Surfactant composition for flexible polyurethane foam

Abstract

The present invention relates to a silicone surfactant composition used in polyurethane foam, comprising (A) one or more silicone surfactant compounds; (B) one or more surfactant efficacy enhancers, in particular one or more organic acids; and (C) optionally one or more diluents. The present invention also relates to a method for manufacturing a polyurethane foam comprising a silicone surfactant composition, a polyurethane foam-forming composition comprising a silicone surfactant composition, and a polyurethane foam formed from a polyurethane foam-forming composition comprising a silicone surfactant composition.

Description

Technology Field

[0001] The present invention relates to a high-potency silicone surfactant composition containing a surfactant potency-enhancing agent, particularly an organic acid, for flexible polyurethane foam; a method for preparing a high-potency silicone surfactant composition containing a surfactant potency-enhancing agent, particularly an organic acid; the use of a high-potency silicone surfactant containing a surfactant potency-enhancing agent, particularly an organic acid, in the manufacture of flexible polyurethane foam; a method for preparing flexible polyurethane foam relying on a high-potency silicone surfactant containing a surfactant potency-enhancing agent, particularly an organic acid; and a polyurethane foam prepared with a silicone surfactant composition containing a surfactant potency-enhancing agent, particularly an organic acid.

[0002] In polyurethane foam processing technology, the primary effect of silicone surfactants is to stabilize the foam cell structure. The stabilization ability (efficacy) of silicone surfactants generally depends on the molecular structure of the silicone surfactant, which includes the silicone backbone and the polyether chain structure bonded to this backbone.

[0003] Because critical polyurethane systems, such as low-density foams or fill foams, easily split and collapse, high-efficacy silicone surfactants are required to stabilize the foam until the product-forming chemical reaction is sufficiently completed and the foam can stand on its own. Therefore, there is a demand for silicone surfactants with high stabilization capabilities for stabilizing the cell structure of urethane foams.

[0004] The present invention presents a novel approach, namely, to further enhance the stabilization ability of a silicone surfactant by combining a surfactant efficacy-enhancing agent, particularly an organic acid, with one or more silicone surfactant compounds within a silicone surfactant composition.

[0005] A novel approach for providing a high-efficacy silicone surfactant composition comprising a surfactant efficacy enhancer, particularly an organic acid, a silicone surfactant compound, and optionally one or more diluents, provides remarkably high efficacy in the manufacture of urethane foam at low weight percent of the surfactant efficacy enhancer, particularly the organic acid. Background Technology

[0006] U.S. Patent Publication US9334382 B2 discloses a method for manufacturing flexible polyurethane foam, and the composition disclosed in the document comprises a cell opener, a cell opener aid, a tertiary amine catalyst, and optionally an acid. Examples of suitable acids comprise organic carboxylic acids containing saturated or unsaturated and substituted or unsubstituted aliphatic or aromatic groups, having single or multiple acid groups, with or without isocyanate reactive groups. The acid is added to block the amine catalyst used in the foaming process.

[0007] The composition claimed in U.S. Patent US9334382 requires the presence of at least one silicone surfactant, wherein the type and amount of the silicone surfactant and the amount of any optional acidic component in the composition are not specified.

[0008] U.S. Patent US5489617A relates to a high-viscosity, non-hydrolyzable silicone surfactant used in the manufacture of polyurethane foam, wherein such surfactant increases the high rise height of the foam and reduces the upper collapse of the foam.

[0009] U.S. Patent Publication US8044109 B2 discloses a method for manufacturing low-density polyurethane foam, wherein a high-efficacy silicone copolymer surfactant is applied to address the problem of low surfactant efficacy in coarse cell structure and cell stabilization.

[0010] W02008 / 019928 A1 discloses a silicone surfactant composition comprising polyethersiloxane, water, dipropylene glycol, and a sodium salt of a linear alkylbenzenesulfonate. Additionally, a surfactant composition comprising polyethersiloxane, water, and a surfactant (PEG 20 sorbitan monolaurate, and may be an ester or cocoamphoacetate, a carboxylic acid salt) is disclosed, but this document does not disclose any surfactant compositions comprising a carboxylic acid.

[0011] WO 2024 / 020776 A1 discloses a surfactant composition comprising water and acetic acid, a silicone surfactant having a pendant alkyl chain, which is introduced into a polyurethane (PU) foam-forming composition to manufacture a PU foam.

[0012] WO 2017 / 180741 A1 discloses a composition comprising a silicone surfactant and a rapeseed methyl ester, which is used to manufacture a polyurethane foam from a foam composition. The problem to be solved

[0013] The present invention aims to provide a simple method for preparing a silicone surfactant composition containing a surfactant efficacy-enhancing agent, particularly an organic acid, having high efficacy in stabilizing urethane foam; a silicone surfactant composition containing a surfactant efficacy-enhancing agent, particularly an organic acid, which exhibits a strong stabilizing effect in the processing of polyurethane foam regardless of the presence or absence of fillers; and a method for manufacturing polyurethane foam in which the silicone surfactant composition containing a surfactant efficacy-enhancing agent, particularly an organic acid, is applied to utilize the excellent stabilizing properties of the surfactant.

[0014] The present invention provides a novel approach for designing a silicone surfactant composition that exhibits high foam stabilization efficacy even at low silicone copolymer concentrations. The silicone surfactant composition according to the present invention has low viscosity and is easy to fill during the foaming process. The silicone surfactant composition according to the present invention provides foam blocks exhibiting improved, i.e., higher stability, and offers a wide tolerance for both pure and high-filled foam formulations by reducing the amount of metal gelling catalyst (e.g., tin octanoate) used in the formulation. Foams formed with this type of silicone surfactant composition possess better stiffness and tensile strength in flexible polyurethane foams. The foam performance of flexible polyurethane foams is optimized when the airflow is reduced. Since airflow is directly correlated with the hardness of polyurethane foam, a reduced airflow of polyurethane foam is advantageous. Generally, lower airflow results in thicker struts and cell walls of the polyurethane foam, leading to higher hardness. When the silicone surfactant composition according to the present invention is used in the manufacture of polyurethane foam, the air flow rate can be reduced and the hardness improved without significantly affecting other properties.

[0015] Accordingly, the present invention aims to provide a silicone surfactant composition that reduces air flow while maintaining or improving the hardness and tensile strength of a flexible polyurethane foam. Likewise, the improved characteristics in terms of uniformity of the polyurethane foam obtained when using the silicone surfactant composition according to the present invention are manifested by a reduction in the difference between the upper core density value and the lower core density value of the polyurethane foam, and a reduction in the difference between the upper and lower compression force deflection (CFD) values ​​at 40%. means of solving the problem

[0016] To address the need for a surfactant composition exhibiting enhanced performance in the stabilization of polyurethane foam, the present invention relates to a silicone surfactant composition for use in polyurethane foam, comprising a surfactant efficacy-enhancing agent, particularly an organic acid, wherein the silicone surfactant composition comprises

[0017] (A) One or more silicone surfactant compounds,

[0018] (B) One or more surfactant efficacy enhancers,

[0019] (C) Optionally composed of one or more diluents.

[0020] The present invention also relates to a method for preparing a silicone surfactant composition containing a surfactant efficacy enhancer, particularly an organic acid; the use of a silicone surfactant composition containing a surfactant efficacy enhancer, particularly an organic acid, in the manufacture of flexible polyurethane foam; a method for manufacturing flexible polyurethane foam using a silicone surfactant containing a surfactant efficacy enhancer, particularly an organic acid; and a polyurethane foam manufactured using a silicone surfactant composition containing a surfactant efficacy enhancer, particularly an organic acid. Specific details for implementing the invention

[0021] The present invention will be described in detail below.

[0022] Specific selections of all features and scopes according to the present invention described below may be combined without any limitations or restrictions, except where combination is impossible due to logical requirements. Likewise, various embodiments of the present invention described below may be combined, and a single feature or option of the features or scopes of the embodiments of the present invention may be combined with other embodiments of the present invention.

[0023] As described above, the present invention relates to a silicone surfactant composition for use in polyurethane foam, comprising the following components:

[0024] (A) One or more silicone surfactant compounds,

[0025] (B) One or more surfactant efficacy enhancers,

[0026] (C) Optionally one or more diluents.

[0027] In the description of the present invention, the terms "silicone surfactant composition" and "surfactant composition" may be used interchangeably.

[0028] In one embodiment, one or more of the silicon surfactant compound (A) comprises a silicon backbone and one or more polyether substituents R, which may be the same or different, attached to one or more Si atoms of the silicon backbone. * It is a silicone surfactant compound composed of including

[0029] According to the present invention, component (B) of the silicone surfactant composition is preferably a carboxylic acid having four or more carbon atoms, wherein one or more of the silicone surfactant compound (A) comprises a silicone backbone and one or more identical or different polyether substituents R attached to one or more Si atoms of the silicone backbone. * The silicone surfactant comprises a component (A) and a carboxylic acid, wherein the amount of component (A) in the silicone surfactant composition is 15.0 weight% or more based on the total weight of the surfactant composition. Preferably, the carboxylic acid is a monocarboxylic acid, and also preferably a carboxylic acid having 6 or more carbon atoms, and more preferably a monocarboxylic acid having 6 or more carbon atoms.

[0030] Silicone surfactant compound (A)

[0031] According to the present invention, the silicone surfactant compound is a class of surfactants having a polydimethylsiloxane backbone and one or more groups R attached to an inner or terminal Si atom of the siloxane backbone, wherein the group R is a hydrophilic polar organyl group and the polydimethylsiloxane backbone is hydrophobic.

[0032] According to the present invention, (CH3)3SiO2 directly bonded to each other 1 / 2 or (CH3)2RSiO 1 / 2 M representing * ; (CH3)2SiO 2 / 2 D representing (CH3)RSiO 2 / 2 D" representing (CH3)SiO 3 / 2 or RSiO 3 / 2 Any structure comprising 5 or more, preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more siloxy units selected from T and Q-unit SiO2 representing T and Q-units forms a silicon backbone, in particular a polydimethylsiloxane backbone.

[0033] The silicon backbone can be linear, branched, ring-shaped, or include a ring-shaped structure.

[0034] The silicon backbone formed by the aforementioned units comprises at least one hydrophilic polar organyl group R, preferably a polyether group R * has

[0035] The silicone surfactant compound A) defined above is preferably (CH3)3SiO2 directly bonded to each other, corresponding to the structure of the polysiloxane backbone defined above. 1 / 2 or (CH3)2HSiO 1 / 2 M representing F *; (CH3)2SiO 2 / 2 D representing F ; (CH3)RSiO 2 / 2D representing F "; (CH3)SiO 3 / 2 or HSiO 3 / 2 T representing F A polysiloxane hydride compound having a polysiloxane backbone structure composed of 5 or more, preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more, siloxy units selected from , and Q-unit SiO2, comprising one or more Si-H moiety at the terminals, on the inside, or both at the terminals and on the inside, and a precursor compound of a hydrophilic polar organyl group R, particularly a polyether group R * It is prepared by a hydrosilylation reaction between polyether compounds containing at least one unsaturated CC bond, particularly a terminal CC double bond, which is a precursor of the.

[0036] Preferably, the polysiloxane hydride providing the backbone structure of the silicone surfactant compound has the following formula and

[0037] M F *(D F ) x (D F ") y M F *,

[0038] (Here, M F *, D F and D F is as defined above, x is 0–200, y is 2 or greater, x+y is 10–250, and the ratio of x to y is 2–50),

[0039] Forms a silicone surfactant compound of the following general formula (I):

[0040] M * D x D" y M * (I),

[0041] (Here, M *is (CH3)3SiO 1 / 2 or (CH3)2RSiO 1 / 2 It represents, and D is (CH3)2SiO 2 / 2 It represents, and D" is (CH3)RSiO 2 / 2 It represents, where x, y, x+y, and the ratio of x to y are as defined above, and R is the hydrophilic group described earlier, preferably R is a polyether substituent R * Represents ).

[0042] More preferably, formula M F *(D F ) x (D F ") y M F In *, M F * is (CH3)3SiO 1 / 2 Representing only, D F and D F ", x, y, x+y, and the ratio of x to y are as defined above, forming a silicone surfactant compound without terminal hydrophobic groups.

[0043] The hydride-containing silicon compounds described above are commercially available, and their synthesis methods are known to those skilled in the art. For example, the synthesis of a hydride-containing silicon compound, also known as a silicon fluid, is described in US 5489617 A.

[0044] Various silicone compounds having polyether substituents are commercially available, examples of which include products such as NIAX® L-895, L-865, or L-580 sold under the NIAX® brand of Momentive Performance Materials, and methods for the hydrosilylation reaction of such compounds and for providing the necessary starting materials are known to those skilled in the art, and are disclosed, for example, in W02023 / 009390 A1, US 5489617 A, and US 2009 / 0253817 A1, which are incorporated herein by reference.

[0045] The hydrosilylation reaction is preferably a transition metal-catalyzed hydrosilylation reaction, generally catalyzed by a platinum compound, e.g., H2PtCl6 or a Karsted catalyst, and can be carried out with or without the presence of a solvent. The hydrosilylation reaction is generally carried out quantitatively.

[0046] Silicone surfactants can be classified into nonionic, anionic, cationic, and amphoteric silicone surfactants depending on the chemical properties of the hydrophilic group R within their chemical structure. According to the present invention, nonionic silicone surfactants are preferred.

[0047] Cationic silicone surfactants include cationic structural groups in the R group, examples of which are alkyl quaternary ammonium compounds, amido quaternary ammonium compounds, and imidazoline-derived quaternary ammonium compounds; anionic silicone surfactants include anionic structural units in the R group, examples of which are phosphate ester salts, sulfate salts, carboxylic acid salts, sulfonate salts, and sulfosuccinamide esters; amphoteric or zwitterionic silicone surfactants include a structure in the R group that has both anionic and cationic properties, examples of which are phosphate betaine or betaine groups.

[0048] In nonionic silicone surfactants, the R group does not contain anionic or cationic functional groups. The R group contains units such as polyethers, alkanolamides, esters, and glycosides, and according to the present invention, an R group containing a polyether unit (hereinafter referred to as a polyether substituent R) * (also referred to as) is preferred. Such silicone surfactants are generally referred to as polyether functional silicone surfactants, polyether silicone surfactants, silicone polyether surfactants, or siloxane-oxyalkylene copolymer surfactants. These terms and similar terms may be used interchangeably in this specification. By definition, any organyl group R containing two or more ether moiety (-O-), i.e., oxygen atoms substituted with two organyl residues, is a polyether substituent R * It is considered as.

[0049] More specifically, polyether substituent R * Generally, it is characterized by containing one or more polyalkylene oxide units, preferably polyalkylene oxide units selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) units, wherein the polyether substituent may contain one, two, or three types of the EO, PO, and BO units, and there is no general limitation on the ratio of these units.

[0050] Polyether substituent R bonded to the silicon backbone of a silicone surfactant compound *The precursor compound, particularly the alkenyl-terminated polyester, can be purchased or prepared by combining an alcohol comprising a CC double bond, specifically an allyl alcohol, with one or more alkylene oxides, particularly one, two, or three types of ethylene oxide, propylene oxide, and butylene oxide, in the presence of a Lewis acid or base to produce a polyether having the desired terminal hydroxyl group. The epoxides may be block-fed or randomly distributed along the ether chain. The polyether thus obtained is generally capped through a further reaction with an alkylating agent or an acylating agent, such as a methyl halide or an acetate anhydride. Such a procedure is common in the art and known to those skilled in the art, and is disclosed, for example, in U.S. Patent No. 4814409, which is incorporated herein by reference.

[0051] In one embodiment of the present invention, the silicone surfactant compound (A) comprises two or more different types of polyether substituents R * It is composed including, preferably, two different types of polyether substituents R * Includes

[0052] R * The type may vary depending, for example, its molecular weight, the number of ether groups, the number of alkylene oxide repeating units and / or the terminal type of the substituent (e.g., alkoxy group or alkanoyl group).

[0053] In many cases, the number of repeating units and molecular weight of available polyethers are not completely uniform, and in such cases, these precursors and the generated R * The molecular weight of a group is expressed as the number-average molecular weight. R *The number average molecular weight of a polyether compound that is a precursor of the group is evaluated by a gel permeation chromatography (GPC) standard method and, after appropriate correction, is measured by GPC using a polystyrene standard in particular.

[0054] In a preferred embodiment according to the present invention, the polyether substituent R of the silicone surfactant compound (A) * is the same or different and has the following equation (II):

[0055] -C n H 2n O(C2H4O) a (C3H6O) b R 1 (II)

[0056] Here,

[0057] n is 2-10, and

[0058] a is an ethylene oxide residue that is a polyether substituent R * The number is such that it accounts for about 30% to about 100% by weight of the alkylene oxide residues;

[0059] b is a propylene oxide residue, which is a polyether substituent R * The number is such that it accounts for about 0% to about 70% by weight of the alkylene oxide residues;

[0060] R 1 is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group, and

[0061] And substituent R * It has a number average molecular weight between about 200 daltons and about 6000 daltons.

[0062] The number average molecular weight is R present in the silicone surfactant. * It refers to the number average of the masses. Therefore, R in silicone surfactants * In the case where only one type of group exists, such substituent R *The number-average molecular weight of this substituent R * It is equal to the mass of.

[0063] Remaining R * Since it is connected to the surfactant backbone via a hydrosilylation reaction, a person skilled in the art would know that residue R * The mass of (m R* ) is the molecular mass (m) of the corresponding unsaturated polyether compound in Daltons. 불포화 폴리에테르 It can be seen that it is equal to the value obtained by adding 1 to ). This is because in the hydrosilylation reaction, Si atoms and hydrogen of the silicon backbone are added to unsaturated sites, mainly CC double bonds.

[0064] This is expressed by the following formula;

[0065] m R* [Dalton] = m 불포화 폴리에테르 [Dalton] + 1 Dalton

[0066] More preferably, n, b, and R in Equation (II) 1 is as defined above, and polyether substituent R * In this, "a" is an ethylene oxide residue that is a polyether substituent R * The alkylene oxide residue accounts for about 35% to about 100% by weight, preferably 40% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 80% to 100% by weight.

[0067] In another preferred embodiment according to the present invention, the polyether substituent R of the silicone surfactant compound (A) * is a polyether substituent having a number average molecular weight of 400 daltons to 4000 daltons, preferably 500 daltons to 3000 daltons, more preferably 700 daltons to 2000 daltons.

[0068] In a preferred embodiment according to the present invention, the silicone surfactant compound (A) comprises one or more polyether substituents R selected from a group (i) having the structure of Formula (II') below and a group (ii) having the structure of Formula (II'') below. * It consists of:

[0069] (i) -C n' H 2n' O(C2H4O) a' (C3H6O) b' R 2 (II')

[0070] (wherein, n' is 2–10; a' is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide residue of the polyether substituent; b' is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether; R 2 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group);

[0071] (ii) -C n'' H 2n'' O(C2H4O) a'' (C3H6O) b'' R 3 (II'')

[0072] (wherein, n" is 2-10; a" is the number in which ethylene oxide residues account for 30% to 100% by weight of the alkylene oxide residues of the polyether substituents; b" is 0 to the number in which propylene oxide residues account for 70% or less by weight of the alkylene oxide residues of the polyether; R 3 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group).

