Organo polysiloxane elastomer and use therefor

• US 9,301,913 B2
• Filed: 05/22/2012
• Issued: 04/05/2016
• Est. Priority Date: 05/30/2011
• Status: Active Grant

• Current Assignee: Dow Toray Co., Ltd. (Dow, Inc.)
• Original Assignee: Dow Corning Toray Company Limited (Dow, Inc.)
• Inventors: Tamura, Seiki, Souda, Tatsuo, Hori, Seiji
• Primary Examiner(s): Zimmer, Marc
• Application Number:
  US14/122,689
• Publication Number:
  US 20140161758A1
• Time in Patent Office: 1,414 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: A61K 2800/10 General cosmetic use
• CPC Class Codes: A61K 47/34 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers A61K47/10 takes precedence
• CPC Class Codes: A61K 8/0241 Containing particulates characterized by their shape and/or structure see also A61K8/04, A61K8/11, and A61K8/14, further aspects are classified in A61K2800/40 and subcodes
• CPC Class Codes: A61K 8/892 modified by a hydroxy group, e.g. dimethiconol
• CPC Class Codes: A61K 8/893 modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
• CPC Class Codes: A61K 8/895 containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• CPC Class Codes: A61K 9/0014 Skin, i.e. galenical aspects of topical compositions non-active ingredients are additionally classified in A61K47/00; A61K9/0009, A61K9/0021, A61K9/7015, A61K9/7023 take precedence; cosmetic preparations A61K8/00, A61Q; preparations for wound dressings or bandages A61L26/00
• CPC Class Codes: A61K 9/107 Emulsions ; Emulsion preconcentrates; Micelles composition of emulsions A61K47/00
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 19/007 Preparations for dry skin
• CPC Class Codes: A61Q 19/08 Anti-ageing preparations
• CPC Class Codes: A61Q 5/00 Preparations for care of the hair
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C08L 83/12 containing polyether sequences
• CPC Class Codes: C08L 83/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08L83/10 takes precedence
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

The present invention relates to an organopolysiloxane elastomer having a group having a siloxane dendron structure bonded to a silicon atom, and having a crosslinked structure that includes a carbon-silicon bond in the crosslinking portion, and relates to a glycerin derivative-modified organopolysiloxane elastomer having a siloxane dendron structure bonded to a silicon atom and a hydrophilic group bonded to a different silicon atom from the silicon atom, and having a crosslinked structure that includes a carbon-silicon bond in the crosslinking portion. The organopolysiloxane elastomer of the present invention, for example, has affinity with a variety of oil agents, has excellent structuring properties and gelling characteristics, and further retains excellent tactile sensation, particularly a velvety thick smoothness, and moreover imparts an excellent tactile sensation from initial application to after drying without producing any stickiness at all, and furthermore, provides superior cosmetic effects, such as wrinkle concealing effect (masking effect), and the like.

Claims

1. An organopolysiloxane elastomer comprising:

a group having a siloxane dendron structure represented by L¹ that is bonded to a silicon atom, and having a crosslinked structure that includes a carbon-silicon bond in a crosslinking portion;

wherein, L¹ is a silylalkyl group having a siloxane dendron structure and, when i=1, represented by following general formula (2);

2. The organopolysiloxane elastomer according to claim 1, wherein L¹ in general formula (2) is a functional group represented by following general formula (2-1) or general formula (2-2):

3. The organopolysiloxane elastomer according to claim 1, comprising the group having a siloxane dendron structure represented by L¹ that is bonded to a silicon atom, and having a hydrophilic group represented by Q bonded to a different silicon atom from the silicon atom, and having the crosslinked structure that includes a carbon-silicon bond in the crosslinking portion;

wherein, Q is a hydrophilic group bonded to a silicon atom via a linking group that is at least divalent including at least one type of hydrophilic unit selected from hydrophilic units represented by following general formulae (3-1) to (3-4);

—

C_rH_2r—

O—

 

 

(3-1)

wherein, r is a number in a range of 1 to 6;

