Thermosetting compositions, methods of coating and coated articles

• US 5,660,937 A
• Filed: 03/09/1995
• Issued: 08/26/1997
• Est. Priority Date: 04/10/1990
• Status: Expired due to Term

• Current Assignee: Nippon Oil and Fats Co., Ltd.
• Original Assignee: Nippon Oil and Fats Co., Ltd.
• Inventors: Ishidoya, Masahiro, Shibamoto, Kenji, Mashita, Mitsuyuki, Ohe, Osamu, Shibato, Kishio, Komoto, Keiji
• Primary Examiner(s): DUDASH, DIANA L
• Application Number:
  US08/401,368
• Time in Patent Office: 901 Days
• Field of Search: 427/407.1, 427/409, 427/385.5, 427/386, 427/387, 525/119, 525/124, 525/127, 525/167, 525/175, 525/176, 525/206, 525/208, 525/209, 525/212, 525/217, 525/210, 525/221, 525/223, 525/329.5, 525/329.7, 525/312, 525/438 , 525/439, 525/440, 525/444, 525/437, 525/15, 525/28, 428/423.1, 428/520, 428/463, 428/482, 428/483, 528/363, 524/512
• US Class Current: 428/423.1
• CPC Class Codes: C08L 101/02 characterised by the presence of specified groups , e.g. terminal or pendant functional groups
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 133/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 167/00 Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09D177/12; based on polyester-imides C09D179/08; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 201/02 characterised by the presence of specified groups , e.g. terminal or pendant functional groups
• CPC Class Codes: C09J 167/00 Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain based on polyester-amides C09J177/12; based on polyester-imides C09J179/08; Adhesives based on derivatives of such polymers
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31518 Next to glass or quartz
• CPC Class Codes: Y10T 428/31529 Next to metal
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31699 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31794 Of cross-linked polyester
• CPC Class Codes: Y10T 428/31797 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer

Abstract

Thermosetting composition comprises a compound having in the molecule two or more carboxyl groups blocked by a vinyl ether compound, a vinyl thioether compound or a hetero compound having a vinyl type double bond and oxygen or sulfur as the hetero atom, a compound having two or more reactive functional groups which can form a chemical bond with the blocked carboxyl compound by heating, a specific vinyl ether or vinyl thioether and a thermal latent acid catalyst. The blocked carboxyl group of the first compound and the reactive functional group of the second compound may be comprised in the same molecule. The thermosetting composition gives cured products having excellent chemical properties, physical properties, weathering resistance and storage stability and is advantageously utilized for coating compositions, ink, adhesive and molded plastics.

Claims

1. A thermosetting composition which comprises:

(A) a compound having in the molecule two or more functional groups of the formula (1);

##STR13## wherein R¹, R² and R³ are respectively selected from the group consisting of a hydrogen atom and an organic group of 1 to 18 carbon atoms, R⁴ is an organic group of 1 to 18 carbon atoms, Y¹ is selected from the group consisting of an oxygen atom and a sulfur atom, or R³ and R⁴ are bonded with each other to form a heterocyclic structure which comprises Y¹ as a hetero atom component;

(B) a compound having in the molecule two or more reactive functional groups which can form chemical bonds with the functional groups of the compound (A) by heating, wherein the reactive functional groups of the compound (B) are groups of at least one kind selected from the group consisting of an epoxy group, an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, an aminomethylol group, an alkylated aminomethylol group, an acetal group and a ketal group, a ratio of the functional groups of the formula (1) of compound (A) and the reactive functional groups of the compound (B) being 0.2;

1.0 to 1.0;

0.2;

(E) a compound of the formula (2) ##STR14## wherein R¹, R², R³, R⁴ and Y¹ have the same meanings as in the compound (A), said compound (E) being in an amount of 0.1 to 20 weight % based on the amount of the thermosetting composition; and

,

optionally, (C) a thermal latent acid catalyst which is activated during curing of the composition by heating, said thermal latent acid catalyst being in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of a total solid content, which is the sum of the compound (A) and the compound (B).