[0073] Also preferably, the silicone surfactant compound (A) has the structure of formula (II'), has a mass in the range of 2000 to 6000 daltons, and has one or more polyether substituents R selected from groups (i) having at least one mass of 3000 daltons or more. * ; and one or more polyether substituents R selected from groups (ii) having the structure of formula (II'') and having a mass in the range of 350 to 1800 daltons * It consists of:

[0074] (i) -C n' H 2n' O(C2H4O) a' (C3H6O) b' R 2 (II')

[0075] (wherein, n' is 2–10; a' is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide residue of the polyether substituent; b' is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether; R 2 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group)

[0076] (ii) -C n'' H 2n'' O(C2H4O) a'' (C3H6O) b'' R 3 (II')

[0077] (wherein" is 2-10, a" is the number in which ethylene oxide residues account for 30% to 100% by weight of the alkylene oxide residues of the polyether substituent, b" is 0 to the number in which propylene oxide residues account for 70% or less by weight of the alkylene oxide residues of the polyether, and R 3represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group).

[0078] Here, all polyether substituents R present in silicone surfactant compound A) * It is preferable that the polyether substituent be selected from type (i) and type (ii).

[0079] Generally, R group (also especially R * There are two types of connections between the siloxane backbone: the Si-OC type and the Si-C type. The former is unstable under aqueous conditions and belongs to the hydrolytic type, while the latter is stable in water and is called the non-hydrolytic type. According to the present invention, the non-hydrolytic type is preferred.

[0080] According to the present invention, the siloxane backbone is preferably represented by the following general formula (I).

[0081] M * D x D" y M * (I),

[0082] Here,

[0083] M * is (CH3)3SiO 1 / 2 or (CH3)2RSiO 1 / 2 Representing;

[0084] D is (CH3)2SiO 2 / 2 Representing;

[0085] D" is (CH3)RSiO 2 / 2 Representing;

[0086] x is 0-200, and

[0087] y is 2 or more, and

[0088] x+y is 10~250, and

[0089] The ratio of x to y is 2 to 50, and

[0090] R is a hydrophilic group as previously described, and preferably, R is a polyether substituent R * It represents.

[0091] In a preferred embodiment of the present invention, one or more silicone surfactant compounds (A) have the following formula and

[0092] M * D x D" y M * (I),

[0093] Here,

[0094] M * is (CH3)3SiO 1 / 2 or (CH3)2R * SiO 1 / 2 Representing;

[0095] D is (CH3)2SiO 2 / 2 Representing;

[0096] D" is ((CH3)R * SiO 2 / 2 Representing;

[0097] x is 0-200 and;

[0098] y is 2 or more, and;

[0099] x+y is 10-250 and;

[0100] The ratio of x to y is 2-50; and

[0101] R * is the same or different -C n H 2n O-group-starting polyether substituent (-C n H 2n It is a polyether substituent independently selected from O-group-started polyether substituents, where n is 2-10.

[0102] term "-C n H 2n "O-group-starting polyether substituent" is a polyether group R *a polyether substituent R * It means that it is linked to the silicon backbone by the terminal C-atom of an alkylene group consisting of n carbon atoms constituting the non-terminal part.

[0103] In another preferred embodiment of the present invention, one or more silicone surfactant compounds (A) have the following formula and

[0104] M * D x D" y M * (I),

[0105] Here,

[0106] M * is (CH3)3SiO 1 / 2 or (CH3)2R * SiO 1 / 2 Represents,

[0107] D is (CH3)2SiO 2 / 2 Represents

[0108] D" is (CH3)R * SiO 2 / 2 Represents,

[0109] x is 0 to 200, and

[0110] y is 2 or more, and

[0111] x+y is 10~250, and

[0112] The ratio of x to y is 2 to 50, and

[0113] R * is the same or different -C n H 2n A polyether substituent independently selected from O-group-starting polyether substituents, wherein n is 2 to 10, and said substituent R * It has a number average molecular weight of 200 daltons to 6000 daltons.

[0114] -C n H 2n The O-group-starting polyether substituent is the polyether substituent R* A polyether group R connected to a silicon backbone by the terminal carbon atoms of an alkylene group comprising n carbon atoms constituting the non-terminal part of the polyether group. * It means.

[0115] Preferably, y is 3 to 20, more preferably 4 to 10, and M * , D, D", x, x+y, the ratio of x to y and R * is as defined above.

[0116] In another preferred embodiment according to the present invention, one or more polyether substituents R of a silicone surfactant compound (A) * It is independently terminated by an alkoxy group or an acyl group, preferably a methoxy group or an acetoxy group.

[0117] More preferably, the silicone surfactant according to the present invention, in particular the silicone surfactant compound represented by formula (I), comprises one or more polyether substituents R having the general structure of formula (II) below. * It consists of:

[0118] -C n H 2n O(C2H4O) a (C3H6O) b R 1 (II)

[0119] Here,

[0120] n is 2-10, and

[0121] a is an ethylene oxide residue that is a polyether substituent R * The number is such that it accounts for about 30% to about 100% by weight of the alkylene oxide residues,

[0122] b is a propylene oxide residue, which is a polyether substituent R * The number is such that it accounts for about 0% to about 70% by weight of the alkylene oxide residues, and

[0123] R 1 is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group. More preferably, substituent R * It has a number average molecular weight of about 200 daltons to about 6000 daltons.

[0124] In another preferred embodiment according to the present invention, the silicone surfactant compound (A) has the following formula (I), and

[0125] M * D x D" y M * (I)

[0126] (Here, M * , D, and D' are as described above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15),

[0127] The above silicone surfactant compound (A) comprises one or more polyether substituents R selected from groups (iii) having the structure of the following formula (II'''). * and one or more polyether substituents R selected from groups (iv) having the structure of the formula (II'''') below. * It consists of:

[0128] (iii) -C n'" H 2n'" O(C2H4O) a'" (C3H6O) b'" R 4 (II'")

[0129] (Here, n''' is 2 to 4, preferably 3, and a''' is an ethylene oxide residue that is a polyether substituent R *The number such that the alkylene oxide accounts for 30% to 60% by weight of the alkylene oxide; b''' is a propylene oxide residue that is a polyether substituent R * The number is such that it accounts for 40% to 70% by weight of the alkylene oxide residues of; R 4 represents a methyl group or an acetyl group),

[0130] (iv) -C n"" H 2n"" O(C2H4O) a"" (C3H6O) b"" R 5 (II"")

[0131] (Here, n'''' is 2 to 4, preferably 3, and a'''' is an ethylene oxide residue that is a polyether substituent R * The number such that the alkylene oxide residue occupies 30% to 100% by weight of; b'''' is 0 to, where the propylene oxide residue is a polyether substituent R * It is a number that accounts for 70% or less of the alkylene oxide residues of, and R 5 represents a methyl group or an acetyl group).

[0132] According to the present embodiment, one or more polyether substituents R selected from groups (iii) having the structure of formula (II''') * is one or more polyether substituents R selected from groups (iv) having the structure of formula (II''') having a mass of 3500 to 6000 daltons. * It is desirable that it have a mass of 350 to 1800 daltons.

[0133] In addition, all polyether substituents R present in the silicone surfactant compound (A) * It is preferable that the polyether substituents of (iii) and (iv) be selected.

[0134] According to the present invention, the polyether substituent R *In particular, it is desirable that one or more of the polyether substituents having formula (II), more preferably all of them, are directly bonded to one or more inner or terminal Si atoms of the siloxane backbone, that is, bonded in a non-hydrolytic manner. This is because, in the case of a silicone surfactant compound represented by formula (I), the polyether substituent R of general formula (II) * It is absolutely clear regarding.

[0135] In one embodiment of the present invention, the amount of component (A) in the silicone surfactant composition is 15.0 wt% or more, preferably 20.0 wt% or more, more preferably 30.0 wt% or more, more preferably 40.0 wt% or more, more preferably 50 wt% or more, based on the total weight of the surfactant composition.

[0136] In particular, in the absence of a diluent (C), a silicone surfactant (A) is generally the main component of the silicone surfactant composition according to the present invention.

[0137] Surfactant Efficacy Enhancer (B)

[0138] According to the present invention, a surfactant efficacy enhancer is a compound capable of improving the performance of a silicone surfactant in a polyurethane (PU) foam forming process. This means that the addition of a surfactant efficacy enhancer to a silicone surfactant used in PU foam forming provides a foam block exhibiting improved high stability and a wide processing latitude in both pure and high-filled foam formulations with a smaller amount of metal gelation catalyst (e.g., tin octanoate) in the formulation, and provides a foam with superior firmness and tensile strength in flexible polyurethane foams. This also means that by adding a surfactant efficacy enhancer, the amount of silicone surfactant required to achieve a specific level of parameters, such as the stability of the polyurethane foam or the firmness or tensile strength of the flexible polyurethane foam, is reduced.

[0139] According to the present invention, the surfactant efficacy enhancer is preferably an organic acid or an organic acid-based compound. According to the present invention, "organic acid-based compound" refers to a compound formed by salt formation from an organic acid, i.e., an organic acid salt, or a compound formed by esterification, i.e., an organic acid ester. Here, the cationic counterion of the anion formed from the organic acid as defined herein is not limited in a particular way. A preferred cation of the organic acid salt is an alkali metal ion (Li + , Na* + , K + , Rb + , Cs + , especially Na + and K + ), alkaline earth metal ions (especially Mg 2+ , Ca 2+ ), and Al 3+ , Sn4+ , or Fe 2+ or Fe 3+ Other metal ions such as ammonium cations (NH4 + ) and organically substituted ammonium cations, in particular having four organyl groups, preferably hydrocarbyl groups, N(Me) 4+ , N(Et) 4+ , N(Bu) 4+ ), quaternary ammonium cations such as dimethyldialkylammonium cations and diester quats; phosphonium cations (PH4 + ) and organosubstituted phosphonium cations, in particular quaternary phosphonium cations having four organyl groups.

[0140] In one embodiment according to the present invention, one or more of the components (B) are organic acids.

[0141] According to the present invention, the organic acid is selected from the group consisting of organic acids having at least one acidic functional group A*, and the acidic functional group A* is preferably,

[0142] -C(=O)(-OH);

[0143] -C(=S)(-OH);

[0144] -S(=O)2(-OH);

[0145] -OS(=O)2(-OH);

[0146] -S(=O)(-OH);

[0147] -OS(=O)(-OH);

[0148] (-O)2P(=O)(-OH);

[0149] -OP(=O)(-OH);

[0150] -OP(=O)2(-OH); and

[0151] It is selected from the group consisting of -ON(=O)(-OH), and preferably, the at least one acidic functional group is a carboxylic acid group (-C(=O)(-OH)) or a sulfonic acid group (-S(=O)2(-OH)), most preferably a carboxylic acid group (-C(=O)(-OH)).

[0152] These organic acids can have the following general formula (V):

[0153] R ** -(A * ) o (V),

[0154] Here, R ** It may have 30 or fewer, preferably 20 or fewer, more preferably 12 or fewer carbon atoms that are optionally substituted, and an acidic functional group A * An organic group such as an aromatic or aliphatic group that may optionally comprise additional heteroatoms such as halogens (F, Cl, Br, I), O, N, S, P, Si, B, etc., other than those provided by, wherein the optional substituent is preferably selected from halogens (F, Cl, Br, I), hydroxy, alkoxy, acyl, cyano, nitro, etc., and wherein an acidic functional group A * is as previously defined, and o is an integer of 1 to 4, preferably 1 to 3, more preferably 1 to 2.

[0155] As previously defined, the organic acid-based compound corresponding to the organic acid is obtained through salt formation (where A * ga forms an anion by partial abstraction), or is obtained through an esterification reaction (wherein the (-OH) group is formally an organyloxy group, preferably an alkoxy group (-OR *** Substituted with ), where R *** is an organyl group, preferably a C1-C24 alkyl group.

[0156] The organic acid may be selected from the group consisting of organic acids having four or more carbon atoms selected from carboxylic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids, and phosphoric acids, which are optionally connected to organic groups such as alkyl, haloalkyl, perfluoroalkyl, cycloalkyl, alkenyl, aryl, aralkyl, substituted alkyl, cycloalkyl, alkenyl, aryl, aralkyl, and carboxylic acids, which contain, optionally as substituents, halides such as F, Cl, Br, I, nitro groups, cyano groups, thiocyano groups, hydroxyl groups, sulfhydryl groups, alkoxy groups, alkylthio or arylthiol groups, acyl groups, carboxylic acid esters or acid groups, sulfonic acid esters or acid groups, phosphate esters or acid groups. Preferably, the organic acid is selected from carboxylic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids, and phosphoric acids connected to an organic group as defined above, wherein the organic group has four or more consecutive carbon atoms, more preferably the organic group is an alkyl group having four or more carbon atoms, and most preferably the organic group is an unsubstituted alkyl group having four or more carbon atoms. Among these, carboxylic acids are most preferred.

[0157] In one embodiment of the present invention, component (B) is an organic acid, an organic acid salt, or an organic acid ester having 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. Here, the number of carbon atoms refers to the total number of carbon atoms present in a specific structure of the corresponding compound, which is the number of carbon atoms present in the anion in the case of an organic acid salt, and the sum of the number of carbon atoms present in the cation if present.

[0158] The above acid may be an organic sulfonic acid or organic sulfinic acid such as benzenesulfinic acid, 4-dodecylbenzenesulfonic acid, p-toluenesulfonic acid; a halogenated carboxylic acid such as perfluorobutanoic acid, 2-bromobenzoic acid, fluorinated or chlorinated carboxylic acid; a phosphorus-based organic acid such as octylphosphonic acid, 12-mercaptododecylphosphonic acid; a carboxylic acid such as oxalic acid, pyruvate, 3-oxobutanoic acid, maleic acid or fumaric acid, cis or trans-1,2-cyclopropanedicarboxylic acid and terephthalic acid, and combinations thereof. Additional examples include salicylic acid, malic acid, 1-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 1,5-naphthalenedisulfonic acid, 10-camphorsulfonic acid, 1-hexanesulfonic acid, aminoethanesulfonic acid, diphenylphosphate, phenylphosphonic acid, p-nitrobenzenesulfonic acid, and combinations thereof. An organic acid-based compound according to this aspect of the invention is selected from a corresponding salt or ester formed from said organic acid.

[0159] According to the present invention, the organic acid or organic acid-based compound is preferably selected from carboxylic acid, carboxylic acid salt, carboxylic acid ester, organosulfic acid, organosulfate salt, organosulfate ester, organosulfonic acid, organosulfonic acid salt, organosulfonic acid ester, organophosphonic acid, organophosphonic acid salt, organophosphonic acid ester, organophosphonic acid, organophosphonic acid salt, and organophosphonic acid salt.

[0160] Here, the group of carboxylic acids, carboxylic acid esters, and carboxylic acid salts (i.e., carboxylic acid esters and carboxylic acid salts of organic acids containing a carboxyl group -C(O)O-) is more preferred as surfactant efficacy enhancers. The most preferred type of surfactant efficacy enhancer is a carboxylic acid.

[0161] In a preferred embodiment according to the present invention, component (B) is an organic acid having 4 or more carbon atoms, preferably 6 or more, more preferably a carboxylic acid having 6 or more carbon atoms, more preferably a monocarboxylic acid having 6 or more carbon atoms; or component (B) is an organic acid salt having 4 or more carbon atoms in the anionic portion, preferably an organic acid salt having 6 or more carbon atoms in the anionic portion, more preferably a carboxylic acid salt having 6 or more carbon atoms in the anionic portion, more preferably a monocarboxylic acid salt having 6 or more carbon atoms in the anionic portion; or component (B) is an organic acid ester having 4 or more carbon atoms in a structure corresponding to the organic acid, preferably an organic acid ester having 6 or more carbon atoms in a structure corresponding to the organic acid, more preferably a carboxylic acid ester having 6 or more carbon atoms in a structure corresponding to the organic acid, more preferably a carbon It is a monocarboxylic acid ester or a dicarboxylic acid ester having 6 or more atoms.

[0162] Here, in the case of organic acid salts, only the number of carbon atoms present in the anions of the salt constituting component (B), obtained from the corresponding organic acid by deprotonation, that is, the number of carbon atoms of the organic sulfonate or carboxylate anions, is considered. In the case of organic acid esters, the number of carbon atoms of the structure corresponding to the organic acid is considered, which means that the carbon atoms of the organyloxy group (especially the alkoxy group) that formally replaces the -OH group of the organic acid that forms the organic acid ester are not considered. For example, methyl oleate has a total of 19 carbon atoms, whereas the number of carbon atoms of the structure corresponding to the organic acid (in this case, oleic acid) is 18.

[0163] In a preferred embodiment of the present invention, one or more of component (B) is a carboxylic acid (preferably a monocarboxylic acid), a carboxylic acid salt (preferably a monocarboxylic acid salt), or a carboxylic acid ester (preferably a monocarboxylic acid ester or a dicarboxylic acid ester).

[0164] carboxylic acid

[0165] As defined above, all organic compounds comprising at least one -C(O)OH group, that is, at least one carboxyl group, are considered to be carboxylic acids.

[0166] In one embodiment of the present invention, component (B) is an aliphatic carboxylic acid or an aromatic carboxylic acid, preferably an aliphatic carboxylic acid, and more preferably an alkanic acid.

[0167] In a preferred embodiment of the present invention, component (B) is an alkanic acid or alkenoic acid having 4 to 30 carbon atoms, preferably 6 to 24 carbon atoms, and more preferably 9 to 20 carbon atoms. Here, the carboxylic acid is selected from saturated fatty acids, monounsaturated fatty acids, and diunsaturated fatty acids, and is particularly preferably selected from caproic acid, caprylic acid, capric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, linoleic acid, α-linoleic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and ricinoleic acid.

[0168] According to the present invention, a preferred monocarboxylic acid is selected from C4 to C24 carboxylic acids, in particular butyric acid, valeric acid, caproic acid, enantic acid, caprylic acid, pelargonic acid, capric acid, undecanic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanic acid, palmitic acid, margaric acid, stearic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, nonadecylic acid, arachidic acid, midic acid, arachidonic acid, heneicosanoic acid, docosanoic acid, tricosylic acid and lignoceric acid, benzoic acid and 4-methoxybenzoic acid. The carboxylic acid may also be selected from dicarboxylic acids, preferably dicarboxylic acids having 9 or more carbon atoms, in particular sebacic acid, dimer acids, amino-functional dicarboxylic acids, tricarboxylic acids, preferably tricarboxylic acids having 13 or more carbon atoms, and tetracarboxylic acids, preferably tetracarboxylic acids having 16 or more carbon atoms. Examples of preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, souveric acid, azelaic acid, sebacic acid, undecanedionic acid, dodecanedionic acid, tridecanedionic acid, hexadecanedionic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, citraconic acid, mesaconic acid, and itaconic acid.