4. The organopolysiloxane elastomer according to claim 3, wherein the Q

has a linear hydrophilic segment having a plurality of the hydrophilic units bonded in a linear fashion, or

has a branched hydrophilic segment having a plurality of the hydrophilic units bonded in a branched fashion via at least one branching unit selected from groups represented by following structural formulae (3-5) to (3-7):

5. The organopolysiloxane elastomer according to claim 3, wherein the Q is a hydrophilic group represented by any one of following general formulae (4-1) to (4-4):

General Formula (4-1);

—

R³(—

O—

X¹_m—

R⁴)_p 

 

(4-1)

wherein,

R³ is an organic group having (p+1) valency,

p is a number in a range of 1 to 3;

X¹ are each independently at least one hydrophilic unit selected from the hydrophilic units represented by the general formulae (3-1) to (3-4) above;

m is a number in a range of 1 to 100; and

R⁴ is a hydrogen atom or a group selected from the group consisting of alkyl groups, acyl groups, and glycidyl groups having from 1 to 20 carbons;

General Formula (4-2);

—

R³(—

O—

X²)_p 

 

(4-2)

wherein,

R³ is synonymous with the groups described above,

p is the same number as described above, and

X² is a hydrophilic group represented by the following structural formal (4-2-1);

6. The organopolysiloxane elastomer according to claim 1, the organopolysiloxane elastomer being obtained by causing reactions between at least the following:

(A) an organohydrogenpolysiloxane;

(B) a siloxane dendron having one reactive unsaturated group in a molecule; and

(C) at least one organic compound selected from the group consisting of (C1) organic compounds having an average of more than one reactive unsaturated groups in a molecule, and (C2) organic compounds having at least one reactive unsaturated group and at least one epoxy group in a molecule.

7. The organopolysiloxane elastomer according to claim 1, the organopolysiloxane elastomer being obtained by causing reactions between at least the following:

(A) an organohydrogenpolysiloxane;

(B) a siloxane dendron having one reactive unsaturated group in a molecule;

(C) at least one organic compound selected from the group consisting of (C1) organic compounds having an average of more than one reactive unsaturated groups in a molecule, and (C2) organic compounds having at least one reactive unsaturated group and at least one epoxy group in a molecule, provided that the (C) is optional in cases where (D) has an average of more than one reactive unsaturated group in a molecule; and

(D) a hydrophilic derivative having a reactive unsaturated group and a hydrophilic group that includes at least one hydrophilic unit selected from the hydrophilic units represented by the structural formulae (3-1) to (3-4).

8. The organopolysiloxane elastomer according to claim 6, wherein an average number of silicon-bonded hydrogen atoms in a molecule of the component (A) that react with an unsaturated bond in the component (C) and/or component (D) is 0.1 or greater.

9. The organopolysiloxane elastomer according to claim 6, wherein the component (A) is represented by average composition formula (1):

R⁵_aH_bSiO_(4-a-b)/2 

 

(1)

wherein,

R⁵ each independently represent monovalent organic groups, wherein 1.0≦

a≦

3.0 and 0.001≦

b≦

1.5.

10. The organopolysiloxane elastomer according to claim 6, wherein the component (B) is a compound having a siloxane dendron structure having one carbon-carbon double bond at a molecular terminal, and represented by following general formula (2′

);

11. The organopolysiloxane elastomer according to claim 6, wherein the component (C) is at least one organic compound selected from following (C1-1) to (C1-5) and (C2-1) to (C2-2):

(C1-1) an α

,ω

-diene represented by general formula (5-1);

CH₂═

CH(CH₂)_xCH═

CH₂ 

 

(5-1)

wherein, 1≦

x≦

20;

(C1-2) an α

,ω

-diyne represented by general formula (5-2);

CH≡

C(CH₂)_xC≡

CH 

 

(5-2)

wherein, 1≦

x≦

20;

(C1-3) an α

,ω

-ene-yne represented by general formula (5-3);

CH₂═

CH(CH₂)_xC≡

CH 

 

(5-3)

wherein, 1≦

x≦

20;

(C1-4) a bisalkenyl polyether compound represented by general formula (5-4);

