Modified propylene-(α-olefin) copolymer, method for producing same, coating material comprising same, resin composition for molding use, and hot-melt composition

Patent metadata

Field	Value
Publication number	US-10072116-B2
Application number	US-201415034136-A
Country	US
Kind code	B2
Filing date	Nov 5, 2014
Priority date	Nov 5, 2013
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

The purpose of the present invention is to provide a polar-group-containing propylene-type wax having excellent properties including a low melting point. A modified propylene-(α-olefin) copolymer (A) according to the present invention is produced by grafting at least one compound selected from an unsaturated carboxylic acid, a derivative of the unsaturated carboxylic acid and an unsaturated sulfonic acid salt onto a propylene-(α-olefin) copolymer (A1) and has an acid value of 1 to 100 KOHmg/g, wherein the propylene-(α-olefin) copolymer (A1) comprises 60 to 95 mol % of a propylene-derived constituent unit (a) and 5 to 40 mol % of a constituent unit (b) derived from an α-olefin having 4 or more carbon atoms, and satisfies the specific requirements (i) to (iii).

First claim

The invention claimed is:

1. A modified propylene-α-olefin copolymer (A) having an acid value of 0.5 to 100 KOHmg/g obtained by grafting at least one selected from unsaturated carboxylic acids and derivatives thereof and unsaturated sulfonic acids and salts thereof onto a propylene-α-olefin copolymer (A1),
wherein the propylene-α-olefin copolymer (A1) contains 60 to 95 mol % of a propylene-derived constitutional unit (a) and 5 to 40 mol % of a C 4+ α-olefin-derived constitutional unit (b), a total amount of the constitutional unit (a) and the constitutional unit (b) being 100 mol %, and the propylene-α-olefin copolymer (A1) satisfies all of requirements below (i) to (iv):
(i) a weight average molecular weight (Mw) measured by GPC of 3,000 to 40,000;
(ii) a melting point (Tm) measured by DSC of 60 to 110° C.;
(iii) a half width of a crystalline melting point peak measured by the DSC of 1 to 20° C.; and
(iv) a number of vinylidene groups per 1,000 carbon atoms measured by 1 H-NMIR of 0.5 to 5; and
wherein a crystallization temperature ratio Tc(A1)/Tc(A) is 1.0 to 1.6, the Tc(A) being a crystallization temperature (° C.) of the modified propylene-α-olefin copolymer (A) and the Tc(A1) being a crystallization temperature (° C.) of the propylene-α-olefin copolymer (A1).

2. The modified propylene-α-olefin copolymer (A) according to claim 1 , wherein the propylene-α-olefin copolymer (A1) is obtained by thermally decomposing a propylene-C 4+ α-olefin copolymer (A2).

3. The modified propylene-α-olefin copolymer (A) according to claim 2 , wherein the propylene-C 4+ α-olefin copolymer (A2) contains 60 to 95 mol % of a propylene-derived constitutional unit (a′) and 5 to 40 mol % of a C 4+ α-olefin-derived constitutional unit (b′), wherein a total amount of the constitutional unit (a′) and the constitutional unit (b′) is 100 mol %, and satisfies all of requirements below (i′) to (iii′):
(i′) a weight average molecular weight (Mw) measured by the GPC of 50,000 to 1,000,000;
(ii′) a melting point (Tm) measured by the DSC of 60 to 120° C.; and
(iii′) a half width of a crystalline melting point peak measured by the DSC of 1 to 20° C.

4. The modified propylene-α-olefin copolymer (A) according to claim 1 , wherein the propylene-α-olefin copolymer (A1) further satisfies requirement below (v):
(v) a ΔH of a melting peak measured by the DSC of 40 to 100 J/g.

5. A method for producing a modified propylene-α-olefin copolymer (A) comprising:
thermally decomposing a propylene-C4+ α-olefin copolymer (A2) to obtain a propylene-α-olefin copolymer (A1) containing 60 to 95 mol % of a propylene-derived constitutional unit (a) and 5 to 40 mol % of a C4+ α-olefin-derived constitutional unit (b), wherein a total amount of the constitutional unit (a) and the constitutional unit (b) is 100 mol %, and satisfying all of requirements below (i) to (iv):
(i) a weight average molecular weight (mw) measured by GPC of 3,000 to 40,000;
(ii) a melting point (Tm) measured by DSC of 60 to 110° C.;
(iii) a half width of a crystalline melting point peak measured by the DSC of 1 to 20° C.; and
(iv) a number of vinylidene groups per 1,000 carbon atoms measured by 1 H-NMR of 0.5 to 5; and
graft polymerizing at least one selected from unsaturated carboxylic acids and derivatives thereof and unsaturated sulfonic acids and salts thereof onto the propylene-α-olefin copolymer (A1) to obtain a modified propylene-α-olefin copolymer (A) having an acid value of 0.5 to 100 KOHmg/g, and
wherein a crystallization temperature ratio Tc(A1)/Tc(A) is 1.0 to 1.6, Tc(A) being a crystallization temperature (° C.) of the modified propylene-α-olefin copolymer (A) and Tc(A1) being a crystallization temperature (° C.) of the propylene-α-olefin copolymer (A1).