[0169] As described above, in one aspect of the present invention, the carboxylic acid is preferably selected from fatty acids.

[0170] In this specification, the term "fatty acid" refers to a carboxylic acid having a chain-like organyl group and typically having a terminal carboxyl group, in particular an unbranched aliphatic monocarboxylic acid having a terminal carboxyl group. Fatty acids differ from one another according to the number of carbon atoms (chain length), and in the case of unsaturated fatty acids, are classified according to the number and position of double bonds. Fatty acids may be classified into short-chain fatty acids having 7 or fewer carbon atoms, medium-chain fatty acids having 8 to 12 carbon atoms, long-chain fatty acids having 13 to 21 carbon atoms, and extra-long-chain fatty acids having 22 or more carbon atoms. C7-C25 fatty acids having a terminal carboxyl group and no additional substituents are preferred.

[0171] In another preferred embodiment of the present invention, component (B) is a branched or cyclic alkanic acid, preferably a branched alkanic acid, and more preferably a branched alkanic acid having 5 to 24 carbon atoms.

[0172] In a preferred embodiment according to the present invention, component (B) is a carboxylic acid containing one or more quaternary carbon atoms, preferably an aliphatic carboxylic acid containing one or more quaternary carbon atoms, and more preferably an acyclic alkanic acid containing one or more quaternary carbon atoms.

[0173] Carboxylic acids containing a quaternary C-atom, a C-atom connected to four other carbon atoms through a single bond, have been found to be a particularly desirable group of carboxylic acids, especially alkanes.

[0174] Additionally, preferably, component (B) is a branched alkyl monocarboxylic acid having 5 to 20 carbon atoms, containing one or more quaternary carbon atoms, preferably containing a quaternary carbon atom at the α-position of the carboxylic acid group. It is also preferable that component (B) be selected from the group consisting of C8-neoalkaniol, C9-neoalkaniol, C10-neoalkaniol, C11-neoalkaniol, C12-neoalkaniol, C13-neoalkaniol, and C14-neoalkaniol, among which neononalanic acid, neodecanoic acid, and neoundecanoic acid are preferred.

[0175] Carboxylic acid salt

[0176] As defined above, an organic compound comprising at least one carboxylate anion, i.e., at least one deprotonated carboxyl group (-C(O)O- group), is considered a carboxylic acid salt. Any carboxylic acid salt mentioned in a general or specific form according to the present invention may be used according to the present invention, and the same applies to a preferred carboxylic acid salt according to the present invention.

[0177] Here, there is no limitation on the cation used as a counter-ion for the anion formed from the carboxylic acid. The same cation described above as preferred for organic acid salts is also preferred for carboxylic acid salts.

[0178] Accordingly, in one embodiment of the present invention, component (B) is an aliphatic carboxylic acid salt or an aromatic carboxylic acid salt, preferably an aliphatic carboxylic acid salt, and more preferably an alkanate salt. Additionally, preferably, component (B) is an alkanate salt or an alkene salt having 4 to 30 carbon atoms in the anionic portion, preferably 6 to 24 carbon atoms in the anionic portion, and more preferably 9 to 20 carbon atoms in the anionic portion.

[0179] In a preferred embodiment according to the present invention, component (B) is a branched or cyclic alkanate salt, preferably a branched alkanate salt, and more preferably a branched alkanate salt having 5 to 24 carbon atoms in the anionic portion.

[0180] In another preferred embodiment of the present invention, component (B) is preferably a carboxylic acid salt comprising one or more quaternary carbon atoms, preferably an aliphatic carboxylic acid comprising one or more quaternary carbon atoms, and more preferably an acyclic alkanic acid comprising one or more quaternary carbon atoms.

[0181] Carboxylic acid ester

[0182] As defined above, at least one ester group -C(O)OR *** G, that is, alcohol R *** An organic compound comprising at least one group formally derived from a carboxyl group by an esterification reaction with -OH is considered a carboxylic acid ester.

[0183] According to the present invention, esters of all carboxylic acids mentioned above in general or specific forms may be applied according to the present invention, and preferred esters of carboxylic acids according to the present invention are likewise preferred. The ester group is an organyl group R *** The structure of is not particularly limited, but preferably R *** is a C1 to C24 alkyl group, which may be linear, branched, or cyclic. Preferred R ***The groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, pentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, and particularly methyl, ethyl, and propyl groups are preferred. Accordingly, in an embodiment of the present invention, component (B) is an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester, preferably an aliphatic carboxylic acid ester, and more preferably an alkanic acid ester.

[0184] In a preferred embodiment of the present invention, component (B) is an alkanic acid ester or alkenoic acid ester having 4 to 30 carbon atoms with a structure corresponding to an organic acid, preferably an alkanic acid ester having 6 to 24 carbon atoms with a structure corresponding to an organic acid, and more preferably an alkanic acid ester having 9 to 20 carbon atoms with a structure corresponding to an organic acid. In another preferred embodiment of the present invention, component (B) is a linear or branched alkanic acid ester, preferably a linear alkanic acid ester, more preferably a linear alkanic acid ester having 5 to 24 carbon atoms with a structure corresponding to an organic acid, and more preferably a linear mono- or di-alkanic acid ester having 5 to 24 carbon atoms with a structure corresponding to an organic acid.

[0185] In one embodiment of the present invention, component (B) is contained in the surfactant composition in an amount of 0.01 to 70 weight% based on the total weight of the surfactant composition, preferably in an amount of 0.2 to 20 weight% based on the total weight of the surfactant composition. According to the present embodiment, the ratio (weight ratio) of component (A) to component (B) is preferably 100:1 to 2:1, preferably 50:1 to 3:1, more preferably 20:1 to 4:1, and very preferably 15:1 to 5:1.

[0186] In another embodiment of the present invention, the amount of component (B) in the silicone surfactant composition is 0.02 to 50 weight%, preferably 0.5 to 25 weight%, more preferably 1.0 to 10 weight%, very preferably 1.5 to 8 weight%, and even more preferably 2.5 to 7 weight% based on the total weight of components (A), (B), and (C) of the silicone surfactant composition.

[0187] Diluent (C)

[0188] Additionally, according to the present invention, the diluent is a liquid compound other than component (A) and component (B) or a liquid mixture of these compounds. Preferably, the diluent can be completely miscible with component (A), component (B), and combinations of components (A) and (B), and more preferably, can be miscible in any proportion.

[0189] The types of diluents (C) according to the present invention include, for example, water, alcohols, particularly alkanols, di- and poly-ols, particularly di- and poly-hydroxylated alkanes, mono-, di- and poly-ethers, particularly alkyl and alkylene di- and poly-ethers, aliphatic and aromatic hydrocarbons, particularly alkanes and alkylated phenyl compounds, halogenated hydrocarbons, particularly partially halogenated or perhalogenated alkanes and partially halogenated or perhalogenated alkylated phenyl compounds), ketones, organic amides, organic nitriles, organic sulfoxides, and organocarbonates. Accordingly, in one embodiment of the present invention, the diluent (C) is selected from water, monoalcohol, di- or poly-ol, mono-, di- or poly-ether, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, particularly partially halogenated or perhalogenated alkanes and partially halogenated or perhalogenated alkylated phenyl compounds, ketones, amides, nitriles, sulfoxides, or organocarbonates, or a combination of two or more of these.

[0190] In a preferred embodiment of the present invention, the diluent (C) is completely miscible with component (A) and component (B), preferably a mono- or poly-ether having up to 40 ether groups, and more preferably a mono- or poly-ether having 8 or fewer ether groups.

[0191] Regarding the requirement for complete miscibility, it should be noted first that complete miscibility means that the surfactant compound (A) and compound (B) must be in a liquid state at room temperature (20°C) and can be diluted by a diluent (C) in any mixing ratio to obtain a homogeneous mixture. When compound (A) and / or particularly compound (B) is solid at room temperature (20°C), for example, when compound (B) is a solid organic acid salt, complete miscibility is considered to exist when compound (A) and / or compound (B) can be dissolved in the diluent at room temperature (20°C) in an amount of at least 100 g / L, preferably 200 g / L, more preferably 300 g / L, more preferably 500 g / L, more preferably 750 g / L, more preferably 1000 g / L, and most preferably 1500 g / L. Preferred diluents are polyalkylene oxides, polyols, and glycols, in particular glycols selected from hexylene glycol, dipropylene glycol, diethylene glycol, monopropylene glycol, monoethylene glycol, methylpentanediol, and methylpropanediol.

[0192] In a preferred embodiment according to the present invention, the diluent (C) comprises a mono- or poly-ether alcohol, preferably a glycol ether, and more preferably, the diluent (C) is a mono- or poly-ether alcohol, specifically a glycol ether. Specifically, the diluent (C) is preferably composed of an ethylene glycol ether or a propylene glycol ether, preferably a dipropylene glycol, and more preferably, the diluent (C) is an ethylene glycol ether or a propylene glycol ether, particularly a dipropylene glycol.

[0193] In one embodiment of the present invention, the composition comprises one or more diluents (C), preferably the amount of diluent is 20% by weight or more, more preferably 35% by weight or more, more preferably 50% by weight or more, more preferably 65% ​​by weight or more, more preferably 75% by weight or more, and most preferably 85% by weight or more, based on the total weight of the surfactant composition.

[0194] Surfactant composition

[0195] In the application of silicone surfactant compositions to polyurethane (PU) foam-forming compositions, high-viscosity silicone surfactant compositions are not suitable in terms of processability.

[0196] In one embodiment of the present invention, the viscosity of the surfactant composition is 5000 cSt or less at 25°C when measured by a capillary viscometer, preferably 4000 cSt or less at 25°C, more preferably 3000 cSt or less at 25°C, even more preferably 2500 cSt or less at 25°C, and most preferably 2000 cSt or less at 25°C.

[0197] According to the present invention, a surfactant composition can be prepared by mixing component (A), component (B), and, if present, component (C), and optional additives, and there are no restrictions on the order of addition or the device used for mixing. Generally, any type of commercial and industrial mixer, such as a drum mixer, ribbon blender, planetary mixer, paddle mixer, or any vessel or tank equipped with a stirrer, may be used.

[0198] The mixture can also be prepared by putting the ingredients into a container, closing the container, and mixing by hand or by shaking with a shaker.

[0199] In one embodiment of the present invention, component (A) and component (B) are 20% by weight or more, preferably 25% by weight or more, more preferably 30% by weight or more, more preferably 35% by weight or more, based on the total weight of components (A), (B) and (C) of the silicone surfactant composition.

[0200] In another embodiment of the present invention, the sum of components (A), (B) and (C) is 70% by weight or more, preferably 80% by weight or more, more preferably 85% by weight or more, even more preferably 90% by weight or more, and most preferably 95% by weight or more of the total weight of the composition. Preferably, the sum of components (A), (B) and (C) is 100% by weight of the total weight of the surfactant composition.

[0201] In one preferred embodiment of the present invention, in a silicone surfactant composition, the silicone surfactant compound (A) has the following formula (I).

[0202] M * D x D" y M * (I),

[0203] (Here, M* , D, and D' are as described above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15;

[0204] The above silicone surfactant compound (A) has the structure of formula (II') and has a mass in the range of 2000 to 6000 daltons, wherein at least one polyether substituent R is selected from group (i) having a mass of 3000 daltons or more. * ; and one or more polyether substituents R selected from groups (ii) having the structure of formula (II') and having a mass in the range of 350 to 1800 daltons * Composed of including;

[0205] (i) -C n' H 2n' O(C2H4O) a' (C3H6O) b' R 2 (II')

[0206] (wherein, n' is 2–10; a' is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide residue of the polyether substituent; b' is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether; R 2 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group),

[0207] (ii) -C n'' H 2n'' O(C2H4O) a'' (C3H6O) b'' R 3 (II')

[0208] (wherein" is 2-10, a" is the number in which ethylene oxide residues account for 30% to 100% by weight of the alkylene oxide residues of the polyether substituent, b" is 0 to the number in which propylene oxide residues account for 70% or less by weight of the alkylene oxide residues of the polyether, and R 3 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group);

[0209] Component (B) is a carboxylic acid, a carboxylic acid salt, or a carboxylic acid ester, preferably a carboxylic acid,

[0210] The above composition is optionally composed of a diluent (C), preferably glycol ether, most preferably dipropylene glycol.

[0211] In another preferred embodiment according to the present invention, the silicone surfactant compound (A) has the following formula (I) and

[0212] M * D x D" y M * (I)

[0213] (Here, M * , D, and D' are as defined above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15);

[0214] The above silicone surfactant compound (A) comprises one or more polyether substituents R selected from groups (iii) having the structure of the following formula (II'''). * , and one or more polyether substituents R selected from groups (iv) having the structure of the formula (II''') below. * Composed of including

[0215] (iii) -C n'" H 2n'" O(C2H4O) a'" (C3H6O) b'" R 4 (II'")

[0216] (wherein, n'" is 2 to 4, preferably 3, and a'" is a number such that the ethylene oxide residue accounts for 30% to 60% by weight of the alkylene oxide of the polyether substituent; b'" is a number such that the propylene oxide residue accounts for 40% to 70% by weight of the alkylene oxide residue of the polyether; R 4 represents a methoxy group, acetoxy group, or butoxyl group),

[0217] (iv) -C n'''' H 2n'''' O(C2H4O) a'''' (C3H6O) b'''' R 5 (II'''')

[0218] (wherein, n'''' is 2 to 4, preferably 3, and a'''' is a number such that the ethylene oxide residue occupies 30% to 100% by weight of the alkylene oxide residue of the polyether substituent; b'''' is a number such that the propylene oxide residue occupies 70% or less of the alkylene oxide residue of the polyether, and R 5 represents a methoxy group, acetoxy group, or butoxyl group);

[0219] Component (B) is an organic acid, and the organic acid (B) is an alkyl carboxylic acid having 5 to 24 carbon atoms, preferably a branched alkyl carboxylic acid having 5 to 24 carbon atoms, more preferably selected from the group consisting of C8-neoalkanoic acid, C9-neoalkanoic acid, C10-neoalkanoic acid, C11-neoalkanoic acid, C12-neoalkanoic acid, C13-neoalkanoic acid, and C14-neoalkanoic acid, and most preferably a neodecanoic acid.

[0220] And the above composition is optionally composed of a diluent (C), the diluent (C) is preferably a glycol ether and most preferably a dipropylene glycol.

[0221] More preferably, according to the present embodiment, the silicone surfactant compound (A) has one or more polyether substituents R selected from groups (iii) having a mass in the range of 3500 to 6000 daltons and having the structure of formula (II''') below. * , and one or more polyether substituents R selected from groups (iv) having the structure of the formula (II"") below and having a mass of 350 to 1800 daltons. * Composed of including;

[0222] (iii) -C n''' H 2n''' O(C2H4O) a''' (C3H6O) b''' R 4 (II''')

[0223] (wherein, n''' is 2 to 4, preferably 3, and a''' is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide of the polyether substituent; b''' is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether; R 4 represents a methoxy group, acetoxy group, or butoxyl group),

[0224] (iv) -C n"" H 2n"" O(C2H4O) a"" (C3H6O) b"" R 5 (II"")

[0225] (wherein, n'''' is 2 to 4, preferably 3, and a'''' is a number such that the ethylene oxide residue occupies 30% to 100% by weight of the alkylene oxide residue of the polyether substituent; b'''' is a number such that the propylene oxide residue occupies 70% or less of the alkylene oxide residue of the polyether, and R 5 represents a methoxy group, acetoxy group, or butoxyl group).

[0226] According to the above embodiment, all polyether substituents R present in the silicone surfactant compound (A) * It is more preferable that it be selected from the polyether substituents of group (iii) and group (iv).

[0227] In one embodiment of the present invention, the silicone surfactant composition comprises, based on the weight of the surfactant composition, 20 to 80 weight% of a silicone surfactant compound (A), 1 to 8 weight% of a component (B), and 12 to 79 weight% of a diluent (C), respectively, and the sum of components (A), (B) and (C) is 95 weight% or more, preferably 100 weight%, of the surfactant composition.

[0228] Here, preferably, component (B) is an organic acid (B), and more preferably, the carboxylic acid described above.

[0229] In another preferred embodiment of the present invention, the ratio (weight ratio) of component (A) to component (B) is in the range of 100:1 to 2:1, preferably 50:1 to 3:1, more preferably 20:1 to 4:1, and even more preferably 15:1 to 5:1.

[0230] One aspect of the present invention relates to a method for preparing a surfactant composition according to the above description, said method comprising the step of mixing component (A), component (B), and optionally component (C). As previously mentioned, any type of commercial and industrial mixer generally known to a person skilled in the art, such as a drum mixer, ribbon blender, planetary mixer, paddle mixer, or a container or tank equipped with a stirrer, may be used. Additionally, the mixture may be prepared by placing the components into a container, sealing the container, and then mixing by shaking manually or using a shaker. Preferably, the mixing process yields a homogeneous surfactant composition without solids or phase separation.

[0231] One aspect of the present invention relates to using a surfactant composition according to the present invention as described above in the manufacture of polyurethane foam, particularly flexible polyurethane foam. Preferably, the surfactant composition is used as a component of a polyurethane foam forming composition to form a polyurethane foam.

[0232] According to the present invention, when combining the components of a polyurethane (PU) foam-forming composition, it is preferable to add the surfactant composition described herein as a formulation. Alternatively, the components of the silicone surfactant composition may be combined by adding the components individually when forming the PU foam-forming composition.

[0233] According to the present invention, in a process for manufacturing a polyurethane foam, the surfactant composition described above is combined with at least one polyol and at least one isocyanate compound. Accordingly, in one embodiment of the present invention, a method for manufacturing a polyurethane foam comprises the step of combining the surfactant composition described above with at least one isocyanate and at least one polyol. As mentioned above, components (A), (B), and (C) can each be added individually.

[0234] There are no particular restrictions on the order in which the surfactant composition, polyol, isocyanate, and additional optional components and additives for forming the polyurethane foam, such as catalyst, solvent, filler, and additional processing aid, are combined, but it is preferable to add the catalyst and isocyanate after combining the surfactant composition and the polyol. More preferably, the surfactant composition, polyol, optionally filler and / or solvent, and additional additives are combined and mixed with the catalyst, then the catalyst is added, and subsequently the isocyanate is added. Through this process, a polyurethane foam comprising the silicone surfactant composition as described above is obtained.

[0235] A polyurethane foam is formed by mixing the surfactant composition of the present invention, a polyol, an isocyanate, and preferably a catalyst and additional additives.

[0236] In one aspect according to the present invention, a polyurethane foam-forming composition comprises: (a) one or more polyols; (b) one or more polyisocyanates; (c) one or more catalysts; (d) water; (e) a silicone surfactant composition of the present invention as described herein; and (f) optionally additional additives and auxiliary compounds.

[0237] In such polyurethane foam-forming compositions, the foaming process is more stable than without the surfactant efficacy enhancer applied according to the present invention, which is manifested by a low settling value and no split issues.