C_qH_2q-1O(C_nH_2nO)_yC_qH_2q-1 

 

(5-4)

wherein, 2≦

q≦

20 and 2≦

n≦

4, y is the total number of repetitions of oxyethylene units, oxypropylene units, or oxybutylene units, and 1≦

y≦

180;

(C1-5) unsaturated group-containing silicone compound represented by average composition formula (5-5);

R⁷_cR⁸_dSiO_(4-c-d)/2 

 

(5-5)

wherein, R⁷ may each independently represent a monovalent organic group that differs from R⁸;

R³ is each independently a monovalent unsaturated aliphatic hydrocarbon group having from 2 to 30 carbons, 1.0≦

c≦

2.5, and 0.001≦

d≦

1.5;

(C2-1) an unsaturated epoxy compound represented by general formula (5-6);

12. The organopolysiloxane elastomer according to claim 9, wherein the monovalent organic group that is R⁵ in the average composition formula (1) is selected from following (E1) to (E9):

(E1) a substituted or unsubstituted, straight or branched monovalent hydrocarbon group having from 1 to 60 carbons;

(E2) a polyoxyalkylene group represented by —

R¹³O(AO)_zR¹⁴, wherein, AO is an oxyalkylene group having from 2 to 4 carbons, R¹³ is a substituted or unsubstituted, straight or branched divalent hydrocarbon group having from 3 to 5 carbons, R¹⁴ is a hydrogen atom, a substituted or unsubstituted, straight or branched monovalent hydrocarbon group having from 1 to 24 carbons, or a substituted or unsubstituted, straight or branched acyl group having from 2 to 24 carbons, and z=1 to 100;

(E3) a substituted or unsubstituted, straight or branched alkoxy group having from 1 to 30 carbons;

(E4) a hydroxyl group;

(E5) an ester group represented by —

R¹⁵—

COOR¹⁶, wherein, R¹⁵ represents a substituted or unsubstituted, straight or branched divalent hydrocarbon group having from 2 to 20 carbons, and R¹⁶ represents a substituted or unsubstituted, straight or branched monovalent hydrocarbon group having from 1 to 30 carbons;

(E6) an ester group represented by —

R¹⁷—

OCOR¹⁸, wherein, R¹⁷ represents a substituted or unsubstituted, straight or branched divalent hydrocarbon group having from 2 to 20 carbons, and R¹⁸ represents a substituted or unsubstituted, straight or branched monovalent hydrocarbon group having from 1 to 30 carbons;

(E7) an alkyl group substituted with a polysiloxane chain structure and represented by following general formula (6);

13. The organopolysiloxane elastomer according to claim 1, wherein the organopolysiloxane elastomer is in a form of a particle.

14. The organopolysiloxane elastomer according to claim 13, wherein the organopolysiloxane elastomer is in the form of a particle having a volume average particle size in a range of 20 to 1,000 μ

m.

15. The organopolysiloxane elastomer according to claim 1, wherein:

the organopolysiloxane elastomer is capable of swelling as a result of including a weight amount of an oil agent that is at least the weight of the organopolysiloxane elastomer itself.

16. A composition comprising the organopolysiloxane elastomer according to claim 1 and at least one oil agent.

17. The composition according to claim 16, wherein the composition is in the form of a paste.

18. The composition according to claim 16, the composition being obtained by using mechanical force to pulverize the organopolysiloxane elastomer, and then mixing the same with at least one oil agent, or by using mechanical force to pulverize a mixture of the organopolysiloxane elastomer and at least one oil agent.

19. An organopolysiloxane elastomer, the organopolysiloxane elastomer or a composition thereof being obtained by treating the organopolysiloxane elastomer according to claim 1 by adding at least one type of acidic substance, and then removing volatile components by heating or reducing pressure.

20. The composition according to claim 16, the composition being in the form of an emulsion.

21. An external use preparation raw material comprising the organopolysiloxane elastomer according to claim 1.

22. An external use preparation raw material according to claim 21, the external use preparation raw material being a gelling agent, a structuring agent, a thickener, a tactile sensation improver, a moisturizing agent, a masking agent, a surfactant, an emulsifier, or a powder dispersion stabilizer.

