Method of producing amino acid-modified organopolysiloxane emulsions

1. A method of producing an amino acid-modified organopolysiloxane emulsion, characterized by reacting

(a) a carboxy-unprotected amino acid and

(b) organopolysiloxane that has an epoxy group in the molecule in an aqueous medium in the presence of a surfactant;

wherein the carboxy-unprotected amino acid (a) is a basic amino acid selected from the group consisting of lysine, arginine, and histidine.

2. The method according to claim 1 , wherein the carboxy-unprotected amino acid (a) is arginine as represented by the following formula:

3. The method according to claim 1 , wherein the organopolysiloxane that has an epoxy group in the molecule (b) is organopolysiloxane represented by the following general formula (1):

{wherein

each R 1 independently represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl, unsubstituted or substituted alkoxy, an unsubstituted or substituted polyether group, hydroxyl, -A-NH—B—NH 2 , -A-N(—B—NH 2 ) 2 , or —CH 2 CH 2 Si(CH 3 ) 2 —{OSi(CH 3 ) 2 } t —OSi(CH 3 ) 3 (in these formulas, A and B each independently represent unsubstituted or substituted alkylene or —C u H 2u —O—C v H 2v — (u and v each independently represent an integer in the range from 1 to 5) and t represents an integer in the range from 0 to 500);

Q is a group represented by the following formula:

(wherein a represents an integer in the range from 1 to 20, b represents an integer in the range from 1 to 10, c represents an integer in the range from 0 to 50, and n represents an integer in the range from 1 to 20), or represents a group as defined for R 1 above, with the proviso that all of the Q groups are not R 1 ;

x represents an integer in the range from 1 to 10000; and

y represents an integer in the range from 0 to 1000},

or is represented by the following general formula (2):

(wherein

R 1 and Q are defined as above;

r represents an integer in the range from 1 to 10;

s represents an integer in the range from 1 to 10; and

r +s represents an integer in the range from 3 to 20).

4. The method according to claim 3 , wherein the organopolysiloxane that has an epoxy group in the molecule (b) is organopolysiloxane that has an epoxy group and an ether chain in the molecule and is represented by the following general formula (1′):

{wherein

each R 1′ independently represents unsubstituted or substituted C 1-20 alkyl, unsubstituted or substituted C 6-20 aryl, unsubstituted or substituted C 7-20 aralkyl, or hydroxyl;

Q′ is a group represented by

(wherein

n and a are defined as above,

d represents an integer in the range from 0 to 10, and

e represents an integer in the range from 0 to 10), or represents a group as defined for R 1′ above, with the proviso that all of the Q′ groups are not R 1′ ;

x′ represents an integer in the range from 5 to 1000; and

y′ represents an integer in the range from 0 to 100}.

5. The method according to claim 1 , wherein the surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants, and their mixtures.

6. The method according to claim 1 , wherein the surfactant is selected from the group consisting of nonionic surfactants, cationic surfactants, and their mixtures.

7. An amino acid-modified organopolysiloxane emulsion comprising:

(A) An amino acid-modified organopolysiloxane represented by the following general formula (3′):

{wherein

Z represents an organopolysiloxane residue;

R 2 represents

—CH(COOH)—(CH 2 ) 3 —NH—C(═NH)—NH 2 ,

—C(═NH)—NH—(CH 2 ) 3 —CH(COOH)—NH 2 ,

—CH(COOH)—(CH 2 ) 3 —N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—C(═NH)—NH 2 ,

—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—(CH 2 ) 3 —CH(COOH)—NH 2 ,

—C(═NH)—NH—(CH 2 ) 3 —CH(COOH)—NH—CH 2 —CH(OH)—(CH 2 ) n′ —Z′,

—CH(COOH)—(CH 2 ) 3 —N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—C(═NH)—NH—CH(OH)—CH 2 ) n″ —Z″,

—C(═NH)—NH—(CH 2 ) 3 —CH(COOH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ —Z″,

—CH(COOH)—(CH 2 ) 3 —NH—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH(OH)—(CH 2 ) n″ —Z″,

—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′″ —Z′″)—(CH 2 ) 3 —CH(COOH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ —Z″,

—CH(COOH)—(CH 2 ) 3 —N(—CH 2 —CH(OH)—(CH 2 ) n′″ —Z′″)—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH(OH)—(CH 2 ) n″ —Z″,

—(CH 2 ) 4 —CH(NH 2 )COOH,

—CH(COOH)—(CH 2 ) 4 —NH 2 ,

—(CH 2 ) 4 —CH(NH—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)COOH,

—(CH 2 ) 4 —CH(N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ —Z″),

—CH(COOH)—(CH 2 ) 4 —N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ —Z″, or