[0238] Furthermore, the physical performance of the polyurethane foam formed from the composition according to the present invention is superior to that of a foam without a surfactant efficacy enhancer, which is manifested by relatively low density, high hardness (CFD), and foam uniformity. Additionally, in the polyurethane foam formed from the foam-forming composition described above according to the present invention, it can be observed that the hardness of the polyurethane foam increases as the airflow value decreases. As the airflow decreases, the foam struts and cell walls can become thicker, leading to higher hardness. It is observed that a relatively low airflow does not significantly affect other physical properties of the foam, but contributes to an improvement in hardness.

[0239] In a preferred embodiment of the present invention, in the polyurethane foam forming composition, the silicone surfactant composition of the present invention is present in an amount of about 0.1 to 7.0 parts by weight based on the total weight of the polyol component.

[0240] In another preferred embodiment of the present invention, the amount of the silicone surfactant composition is such that the amount of organic acid (B) contained in the polyurethane foam-forming composition is about 0.01 to 1.0 parts by weight based on the total weight of the polyol component, and the amount of silicone surfactant compound (A) contained in the silicone surfactant composition is about 0.099 to 6.99 parts by weight based on the total weight of the polyol component.

[0241] In another preferred embodiment of the present invention, the CFD top-bottom difference of the PU foam sample obtained when foaming the polyurethane foam forming composition is 15% or less.

[0242] The "CFD difference," referred to as the "CFD upper-lower difference," refers to the difference in percentage values ​​obtained from the measurement of 40% CFD values ​​according to ISO 3386 / 1 between an upper foam sample and a lower foam sample taken from a polyurethane block with a base of 10 cm x 10 cm and a height of 5 cm, which is calculated as "[(Upper CFD value - Lower CFD value) / Average value] x 100". Here, the "average value" is the sum of the "upper CFD value" and the "lower CFD value" divided by 2. The "upper" foam sample refers to a sample taken from approximately 3 cm below the upper surface of the foam block to approximately 5 cm below thereafter, and the "lower" foam sample refers to a sample taken from approximately 3 cm above the lower surface of the polyurethane block to approximately 5 cm above thereafter. The foam block from which the sample is taken is obtained by mixing the components of a polyurethane foam composition, pouring the resulting liquid foam into a paper box measuring 20x20x20cm, curing it in a forced air oven for 15 minutes after the foam has finished rising, cooling it for 24 hours, and then taking a foam sample.

[0243] From the polyurethane foam-forming composition described above, a polyurethane foam according to the present invention is obtained. As previously explained, such a foam preferably exhibits a CFD top-bottom difference of 15% or less.

[0244] The components of the polyurethane foam composition according to this aspect of the present invention are further described below.

[0245] Polyol (a)

[0246] Polyol (a) is composed of single polyols and mixtures of polyols used in the manufacture of polyurethanes and, in particular, polyurethane foams (see, e.g., Mark F. Sonnenschein, Ph.D, Polyurethanes Science, Technology, Markets, and Trends, Wiley 2015). Polyol (a) is used in commercial purity grades of 95 wt% or higher.

[0247] The kinematic viscosity of component (a) is preferably in the range of about 200 to 6500 cSt (25°C), and more preferably in the range of about 300 to 1000 cSt (25°C).

[0248] As polyol (a), copolymer polyols known as polyether polyols, polyester polyols, or graft polyols may be used. Generally, polyol (a) is a polyol with a hydroxyl value of about 10 to about 700 [see, e.g., Chemistry and Technology of Polyols for Polyurethanes, by Mihail Ionescu, Rapra Technology LTD. (2005)]. Polyols useful for the compositions of the present invention and for the manufacture of polyurethanes (particularly for the manufacture of polyurethanes via a one-shot foaming procedure) are all types of polyols currently used in the art for the manufacture of flexible slabstock foam, flexible molded foam, semi-flexible foam, and rigid foam. These polyols are generally liquid at room temperature and pressure and include polyether polyols and polyester polyols with a hydroxyl value in the range of about 15 to about 700. Preferably, the hydroxyl value is about 20 to about 60 for flexible foam, about 100 to about 300 for semi-flexible foam, and about 250 to about 700 for rigid foam. For flexible foam, the preferred functionality of the polyol, i.e., the average hydroxyl value per polyol molecule, is preferably about 2 to about 4, and most preferably about 2.3 to about 3.5. For rigid foam, the preferred functionality is about 2 to about 8, and most preferably about 3 to about 5. The composition of the present invention comprises, for example, but is not limited to the following types of polyols as polyol (a):

[0249] (1) Polyether polyol derived from the reaction of a polyhydroxyalkane with one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, etc.);

[0250] (2) Polyether polyol derived from the reaction of a high-functionality alcohol, sugar alcohol, saccharide and / or high-functionality amine (addition mixture with a low-functionality alcohol and / or amine as needed) and an alkylene oxide such as ethylene oxide, propylene oxide, etc.;

[0251] (3) Polyether polyol derived from the reaction of phosphoric acid and polyphosphoric acid with alkylene oxides such as ethylene oxide, propylene oxide, etc.;

[0252] (4) Polyether polyol derived from the reaction of a polyaromatic alcohol with an alkylene oxide such as ethylene oxide, propylene oxide, etc.;

[0253] (5) Polyether polyol derived from the ring-opening polymerization reaction of tetrahydrofuran;

[0254] (6) Polyether polyol derived from the reaction of ammonia and / or amine with alkylene oxides such as ethylene oxide, propylene oxide, etc.;

[0255] (7) Polyester polyol derived from the reaction of a polyfunctional initiator (e.g., diol) and a hydroxycarboxylic acid or its lactone (e.g., hydroxylcaproic acid or ε-caprolactone);

[0256] (8) Polyoxamate polyol derived from the direct reaction of an oxalic acid ester and a diamine (e.g., hydrazine, ethylenediamine, etc.) in a polyether polyol;

[0257] (9) Polyurea polyol derived from the direct reaction of a diisocyanate and a diamine (e.g., hydrazine, ethylenediamine, etc.) in a polyether polyol.

[0258] For flexible foams, preferred types of alkylene oxide adducts of polyhydroxyalkanes are ethylene oxide and propylene oxide adducts of aliphatic triols such as glycerol, trimethylol, and propane. For rigid foams, preferred types of alkylene oxide adducts are ethylene oxide and propylene oxide adducts of ammonia, toluenediamine, sucrose, and phenol-formaldehyde-amine resins (Mannich bases). Graft-type or polymeric polyols are widely used in the manufacture of flexible foams and, along with standard polyols, are one of the preferred types of polyols useful in the present invention. A polymeric polyol is a polyol containing a stable dispersion of a polymer within, for example, the polyols of 1) to 5), more preferably the polyol of type 1). Other polymeric polyols useful in the present invention include polyurea polyols and polyoxamate polyols. It is preferable to use polyesterols and / or polyetherols as polyol (a). The average hydroxy-functionality of polyetherols and / or polyesterols is generally 1.9 to 8, preferably 2.4 to 6, and particularly preferably 2.6 to 4. In the case of polyetherols, the average functionality is calculated based on the hydroxy-functionality of the starting molecule. Polyol (a) generally has a hydroxyl value of 20 mg KOH / g or more, preferably 30 mg KOH / g or more, and particularly preferably 40 mg KOH / g or more. 700 mg KOH / g, preferably 600 mg KOH / g, particularly 500 mg KOH / g, and very preferably 400 mg KOH / g is generally known as an appropriate upper limit for the hydroxyl value. The above OH value is for the entire polyol (a) and does not exclude the possibility that individual components of the mixture may have higher or lower values. The number average molecular weight of the polyol (a) is preferably greater than 400 g / mol.Preferably, component (a) comprises a polyether polyol prepared by anionic polymerization having the addition of a starting molecule comprising 2 to 8, preferably 3 to 8, reactive hydrogen atoms in a bonded form, or by cationic polymerization using a Lewis acid such as antimony fluoride, boron etherate, or bleached clay as a catalyst.

[0259] Suitable alkylene oxides include, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide, preferably ethylene oxide and 1,2-propylene oxide. These alkylene oxides may be used alone, alternately in succession, or as a mixture.

[0260] Possible starting molecules include alcohols such as glycerol, trimethylolpropane (TMP), and pentaerythritol, sugar compounds such as sucrose and sorbitol, and amines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine (TDA), naphthylamine, ethylenediamine (EDA), diethylenetriamine, 4,4'-methylenedianiline, 1,3-propanediamine, 1,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine, etc. In addition, condensation products such as formaldehyde, phenol and diethanolamine or ethanolamine; formaldehyde, alkylphenol and diethanolamine or ethanolamine; formaldehyde, bisphenol A and diethanolamine or ethanolamine; formaldehyde, aniline and diethanolamine or ethanolamine; formaldehyde, cresol and diethanolamine or ethanolamine; formaldehyde, toluidine and diethanolamine or ethanolamine and formaldehyde; toluenediamine (TDA) and diethanolamine or ethanolamine may be used as starting molecules. It is preferable to use glycerol, sucrose, sorbitol, and TDA as starting materials. These polyols are commercially available, for example, VORANOL under the Voranol® trademark of Dow Corning. TM Including 3322 Polyol (nominal molecular weight 3400, heteropolymer triol), RENUVA TM FF 60, VORANOL TM 3010, VORANOL TM 3010A, VORANOL TM 3011, VORANOL TM 3022J, VORANOL TM 3322, VORANOL TM 3535, VORANOL TM 4730-N, VORANOL TM 8010, VORANOL TM 8010A, VORANOL TM 8010G, VORANOL TM 8022, VORANOL TM8136, VORANOL TM 8322, VORANOL TM 8595, VORANOL TM WK 3138, VORANOL TM WL 4010, VORANOL TM 3136, DWJ 4001.01 DEV, VORALUX TM HF 505, VORALUX TM HN 395, VORANOL TM 4150, VORANOL TM 6150, SPECFLEX TM 334-028, VORALUX TM HK 643, VORALUX TM HT 760, VORALUX TM HT 762, VORALUX TM HT 767, VORALUX TM HT 1080, VORANOL TM 8150, VORANOL TM WK 3140, VORANOL TM WK 8140, VORANOL TM There is WL 4099.

[0261] polyisocyanate(b)

[0262] The polyisocyanate (b) useful in the polyurethane foam forming process of the present invention is an organic compound containing at least two isocyanate groups and is one of the generally known aromatic or aliphatic polyisocyanates. Suitable organic polyisocyanates (b) include, for example, hydrocarbon diisocyanates, alkylene diisocyanates such as, for example, methylene diphenyl diisocyanate (MDI) and 2,4- and 2,6-toluene diisocyanate (TDI), and arylene diisocyanates; also include known triisocyanates and polymethylene poly(phenylene isocyanate), also known as polymeric or crude MDI. For flexible and semi-flexible foams, the preferred isocyanate is generally, for example, a mixture of 2,4-tolurene diisocyanate and 2,6-tolurene diisocyanate (TDI), mixed in a weight ratio of about 80% and about 20%, or about 65% and about 35%, respectively, relative to the total weight of the composition; a mixture of TDI and polymeric MDI, preferably mixed in a weight ratio of about 80% TDI and about 20% crude polymeric MDI, or about 50% TDI and about 50% crude polymeric MDI, relative to the total weight of the composition; and all MDI-type polyisocyanates. For rigid foams, the preferred isocyanate is, for example, an MDI-type polyisocyanate, preferably crude polymeric MDI. The amount of polyisocyanate contained in a foam formulation is described by the “isocyanate index” as a ratio to the amount of other substances in the composition. The “isocyanate index” is defined as the value obtained by dividing the amount of polyisocyanate actually used by the theoretically required stoichiometric amount of polyisocyanate needed to react with all active hydrogens in the reaction mixture, and then multiplying by 100 (e.g., see Oertel, Polyurethane Handbook). The isocyanate index of the reaction mixture used in the process of the present invention is generally between 60 and 140.More generally, the isocyanate index is typically between 80 and 130 for flexible TDI foam; between 90 and 105 for molded TDI foam; and between 70 and 90 for molded MDI foam. For rigid MDI foam, it is typically between 90 and 130. For rigid polyisocyanurate foam, there are also products that exhibit high indices reaching 250 to 400.

[0263] catalyst (c)

[0264] The polyurethane foam-forming composition of the present invention comprises one or more catalysts as polyurethane foaming additives. The catalyst may include suitable catalysts or catalyst mixtures known in the art as catalysts used for polyurethane formation. Examples of suitable catalysts include gelation amine catalysts such as triethylenediamine, amine blowing catalysts such as bis(dimethylaminoethyl)ether, and metal catalysts such as tin octosate or bismuth octosate, which are described in more detail below.

[0265] Amine catalyst

[0266] Particularly desirable additives include an amine catalyst for the formation of a polyisocyanate addition polymerization product, which is an amine different from the isocyanate reactive compound used, for example, in the formation of polyurethane.

[0267] These catalysts are, for example, alkylamines such as bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, N,N,N',N',N''pentamethyldiethylenetriamine, N,N,N',N''pentamethyldipropylentriaamine, and triethylenediamine; ethanolamines such as 2-aminoethanol, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methylethanolamine, and N-ethylethanolamine; diisopropylamine; bis(2-hydroxypropyl)amine; 2-[2-(dimethylamino)ethoxy]ethanol; 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol; and 3-dimethylamino-N,N-dimethylpropionamide, Ethanolamines such as N,N'-dimorpholinodiethyl ether, N,N'-dimethylpiperazine, N-methylmorpholine, and N-ethylmorpholine are included.2-{[2-(dimethylamino)ethyl]methylamino}ethanol, 3,3'-iminobis(N,N-dimethylpropylamine), 3-(dimethylamino)-1-propylamine, 3-(diethylamino)-1-propanol, 1-(3-hydroxypropyl)pyrrolidine, 1-(2-hydroxypropyl)pyrrolidine, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidine, 1-(3-hydroxypropyl)piperidine, 1-(2-hydroxypropyl)piperidine, 1-(3-aminopropyl)pyrrolidine, 1-(2-aminoethyl)pyrrolidine, 1-(3-aminopropyl)piperidine, 1-(2-aminoethyl)piperidine, 1-(1-pyrrolidinyl)-2-propanamine, 1-(piperidine-1-yl)propane 2-amine, N-methoxyethylmorpholine, N-methylimidazole, 1-(3-aminopropyl)imidazole, 2-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]ethanol, N-methyldicyclohexylamine, 3-{[3-(dimethylamino)propyl]methylamino}propanol, tris(dimethylaminopropyl)amine, 2-{[3-(dimethylamino)propyl]methylamino}ethanol, N,N,N',N'-tetramethyl-hexamethylenediamine, N,N,N',N'-tetramethylethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine, N,N-dimethylbenzylamine, 1,8-diazabicyclo 5,4,0-undecene 7, N-methyl-N'-(2-dimethylamino)ethyl-piperazine, N,N'-bis[3-(dimethylamino)propyl]urea, N-[3-(dimethylamino)propyl]urea. Includes N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine.

[0268] Preferred amines include alkylamines such as bis(2-dimethylaminoethyl)ether, N,N-dimethylaminopropylamine, N,N-dimethylcyclohexylamine, N,N,N',N''-pentamethyldiethylenetriamine, and triethylenediamine, diethanolamine, 2(2-dimethylaminoethoxy)ethanol, ethanolamines such as N-[2-(dimethylamino)ethyl]-N-methylethanolamine and dimethylethanolamine, or other amines such as 3-dimethylamino-N,N-dimethylpropionamide and N-ethylmorpholine, triethanolamine, 2-dimethylaminoethanol, N,N-dimethylaminopropylamine, diethanolamine, trimethylamine, triethylenediamine, and bis(2-dimethylaminoethyl)ether.

[0269] These amine catalysts are available on the market. For example, there are the following: 2,4,6-tris(dimethylaminomethyl)phenol (DABCO TMR-30; JEFFCAT TR30; RC Catalyst 6330), N,N,N',N'-tetramethyl-1,3-butanediamine (TMBDA), N,N-dimethylcyclohexylamine (POLYCAT 8; JEFFCAT DMCHA), N,N-diethylethanolamine (DEEA), N-ethylmorpholine (JEFFCAT NEM; TOYOCAT NEM; RC Catalyst 6072), 1-azabicyclo[2,2,2]octane (quiniclidine), triethanolamine (TEA), N,N,4-trimethyl-1-piperazine ethanolamine (TOYOCAT -NP), N,N'-dimethylpiperazine (JEFFCAT DMP; RC Catalyst 6117), dimethylethanolamine (DABCO) DMEA (JEFFCAT DMEA), N-methylmorpholine (JEFFCAT NNM; RC Catalyst 101), N,N-dimethylaminopropylamine (DMAPA; TOYOCAT RH2), N,N,N',N'-tetramethylethylenediamine (TMEDA; TOYOCAT-TE; JEFFCAT TMEDA), 1,3-bis(dimethylamino)propane, N,N,N',N'-tetramethylhexamethylenediamine (TMHDA; TOYOCAT-MR), diethanolamine DABCO DEOA-LF; DEOA LFG; Dimethyldodecylamine (DM-12D), N,N-dimethylhexadecylamine (DM-16D; DABCO B-16), triethylamine (ACCLIRE C(Allied), N,N-diisopropylethanolamine (DIEA), ethanolamine (monoethanolamine) (MEA), triethylenediamine (TEDA; NIAX A-100, DABCO Crystal; RC Catalyst 105; JEFFCAT TD-100; TOYOCAT TEDA; RC Catalyst 104), 4-butylmorpholine (NBM), 2(2-dimethylaminoethoxy)ethanol (PAK-LOC V; JEFFCAT ZR-70), 1,2-dimethylimidazole (DIME 12), N-[2-(dimethylamino)ethyl]-N-methylethanolamine (DABCO T;TOYOCAT RX55) N,N,N',N',N''-pentamethyldiethylenetriamine (POLYCAT 5; TOYOCAT DT; JEFFCAT PMDETA), bis(2-dimethylaminoethyl)ether (NIAX A-99; DABCO BL-19; TOYOCAT ETS; JEFFCAT ZF-20; RC Catalyst 6433), N,N'-bis(1,4-dimethylpentyl)-1,4-benzenediamine (TENAMENE 4), N-[3-(dimethylamino)propyl]-N,N',N'-trimethyl-1,3-propanediamine (POLYCAT 77; JEFFCAT ZR40), 4-[2-(dimethylamino)ethyl]-morpholine (DABCO XDM), N-cyclohexyldiethanolamine (DECA), N-hydroxyethyl-N'-methylpiperazine (TOYOCAT-HP), N-(3-dimethylaminopropyl)formamide, 1,3-bis(dimethylamino)-2-propanol (UC-2(Sipene)), 2,2'-dimorpholinodiethyl ether (JEFFCAT DMDEE), 1,8-diazabicyclo[5.4.0]undec-7-ene (POLYCAT DBU; RC Catalyst 6180), tetramethyliminobis(propylamine) (POLYCAT 15; JEFFCAT ZR-50B), N-methyldicyclohexylamine (POLYCAT 12), 4-(2-methoxyethyl)-morpholine (JEFFCAT MM), N,N,N'-tris(2-hydroxypropyl)ethylenediamine (EFFCAT DPA), 1,3,5-Tris[3-(dimethylamino)propyl]hexahydro-s-triazine (POLYCAT 41; JEFFCAT TR41; TOYOCAT TRC; RC Catalyst 6099), 3-dimethylamino-N,N-dimethylpropionamide (DDPA; NIAX A4; NIAX C-191), N,N-dimethyl-(4-methyl-1-piperazinyl)-ethanolamine (JEFFCAT TAP; RC Catalyst) 6076), tris(3-dimethylamino)propylamine (POLYCAT 9;JEFFCAT Z80), ethanolamine, 2,2'-[methylenebis(oxy)]bis[N,N-dimethyl-(CI-710), 4-(2-aminopropyl)morpholine (MAEM), 1-[bis(3-dimethylaminopropyl)amino]-2-propanol (JEFFCAT ZR-50), N,N,N',N'-2-pentamethyl-1,2-propanediamine (PMT), N-cocomorpholine (DABCO NCM; JEFFCAT NCM), N-methyl,N-(N',N'-2-dimethylaminopropyl)ethanolamine (POLYCAT 17), 2-(2-(2-dimethylaminoethoxy)-ethylmethylamino)-amino (JEFFCAT ZF-10).;

[0270] The amine catalyst disclosed in WO 2021 / 177946 and the catalyst composition disclosed in WO 2021 / 177944 may also be further mentioned, the full contents of which are incorporated herein by reference.

