Carboxylic acid modified-nitrile based copolymer latex for dip-forming, latex composition for dip-forming comprising the same, and product thereof

• US 9,803,070 B2
• Filed: 11/13/2012
• Issued: 10/31/2017
• Est. Priority Date: 11/22/2011
• Status: Active Grant

• Current Assignee: LG Chem Limited (LG Corporation)
• Original Assignee: LG Chem Limited (LG Corporation)
• Inventors: Yang, Seung Hun, Han, Jung Su, Yeu, Seung Uk, Kim, Byoung Yun, Kim, Jung Eun
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): Grinsted, Ronald
• Application Number:
  US14/353,016
• Publication Number:
  US 20140302265A1
• Time in Patent Office: 1,813 Days
• Field of Search: 428 368
• CPC Class Codes: B29C 41/003 characterised by the choice of material
• CPC Class Codes: B29C 41/14 Dipping a core B29C41/10 takes precedence
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 212/10 with nitriles
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 220/44 Acrylonitrile
• CPC Class Codes: C08F 236/06 Butadiene
• CPC Class Codes: C08F 236/12 with nitriles
• CPC Class Codes: C08F 236/14 containing elements other than carbon and hydrogen
• CPC Class Codes: C08L 25/12 with unsaturated nitriles
• CPC Class Codes: C08L 55/02 ABS [Acrylonitrile-Butadiene-Styrene] polymers
• CPC Class Codes: C08L 9/04 Latex
• CPC Class Codes: C09D 125/12 with unsaturated nitriles
• CPC Class Codes: Y10T 428/1386 Natural or synthetic rubber or rubber-like compound containing
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

Disclosed are a carboxylic acid-modified nitrile copolymer latex for dip molding comprising a combination of a carboxylic acid-modified nitrile copolymer latex and a carboxylic acid-modified styrene copolymer latex, a latex composition for dip molding comprising the same and a molded article prepared therefrom. Molded articles with superior tensile strength are produced by respectively preparing a carboxylic acid-modified nitrile latex having a low glass transition temperature and an average particle diameter of 90 nm or higher, and a carboxylic acid-modified styrene latex having a glass transition temperature of 80° C. or higher and an average particle diameter less than 90 nm and then mixing the two latexes.

Claims

1. A carboxylic acid-modified nitrile copolymer latex for dip molding comprising:

a carboxylic acid-modified nitrile copolymer latex having a glass transition temperature of −

50°

C. to −

15°

C. and an average particle diameter not less than 90 nm and not more than 200 nm; and

a carboxylic acid-modified styrene copolymer latex having a glass transition temperature of 80°

C. or higher and an average particle diameter not less than 15 nm and less than 90 nm,

wherein the carboxylic acid-modified nitrile copolymer latex and the carboxylic acid-modified styrene copolymer latex are present at a weight ratio of 97;

3 to 85;

15, and

wherein the carboxylic acid-modified styrene copolymer latex is polymerized from a monomer mixture comprising 80 to 99% by weight of an aromatic vinyl monomer, 1 to 20% by weight of an ethylenically unsaturated nitrile monomer, and 0.1 to 10% by weight of an ethylenically unsaturated acid monomer.

2. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1, wherein the carboxylic acid-modified nitrile copolymer latex is polymerized from a monomer mixture comprising 40 to 89% by weight of a conjugated diene monomer, 10 to 50% by weight of an ethylenically unsaturated nitrile monomer and 0.1 to 10% by weight of an ethylenically unsaturated acid monomer.

3. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 2, wherein the conjugated diene monomer comprises at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene.

4. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 2, wherein the ethylenically unsaturated nitrile monomer comprises at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α

-chloronitrile and α

-cyanoethylacrylonitrile.

5. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 2, wherein the ethylenically unsaturated acid monomer comprises at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate.

6. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1, wherein the aromatic vinyl monomer comprises at least one selected from the group consisting of styrene and α

-methyl styrene.

7. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1, wherein the ethylenically unsaturated nitrile monomer comprises at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, α

-chloronitrile and α

-cyanoethylacrylonitrile.

8. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1, wherein the ethylenically unsaturated acid monomer comprises at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate.

9. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1, wherein the carboxylic acid-modified nitrile copolymer latex further comprises an ethylenically unsaturated monomer copolymerizable with the monomers constituting the copolymer in an amount of 5% by weight or less, based on the total weight of the copolymer.

10. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 9, wherein the copolymerizable ethylenically unsaturated monomer comprises at least one selected from the group consisting of vinyl aromatic monomers, fluoroalkyl vinyl ethers, ethylenically unsaturated amide monomers, non-conjugated diene monomers and ethylenically unsaturated carboxylic acid ester monomers.

11. The carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1, further comprising 0.3 to 30 parts by weight of an emulsifier, 0.01 to 2 parts by weight of a polymerization initiator, and 0.1 to 2.0 parts by weight of a molecular weight controller, with respect to 100 parts by weight in total constituting the carboxylic acid-modified nitrile copolymer.

12. A latex composition for dip molding comprising the carboxylic acid-modified nitrile copolymer latex for dip molding according to claim 1.

13. The latex composition for dip molding according to claim 12, wherein the carboxylic acid-modified nitrile copolymer latex for dip molding is present in an amount of 80 to 99% by weight in the composition.

14. The latex composition for dip molding according to claim 12, wherein the latex composition comprises at least one additive selected from the group consisting of pigments, vulcanizing agents, fillers, thickeners and pH controllers.

15. A dip-molded article obtained by dip molding the latex composition for dip molding according to claim 12.

16. The dip-molded article according to claim 15, wherein the dip-molded article is a medical examination glove, a condom, a catheter, an industrial glove, a household glove or a health care product.