2. The thermosetting composition as claimed in claim 1, which further contains 0.1 weight % or more of water.

3. The thermosetting composition as claimed in claim 1, which contain the thermal latent acid catalyst (C) and wherein the thermal latent acid catalyst (C) is at least one kind selected from the group consisting of a compound prepared by neutralizing a Br.o slashed.nsted acid or a Lewis acid with a Lewis base, a complex compound formed from a Lewis acid and a Br.o slashed.nsted acid, a complex compound formed from a Lewis acid and a Br.o slashed.nsted salt, an ester of a sulfonic acid, an ester of phosphoric acid and an onium compound.

4. The thermosetting composition as claimed in claim 1, wherein the compound (A) and/or the compound (B) are polymers of α

,β

-unsaturated compounds.

5. The thermosetting composition as claimed in claim 1, wherein the compound (A) and/or the compound (B) are polyester resins.

7. A method of coating which comprises coating a substrate with a composite coating layer by forming a base coat on the substrate with a composition forming a colored film, followed by forming a clear top coat on the base coat with a composition forming a clear film, the composition forming a clear film alone or both of the composition forming a clear film and the composition forming a colored film comprising the thermosetting composition claimed in claim 1.

10. The thermosetting composition as claimed in claim 1, wherein the thermal latent acid catalyst is present in an amount of 0.01 to 10 weight parts per 100 weight parts of a total solid component comprising the compound (A) and the compound (B).

11. A method of coating which comprises coating a substrate with a top coating material and the thermosetting composition claimed in claim 3, the top coating material optionally containing at least one pigment in an amount of 0 to 100 weight parts based on 100 weight parts of the thermosetting composition.

12. A method of coating which comprises coating a substrate with a composite coating layer by forming a base coat on the substrate with a composition forming a colored film, followed by forming a clear top coat on the base coat with a composition forming a clear film, the composition forming a clear film and the composition forming a colored film each comprising the thermosetting composition claimed in claim 3.

15. An article coated by the method of coating claimed in claim 7.

16. An article coated by the method of coating claimed in claim 11.

17. An article coated by the method of coating claimed in claim 12.

20. The thermosetting composition as claimed in claim 1, wherein said (E) is selected from the group consisting of methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, methyl vinyl thioether, ethyl vinyl thioether, isopropyl vinyl thioether, n-propyl vinyl thioether, n-butyl vinyl thioether, isobutyl vinyl thioether, 2-ethylhexyl vinyl thioether, cyclohexyl vinyl thioether, 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, sodium 3,4-dihydro-2H-pyran-2-carboxylate, 2,3-dihydrothiophene, 3,4-dihydrothiophene, 2,3-dihydro-2H-thiopyran, 3,4-dihydro-2H-thiopyran, 3,4-dihydro-2-methoxy-2H-thiopyran, 3,4-dihydro-4,4-dimethyl-2H-thiopyran-2-one, 3,4-dihydro-2-ethoxy-2H-thiopyran and sodium 3,4-dihydro-2H-thiopyran-2-carboxylate.

21. The thermosetting composition as claimed in claim 1, wherein compound (A) is a compound prepared by the half-esterification of (i) a polyol having two or more hydroxyl groups in the molecule and (ii) an acid anhydride;

and compound (B) is an acrylic resin having two or more epoxy groups in the molecule.

6. A method of coating which comprises coating a substrate with a top coating material and the thermosetting composition claimed in claim i, the top coating material optionally containing pigments, the amount of the pigments being 0 to 100 weight parts based on 100 weight parts of the thermosetting composition.

8. An article coated by the method of coating claimed in claim 6.

9. The thermosetting composition as claimed in 1, wherein the compound (A) is a thermal latent carboxyl compound prepared by a reaction of a polycarboxyl compound prepared by a half-esterification of a polyol having two or more hydroxyl groups in the molecule and an acid anhydride with a vinyl ether compound, whereby the carboxyl group is transformed into the functional group of the formula (1), and the compound (E) is mixed together with the compound (A).

13. A method of coating which comprises coating a substrate with a top coating material and the thermosetting composition claimed in claim 9, the top coating material optionally containing at least one pigment in an amount of 0 to 100 weight parts based on 100 weight parts of the thermosetting composition.

14. A method of coating which comprises coating a substrate with a composite coating layer by forming a base coat on the substrate with a composition forming a colored film, followed by forming a clear top coat on the base coat with a composition forming a clear film, the composition forming a clear film and the composition forming a colored film each comprising the thermosetting composition claimed in claim 9.

18. An article coated by the method of coating claimed in claim 13.

19. An article coated by the method of coating claimed in claim 14.