[0271] In particular, the amine catalyst is selected from the following:

[0272] i. A tertiary amino compound having at least one additional amino group selected from primary, secondary, and tertiary amino groups,

[0273] ii. A tertiary amino compound having at least one active hydrogen or hydroxyl group, such as -OH, -NH, NH2 and -SH groups,

[0274] iii. A tertiary amino compound having one or more ether groups (wherein, the number of carbon atoms connecting the nitrogen atom of the tertiary amino group),

[0275] iv. Aliphatic saturated tertiary amino compounds,

[0276] v. Dimethylaminopropylurea, N,N'-bis[3-(dimethylamino)propyl]urea, triethylamine, 1,2-dimethylimidazole, N-(3-aminopropyl)imidazole, N-(hydroxypropyl)imidazole, N-(2-hydroxyethyl)imidazole, tris(dimethylaminopropyl)hexahydro-1,3,5-triazine, 1,1,3,3-tetramethylguanidine, 1,5,7-triaz-bicyclo[4.4.0]dek-5-en, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine), 4-ethyl-2,2-dimethyl-1-oxa-4-aza-2-silacyclohexane, A tertiary amino compound selected from the group consisting of N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine) (bis(2-dimethylaminoethyl)ether), and triethylenediamine (1,4-diazabicyclo[2.2.2]octane),

[0277] vi. Any of the above-mentioned amine catalysts blocked by an organic acid, and

[0278] vii. A mixture of the above-mentioned amine catalysts.

[0279] Particularly preferred amine catalysts are bis(dimethylaminoethyl) ether ((BDMAEE) BDMAEE: Niax Catalyst A-99), triethylenediamine (TEDA: Niax Catalyst A-100), and N,N'-bis[3-(dimethylamino)propyl]urea (Niax Catalyst EF-700).

[0280] metal catalyst

[0281] In addition to amine catalysts, metal catalysts are suitable catalysts, examples of which are as follows:

[0282] Strong basic metal compounds such as alkali metal and alkaline earth metal hydroxides, alkoxides, phenoxides, etc.;

[0283] Acidic metal salts of strong acids such as ferric chloride, tin chloride, antimony trichloride, bismuth nitrate, and bismuth chloride;

[0284] Acetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone alkylenediimine, salicylaldehydeimine, etc., and metals such as Be, Mg, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, or MoO2 ++ , UO2 ++ Chelates of various metals, such as chelates that can be obtained from metal ion compounds such as the like;

[0285] Alcoholates and phenolates of various metals such as Ti(OR)4, Sn(OR)4, Sn(OR)2, Al(OR)3, etc. (where R is an organic group such as an alkyl or aryl having 1 to about 12 carbon atoms), and reaction products of alcoholates with carboxylic acids, beta-diketones, and 2-(N,N-dialkylamino)alkanols (e.g., well-known titanium chelates obtained by the method of this invention or an equivalent method);

[0286] Salts of various metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Bi, and Cu, and organic acids (e.g., metal desiccants such as sodium acetate, potassium laurate, calcium hexanoate, tin acetate, tin octosate, tin oleate, lead octosate, manganese naphthenate, and cobalt naphthenate);

[0287] Organometallic derivatives of metal carbonyls of tetravalent tin, trivalent and pentavalent arsenic, antimony and bismuth and iron and cobalt; and

[0288] A combination of two or more of these.

[0289] In one embodiment, the catalyst additive is an organotin compound that is a dialkyltin salt of a carboxylic acid, and non-limiting examples include dibutyltin diacetate, dibutyltin dilaureate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin-dilauryl mercaptide, dibutyltin-bis(6-methylaminocaproate), etc., and combinations of two or more of these.

[0290] Likewise, in other embodiments, trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride may be used, and combinations of two or more of these may also be used. Non-limiting examples of such compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, etc., and combinations of two or more of these are also included.

[0291] In one embodiment, the catalyst is an organotin catalyst such as tin octosate, dibutyltin dilaurate, dibutyltin diacetate, tin oleate, or a combination of two or more of these.

[0292] water (d)

[0293] Water is used as a reactive / chemical blowing agent in both flexible and rigid polyurethane foams. When producing flexible slabstock foam, water can generally be used at a concentration of 0.5 to 6.5 pphp (parts per 100 parts) of the polyol blend, and more commonly at a concentration of 1 to 4.5 pphp. For TDI molded foam, the water concentration is generally in the range of 2 to 3.5 pphp of the polyol blend. For MDI molded foam, the water concentration is generally in the range of 2.5 to 5 pphp. For rigid foam, the water concentration is, for example, in the range of 0.5 to 5 pphp, and more commonly in the range of 0.5 to 2 pphp. When producing polyurethane foam according to the present invention, physical blowing agents such as blowing agents based on volatile hydrocarbons or halogenated hydrocarbons and other non-reactive gases may also be used.

[0294] Common physical blowing agents include, but are not limited to, methylene chloride, acetone, chlorofluorocarbon, hydrocarbons (pentane, cyclopentane) and liquid carbon dioxide.

[0295] In the production of flexible slabstock foam, water is the main blowing agent, but other blowing agents may also be used as auxiliary blowing agents.

[0296] Silicone surfactant composition (e)

[0297] As generally described above and further exemplified by embodiments, the polyurethane foam-forming composition according to the present invention comprises a silicone surfactant composition. Accordingly, the silicone surfactant composition is based on a polyether-functional silicone compound (A). Such a surfactant composition generally supports the homogenization of the blowing agent and the polyol component and controls the cell structure of the polyurethane foam product by controlling foam stability during the foaming process. The surfactant composition according to the present invention may comprise any suitable surfactant compound (A) or a mixture of surfactant compound A) known to fall within the definition of a surfactant compound described herein. Suitable silicone surfactant compounds are described, for example, in U.S. Patents 5,489,617, 8,044,109, 5,145,879, EP3307801A1 / W02016201073A1), WO16164552 A1, W016201073 A1, EP1753799B1, U.S. Patent 9587068B2, W02023 / 009390, and "Dipak D. Pukale et al.: "Review on Silicone Surfactants: Silicone-based Gemini Surfactants, Physicochemical Properties and Applications", Tenside Surf. Det. 56 (2019) 4, all of which are incorporated herein by reference. These are commercially available, for example, under the trademark NIAX® of Momentive Performance Materials (e.g., NIAX® L-895 or L-865).

[0298] A particularly preferred silicone surfactant compound is a polyether-functional silicone surfactant compound, preferably comprising two different polyether substituents (as described in W02016201073A1) and preferably having an average molecular weight of about 500 to 10000 (e.g., 1500 or 4000), wherein the polyether moiety comprises an ethylene oxide (EO) unit and preferably comprises 20% or more EO, more preferably 40% or more EO.

[0299] Additionally, a preferred silicone surfactant is a polyether-functional silicone compound as described in W02023 / 009390, which is incorporated herein by reference.

[0300] Additional additives and auxiliary compounds (f)

[0301] The polyurethane foam-forming composition according to the present invention may further include additives and auxiliary compounds that facilitate polyurethane foam processing, particularly at low dosage levels (generally a few parts by weight per 100 parts of polyol). These additives and auxiliary compounds include flame or fire retardants such as chlorinated phosphate esters, chlorinated paraffin, and melamine powder; light stabilizers such as chain extenders, chain terminators, crosslinking agents, adhesion promoters, antistatic additives, hydrolysis stabilizers, ultraviolet light absorbers (UVA), and hindered amine light stabilizers (HALS); lubricants, antimicrobial agents, and processing aids; and antioxidants such as hindered phenols and hindered amine stabilizers, phosphites, hydroxylamines, and lactone-based stabilizers. There are defoaming agents, anti-foaming agents, emission control agents (such as those disclosed in WO23034354A1, incorporated herein by reference), water scavengers, molecular sieves, fillers such as fumed silica, calcium carbonate, and microcellulose, thixotropic agents, silicone, colorants or pigments such as titanium dioxide (white), iron(III) oxide (red), chromium(III) oxide (green), and carbon (black), color pastes, inert diluents, and combinations thereof (e.g., The polyurethanes book, Editors David Randall and Steve Lee, John Willey & Sons, LTD, 2002; see Szycher's Handbook of Polyurethanes, 2nd edition, 2013, chapter 18; each document incorporated herein by reference).

[0302] Preferred additives are flame lamination additives, antioxidants, and processing aids. Flame lamination additives are described, for example, in WO16164552 A1 and are composed of compounds that improve adhesive strength, particularly in flame lamination. Examples of suitable flame lamination additives include, but are not limited to, phosphorus-containing flame retardants and polyols having aromatic structural units. Particularly suitable flame lamination additives include, but are not limited to, high molecular weight flame retardants such as Fyrol PNX of AKZO and Exolit OP 560 of Clariant, bisphenol A alkoxylates, and commercially available flame lamination additives such as Niax Flame Lamination Additive FLE-200LF and Niax Flame Lamination Additive FLE-500LF.

[0303] The flame-retardant lamination additive can be used in a polyurethane foam-forming composition at a concentration of about 1 to about 10 pphp, more specifically about 1 to about 8 pphp, and even more specifically about 1 to about 6 pphp, where pphp means parts per 100 parts of total polyol used.

[0304] Antioxidants delay the thermal oxidation of polyurethanes by inhibiting chain-breaking reactions initiated by oxygen and / or oxygen free radicals. Antioxidants in the form of synergistic mixtures with phosphite or phosphine are particularly effective. A list of various antioxidants that can be used in polyurethane foams is disclosed, for example, in WO2019 / 110726 (see particularly the "Background of the Invention" section), the contents of which are incorporated herein by reference. Additionally, suitable antioxidants are described in "Szycher's Handbook of Polyurethanes, 2nd edition, 2013" (see particularly chapter 18).

[0305] Processing aids include products that stabilize the foaming process, prevent foam splitting, and provide uniform foaming performance along the foaming rising direction, such as Geocell GM-280, GM-225, Niax GM-206, and GM-210, as well as other products that improve foaming process capabilities, such as lubricants, polymer processing aids, and release agents, including (C14-C18) fatty alcohols, dicarboxylic acid esters, fatty acid esters, fatty acid amines, fatty acids, fatty acid soaps, and fatty acid amines.

[0306] The method for producing a polyurethane foam from the polyurethane foam-forming composition of the present invention, comprising the silicone surfactant composition described herein, is not particularly limited. Various methods commonly used in the art may be used. For example, various methods described in Keiji Iwata’s “Polyurethane Resin Handbook” (Nikkan Kogyo Shinbun, Ltd., 1987) may be used. For example, the composition of the present invention may be prepared by combining additional compounds comprising a polyol, a catalyst, a surfactant, a blowing agent, a polyether-functional siloxane, and optional components into a premix.

[0307] The viscosity of surfactant compounds and surfactant compositions can be measured using a Ubbelohde glass capillary viscometer according to ISO 3105.

[0308] The viscosity mentioned in this application was measured according to the above standard.

[0309] Preferred embodiment according to the present invention

[0310] The following is a summary of preferred embodiments according to the present invention.

[0311] 1. (A) One or more silicone surfactant compounds,

[0312] (B) One or more surfactant efficacy enhancers,

[0313] (C) A surfactant composition for use in polyurethane foam, comprising optionally one or more diluents.

[0314] 2. In Embodiment 1, one or more of the silicone surfactant compound (A) may be the same as or different from the silicone backbone, and one or more polyether substituents R bonded to one or more Si atoms of the silicone backbone. *A surfactant composition comprising a silicone surfactant.

[0315] 3. A surfactant composition in Embodiment 1 or 2, wherein one or more of the components (B) are an organic acid or an organic acid-based compound, preferably an organic acid.

[0316] 4. A surfactant composition in any one of embodiments 1 to 3, wherein one or more of the components (B) are an organic acid, an organic acid salt, or an organic acid ester.

[0317] 5. A surfactant composition characterized in that, in any one of embodiments 1 to 4, one or more of the components (B) are organic acids.

[0318] 6. A surfactant composition characterized in that, in any one of embodiments 1 to 4, one or more of the components (B) are a carboxylic acid, a carboxylic acid salt, or a carboxylic acid ester, preferably a carboxylic acid.

[0319] 7. A surfactant composition characterized in that, in any one of embodiments 1 to 6, one or more of the components (B) are carboxylic acids, preferably monocarboxylic acids.

[0320] 8. A surfactant composition characterized in that, in any one of embodiments 1 to 4 and 6, one or more of the components (B) are carboxylic acid salts, preferably monocarboxylic acid salts.

[0321] 9. A surfactant composition characterized in that, in any one of embodiments 1 to 4 and 6, one or more of the components (B) are carboxylic acid esters, preferably monocarboxylic acid esters or dicarboxylic acid esters.

[0322] 10. A surfactant composition characterized in that, in any one of embodiments 1 to 4 and 6, the component (B) is an organic acid, an organic acid salt, or an organic acid ester having 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and more preferably 10 or more.

[0323] 11. A surfactant composition in any one of embodiments 1 to 7 and 10, wherein the component (B) is an organic acid having 4 or more carbon atoms, preferably 6 or more, more preferably a carboxylic acid having 6 or more carbon atoms, and more preferably a monocarboxylic acid having 6 or more carbon atoms.

[0324] 12. In any one of embodiments 1 to 7, 10 or 11, the component (B) is a carboxylic acid having 4 or more carbon atoms, preferably a monocarboxylic acid having 6 or more carbon atoms, more preferably a monocarboxylic acid having 6 or more carbon atoms, and one or more of the silicone surfactant compound (A) is one or more polyether substituents R bonded to a silicon backbone and one or more Si atoms of the silicon backbone. * A surfactant composition comprising a silicone surfactant, wherein the amount of component (A) in the silicone surfactant composition is 15.0 weight% or more based on the total weight of the surfactant composition.

[0325] 13. A surfactant composition characterized in that, in any one of embodiments 1 to 4, 6, 8 and 10, the component (B) is an organic acid salt having 4 or more carbon atoms in the anionic portion, preferably an organic acid salt having 6 or more carbon atoms in the anionic portion, more preferably a carboxylic acid salt having 6 or more carbon atoms in the anionic portion, and more preferably a monocarboxylic acid salt having 6 or more carbon atoms in the anionic portion.

[0326] 14. A surfactant composition in any one of embodiments 1 to 4, 6, 9 and 10, wherein the component (B) is an organic acid ester having 4 or more carbon atoms in a structure corresponding to the organic acid, preferably an organic acid ester having 6 or more carbon atoms in a structure corresponding to the organic acid, more preferably a carboxylic acid ester having 6 or more carbon atoms in a structure corresponding to the organic acid, and more preferably a monocarboxylic acid ester or dicarboxylic acid ester having 6 or more carbon atoms in a structure corresponding to the organic acid.

[0327] 15. A surfactant composition characterized in that, in any one of embodiments 1 to 14, component (B) is contained in an amount of 0.01 to 70 weight% based on the total weight of the surfactant composition, preferably in an amount of 0.2 to 20 weight%, and optionally, the ratio (w / w) of component (A) to (B) is in the range of 100:1 to 2:1, preferably in the range of 50:1 to 3:1, more preferably in the range of 20:1 to 4:1, and even more preferably in the range of 15:1 to 5:1.

[0328] 16. A surfactant composition characterized in that, in any one of embodiments 1 to 15, one or more siloxane backbones of the silicon compound (A) are represented by the following general formula (I):

[0329] M * D x D" y M * (I),

[0330] (Here

[0331] M * is (CH3)3SiO 1 / 2 or (CH3)2RSiO 1 / 2 and D is (CH3)2SiO 2 / 2 It represents, and D" is (CH3)RSiO 2 / 2It represents, where x is 0–200, y is 2 or greater, x+y is 10–250, the ratio of x to y is 2–50, and R is a polyether substituent R * lim).

[0332] 17. A surfactant composition in any one of embodiments 1 to 16, wherein one or more of the silicone surfactant compounds (A) have the following formula:

[0333] M * D x D" y M * (I),

[0334] (Here, M * is (CH3)3SiO 1 / 2 or (CH3)2R * SiO 1 / 2 It represents, and D is (CH3)2SiO 2 / 2 It represents, and D" is (CH3)R * SiO 2 / 2 Represents, where x is 0–200, y is 2 or greater, x+y is 10 to 250, the ratio of x to y is 2 to 50, and R * is identical or different, -C n H 2n O--a polyether substituent independently selected from the starting polyether substituent, where n is 2 to 10).

[0335] 18. In any one of embodiments 1 to 17, a surfactant composition wherein one or more silicone surfactant compounds (A) have the following formula (I):

[0336] M * D x D" y M * (I),

[0337] (Here, M * is (CH3)3SiO 1 / 2 or (CH3)2R * SiO 1 / 2 It represents; D is (CH3)2SiO2 / 2 It represents; D" is (CH3)R * SiO 2 / 2 Representing; x is 0 to 200; y is 2 or greater; x+y is 10 to 250, the ratio of x to y is 2 to 50, and R * is the same or different -C n H 2n It is a polyether substituent independently selected from O-group-starting polyether substituents, where n is 2–10, and substituent R * (Its number average molecular weight is 200 daltons to 6000 daltons).

[0338] 19. In any one of embodiments 2 to 18, the polyether substituent R of the silicone surfactant compound (A) * A surfactant composition in which one or more of the alkoxy group or acyl group, preferably a methoxy group or acetoxy group, are independently terminated.