6. The method for producing a modified propylene-α-olefin copolymer (A) according to claim 5 , wherein the propylene-α-olefin copolymer (A1) is obtained by thermally decomposing the propylene-C 4+ α-olefin copolymer (A2) at 300 to 450° C. for 5 minutes to 10 hours.

7. The method for producing a modified propylene-α-olefin copolymer (A) according to claim 5 , wherein the propylene-C 4+ α-olefin copolymer (A2) contains 60 to 95 mol % of a propylene-derived constitutional unit (a′) and 5 to 40 mol % of a C 4+ α-olefin-derived constitutional unit (b′), wherein a total amount of the constitutional unit (a′) and the constitutional unit (b′) is 100 mol %, and satisfies all of requirements below (i′) to (iii′):
(i′) a weight average molecular weight (Mw) measured by the GPC of 50,000 to 1,000,000;
(ii′) a melting point (Tm) measured by the DSC of 60 to 120° C.; and
(iii′) a half width of a crystalline melting point peak measured by the DSC of 1 to 20° C.

8. A resin composition comprising the modified propylene-α-olefin copolymer (A) according to claim 1 , and a second resin (B1),
wherein a weight ratio between the modified propylene-α-olefin copolymer (A) and the second resin (B1) is 1/99 to 90/10.

9. A coating material comprising 100 parts by weight of water or an organic solvent, and 0.1 to 100 parts by weight of the modified propylene-α-olefin copolymer (A) according to claim 1 dissolved or dispersed in the water or the organic solvent.

10. A coating material comprising 100 parts by weight of water or an organic solvent, and 0.1 to 100 parts by weight in total of the modified propylene-α-olefin copolymer (A) according to claim 1 and a second resin (B1) dissolved or dispersed in the water or the organic solvent,
wherein a weight ratio between the modified propylene-α-olefin copolymer (A) and the second resin (B1) is 1/99 to 90/10.

11. The coating material according to claim 9 , wherein the organic solvent has a solubility parameter value in a range of 7 to 12 (cal/cm 3 ) 1/2 .

12. The coating material according to claim 9 , wherein the organic solvent contains at least one selected from hydrocarbon-based solvents, alcohol-based solvents and ester-based solvents.

13. The coating material according to claim 9 , wherein the modified propylene-α-olefin copolymer (A) is completely dissolved in the organic solvent at a temperature of 50° C. or more.

14. A moldable resin composition comprising:
100 to 50 parts by weight of at least one resin (B2) selected from the group consisting of thermoplastic resins and thermosetting resins;
0 to 50 parts by weight of an inorganic reinforcing material (C), wherein a total amount of the resin (B2) and the reinforcing material (C) is 100 parts by weight; and
0.01 to 10 parts by weight of the modified propylene-α-olefin copolymer (A) according to claim 1 .

15. A hot melt composition comprising:
100 parts by weight of a base polymer (B3);
10 to 300 parts by weight of a tackifier (D); and
1 to 100 parts by weight of the modified propylene-α-olefin copolymer (A) according to claim 1 .

16. A paint comprising the modified propylene-α-olefin copolymer (A) according to claim 1 , or the modified propylene-α-olefin copolymer (A) according to claim 1 and a second resin (B1).

17. A primer comprising the modified propylene-α-olefin copolymer (A) according to claim 1 , or the modified propylene-α-olefin copolymer (A) according to claim 1 and a second resin (B1).

18. An adhesive comprising the modified propylene-α-olefin copolymer (A) according to claim 1 , or the modified propylene-α-olefin copolymer (A) according to claim 1 and a second resin (B1).

19. A pressure-sensitive adhesive comprising the modified propylene-α-olefin copolymer (A) according to claim 1 , or the modified propylene-α-olefin

Assignees

• Mitsui Chemicals Inc

Inventors

• Kawabe Kuniaki
• Kanaya Hirotaka
• Tanaka Masakazu
• Ito Toshiyuki
• Yoshida Masako

Classifications

• C09D151/06

  grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond · CPC title

• C09D123/26

  modified by chemical after-treatment · CPC title

• C08F255/08

  on to polymers of olefins having four or more carbon atoms · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F210/06 Primary

  Propene · CPC title