# US 6,294,007 B1 · Paintable organopolysiloxane mold release compositions and processes for their use

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- Number: US 6,294,007 B1
- Document ID: US6294007B1
- Status: Granted
- Kind: B1
- Application number: 09/206,687
- Filed: 1998-12-07
- Granted: 2001-09-25
- Earliest claimed: 1998-12-07
- Assignees: Wacker Silicones Corporation
- Inventors: Eugene R. Martin
- Web page: https://patentgrep.com/patent/US6294007B1

## CPC

- C08L 83/04: Polysiloxanes
- B29C 33/64: Silicone
- C09D 183/04: Polysiloxanes
- C08G 77/12: containing silicon bound to hydrogen
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/28: sulfur-containing groups
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Silicone mold release compositions which are a stable blend of hydrophobic-modified organopolysiloxane and an aminoorgano- or mercaptoorgano-functional organopolysiloxane, or a solution in organic solvent of a stable or unstable blend, provide exceptional mold release properties while retaining paintability of molded parts.

## Claims

### Claim 1

A neat mold release composition providing for molded part paintability, comprising a stable blend of hydrophobic-modified organopolysiloxane and an organofunctional organopolysiloxane, said organofunctional organopolysiloxane containing aminoorgano-functional, mercaptoorgano-functional, or both aminoorgano- and mercaptoorgano-functional groups.

### Claim 2 (depends on 1)

The neat mold release composition of claim 1, wherein said hydrophobic-modified oranopolysiloxane comprises a branched or linear polyorganosiloxae comprising moieties of the formulae
RaRb1SiO1/2 (I)
RaRb1SiO2/2 (II)
and optionally, moieties of either or both of the formulae
RaRb1SiO3/2 (III)
or
SiO4/2 (IV)
wherein
R is lower alkyl or alkylene, optionally interrupted by ether oxygen or thioether sulfur;
R1 is a C4-C30 hydrophobic group optionally containing not more than one ether oxygen or thioether sulfur when the carbon content is less than C10, and not more than two ether oxygen or thioether sulfur atoms when the carbon content is C10 or greater, R1 containing insufficient interspersed —O— and/or —S— atoms to defeat the hydrophobicity of the R1 hydrophobic group wherein a and b are 0, 1, 2, or 3, and the sum (a+b) is 3 for formula (I), 2 for formula (II), and 1 for formula (III), with the proviso that the hydrophobic-modified organopolysiloxane contain at least one R1 hydrophobic group.

### Claim 3 (depends on 1)

The neat mold release of claim 1 wherein said organofunctional organopolysiloxane contains at least one R6 HN—X— organofunctional group, at least one HS—X— organofunctional group, or at least one R6 HN—X— organofunctional group and at least one HS—X— organofunctional group, wherein X is a C1-30 hydrocarbon linking group optionally containing one or more interposed hetroatoms selected from the group consisting of —O—, —S—, and heteroatom-containing groups
wherein R6 s hydrogen a C1-C18 alkyl or aryl radical.

### Claim 4 (depends on 2)

The neat mold release of claim 2 wherein said organofunctional organopolysiloxane contains at least one R6 HN—X— organoftinctional group, at least one HS—X— organofunctional group, or at least one R6 HN—X— organofunctional group and at least one HS—X— organofunctional group, wherein X is a C1-30 hydrocarbon linking group optionally containing one or more interposed hetroatoms of —O—, —S—, and heteroatom-containing groups
wherein R6 is hydrogen or a C1-C18 alkyl or aryl radical.

### Claim 5 (depends on 1)

The neat mold release composition claim 1, wherein said aminoorgano-functional organopolysiloxane contains aminoorgano groups corresponding to the formulae VI
—R5—[(NR6)—R7]tNR8R9 (VI)
in which
R5 is a divalent C1-C18-hydrocarbon radical,
R6 is a hydrogen atom or an unsubstituted C1-C10-alkyl radical,
R7 is a divalent C1-C18-hydrocarbon radical ,
R8 is a hydrogen atom or an unsubstituted C1-C10-alkyl radical or aryl radical,
R9 is a hydrogen atom or an unsubstituted C1-C10-alkyl radical or aryl radical and
t is an integer from 0 to 6.