[0339] 20. In any one of Embodiments 2 to 19, the polyether substituent R of the silicone surfactant compound (A) * A surfactant composition characterized by having the following formula, wherein the formulas are identical or different:

[0340] -C n H 2n O(C2H4O) a (C3H6O) b R 1 (II)

[0341] (Here, n is 2 to 10, and a is an ethylene oxide residue that is a polyether substituent R * The number such that the alkylene oxide residues comprise about 30% to about 100% by weight of; and b is the propylene oxide residue comprising the polyether substituent R * The number is such that it accounts for about 0% to about 70% by weight of the alkylene oxide residues of; R 1is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group).

[0342] 21. In any one of Embodiments 2 to 20, the polyether substituent R of the silicone surfactant compound (A). * A surfactant composition characterized by having the following formula, wherein the formulas are identical or different:

[0343] -C n H 2n O(C2H4O) a (C3H6O) b R 1 (II)

[0344] (Here, n is 2–10, and a is an ethylene oxide residue that is a polyether substituent R * The number such that the alkylene oxide residues comprise about 30% to about 100% by weight of; and b is the propylene oxide residue comprising the polyether substituent R * The number is such that it accounts for about 0% to about 70% by weight of the alkylene oxide residues of; R 1 is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group, and substituent R * It has a number average molecular weight of about 200 daltons to about 6,000 daltons).

[0345] 20. In any one of Embodiments 2 to 19, the polyether substituent R of the silicone surfactant compound (A) * A surfactant composition characterized by having the following formula, wherein the components are identical or different from each other:

[0346] -C n H 2n O(C2H4O) a (C3H6O) b R 1 (II)

[0347] (Here, n is 2 to 10, and a is an ethylene oxide residue that is a polyether substituent R* The number such that the alkylene oxide residue occupies about 30% to about 100% by weight of; and b is the propylene oxide residue comprising the polyether substituent R * The number of alkylene oxide residues is such that they account for about 0 weight % to about 70 weight %; R 1 is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group).

[0348] 21. In any one of Embodiments 2 to 20, the polyether substituent R of the silicone surfactant compound (A). * A surfactant composition characterized by having the following formula, wherein the formulas are identical or different:

[0349] -C n H 2n O(C2H4O) a (C3H6O) b R 1 (II)

[0350] (Here, n is 2–10, and a is an ethylene oxide residue that is a polyether substituent R * The number such that the alkylene oxide residues comprise about 30% to about 100% by weight of; and b is the propylene oxide residue comprising the polyether substituent R * A number such that it accounts for about 0% to about 70% by weight of the alkylene oxide residues of; R 1 is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group, and a substituent R * It has a number average molecular weight of about 200 daltons to about 6,000 daltons).

[0351] 22. In embodiments 20 and 21, n, b, and R in Equation (II). 1 is as defined in the previous embodiment, and the polyether substituent R * The "a" of is an ethylene oxide residue, which is a polyether substituent R *A surfactant composition comprising about 35% to about 100% by weight, preferably 40% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 80% to 100% by weight of an alkylene oxide residue.

[0352] 23. In any one of Embodiments 2 to 22, the polyether substituent R of the silicone surfactant compound (A) * A surfactant composition having a number average molecular weight of 400 daltons to 4000 daltons, preferably 500 daltons to 3000 daltons, more preferably 700 daltons to 2000 daltons.

[0353] 24. In any one of embodiments 16 to 23, M in the silicone surfactant compound (A) of formula (I). * , D, and D", x, x+y, the ratio of x to y and R * A surfactant composition as described above, wherein y is 3 to 20, more preferably 4 to 10.

[0354] 25. In any one of Embodiments 2 to 24, the silicone surfactant compound (A) comprises two or more different types of polyether substituents R * Containing, preferably, the silicone surfactant compound (A) comprises two different types of polyether substituents R * A surfactant composition characterized by containing

[0355] 26. In any one of Embodiments 2 to 25, in a preferred embodiment according to the present invention, the silicone surfactant compound (A) comprises one or more polyether substituents R selected from a group (i) having the structure of Formula (II') below and a group (ii) having the structure of Formula (II'') below. * Surfactant composition comprising:

[0356] (i) -C n' H 2n' O(C2H4O) a' (C3H6O) b' R 2 (II')

[0357] (wherein, n' is 2–10; a' is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide residue of the polyether substituent; b' is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether; R 2 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group);

[0358] (ii) -C n'' H 2n'' O(C2H4O) a'' (C3H6O) b'' R 3 (II'')

[0359] (wherein, n" is 2–10; a" is the number in which ethylene oxide residues account for 30% to 100% by weight of the alkylene oxide residues of the polyether substituents; b" is 0 to the number in which propylene oxide residues account for 70% or less by weight of the alkylene oxide residues of the polyether; R 3 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group).

[0360] 27. In any one of embodiments 2 to 26, the silicone surfactant compound (A) has a structure of formula (II'), has a mass in the range of 2000 to 6000 daltons, and has one or more polyether substituents R selected from groups (i) having at least one mass of 3000 daltons. *; and one or more polyether substituents R selected from groups (ii) having the structure of formula (II'') and having a mass in the range of 350 to 1800 daltons * A surfactant composition comprising:

[0361] (i) -C n' H 2n' O(C2H4O) a' (C3H6O) b' R 2 (II')

[0362] (wherein, n' is 2–10; a' is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide residue of the polyether substituent; b' is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether; R 2 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group);

[0363] (ii) -C n'' H 2n'' O(C2H4O) a'' (C3H6O) b'' R 3 (II'')

[0364] (wherein" is 2-10, a" is the number in which ethylene oxide residues account for 30% to 100% by weight of the alkylene oxide residues of the polyether substituent, b" is 0 to the number in which propylene oxide residues account for 70% or less by weight of the alkylene oxide residues of the polyether, and R 3 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group).

[0365] 28. In embodiments 26 and 27, all polyether substituents R present in the silicone surfactant compound (A) *A surfactant composition comprising a polyether substituent selected from types (i) and (ii), wherein the silicone surfactant compound (A) comprises at least one polyether substituent of type (i) and at least one polyether substituent of type (ii).

[0366] 29. In any one of embodiments 16 to 28, the silicone surfactant compound (A) has the following formula (I).

[0367] M * D x D" y M * (I)

[0368] (Here, M * , D, and D' are as defined above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15),

[0369] And, the above silicone surfactant compound (A) comprises one or more polyether substituents R selected from groups (iii) having the structure of the formula (II'") below. * and one or more polyether substituents R selected from groups (iv) having the structure of the formula (II"") below. * A surfactant composition comprising:

[0370] (iii) -C n'" H 2n'" O(C2H4O) a'" (C3H6O) b'" R 4 (II'")

[0371] (wherein, n'" is 2 to 4, preferably 3, and a'" is a number such that the ethylene oxide residue accounts for 30% to 60% by weight of the alkylene oxide of the polyether substituent; b'" is a number such that the propylene oxide residue accounts for 40% to 70% by weight of the alkylene oxide residue of the polyether; R 4 represents a methyl group or an acetyl group),

[0372] (iv) -C n"" H 2n"" O(C2H4O) a"" (C3H6O) b"" R 5 (II"")

[0373] (wherein, n'''' is 2 to 4, preferably 3, and a'''' is a number such that the ethylene oxide residue occupies 30% to 100% by weight of the alkylene oxide residue of the polyether substituent; b"' is a number such that the propylene oxide residue occupies 70% or less of the alkylene oxide residue of the polyether, and R 5 represents a methyl group or an acetyl group).

[0374] 30. In any one of embodiments 16 to 29, the silicone surfactant compound (A) has the following formula (I).

[0375] M * D x D" y M * (I),

[0376] (Here, M * , D and D' are as described above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15);

[0377] And, the silicone surfactant compound (A) comprises one or more polyether substituents R selected from the group (iii) having the structure of formula (II'"). * and one or more polyether substituents R selected from groups (iv) having the structure of formula (II'"') and having a mass in the range of 350 to 1800 daltons. * A surfactant composition comprising:

[0378] (iii) -C n'" H2 n"' O(C2H4O) a'" (C3H6O)b"'R 4 (II'"),

[0379] (wherein n'" is 2 to 4, preferably 3, a'" is a number such that the ethylene oxide residue occupies 30% to 60% by weight of the alkylene oxide residue of the polyether substituent, and b'" is a number such that the propylene oxide residue occupies 40% to 70% by weight of the alkylene oxide residue of the polyether, and R 4 represents a methyl group or an acetyl group);

[0380] (iv) -C n"" H 2n"" O(C2H4O) a"" (C3H6O) b"" R 5 (II'"')

[0381] (wherein, n"' is 2 to 4, preferably 3, a"' is a number such that the ethylene oxide residue occupies 30% to 100% by weight of the alkylene oxide residue of the polyether substituent, b"' is a number such that the propylene oxide residue occupies 70% by weight or less of the alkylene oxide residue of the polyether, and R 5 represents a methyl group or an acetyl group).

[0382] 31. In embodiments 29 and 30, all polyether substituents R present in the silicone surfactant compound (A) * A surfactant composition in which the polyether substituents of group (iii) and (iv) are selected from the polyether substituents of group (iii) and (iv), and the silicone surfactant compound (A) contains at least one polyether substituent R of group (iii) and at least one polyether substituent R of group (iv).

[0383] 32. A surfactant composition in any one of embodiments 1 to 7, 10, 11 and 15 to 31, wherein component (B) is an aliphatic carboxylic acid or an aromatic carboxylic acid, preferably an aliphatic carboxylic acid, and more preferably an alkanic acid.

[0384] 33. A surfactant composition in any one of embodiments 1 to 7, 10, 11 and 15 to 32, wherein component (B) is an alkanic acid or alkenoic acid having 4 to 30 carbon atoms, preferably an alkanic acid having 6 to 24 carbon atoms, and more preferably an alkanic acid having 9 to 20 carbon atoms.

[0385] 34. A surfactant composition in any one of embodiments 1 to 7, 10, 11 and 15 to 33, wherein component (B) is a branched or cyclic alkanic acid, preferably a branched alkanic acid, and more preferably a branched alkanic acid having 5 to 24 carbon atoms.

[0386] 35. A surfactant composition in any one of embodiments 1 to 7, 10, 11 and 15 to 34, wherein component (B) is a carboxylic acid comprising one or more quaternary carbon atoms, preferably an aliphatic carboxylic acid comprising one or more quaternary carbon atoms, and more preferably an acyclic alkanic acid comprising one or more quaternary carbon atoms.

[0387] 36. A surfactant composition in any one of embodiments 1 to 7, 10, 11 and 15 to 35, wherein component (B) is an organic acid having one or more quaternary carbon atoms, preferably a branched alkyl monocarboxylic acid having 5 to 20 carbon atoms at the α position of a carboxylic acid group.

[0388] 37. A surfactant composition in any one of embodiments 1 to 7, 10, 11 and 15 to 36, wherein component (B) is an organic acid selected from the group consisting of C8-neoalkanoic acid, C9-neoalkanoic acid, C10-neoalkanoic acid, C11-neoalkanoic acid, C12-neoalkanoic acid, C13-neoalkanoic acid, and C14-neoalkanoic acid, preferably from the group consisting of neononaline acid, neodecanoic acid, and neoundecanoic acid.

[0389] 38. A surfactant composition in any one of embodiments 1 to 4, 6, 8, 10, 13 and 15 to 31, wherein component (B) is an aliphatic carboxylic acid salt or an aromatic carboxylic acid salt, preferably an aliphatic carboxylic acid salt, and more preferably an alkanate salt.

[0390] 39. A surfactant composition in any one of embodiments 1 to 4, 6, 8, 10, 13 and 15 to 31 and 38, wherein component (B) is an alkanate salt having 4 to 30 carbon atoms in the anionic portion, preferably 6 to 24 carbon atoms in the anionic portion, more preferably 9 to 20 carbon atoms in the anionic portion.

[0391] 40. A surfactant composition in any one of embodiments 1 to 4, 6, 8, 10, 13, 15 to 31, 38 and 39, wherein component (B) is a branched or cyclic alkanate salt, preferably a branched alkanate salt, and more preferably a branched alkanate salt having 5 to 24 carbon atoms in the anionic portion.

[0392] 41. A surfactant composition in any one of embodiments 1 to 4, 6, 8, 10, 13, 15 to 31, and 38 to 40, wherein component (B) is a carboxylic acid salt comprising one or more quaternary carbon atoms, preferably an aliphatic carboxylic acid comprising one or more quaternary carbon atoms, and more preferably an acyclic alkanic acid comprising one or more quaternary carbon atoms.

[0393] 42. A surfactant composition in any one of embodiments 1 to 4, 6, 9, 10 and 14 to 31, wherein component (B) is an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester, preferably an aliphatic carboxylic acid ester, and more preferably an alkanic acid ester.

[0394] 43. A surfactant composition in any one of embodiments 1 to 4, 6, 9, 10, 14 to 31 and 42, wherein component (B) is an alkanic acid ester or an alkenoic acid ester having 4 to 30 carbon atoms in a structure corresponding to the organic acid, preferably an alkanic acid ester having 6 to 24 carbon atoms in a structure corresponding to the organic acid, and more preferably an alkanic acid ester having 9 to 20 carbon atoms in a structure corresponding to the organic acid.

[0395] 44. A surfactant composition in any one of embodiments 1 to 4, 6, 9, 10, 14 to 31, 42 and 43, wherein component (B) is a linear or branched alkanic acid ester, preferably a linear alkanic acid ester, more preferably a linear alkanic acid ester having 5 to 24 carbon atoms in a structure corresponding to the organic acid, and more preferably a linear mono- or di-alkanic acid ester having 5 to 24 carbon atoms in a structure corresponding to the organic acid.

[0396] 45. A surfactant composition in any one of embodiments 1 to 44, wherein the amount of component (A) in the silicone surfactant composition is 15.0 wt% or more, preferably 20.0 wt% or more, more preferably 30.0 wt% or more, more preferably 40.0 wt% or more, and more preferably 50 wt% or more, based on the total weight of the surfactant composition.

[0397] 46. ​​A surfactant composition in any one of embodiments 1 to 45, wherein the amount of component (B) in the silicone surfactant composition is 0.02 to 50 weight%, preferably 0.5 to 25 weight%, more preferably 1.0 to 10 weight%, more preferably 1.5 to 8 weight%, more preferably 2.5 to 7 weight% based on the total weight of components (A), (B) and (C) of the silicone surfactant composition.

[0398] 47. A surfactant composition in any one of embodiments 1 to 46, wherein the sum of components (A) and (B) is 20% by weight or more of the total weight of the composition, preferably 25% by weight or more of the total weight of the composition, more preferably 30% by weight or more of the total weight of the composition, and more preferably 35% by weight or more of the total weight of components (A), (B), and (C) of the silicone surfactant composition.

[0399] 48. A surfactant composition according to embodiments 1 to 47, wherein the sum of components (A), (B) and (C) is 70% by weight or more of the total weight of the composition, preferably 80% by weight or more of the total weight of the composition, more preferably 85% by weight or more of the total weight of the composition, even more preferably 90% by weight or more of the total weight of the composition, and most preferably 95% by weight or more of the total weight of the silicone surfactant composition.

[0400] 49. A surfactant composition in any one of embodiments 1 to 48, wherein the composition comprises one or more diluents (C), and the amount of the diluent is preferably 20% by weight or more, more preferably 35% by weight or more, more preferably 50% by weight or more, more preferably 65% ​​by weight or more, more preferably 75% by weight or more, and most preferably 85% by weight or more, based on the total weight of the surfactant composition.

[0401] 50. A surfactant composition in any one of embodiments 1 to 49, wherein the diluent (C) is selected from water, monoalcohol, diol or polyol, monoether, diether or polyether, aliphatic and aromatic hydrocarbon, halogenated hydrocarbon, particularly partially halogenated or perhalogenated alkanes and partially halogenated or perhalogenated alkylated phenyl compounds, ketones, amides, nitriles, sulfoxides, or organic carbonates, or a combination of two or more of these.

[0402] 51. A surfactant composition in any one of embodiments 1 to 50, wherein the diluent (C) is completely miscible with components (A) and (B), preferably the diluent (C) is a monoether or polyether having 40 or fewer ether groups, and more preferably a monoether or polyether having 8 or fewer ether groups.

[0403] 52. A surfactant composition in any one of embodiments 1 to 51, wherein the diluent (C) comprises a mono- or poly-ether alcohol, preferably a glycol ether, and more preferably the diluent (C) is a mono- or poly-ether alcohol, particularly a glycol ether.

[0404] 53. A surfactant composition in any one of embodiments 1 to 52, wherein the diluent (C) comprises ethylene glycol ether or propylene glycol ether, preferably dipropylene glycol, and more preferably the diluent (C) is ethylene glycol ether or propylene glycol ether, particularly dipropylene glycol.

[0405] 54. A surfactant composition in any one of embodiments 1 to 53, wherein the viscosity of the surfactant composition measured by a capillary viscometer is 5000 cSt or less at 25°C, preferably 4000 cSt or less at 25°C, more preferably 3000 cSt or less at 25°C, even more preferably 2500 cSt or less at 25°C, and most preferably 2000 cSt or less at 25°C.

[0406] 55. In any one of claims 1 to 29 and 32 to 54 above, the silicone surfactant compound (A) has the following formula (I).

[0407] M * D x D" y M * (I),

[0408] (Here, M * , D and D' are as described above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15),

[0409] And, the silicone surfactant compound (A) has a structure of formula (II'), has a mass in the range of 2000 daltons to 6000 daltons, and at least one has a molecular weight of 3000 or more, and has a polyether substituent R selected from group (i). *A polyether substituent R selected from groups (ii) having the structure of , and formula (II'') and having a mass in the range of 350 daltons to 1800 daltons. * Composed of including

[0410] (i) -C n' H 2n' O(C2H4O) a' (C3H6O) b' R 2 (II')

[0411] (wherein, n' is 2–10, a' is a number such that the ethylene oxide residue accounts for 30% to 60% by weight of the alkylene oxide residue of the polyether substituent, b' is a number such that the propylene oxide residue accounts for 40% to 70% by weight of the alkylene oxide residue of the polyether, and R 2 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group),

[0412] (ii) -C n'' H2 n'' O(C2H4O) a'' (C3H6O) b" R 3 (II")

[0413] (wherein" is 2-10, a" is the number in which ethylene oxide residues account for 30% to 100% by weight of alkylene oxide residues of the polyether substituent, b" is 0 to the number in which propylene oxide residues account for 70% or less by weight of the alkylene oxide residues of the polyether, and R 3 represents a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group);

[0414] Component (B) is a carboxylic acid, a carboxylic acid salt or a carboxylic acid ester, preferably a carboxylic acid, and

[0415] A surfactant composition comprising optionally including a diluent (C), wherein the diluent (C) is preferably a glycol ether, most preferably a dipropylene glycol.

[0416] 56. In any one of embodiments 1 to 55, the silicone surfactant compound (A) has formula (I).

[0417] M * D x D" y M * (I),

[0418] (Here, M * , D, and D' are as described above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15),

[0419] And, the above silicone surfactant compound (A) comprises one or more polyether substituents R selected from the group (iii) having the structure of formula (II'"). * , and one or more polyether substituents R selected from groups (iv) having the structure of formula (II'"'). * Composed of including.

