Non-fogging plasticizer and its use in resinous compositions

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...

Reexamination Certificate

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C524S169000

Reexamination Certificate

active

06194498

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a novel plasticizer composition and its use in resinous compositions such as film-forming compositions including adhesives, protective coatings and laminating substrates, to prevent fogging in interior automotive trim assembly parts such as instrument panels, door panels, etc.
BACKGROUND OF THE INVENTION
Plasticizers are materials added to resinous compositions to increase the deformability thereof; i.e., to make them “softer”. Technically, plasticizers are diluents or solvents with low volatility, causing them to remain in the resinous composition during curing or other processing. Their presence in the composition reduces cohesive bonds among the resin molecules, allowing them to flow past each other, thereby lending a degree of deformability to the resinous composition on a macroscopic level.
EP 553651 discloses bissulfonamide plasticizers for use with thermoplastic adhesive materials. U.S. Pat. No. 5,264,474 discloses mixtures of monosulfonamides and mixtures of bissulfonamides suitable for use as plasticizers. U.S. Pat. No. 4,946,933 discloses toluenesulfonamide plasticizers used in conjunction with adhesives derived from polyoxyalkylene amines.
Typically, the adhesive compositions used in vacuum forming processes comprise a film-forming material impregnated with a plasticizer. Vacuum forming is a conventional process for adhering thermoplastic materials to contoured substrates, particularly in the automotive industry. For example, a thermoplastic material (e.g., polyvinyl chloride flexible sheeting) can be laminated onto automobile parts such as consoles, dash boards, door panels, and other interior surfaces using vacuum forming. The substrates can be any conventionally used material, such as acrylonitrile-butadiene-styrene terpolymer (ABS) or fiberboard. The process involves coating the substrate with an adhesive, heating the thermoplastic material past its softening point, draping the thermoplastic material over the substrate, and applying a vacuum through the substrate to pull the thermoplastic material onto the contours of the substrate.
Sulfonamide plasticizers that are N-substituted with lower alkyl groups tend to be volatile and may evaporate from the adhesive composition during the life of an automobile, only to recondense on adjacent substrates, particularly windshields or windows, causing fogging or an unacceptable oily residue.
It would be desirable to provide a composition suitable for use as a non-fogging plasticizer in a resinous composition such as a vacuum forming adhesive, that overcomes the drawbacks of the prior art.
SUMMARY OF THE INVENTION
In accordance with the present invention, a composition of matter is provided comprising a mixture of:
(i) at least one alkyl aromatic sulfonamide containing from 12 to 40 carbon atoms total and at least six carbon atoms in the alkyl group; and
(ii) at least one polyether aromatic sulfonamide different from (i) and having the following structure:
Q—[(OCH(R)CH(R))
y
—NH—SO
2
—A]
z
.
Q is selected from the following structures:
A is an aromatic group containing from 6 to 39 carbon atoms; L is an alkyl group containing from 1 to 20 carbon atoms or
A—SO
2
—NHCH(CH
3
)CH
2
—;
R is independently hydrogen or linear or branched alkyl groups having from 1 to 4 carbon atoms; x ranges from 0 to 40; y ranges from 2 to 40; z ranges from 1 to 3; and a ranges from 0 to 40. Also provided is a resinous composition comprising a film-forming material and a plasticizer, wherein the plasticizer comprises (i) or the mixture of (i) and (ii) above.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term “about”. Note further that the numerical ranges of values for subscripts in chemical structures are intended to encompass average values.
DETAILED DESCRIPTION
