Carboxylic acid modified nitrile based copolymer latex, method for preparing the copolymer latex, latex composition for dip-forming comprising the copolymer latex and article formed by the composition

Patent metadata

Field	Value
Publication number	US-11466112-B2
Application number	US-201816481884-A
Country	US
Kind code	B2
Filing date	Dec 5, 2018
Priority date	Dec 7, 2017
Publication date	Oct 11, 2022
Grant date	Oct 11, 2022

Abstract

Provided is a carboxylic acid-modified nitrile-based copolymer latex, and more particularly, provided are a carboxylic acid-modified nitrile-based copolymer latex which includes a carboxylic acid-modified nitrile-based copolymer including a monomer-derived repeating unit; and a repeating unit derived from a monomer represented by Chemical Formula 1 below, the monomer-derived repeating unit including a conjugated diene-based monomer-derived repeating unit, an ethylenically unsaturated nitrile-based monomer-derived repeating unit, and an ethylenically unsaturated acid monomer-derived repeating unit (see description of the present invention), a method for preparing a carboxylic acid-modified nitrile-based copolymer latex, a latex composition for dip-forming including the copolymer latex, and an article formed by the composition.

First claim

The invention claimed is:

1. A carboxylic acid-modified nitrile-based copolymer latex comprising:
a carboxylic acid-modified nitrile-based copolymer including a monomer-derived repeating unit; and a repeating unit derived from a monomer represented by Chemical Formula 1 below,
the monomer-derived repeating unit including a conjugated diene-based monomer-derived repeating unit, an ethylenically unsaturated nitrile-based monomer-derived repeating unit, and an ethylenically unsaturated acid monomer-derived repeating unit:

wherein,
R 1 is a hydroxyl group or a mercapto group,
R 2 is a C1-C10 alkylene group,
A is an unsaturated group, and
n is an integer selected from 1 to 5.

2. The carboxylic acid-modified nitrile-based copolymer latex of claim 1 , wherein R 1 is a hydroxyl group, R 2 is a C1-C5 alkylene group, A is a (meth)acrylamide group or an allyl amide group, and n is an integer selected from 2 to 3.

3. The carboxylic acid-modified nitrile-based copolymer latex of claim 1 , wherein the monomer represented by Chemical Formula 1 is represented by Chemical Formula 2 below:

wherein,
R 1 is a hydroxy group or a mercapto group,
R 2 is a C1-C10 alkylene group,
R 3 and R 4 are each independently hydrogen, a C1-C10 alkyl group, or an amine group,
Z is a carbon atom or a nitrogen atom, wherein when Z is the carbon atom, at least one of R 3 and R 4 is necessarily an amine group, and when Z is the nitrogen atom, R 3 is not present,
X is a vinyl group, an allyl group or a 2-isopropenyl group, and
n is an integer selected from 1 to 5.

4. The carboxylic acid-modified nitrile-based copolymer latex of claim 1 , wherein the monomer represented by Chemical Formula 1 comprises dopamine (meth)acrylamide, N-(3,4-dihydroxyphenethyl)acrylamide, or dopamine allylamide.

5. The carboxylic acid-modified nitrile-based copolymer latex of claim 1 , wherein an amount of the repeating unit derived from the monomer represented by Chemical Formula 1 is 0.5 to 5 parts by weight based on 100 parts by weight of a total amount of the monomer-derived repeating unit.

6. A method for preparing a carboxylic acid-modified nitrile-based copolymer latex, comprising:
adding and polymerizing a monomer including a conjugated diene-based monomer, an ethylenically unsaturated nitrile-based monomer, and an ethylenically unsaturated acid monomer; and a monomer represented by Chemical Formula 1 below or a polymer including a repeating unit derived from the monomer represented by Chemical Formula 1 below:

wherein,
R 1 is a hydroxy group or a mercapto group, R 2 is a C1-C10 alkylene group,
A is an unsaturated group, and n is an integer selected from 1 to 5.

7. The method of claim 6 , wherein:
(i) an entire amount of each of the conjugated diene-based monomer, the ethylenically unsaturated nitrile-based monomer, the ethylenically unsaturated acid monomer, the monomer represented by Chemical Formula 1, and the polymer including the repeating unit derived from the monomer represented by Chemical Formula 1 is independently added before the polymerization is initiated; or
(ii) a part thereof is added before the polymerization is initiated and a remaining amount thereof is added at a polymerization conversion rate of 10% to 50% after the polymerization is initiated; or
(iii) the entire amount thereof is added at the polymerization conversion rate of 10% to 50% after the polymerization is initiated.

8. The method of claim 7 , wherein at the time of the polymerization of step (S10), the monomer including the conjugated diene-based monomer, the ethylenically unsaturated nitrile-based monomer, and the ethylenically unsaturated acid monomer is added with an entire amount before the polymerization is initiated; and the monomer represented by Chemical Formula 1, or the polymer including the repeating unit derived from the monomer represented by Chemical Formula 1 is added with the entire amount at the polymerization conversion rate of 10% to 50% after the polymerization is initiated.

9. The method of claim 6 , wherein the polymer including the repeating unit derived from the monomer represented by Chemical Formula 1 has a weight average molecular weight of 100 g/mol to 200,000 g/mol.

10. A latex composition for dip-forming comprising:
the carboxylic acid-modified nitrile-based copolymer latex of claim 1 ; and a polyvalent metal cation compound.

11. The latex composition for dip-forming of claim 10 , wherein the polyvalent metal cation compound comprises aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum lactate, or aluminum acetylacetonate.

12. The latex composition for dip-forming of claim 10 , wherein an amount of the polyvalent metal cation compound is 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the carboxylic acid-modified nitrile-based copolymer latex based on solid content.

13. An article comprising:
a layer derived from the latex composition for dip-forming of claim 10 .

Assignees

• Lg Chemical Ltd

Inventors

• Kim Ji Hyun
• Kim Jung Eun
• Jung Yong Seok

Classifications

• C08K5/098

  Metal salts of carboxylic acids · CPC title

• C08K2003/164

  Aluminum halide, e.g. aluminium chloride · CPC title

• C08K2003/2227

  of aluminium · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title

• C08F236/12 Primary

  with nitriles · CPC title