[0420] (iii) -C n'" H2 n'" O(C2H4O) a'" (C3H6O) b'" R 4 (II'")

[0421] (wherein n''' is 2 to 4, preferably 3, a''' is a number such that the ethylene oxide residue accounts for 30% to 60% by weight of the alkylene oxide residue of the polyether substituent, and b''' is a number such that the propylene oxide residue accounts for 40% to 70% by weight of the alkylene oxide residue of the polyether, and R 4 represents a methoxy group, acetoxy group, or butoxy group),

[0422] (iv) -C n'''' H 2n'''' O(C2H4O) a''" (C3H6O) b'''' R 5 (II'''')

[0423] (wherein n'''' is 2 to 4, preferably 3, a'''' is a number such that the ethylene oxide residue accounts for 30% to 100% by weight of the alkylene oxide residue of the polyether substituent, b'''' is a number such that the propylene oxide residue accounts for 70% or less by weight of the alkylene oxide residue of the polyether, and R 5 represents a methoxy group or an acetoxy group);

[0424] Component (B) is an organic acid, and the organic acid (B) is an alkyl carboxylic acid having 5 to 24 carbon atoms, preferably a branched alkyl carboxylic acid having 5 to 24 carbon atoms, more preferably selected from the group consisting of C8-neoalkaniol, C9-neoalkaniol, C10-neoalkaniol, C11-neoalkaniol, C12-neoalkaniol, C13-neoalkaniol, and C14-neoalkaniol, and most preferably a neodecanoic acid.

[0425] The above composition optionally comprises a diluent (C), wherein the diluent (C) is preferably a glycol ether and most preferably a dipropylene glycol, a surfactant composition.

[0426] 57. In any one of embodiments 1-7, 10, 11, 15-37 and 45 to 56, the silicone surfactant compound (A) has formula (I).

[0427] M * D x D" y M * (I),

[0428] (Here, M * , D and D' are as described above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85; and the ratio of x to y is 5 to 20, preferably 7 to 15);

[0429] And, the silicone surfactant compound (A) has the structure of formula (II'") and one or more polyether substituents R selected from group (iii) having a mass in the range of 3500 to 6000 daltons. * and one or more polyether substituents R selected from group (iv) having the structure of (II''') and having a mass of 350 to 1800 daltons. * Composed of including.

[0430] (iii) -C n'" H 2n'" O(C2H4O) a'" (C3H6O) b'" R 4 (II'")

[0431] (wherein n''' is 2 to 4, preferably 3, a''' is a number such that the ethylene oxide residue accounts for 30% to 60% by weight of the alkylene oxide residue of the polyether substituent, b''' is a number such that the propylene oxide residue accounts for 40% to 70% by weight of the alkylene oxide residue of the polyether, and R 4 represents a methoxy group, acetoxy group, or butoxyl group), .

[0432] (v) -C n'''' H 2n'''' O(C2H4O) a'''' (C3H6O) b'''' R 5 (II'''')

[0433] (wherein, n'''' is 2 to 4, preferably 3, a'''' is a number such that the ethylene oxide residue accounts for 30% to 100% by weight of the alkylene oxide residue of the polyether substituent, b'''' is a number such that the propylene oxide residue accounts for 70% or less by weight of the alkylene oxide residue of the polyether substituent, and R 5 represents a methoxy group, acetoxy group, or butoxyl group);

[0434] Component (B) is an organic acid, and the organic acid (B) is an alkyl carboxylic acid having 5 to 24 carbon atoms, preferably a branched alkyl carboxylic acid having 5 to 24 carbon atoms, more preferably selected from the group consisting of C8-neoalkaniol, C9-neoalkaniol, C10-neoalkaniol, C11-neoalkaniol, C12-neoalkaniol, C13-neoalkaniol, and C14-neoalkaniol, and most preferably a neodecanoic acid.

[0435] The above composition optionally comprises a diluent (C), wherein the diluent (C) is preferably a glycol ether and most preferably a dipropylene glycol, a surfactant composition.

[0436] 58. In any one of embodiments 55 to 57, the organic acid (B) is a branched alkanic acid carboxylic acid having 5 to 24 carbon atoms, more preferably selected from the group consisting of C8-neoalkanic acid, C9-neoalkanic acid, C10-neoalkanic acid, C11-neoalkanic acid, C12-neoalkanic acid, C13-neoalkanic acid, and C14-neoalkanic acid, and most preferably is a neodecanoic acid.

[0437] And the above composition is a surfactant composition comprising glycol ether, preferably dipropylene glycol, as a diluent (C).

[0438] 59. In any one of embodiments 56 to 58, all polyether substituents R present in the silicone surfactant compound (A) * A surfactant composition in which the silicone surfactant compound (A) is selected from polyether substituents of group (iii) and (iv), wherein the silicone surfactant compound (A) comprises at least one polyether substituent R1 of group (iii) and polyether substituent R2 of group (iv), and wherein the silicone surfactant compound (A) comprises at least one type of polyether substituent R of group (iii) and polyether substituent R of group (iv).

[0439] 60. A surfactant composition in any one of embodiments 1 to 59, wherein the surfactant composition comprises, based on the total weight of the surfactant composition, 20-80% by weight of a silicone surfactant compound (A), 1-8% by weight of component (B), and 12-79% by weight of a diluent (C), wherein the sum of components (A), (B), and (C) is 95% by weight or more, preferably 100% by weight, of the surfactant composition.

[0440] 61. In any one of embodiments 1-7, 10, 11, 15-37 and 45-60, the composition comprises 20-80 wt% of a silicone surfactant compound (A), 1-8 wt% of an organic acid (B), and 12-79 wt% of a diluent (C) based on the total weight of the surfactant composition, and

[0441] A surfactant composition wherein the sum of components (A), (B) and (C) is 95% by weight or more, preferably 100% by weight, of the surfactant composition.

[0442] 62. A surfactant composition in any one of embodiments 1 to 61, wherein the ratio (w / w) of component (A) to (B) is 100:1 to 2:1, preferably 50:1 to 3:1, more preferably 20:1 to 4:1, and very preferably 15:1 to 5:1.

[0443] 63. A surfactant composition in any one of embodiments 1 to 62, wherein the sum of components (A), (B) and (C) is 100% by weight of the total weight of the surfactant composition.

[0444] 64. A surfactant composition in any one of embodiments 1 to 63, wherein the sum of components (A) and (B) is 100% by weight of the total weight of the composition.

[0445] 65. A method for preparing a surfactant composition according to any one of embodiments 1 to 64, comprising the step of mixing components (A), (B) and optionally (C).

[0446] 66. A method for manufacturing a polyurethane foam, comprising the step of combining a surfactant composition according to any one of embodiments 1 to 63 with one or more isocyanates and one or more polyols.

[0447] 67. Polyurethane foam obtained by the method according to Embodiment 66.

[0448] 68. A polyurethane foam forming composition comprising (a) one or more polyols; (b) one or more polyisocyanates; (c) one or more catalysts; (d) water; (e) a silicone surfactant composition of the present invention according to any one of embodiments 1 to 63; and (f) optionally additional additives and auxiliary compounds.

[0449] 69. A polyurethane foam forming composition according to Embodiment 68, wherein the silicone surfactant composition is present in an amount of about 0.1 to 7.0 parts by weight based on the total weight of the polyol component.

[0450] 70. A polyurethane foam forming composition according to embodiments 68 and 69, wherein the amount of organic acid (B) contained in the polyurethane foam forming composition is about 0.01 to 1.0 parts by weight based on the total weight of the polyol component; and the amount of silicone surfactant compound (A) contained in the silicone surfactant composition is about 0.099 to 6.99 parts by weight based on the total weight of the polyol component.

[0451] 71. A polyurethane foam forming composition according to embodiments 68 to 70, wherein the CFD upper-lower difference of the foam formed from the composition is 15% or less.

[0452] 72. Polyurethane foam formed from any one of the compositions of Embodiments 68 to 71.

[0453] 73. Polyurethane foam according to Embodiment 72, wherein the CFD upper-lower difference is 15% or less.

[0454] 74. Use of the surfactant composition according to Embodiments 1 to 64 in the manufacture of polyurethane foam, particularly flexible polyurethane foam.

[0455] Examples

[0456] The material used and the foam obtained according to the present invention, as shown in the present embodiment, and the method for obtaining the foam are characterized by the following parameters.

[0457] Blow-off time: The blow-off time is the time from the start of mixing the isocyanate until blow-off (cell-opening and gas release) is observed during the foaming up process.

[0458] Settling: Settling is the percentage of height loss after 5 minutes during the foaming process relative to the maximum foam height value.

[0459] Core density: Core density is 10 x 10 x 5 cm according to ASTM D3576. 3 It was measured in a foam sample.

[0460] The 40% compression force deflection (CFD) and Comfort Factor (SAG) are 10 x 10 x 5 cm 3 The foam sample was measured according to ISO3386 / 1.

[0461] "CFD difference" or "CFD top-bottom difference" refers to the difference in numerical values ​​obtained from the measurement of 40% compressive deformation according to ISO 3386 / 1 for two foam samples (top foam sample and bottom foam sample) taken from a polyurethane foam block with a bottom surface of 10 cm × 10 cm and a height of 5 cm, calculated as [higher CFD value - lower CFD value) / average value] × 100. Here, the "top" foam sample refers to a sample taken from a position approximately 3 cm below the top surface of the polyurethane foam block up to a height of 5 cm below that position, and the "bottom" foam sample refers to a sample taken from a position approximately 3 cm above the bottom surface of the polyurethane foam block up to a height of 5 cm above that position. The foam block from which the sample was taken was prepared by mixing the components of a polyurethane foam-forming composition, pouring the liquid foam into a 20x20x20 cm paper box, curing the foam in a forced-draft oven for 15 minutes once it had fully expanded, and cooling it for 24 hours before retrieving the foam sample.

[0462] 40% CFD refers to the compressive stress at 40% compression. SAG (Comfort Factor) is the ratio between the compressive stress at 65% compression and the compressive stress at 25% compression.

[0463] Airflow or foam porosity was measured on a 5 x 5 x 2.5 cm³ foam sample according to the ASTM D3574 test method.

[0464] Cell structure is characterized by visual observation. The relative scale of cell structure varies from "very coarse" (less than 7 cells per cm² on average) to "very fine" (more than 16 to 18 cells per cm² on average). Another designation is for cell structures between these two ends, which are considered "fine" when they are in the range of 13 to 15 cells per cm² on average.

[0465] The viscosity of surfactant compounds and surfactant compositions is measured using the capillary viscometer with a Schott Instruments AVS 470 capillary viscometer. The measurement is performed at 25°C.

[0466] ingredient

[0467] DPG: Industrial dipropylene glycol (99% m / m, isomer mixture; Sigma-Aldrich) Monol Polyol (Molecular weight 1500, EO 60%): n-butanol-initiated ethylene oxide-based solvent

[0468] VA-10: Versatic acid 10 (Neodecanic acid) (Minimum 90% m / m; Hexion)

[0469] Polyol Voranol 3322 is a flexible urethane foam polyol with a hydroxyl value of 48 manufactured by Dow Chemical (glycerin-initiated polyoxypropylene polyoxyethylene triol with a molecular weight of 3500 g / mol).

[0470] TDI 80 / 20 is a mixture of 80 wt% 2,4-toluene diisocyanate and 20 wt% 2,6-toluene diisocyanate manufactured by Covestro (brand name Desmodur T80).

[0471] Niax TM Catalyst B-18 is a balance amine catalyst manufactured by Momentive Performance Materials Corporation.

[0472] Niax TM Catalyst EF-133 is a low emission blowing amine catalyst manufactured by Momentive Performance Materials Corporation.

[0473] Niax TM Catalyst A-33 is a gelling amine catalyst manufactured by Momentive Performance Materials Corporation.

[0474] Niax TM The catalyst tin octosate (tin octosate) is a metal gelling catalyst manufactured by Momentive Performance Materials Corporation.

[0475] The silicone surfactant compounds referred to as "copolymer C1", "copolymer C2", and "copolymer C3" used in this embodiment are as follows.

[0476] Copolymers C1, C2, and C3 were each subjected to a quantitative Pt-catalyzed hydrosilylation reaction with a blend of allyl-terminated polyethers to general formula MD x D' y It is a silicon surfactant compound obtained from a silicon fluid having M, where M is (CH3)3SiO 1 / 2 , D is (CH3)2SiO 2 / 2, D' is (H)(CH3)2SiO 2 / 2 Therefore, these copolymers are characterized by a specific silicone fluid providing a silicone backbone, a specific allyl-terminated polyether forming the side chains of the copolymer, and the ratio of the polyether side chains bonded to the silicone backbone.

[0477] The allyl-terminated polyethers constituting the blend of allyl-terminated polyethers are characterized as follows:

[0478] The initial number followed by H indicates the nominal % of ethylene oxide residue in polyethers based on ethylene oxide and propylene oxide;

[0479] The letter A indicates that the polyether is allyl-started;

[0480] The number that follows indicates the nominal molecular weight of the allyl polyether;

[0481] The letters "Me" and "Ac" indicate whether the polyether is methoxy-capped (Me) or acetoxy-capped (OAc).

[0482] An exception to this nomenclature is the polyether "APEG800-Ac," where A indicates that the polyether starts with an allyl group, "PEG" signifies polyethylene glycol (excluding propylene oxide-based units), the number 800 represents the nominal molecular weight, and "Ac" indicates that the polyether is acetoxy-terminated.

[0483] Copolymer C1 :

[0484] In copolymer C1, formula MD x D' yIn the silicone fluid based on M, x is 78 and y is 7, said copolymer is formed by the hydrosilylation of the silicone fluid with polyether blends of "50HA1000-Me" and "50HA4800-Me", and said polyether blend average molecular weight (number average molecular weight of the combined polyethers of the mixture) is 2500 g / mol.

[0485] Copolymer C2 :

[0486] In copolymer C2, formula MD x D' y In the silicone fluid based on M, x is 78 and y is 7, said copolymer is formed by the hydrosilylation of the silicone fluid with polyether blends of "50HA1000-Ac" and "50HA4800-Ac", and said polyether blend average molecular weight (number average molecular weight of the combined polyethers of the mixture) of said polyether blends is 2000 g / mol.

[0487] Copolymer C3 :

[0488] In copolymer C3, formula MD x D' y In the silicone fluid based on M, x is 56 and y is 5, said copolymer is formed by the hydrosilylation of the silicone fluid with a polyether blend of "50HA4800-Ac" and "APEG800-Ac", and said polyether blend average molecular weight (number average molecular weight of the combined polyether of the mixture) of said polyether blend is 1600 g / mol.

[0489] In each case, the blend average molecular weight is determined based on the nominal molecular weights of the specific polyethers used and their proportions in the blend.

[0490] MD acting as a starting material for C1-C3 x D' y Synthesis of M fluid and corresponding MD x D' yA detailed procedure for the preparation of M surfactant compounds is provided in U.S. Patent 5,489,617.

[0491] Preparation of a silicone surfactant composition

[0492] To prepare a silicone surfactant composition, a silicone surfactant compound (A), a surfactant efficacy enhancer (B) which is an organic acid or an organic acid derivative, and a diluent (C) were blended according to the weight percentages specified below.

[0493] Example 1 - Surfactant Composition 1 (IN1)

[0494] The first base solution 1 (BS1) was prepared by mixing 40.2 g of copolymer C2 and 59.8 g of DPG. Surfactant composition 1 (IN1) was prepared by adding 5 g of VA-10 to the BS1 solution so that the total weight was 100 g, thereby preparing a solution of 5 wt% VA-10, 38.2 wt% C2, and 56.8 wt% DPG.

[0495] Example 2 - Surfactant Composition 2 (IN2)

[0496] The second base solution 2 (BS2) was prepared by mixing 40.0 g of copolymer C3 and 60.0 g of DPG. Surfactant composition 2 (IN2) was prepared by adding 5 g of VA-10 to the BS1 solution so that the total weight was 100 g, thereby preparing a solution of 5 wt% VA-10, 38 wt% C3, and 57 wt% DPG.

[0497] Example 3 - Surfactant Composition 3 (IN3)

[0498] As the third base solution 3 (BS3), 100g of a mixture containing 57% by weight of copolymer C1 and 43% by weight of DPG was taken. Surfactant composition 3 (IN3) was prepared by mixing 53g of the previously formed mixture (BS3) containing copolymer C1 with 5g of VA-10, and adding DPG to the mixture to make the total weight 100g, thereby obtaining a solution of 5% by weight of VA-10, 30.2% by weight of C1, and 64.8% by weight of DPG.

[0499] Example 4 - Surfactant compositions 4a (IN4a) and 4b (IN4b)

[0500] As the fourth base solution 4 (BS4), 100g of a mixture containing 50% by weight of copolymer C3 and 50% by weight of DPG was taken.

[0501] Surfactant composition 4a (IN4a) was prepared by mixing 76g of the above-mentioned mixture containing copolymer C3 with 3g of VA-10, and adding DPG to the mixture to make the total weight 100g, thereby obtaining a solution of 3 wt% VA-10, 38 wt% C3, and 59 wt% DPG. Surfactant composition 4b (IN4b) was prepared by mixing 70g of a pre-molded mixture containing copolymer C3 with 3g of VA-10, and adding DPG to the mixture to make the total weight 100g, thereby obtaining a solution of 3 wt% VA-10, 35 wt% C3, and 62 wt% DPG.

[0502] Example 5 - Surfactant compositions 5a (IN5a), 5b (IN5b), 5c (IN5c), 5d (IN5d), 5e (IN5e) and 5f (IN5f)

[0503] As the fifth base solution 5 (BS5), 100g of a mixture containing 70% by weight of copolymer C3 and 30% by weight of monool polyol was taken.

[0504] Surfactant composition 5a (IN5a) was prepared by mixing 1.51 g of potassium isobutyrate and 80 g of BS5, and adding DPG to the mixture so that the total weight was 100 g, thereby obtaining a solution containing 1.51 wt% potassium isobutyrate, 56 wt% copolymer C3, 24 wt% monool polyol, and 18.49 wt% DPG.

[0505] Surfactant composition 5b (IN5b) was prepared by mixing 2.82g of potassium ethylhexanoate and 80g of BS5, and adding DPG to the mixture so that the total weight was 100g, thereby obtaining a solution containing 2.82% by weight of potassium ethylhexanoate, 56% by weight of copolymer C3, 24% by weight of monool polyol, and 17.18% by weight of DPG.

[0506] Surfactant composition 5c (IN5c) was prepared by mixing 4g of oleic acid and 80g of BS5, and adding DPG to the mixture so that the total weight was 100g, thereby obtaining a solution containing 4% by weight of oleic acid, 56% by weight of copolymer C3, 24% by weight of monool polyol, and 16% by weight of DPG.

[0507] Surfactant composition 5d (IN5d) was prepared by mixing 4g of oleic acid and 96g of BS5, thereby obtaining a solution containing 4% by weight of oleic acid, 68.6% by weight of copolymer C3, and 27.4% by weight of monool polyol.