23. An external use preparation comprising the organopolysiloxane elastomer according to claim 1.

24. An organopolysiloxane elastomer production method comprising a step of causing reactions between at least the following:

(A) an organohydrogenpolysiloxane;

(B) a siloxane dendron having one reactive unsaturated group in a molecule; and

(C) at least one organic compound selected from the group consisting of (C1) organic compounds having an average of more than one reactive unsaturated groups in a molecule, and (C2) organic compounds having at least one reactive unsaturated group and at least one epoxy group in a molecule.

25. The organopolysiloxane elastomer production method according to claim 24, wherein some or all of the reactions are performed in the presence of no solvent or in the presence of at least one solvent selected from a group represented by (P-1) to (P-2):

(P-1);

an organic compound; and

(P-2);

a compound having a silicon atom.

26. The organopolysiloxane elastomer production method according to claim 24, wherein (A) and (B) are reacted first, and then (C) is added and a crosslinking reaction is performed, and wherein an optional component (Q) is reacted with (A) before the (A)-(B) reaction, or is further reacted following the (A)-(B) reaction, or is reacted simultaneous with the (A)-(B) reaction, or is further reacted following crosslinking by (C);

where

(Q) is a compound having one unsaturated group in a molecule, excluding the compound (C2).

27. The organopolysiloxane elastomer production method according to claim 24, wherein (A) and (C) are reacted first to introduce a crosslinking portion, and then (B) is added and reacted, and wherein an optional component (Q) is reacted with (A) before the (A)-(C) reaction, or is further reacted following the (A)-(C) reaction, or is further reacted following the reaction with (B);

where (Q) is a compound having one unsaturated group in a molecule, excluding the compound (C2).

28. An organopolysiloxane elastomer production method comprising a step of causing reactions between at least the following:

(A) an organohydrogenpolysiloxane;

(B) a siloxane dendron having one reactive unsaturated group in a molecule;

(C) at least one organic compound selected from the group consisting of (C1) organic compounds having an average of more than one reactive unsaturated groups in a molecule, and (C2) organic compounds having at least one reactive unsaturated group and at least one epoxy group in a molecule, provided that the (C) is optional in cases where (D) has an average of more than one reactive unsaturated group in a molecule; and

(D) a hydrophilic derivative having a reactive unsaturated group and a hydrophilic group that contains at least one hydrophilic unit selected from the hydrophilic units represented by the structural formulae (3-1) to (3-4).

29. The organopolysiloxane elastomer production method according to claim 28, wherein some or all of the reactions are performed in the presence of no solvent or in the presence of at least one solvent selected from a group represented by (P-1) to (P-2):

(P-1);

an organic compound; and

(P-2);

a compound having a silicon atom.

30. The organopolysiloxane elastomer production method according to claim 28, wherein (B) and (D) are successively reacted with the (A) in any order, provided that (D) is limited to compounds having one reactive unsaturated group in a molecule, after which, (C) is added and a crosslinking reaction is performed, and wherein the optional component (Q) is reacted with (A) before the (A)-(B) reaction or before the (A)-(D) reaction, or is further reacted following the (A)-(B) reaction or following the (A)-(D) reaction, or is reacted simultaneous with the (A)-(B) reaction or simultaneous with the (A)-(D) reaction, or is further reacted following crosslinking by (C);

where

(Q) is a compound having one unsaturated group in a molecule, excluding the compound (C2).

31. The organopolysiloxane elastomer production method according to claim 28, wherein (A) and (C) are reacted first to introduce a crosslinking portion, after which, (B) and (D) are added and successively reacted in any order, provided that (D) is limited to compounds having one reactive unsaturated group in a molecule, and wherein the optional component (Q) is reacted with (A) before the (A)-(C) reaction, or is further reacted following the (A)-(C) reaction, or is further reacted following the reactions with (B) and (D);

where (Q) is a compound having one unsaturated group in a molecule, excluding the compound (C2).