according to claim 19 or 20 , wherein the film is prepared by a co-extrusion.

22. The protective film according to claim 20 , wherein the film is prepared by solvent coating.

23. An article having a painting protected by the protective film according to claim 20 .

24. The article according to claim 23 , wherein the article is an automobile.

25. A process for manufacturing an adhesive composition in a form of pellet for a protective film on a painting, the process comprising the steps of:

dry-blending 100 weight parts of a block copolymer having the formula of S-EB-S or (S-EB)nX with 1 to 20 weight parts of a polar tackifier resin compound to obtain a dry-blend without substantially using a plasticizer oil;

extruding the dry-blend in an extruder to obtain an extrudate;

pelletizing the extrudate with an underwater pelletizer to obtain wet pellets; and

drying the wet pellets to obtain pellets containing the adhesive composition,

wherein the adhesive composition is substantially free of a plasticizer oil,

wherein each S of the formula is independently a polymer block of predominantly styrene, EB is a hydrogenated polymer block of predominantly butadiene, n is an integer equal to or greater than 2, and X is the residue of a coupling agent,

wherein the block copolymer includes 13 to 21 wt % of poly(styrene) content,

wherein the EB block of the block copolymer has hydrogenation degree of at least 80%,

wherein the poly(butadiene) block precursor of the block copolymer has a vinyl content in the range of from 60 to 85 mol %,

wherein the polar tackifier resin compound has a solubility parameter (SP value) of 8.2 to 9.2 calculated by the Small method using Hoy's constant,

wherein the polar tackifier resin compound is selected from the group consisting of terpene resin, terpene phenol resin, hydrogenated terpene resin, aromatic-modified terpene resin, and aliphatic cyclic partially saturated hydrocarbon compounds, and

wherein the tackifier resin compound has a softening point equal to or greater than 110° C. as determined by the Ring and Ball method (ASTM E-28).

26. The process according to claim 25 , further comprising the step of:

treating the wet or dry pellets with a dusting agent in an amount of 0.1 to 10% by weight of the total composition.

27. A method for preventing a surface pollution on a painting, comprising the steps of:

providing an article having a painting;

providing a sheet having a base layer;

forming an adhesive layer on the base layer by applying on the base layer the adhesive composition according to any one of claims 1 - 9 , 10 , 11 , and 12 - 26 ; and

pasting the sheet onto the painting.

28. The method according to claim 27 , wherein a surface pollution is prevented for at least seven days at 70° C.

Assignments (13)