—CH(COOH)—CH 2 —imidazolyl

(wherein in the preceding formulas

Z′, Z″, and Z′″ each independently represent an organopolysiloxane residue, and

n′, n″, and n′″ each independently represent an integer in the range from 1 to 20); and

n is defined as above},

or the following general formula (4′):

{wherein

Z is defined as above;

R 3 represents

—CH(COOH)—(CH 2 ) 3 —NH—C(═NH)—NH 2 ,

—C(═NH)—NH—(CH 2 ) 3 —CH(COOH)—NH 2 ,

—(CH 2 ) 3 —CH(COOH)—NH 2 ,

—CH(COOH)—(CH 2 ) 3 —N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—C(═NH)—NH 2 ,

—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—(CH 2 ) 3 —CH(COOH)—NH 2 ,

—CH(COOH)—(CH 2 ) 3 —NH—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ —Z″,

—C(═NH)—N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—(CH 2 ) 3 —CH(COOH)—N(—CH 2 —CH(OH)—(CH 2 ) n″ —Z″)—CH 2 —CH(OH)—(CH 2 ) n′″ —Z′″,

—(CH 2 4 —CH(NH 2 )COOH,

—CH(COOH)—(CH 2 ) 4 —NH 2 ,

—CH(COOH)—(CH 2 ) 4 —N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ —Z″, or

—CH(COOH)—CH 2 —imidazolyl

(wherein in the preceding formulas Z′, Z″, and Z′″ and n′, n″, and n′″ are defined as above);

R 4 represents

—C(═NH)—NH 2 or

—CH 2 —CH(OH)—(CH 2 ) n″″ —Z″″

(wherein

Z″″ represents a polysiloxane residue, and

n″″ represents an integer in the range from 1 to 20); and

n is defined as above},

or the following general formula (5′):

{wherein

Z is defined as above;

R 5 represents

—CH 2 —CH(NH 2 )COOH,

—CH 2 —CH(NH(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′))COOH, or

—CH 2 —CH(N(—CH 2 —CH(OH)—(CH 2 ) n′ —Z′)—CH 2 —CH(OH)—(CH 2 ) n″ Z″)COOH

(wherein in the preceding formulas

Z′ and Z″ and n′ and n″ are defined as above); and

n is defined as above};

(B) surfactant; and

(C) water.

8. The amino acid-modified organopolysiloxane emulsion according to claim 7 , wherein the organopolysiloxane residue is represented by the following general formula (6):

{wherein

R 1 represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl, unsubstituted or substituted alkoxy, an unsubstituted or substituted polyether group, hydroxyl, -A-NH—B—NH 2 , -A-N(—B—NH 2 ) 2 , or —CH 2 CH 2 Si(CH 3 ) 2 —{OSi(CH 3 ) 2 } t —OSi(CH 3 ) 3 (in these formulas, A and B each independently represent unsubstituted or substituted alkylene or —C u H 2u —O—C v H 2v -(u and v each independently represent an integer in the range from 1 to 5) and t represents an integer in the range from 0 to 500);

D represents —(CH 2 ) a —O—(C b H 2b O) c — (wherein a represents an integer in the range from 1 to 20, b represents an integer in the range from 1 to 10, c represents an integer in the range from 0 to 50), or a group as defined for R 1 above, with the proviso that all of the D groups are not R 1 ;

x represents an integer in the range from 1 to 10000; and

y represents an integer in the range from 0 to 1000);}, or

wherein the organopolysiloxane residue is represented by the following general formula (7):

(wherein R 1 and D are defined as above;

r represents an integer in the range from 1 to 10;

s represents an integer in the range from 1 to 10; and

r+s represents an integer in the range from 3 to 20).

9. The amino acid-modified organopolysiloxane emulsion according to claim 8 , wherein the amino acid-modified organopolysiloxane (A) has in the molecule at least one moiety represented by the following formula (3″), (4″), or (5″):

(n in these formulas is defined as above;

a represents an integer in the range from 1 to 20;

d represents an integer in the range from 0 to 10; and

e represents an integer in the range from 1 to 10).

10. The amino acid-modified organopolysiloxane emulsion according to claim 9 , wherein the amino acid-modified organopolysiloxane (A) is an arginine-modified organopolysiloxane represented by the following general formula (8):

{wherein

R 1′ is defined as above;

Q Arg is a group represented by the following formula:

(wherein n, a, d, and e are defined as above), or represents a group as defined for R 1′ above, with the proviso that all of the Q Arg groups are not R 1′ ;

x′ represents an integer in the range from 5 to 1000; and

y′ represents an integer in the range from 0 to 100}.

11. The amino acid-modified organopolysiloxane emulsion according to claim 7 , comprising 1 to 100 parts by weight of the surfactant (B) and 10 to 10,000 parts by weight of water (C), in each case with reference to 100 parts by weight of the amino acid-modified organopolysiloxane (A).

12. A cosmetic product that comprises an amino acid-modified organopolysiloxane emulsion according to claim 7 .