The composition of the present invention comprises a mixture of:
(i) at least one alkyl aromatic sulfonamide containing from 12 to 40 carbon atoms total and at least six carbon atoms in the alkyl group; and
(ii) at least one polyether aromatic sulfonamide different from (i) and having the following structure:
Q—[(OCH(R)CH(R))
y
—NH—SO
2
—]
3
.
Q is selected from the following structures:
A is an aromatic group containing from 6 to 39 carbon atoms; L is an alkyl group containing from 1 to 20 carbon atoms or
A—SO
2
—NHCH(CH
3
)CH
2
—;
R is independently hydrogen or linear or branched alkyl groups having from 1 to 4 carbon atoms. The subscript x ranges from 0 to 40; y ranges from 2 to 40; z ranges from 1 to 3; and a ranges from 0 to 40.
The alkyl aromatic sulfonamide of (i) may be selected from alkyl benzene sulfonamides, alkyl toluene sulfonamides, alkyl naphthalene sulfonamides, alkyl mesitylene sulfonamides, alkyl hexadecyloxy benzene sulfonamide and the like. Mixtures of various alkyl aromatic sulfonamides having different alkyl and/or aromatic groups may also be used. Alkyl groups typically contain from 6 to 25 carbon atoms, preferably 6 to 10 carbon atoms, and may be cyclic, linear or branched. The alkyl groups may further contain alkoxy linkages. Alkyl aromatic sulfonamides containing alkyl groups having less than 6 carbon atoms tend to be volatile, and may cause fogging. Examples of suitable alkyl aromatic sulfonamides include N-hexyl benzene sulfonamide, cyclohexyl benzene sulfonamide, 2-ethylhexyl benzene sulfonamide, and N-octyl benzene sulfonamide, which is preferred.
In the polyether aromatic sulfonamide of (ii), A is an aromatic group containing from 6 to 39 carbon atoms. Examples include phenyl, tolyl, hexadecyloxy benzene, and naphthyl groups. Phenyl groups are preferred. When Q is monovalent, z is equal to 1; when Q is trivalent, z is equal to 3. When R is an alkyl group, it is preferably a methyl group. When L is an alkyl group, it may be linear or branched, cyclic, or substituted. When L is an alkyl group, it is preferably a methyl group. The polyether aromatic sulfonamide of (ii) may also be a mixture of polyether aromatic sulfonamides having various structures selected from among those indicated above.
In a particular embodiment of the invention, the polyether aromatic sulfonamide of (ii) has the following structure:
A—SO
2
—NHCH(CH
3
)CH
2
—(OCH
2
CH(CH
3
))
5-6
—NH—SO
2
—A
wherein A is a phenyl group.
The polyether aromatic sulfonamide of (ii) is generally prepared by reacting together an aromatic sulfonic acid or sulfonyl halide such as benzene sulfonic acid or benzene sulfonyl chloride with an amine functional polyether having the structure:
Q—[(OCH(R)CH(R))
y
—NH
2
]
z
wherein Q, R, y, and z are as defined above.
Preferred amine functional polyethers used to prepare the polyether aromatic sulfonamide of (ii) are sold under the name JEFFAMINE® by Huntsman Chemicals. Particularly preferred amine functional polyethers include JEFFAMINE® D-400. A particularly preferred polyether aromatic sulfonamide is a reaction product of benzene sulfonyl chloride and JEFFAMINE® D-400 in a 2:1 mole ratio.
The weight ratio of the alkyl aromatic sulfonamide of (i) to the polyether aromatic sulfonamide of (ii) in the composition of the present invention may range between 1:99 and 99:1. The weight ratio of (i) to (ii) is preferably 1:1.
The alkyl aromatic sulfonamide of (i) or the composition of the present invention comprising the mixture of sulfonamides (i) and (ii) may be used as a plasticizer in a resinous composition. Such resinous compositions may include, inter alia, film-forming compositions such as adhesives, protective coatings and laminating substrates. Therefore, in accordance with the present invention, there is further provided a resinous composition comprising:
a) a film-forming material; and
b) a plasticizer for the film-forming material; the plasticizer comprising the alkyl aromatic sulfonamide of (i) or mixtures of sulfonamides (i) and (ii) as described above. Preferred composition

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