### Claim 6 (depends on 1)

The neat mold release of claim 1, wherein at least one of said mercaptoorgano groups is selected from the group consisting of
—CH2SH,
—C2H4SH,
—C3H6SH, (HSCH2)2CHCH2CH2—,
(HSCH2CH2)(HSCH2)CH(CH2)4—,
(HSCH2)CH2)3CCH2CH2—,
(HSCH2CH2)(HSCH2)CHCH(CH2SH)CH2CH2CH2—,
HS(CH2)5CH(CH2CH2SH)CH2CH2CH(CH2CH3)—,
(HSCH2CH2)2CHCH2CH2—,
(HSCH2)2CHSCH2CH2CH2—,
(HSCH2)2(C2H5)CCH2SCH2CH2CH3—,
(HSCH2)3CCH2SCH2CH2CH2—,
(HSCH2)(HSCH2CH2CH2CH2)CHSCH2CH2CH2—,
(HSCH2CH2)2CHCH2SCH2CH2CH2—,
(HSCH2)2(C2H5)CCH2SCH2CH2S(SCH2)3—,
(HSCH2)3CCH2S(CH2)3S(CH2)3—,

### Claim 7 (depends on 5)

The neat mold release of claim 5, wherein at least one of said mercaptoorgano groups is selected from the group consisting of
—CH2SH,
—C2H4SH,
—C3H6SH, (HSCH2)2CHCH2CH2—,
(HSCH2CH2)(HSCH2)CH(CH2)4—,
(HSCH2)CH2)3CCH2CH2—,
(HSCH2CH2)(HSCH2)CHCH(CH2SH)CH2CH2CH2—,
HS(CH2)5CH(CH2CH2SH)CH2CH2CH(CH2CH3)—,
(HSCH2CH2)2CHCH2CH2—,
(HSCH2)2CHSCH2CH2CH2—,
(HSCH2)2(C2H5)CCH2SCH2CH2CH3—,
(HSCH2)3CCH2SCH2CH2CH2—,
(HSCH2)(HSCH2CH2CH2CH2)CHSCH2CH2CH2—,
(HSCH2CH2)2CHCH2SCH2CH2CH2—,
(HSCH2)2(C2H5)CCH2SCH2CH2S(SCH2)3—,
(HSCH2)3CCH2S(CH2)3S(CH2)3—,

### Claim 8 (depends on 1)

The neat mold release composition of claim 1, wherein the top/bottom functional group mol ratio is between about 0.93 and about 1.07.

### Claim 9 (depends on 1)

The neat mold release of claim 1, wherein the organofunctional organopolysiloxanes comprise one or more polydimethylsiloxanes selected from the group consisting of γ-aminopropyl-functional polydimethylsiloxanes, β-aminoethylaminopropyl-functional polydimethylsiloxanes, and γ-mercaptopropyl-functional polydimethylsiloxanes.

### Claim 10 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1;
b) an unstable mold release composition comprising a hydrophobic-modified organopolysiloxane and an organofunctional organopolysiloxane having aminoorgano, mercaptoorgano, or both aminoorgano and mercaptoorgano functionality having a top/bottom functional group mol ratio less than 0.9 or greater than 1.1, wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4 is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 11 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1;
b) an unstable mold release composition comprising hydrophobic-modified organopolysiloxane and organofunctional organopolysiloxane having a top/bottom ratio less than 0.9 or greater than 1.1, wherein said hydrophobic-modified organopolysiloxane comprises a branched or linear polyorganosiloxane comprising moieties of the formulae
RaRb1SiO1/2 (I)
RaRb1SiO2/2 (II)
and optionally, moieties of either or both of the formulae
RaRb1SiO3/2 (III)
or
SiO4/2 (IV)
wherein
R is lower alkyl or alkylene, optionally interrupted by ether oxygen or thioether sulfur;
R1 is a C4-C30 hydrophobic group optionally containing not more than one ether oxygen or thioether sulfur when the carbon content is less than C10, and not more than two ether oxygen or thioether sulfur atoms when the carbon content is C10 or greater, R1 containing insufficient interspersed —O— and/or —S— atoms to defeat the hydrophobicity of the R1 hydrophobic group wherein a and b are 0, 1, 2, or 3, and the sum (a+b) is 3 for formula (I), 2 for formula (II), and 1 for formula (III), with the proviso that said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and contains y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4 is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 12 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1;
b) an unstable mold release composition comprising a hydrophobic-modified organopolysiloxane and an organofunctional organopolysiloxane having aminoorgano, mercaptoorgano, or both aminoorgano and mercaptoorgano functionality having a top/bottom ratio less than 0.9 or greater than 1.1, wherein said organofunctional organopolysiloxane contains
at least one R6HN—X— organofunctional group, at least one HS—X— organofunctional group, or at least one R6HN—X— and at least one HS—X— organofunctional group,
wherein X is a C1-30 hydrocarbon linking group optionally containing one or more interposed hetroatoms of —O— and —S— and heteroatom-containing groups
wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4 is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 13 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1;
b) an unstable mold release composition comprising hydrophobic-modified organopolysiloxane and an aminoorgano-functional organopolysiloxane, said composition having a top/bottom ratio less than 0.9 or greater than 1.1 wherein said aminoorgano-functional organofunctional organopolysiloxane contains aminoalkyl groups corresponding to the formulae VI
—R5—[(NR6)—R7]tNR8R9 (VI)
in which
R5 is a divalent C1-C18-hydrocarbon radical,
R6 is a hydrogen atom or an unsubstituted C1-C18-alkyl radical,
R7 is a divalent C1-C18-hydrocarbon radical,
R8 is a hydrogen atom or an unsubstituted C1-C10-alkyl radical or aryl radical,
R9 is a hydrogen atom or an unsubstituted C1-C10-alkyl radical or aryl radical, and
t is an integer from 0 to 6, wherein said hydrophobic-modified organopolysiloxane and wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4 is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 14 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1;
b) an unstable mold release composition comprising a hydrophobic-modified organopolysiloxane and an organofunctional organopolysiloxane having a top/bottom ratio less than 0.9 or greater than 1.1 wherein organofunctional organopolysiloxane bears a mercaptoorgano group selected from the group consisting of
—CH2SH,
—C24SH,
—C3H6SH, (HSCH2)2CHCH2CH2—,
(HSCH2CH2)(HSCH2)CH(CH2)4—,
(HSCH2)CH2)3CCH2CH2—,
(HSCH2CH2)(HSCH2)CHCH(CH2SH)CH2CH2CH2—,
HS(CH2)5CH(CH2CH2SH)CH2CH2CH(CH2CH3)—,
(HSCH2CH2)2CHCH2CH2—,
(HSCH2)2CHSCH2CH2CH2—,
(HSCH2)2(C2H5)CCH2SCH2CH2CH3—,
(HSCH2)3CCH2SCH2CH2CH2—,
(HSCH2)(HSCH2CH2CH2CH2)CHSCH2CH2CH2—,
(HSCH2CH2)2CHCH2SCH2CH2CH2—,
(HSCH2)2(C2H5)CCH2SCH2CH2S(SCH2)3—,
(HSCH2)3CCH2S(CH2)3S(CH2)3—,
mixtures thereof.

### Claim 15 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1 wherein the top/bottom functional group mol ratio is between about 0.93 and about 1.07;
b) an unstable mold release composition comprising a hydrophobic-modified organopolysiloxane and an organofunctional organopolysiloxane having, aminoorgano, mercaptoorgano, or both aminoorgano and mercaptoorgano functionality having a top/bottom ratio less than 0.9 or greater than 1.1, wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 16 (depends on 1)

A solution of mold release in organic solvent which provides molded part paintability, the solution comprising, in addition to one or more organic solvents, one or more of
a) the stable mold release composition of claim 1;
b) an unstable mold release composition comprising hydrophobic-modified organopolysiloxane and organofunctional organopolysixolane having a top/bottom functional group mol ratio less than 0.9 or greater than 1.1, wherein the organofunctional organopolysiloxane comprises one or more polydimethylsiloxaneene wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 17

A solvent-based mold release for producing paintable molded parts, comprising an unstable neat blend of a hydrophobic organopolysiloxane and an organofunctional organopolysiloxane selected from the group consisting of aminoorgano-functional, mercapto organo-functional, and both amino- and mercaptoorgano-functional organopolysiloxanes, dissolved in a solvent, wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3 is an aryl or aralkyl group, R4 is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 18 (depends on 17)

The solvent-based mold release of claim 17 wherein said organofunctional organopolysiloxane is an aminoalkyl-functional organopolysiloxane, wherein said hydrophobic-modified organopolysiloxane contains x siloxy groups of the formula
and y siloxy groups of the formula
wherein R3is an aryl or aralkyl group, R4 is a C8-20 alkyl group, and x and y are positive whole numbers from 3 to 250.

### Claim 19 (depends on 17)

The solvent-based mold release of claim 17 wherein said organofunctional organopolysiloxane is a mercaptoalkyl-functional organopolysiloxane.