[0508] Surfactant composition 5e (IN5e) was prepared by mixing 4g of methyl oleate and 80g of BS5, and adding DPG to the mixture so that the total weight was 100g, thereby obtaining a solution containing 4% by weight of methyl oleate, 56% by weight of copolymer C3, 24% by weight of monool polyol, and 16% by weight of DPG.

[0509] Surfactant composition 5f (IN5f) was prepared by mixing 4g of bis(2-ethylhexyl)adipate and 80g of BS5, and adding DPG to the mixture so that the total weight was 100g, thereby obtaining a solution of 4% by weight of bis(2-ethylhexyl)adipate, 56% by weight of copolymer C3, 24% by weight of monool polyol, and 16% by weight of DPG.

[0510] Manufacture of flexible slabstock polyurethane foam formulation

[0511] To test the surfactant compositions IN1, IN2, IN3, IN4a, IN4b, IN5a, IN5b, IN5c, IN5d, IN5e, and IN5f described above, three formulations (I) to (III) with or without fillers were prepared.

[0512] To prepare polyether foam in the laboratory, the components listed in Tables 1–3 were blended in the relative amounts indicated in the tables ("phpp" indicates weight ratio) according to the following procedure: polyol, amine catalyst, water, silicone, and other additives (e.g., solvent, filler, if present) were mixed for 60 seconds. Tin octoate (II) was added and mixed for an additional 10 seconds. Then, TDI (TDI 80 / 20) was added and mixed for an additional 5 seconds. Once the mixing was complete, the liquid foam was poured into a paper box measuring 20 x 20 x 20 cm. The foam rise profile was recorded, and the foam was cured in a forced-draft oven at 100°C for 15 minutes and then cooled for 24 hours. The amounts of the components were selected to ensure that the volume of the polyurethane material filled the paper box measuring 20 x 20 x 20 cm.

[0513] Table 1. 20 kg / m² 3 Formulation having the density of (I) (filler-containing)

[0514] ingredient phpp (Parts per 100 parts of polyol) Voranol 3322 100 calcium carbonate 10 water 4.8 Niax catalyst B-18 0.07 methylene chloride 8.0 Surfactants (various) 1.2 Niax catalyst tin octosate 0.18 TDI index 110

[0515] Table 2. 32 kg / m² 3 Formulation (II) having the density of (no filler)

[0516] ingredient phpp Voranol 3322 100 Water, whole 3.10 Niax catalyst EF-133 0.20 Surfactants (various) 0.80 Niax catalyst tin octosate 0.18 TDI index 108

[0517] Table 3. 16 kg / m² 3 Formulation having the density of (III) (no filler)

[0518] ingredient phpp Voranol 3322 100 Water, whole 5.5 Niax catalyst A-33 0.14 Surfactants (various) 1.1 methylene chloride 10 Niax catalyst tin octosate 0.25 TDI index 112

[0519] Examples 6, 7 and Comparative Examples 6a and 7a

[0520] The formation of PU foam using the PU formulation (I) shown in Table 1 was tested using base solutions BS1 and BS2 (acid-free) and surfactant compositions IN1 and IN2 (each containing 5 wt% of VA-10).

[0521] In PU formulation (I), surfactant 1.2 phpp corresponds to 2 phpp of BS1 or IN1 or BS2 or IN2. The results shown in Table 4 were obtained.

[0522] Table 4. Foaming and physical performance of formulation (I)

[0523] Comparative Example 6a Example 6 Comparative Example 7a Example 7 Surfactant (1.2 phpp in Formulation I) BS1 IN1 BS2 IN2 VA-10: 5 wt% in BS1 VA-10: 5 wt% in BS2 Foam exterior split OK split OK

[0524] The appearance of the foam is shown in a photograph in Fig. 1.

[0525] Table 4 shows the results of the foaming process and the foam physical performance of formulation (I) using BS1, IN2, BS2, and IN2 as surfactant additives. Comparative Examples 6a (using BS1) and 7a (using BS2) are comparative experiments using a silicone surfactant mixture containing 60 wt% copolymer C2 and 40 wt% DPG, and a mixture containing 50 wt% copolymer C3 and 50 wt% DPG, respectively. Examples 6 (using IN1) and 7 (using IN2) are experiments according to the present invention, wherein the silicone surfactant composition contains 5 wt% organic acid VA-10 (neodecanic acid) and 95 wt% of a silicone surfactant mixture containing 60 wt% copolymer C2 and 40 wt% DPG, or 95 wt% of a silicone surfactant mixture containing 50 wt% copolymer C3 and 50 wt% DPG. Surfactant BS1 and BS2 failed to form a stable foam and the formed foam split on the inside, whereas IN1 and IN2 formed high-quality foam.

[0526] Examples 8, 9, 10 and Comparative Examples 8a, 9a, and 10a

[0527] The formation of PU foam using the PU formulation (II) shown in Table 2 was tested using base solutions BS1 and BS2 (non-acidic) and surfactant compositions IN1 and IN2 (each containing 5 wt% VA-10). In PU formulation (II), 0.8 phpp of surfactant corresponds to 0.8 phpp of BS1 or IN1, BS2 or IN2, or BS3 or IN3. The results shown in Table 5 were obtained.

[0528] Table 5. Foaming and physical performance of Formulation (II).

[0529] Yes number Comparative Example 8a Example 8 Comparative Example 9a Example 9 Comparative Example 10a Example 10 Surfactant (0.8 phpp in Formulation II): BS1 IN1 BS2 IN2 BS3 IN3 VA-10: 5 wt% in BS1 VA-10: 5 wt% in BS2 VA-10: 5 wt% in a 53:42 (w / w) mixture of BS3 and DPG Blow-off time candle 138 139 139 138 140 136 fix % 1.2 0.5 1.0 0.5 1.2 0.7 Air flow rate L / min 87.5 21.4 87.8 13.9 102.9 13.9 core density kg / m 3 33.2 32.3 32.9 32.3 33.5 33.4 CFD 40% kPa 4.02 4.34 4.17 4.43 3.46 4.10 SAG - 2.10 2.11 2.21 2.12 2.34 2.26 Cell structure - minuteness minuteness minuteness minuteness minuteness minuteness

[0530] Table 5 shows the results of the foaming process and foam physical performance of composition (II) using BS1, IN2, BS2, IN2, BS3, and IN3 as surfactant composition additives. Comparative Example 8a (using BS1) and Comparative Example 9a (using BS2) are comparative experiments using a silicone surfactant mixture containing 60 wt% copolymer C2 and 40 wt% DPG, and a silicone surfactant mixture containing 50 wt% copolymer C3 and 50 wt% DPG, respectively. Example 8 (using IN1) and Example 9 (using IN3) are experiments related to the present invention, in which the silicone surfactant composition contains 5 wt% organic acid (VA-10) and 95 wt% silicone surfactant mixture containing 60 wt% copolymer C2 and 40 wt% DPG, or contains a silicone surfactant mixture containing 50 wt% copolymer C3 and 50 wt% DPG, respectively. Examples 8 and 9 have less precipitation, smoother air flow, and lower density compared to Comparative Examples 8a and 9a. Therefore, blends containing a small amount of organic acid have significantly improved stability compared to silicone surfactants that do not contain organic acid additives.

[0531] In addition, Comparative Example 10a uses a mixture composed solely of copolymer C1 57 wt% and DPG 43 wt%. The composition of Example 10 forms a stable PU foam by adding approximately half the amount of VA-10, i.e. neodecanoic acid, to the mixture composed of copolymer C1 57 wt% and DPG 43 wt% compared to Comparative Example 10a. Surprisingly, the foam obtained in Example 10 exhibits higher efficacy than the foam obtained in Comparative Example 10a, which has lower air flow and density.

[0532] Examples 11, 12 and Comparative Example 11a

[0533] PU foam formation using PU formulation (III) shown in Table 3 was tested using base solution BS4 (acid-free) and surfactant compositions IN4a and IN4b (each containing 3 wt% VA-10). In PU formulation (III), 1.1 phpp of surfactant corresponds to 1.1 phpp of BS4, or IN4a or IN4b. The results shown in Table 6 were obtained.

[0534] Table 6. Foaming and physical performance of formulation (III).

[0535] surfactants (1.1 phpp in PU Formulation III) Comparative Example 11a Example 11 Example 12 BS4 IN4a IN4b VA-10: 3 wt% in a 76:21 (w / w) mixture of BS4 and DPG VA-10: 3 wt% in a 70:27 (w / w) mixture of BS4 and DPG Blow-off time candle 111 110 107 Air flow rate L / min 143 108 128 Core density, lower kg / m 3 16.2 16.5 16.7 Core density, upper kg / m 3 14.6 15 15.1 core density difference 10.4% 9.5% 10.1% CFD 40%, bottom kPa 2.81 3.28 3.09 CFD 40%, upper kPa 2.35 2.91 2.87 CFD difference 17.8% 12.0% 7.4% Cell structure minuteness minuteness minuteness

[0536] Table 6 shows the results of the foaming process and foam physical performance of the PU formulation (III). By optimizing the content of the organic acid and the silicone surfactant, it is possible to achieve performance similar to that of using the pure silicone surfactant (BS4) alone. Table 6 shows the results of Examples 11 and 12, which formed foam using the silicone surfactant composition according to the present invention, and Comparative Example 11a, which formed a comparative foam. Comparative Example 11a is a control experiment using a silicone surfactant containing BS4. IN4a and IN4b applied in Examples 11 and 12 are silicone surfactant compositions containing 3 wt% neodecanoic acid (VA-10) and 76 wt% or 70 wt% BS4, respectively.

[0537] In the low-density foam of PU formulation III, the difference in physical performance along the foam rise direction is expected to be small. Neodecanoic acid (VA-10)-containing surfactant compositions IN4a and 4b exhibit foaming performance similar to surfactant BS4 in PU formulation III, and show a more uniform hardness distribution with smaller CFD differences than Comparative Example 10a. Additionally, the PU foams of Examples 10 and 11 based on formulation III containing surfactant composition IN4a or 4b exhibit slightly higher hardness than the PU foam of Example 10a obtained using surfactant composition BS4.

[0538] Examples 13, 14, 15, 16, 17, 18 and Comparative Example 13a

[0539] In addition, the formation of PU foam using the PU formulation (III) shown in Table 3 was tested using base solution BS5 (non-containing organic acid, salt, or ester) and surfactant compositions IN5a, IN5b, IN5c, IN5d, IN5e, or IN5f (each containing 1.51% to 4.00% by weight of acid, salt, or ester).

[0540] The base solution BS5 and surfactant compositions IN5a, IN5b, IN5c, IN5d, IN5e and IN5f are as shown in Table 7 below.

[0541] Table 7. Components of base solution BS5 and surfactant composition IN5a-5f

[0542] Surfactant composition BS5 IN5a IN5b IN5c IN5d IN5e IN5f Copolymer C3 weight% 70.00 56.00 56.00 56.00 68.60 56.00 56.00 Monol Polyol with Mw 1500, EO 60% weight% 30.00 24.00 24.00 24.00 27.40 24.00 24.00 potassium isobutyrate weight% 1.51 Potassium ethylhexanoate weight% 2.82 oleic acid weight% 4.00 4.00 methyl oleate weight% 4.00 Bis(2-ethylhexyl)adipate weight% 4.00

[0543] In PU formulation (III), surfactant 1.1 phpp corresponds to 1.1 phpp of BS5, or 1.1 phpp of IN5a, IN5b, IN5c, IN5d, IN5e or IN5f.

[0544] Table 8 below presents the results of the foaming process and foam physical performance of the PU formulation (III).

[0545] Table 8. Foaming and foam physical performance of Formulation (III)

[0546] Comparative Example 13a Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Surfactant (1.1 phpp in PU Formulation III) BS5 IN5a IN5b IN5c IN5d IN5e IN5f Blow-off time candle 110 106 104 109 111 111 112 Air flow rate L / min 164 75 19 17 146 21 35 Core density, lower kg / m 3 17.0 16.5 16.4 16.5 16.6 16.6 16.9 Core density, upper kg / m 3 15.7 15.4 15.3 15.3 15.5 15.4 15.7 core density difference 8.0% 6.9% 6.9% 7.5% 6.9% 7.5% 7.4% CFD 40%, bottom kPa 3.35 4.04 4.22 4.20 3.82 4.13 3.67 CFD 40%, upper kPa 2.88 3.53 3.71 3.73 3.32 3.65 3.34 CFD difference 15.1% 13.5% 12.9% 11.9% 14.0% 12.3% 9.4% Cell structure - minuteness minuteness minuteness minuteness minuteness minuteness minuteness

[0547] By optimizing the content of organic acid salts (IN5a and IN5b), organic acids (IN5c and IN5d), or organic acid esters (IN5e and IN5f) and silicone surfactants, it is possible to achieve higher efficacy performance for the surfactant composition than using pure silicone surfactant (BS5) alone. Table 8 shows the results of Examples 13 to 18, in which foam was formed using the silicone surfactant composition according to the present invention, and the results of Comparative Example 13a, in which a comparative foam was formed. Comparative Example 13a is a control experiment using silicone surfactant BS5. IN5a, 5b, 5c, 5d, 5e, and 5f according to the present invention were applied to Examples 13, 14, 15, 16, 17, and 18, respectively. Surfactant compositions IN5a, 5b, 5c, 5d, 5e, or 5f containing potassium isobutyrate, potassium ethylhexanoate, oleic acid, methyl oleate, or bis(2-ethylhexyl)adipate, respectively, provide higher foaming performance, lower air flow, and lower density in PU formulation III compared to surfactant BS5. Examples 13 to 18 also provide better uniform hardness (CFD 40%) and density distribution, as indicated by lower CFD differences and lower core density differences compared to Comparative Example 13a.

[0548] Examples 19, 20, 21, 22 and Comparative Examples 19a, 19b, and 19c

[0549] The formation of PU foam using the PU formulation (III) shown in Table 3 was tested using base solution BS4 (non-containing organic acid, salt, or ester) and surfactant compositions IN6a, IN6b, IN6c, IN6d, IN6e, or IN6f (each containing 3.0 wt% carboxylic acid).

[0550] The base solution BS4 and surfactant compositions IN6a, IN6b, IN6c, IN6d, IN6e, and IN6f are presented in Table 9 below.

[0551] Table 9. Components of base solution BS4 and surfactant compositions IN6a-6f

[0552] Surfactant composition BS4 IN6a IN6b IN6c IN6d IN6e IN6f Copolymer C3 weight% 50 40 40 40 40 40 40 Acetic acid weight% 3.0 propionic acid weight% 3.0 butyric acid weight% 3.0 Hexanoic acid weight% 3.0 Versatic acid 10 weight% 3.0 oleic acid weight% 3.0 DPG weight% 50 57 57 57 57 57 57

[0553] In the PU formulations (III) of these examples, surfactant 1.1 phpp corresponds to 1.1 phpp of BS4 or IN6a, or IN6b, IN6c, IN6d, IN6e or IN6f. Table 10 below presents the results of the foaming process and foam physical performance of the PU formulations (III) using the surfactant compositions.

[0554] Table 10. Foaming and physical performance of formulation (III).

[0555] performance Comparative Example 19a Comparative Example 19b Comparative Example 19c Example 19 Example 20 Example 21 Example 22 Surfactant (1.1 phpp in PU Formulation III) BS4 IN6a IN6b IN6c IN6d IN6e IN6f Blow-off time candle 111 111 111 112 115 111 109 Air flow rate L / min 143 170 168 20 3.4 1.9 5.3 Core density, lower kg / m 3 16.2 16.6 16.2 15.9 16.0 16.0 15.9 CFD 40%, bottom kPa 2.81 3.13 2.95 3.21 3.30 3.02 3.04 Cell structure - minuteness minuteness minuteness minuteness minuteness minuteness minuteness

[0556] When comparing the results of BS4 (Comparative Example 19a) with IN6a and 6b (Comparative Examples 19b and 19c), surfactants containing acetic acid and propionic acid provide a relatively higher air flow rate than the control group (BS4). This means that these organic acids do not exhibit an efficacy-enhancing effect of the surfactant composition.

[0557] Comparing the results of BS4 (Comparative Example 19a) and IN6c to IN6f (Examples 19 to 22), surfactants containing butyric acid, hexanoic acid, versatic acid, and oleic acid provide a relatively lower air flow rate than the control group (BS4). This indicates that organic acids with such a structure provide an efficacy-enhancing effect to the silicone surfactant composition.

[0558] Example 23 and Comparative Example 23a

[0559] The formation of PU foam using the representative PU formulation (III) shown in Table 3 was compared with that using base solution BS4 (non-containing organic acid, salt, or ester) and with that using surfactant compositions IN7a and IN7b. The results are presented in Table 11 below.

[0560] Table 11. Components of surfactant compositions IN7a and IN7b in formulation (III) and their performance

[0561] Surfactant composition (Comparative Example 19a) BS4 Comparative Example 23a IN7a Example 23 IN7b Copolymer C weight% 50 10 20 Versatic acid 10 weight% 3 3 DPG weight% 50 87 77 performance Comments Good foam microcell structure Form collapse Good foam microcell structure

Claims

Claim 1 A surfactant composition for use in polyurethane foam comprises: (A) one or more silicone surfactant compounds; (B) one or more surfactant efficacy enhancers selected from organic acids, organic acid salts, or organic acid esters; and (C) optionally one or more diluents; wherein one or more of the silicone surfactant compounds (A) comprises a silicone backbone and one or more polyether substituents R, which may be identical or different, bonded to one or more Si atoms of the silicone backbone. * A silicone surfactant comprising, wherein one or more of the component (B) is a carboxylic acid having four or more carbon atoms, and wherein the amount of the component (A) in the surfactant composition is 15.0 weight% or more based on the total weight of the surfactant composition. Claim 2 A surfactant composition according to claim 1, wherein the component (B) is contained in the composition in an amount of 0.01 to 70 weight% based on the total weight of the surfactant composition, and the ratio (w / w) of the component (A) to the component (B) is in the range of 100:1 to 2:1, preferably 50:1 to 3:1, more preferably 20:1 to 4:1, and more preferably 15:1 to 5:

1. Claim 3 In claim 1 or 2, the one or more silicone surfactant compounds (A) have the following formula, and M * D x D" y M * (I), here, M * is (CH3)3SiO 1 / 2 or (CH3)2R * SiO 1 / 2 It represents; D is (CH3)2SiO 2 / 2 It represents;D” is (CH3)R * SiO 2 / 2 Representing; x is 0-200; y is 2 or greater; x+y is 10 to 250; the ratio of x to y is 2 to 50; and R * is the same or different -C n H 2n A surfactant composition comprising a polyether substituent independently selected from O-group-starting polyether substituents, wherein n is 2-10. Claim 4 In any one of claims 1 to 3, the polyether substituent R of the silicone surfactant compound (A) * A surfactant composition:-C, which may be the same or different and has the following formula (II): n H 2n O(C2H4O) a (C3H6O) b R 1 (II)(wherein, n is 2 to 10, and a is the ethylene oxide residue of the polyether substituent R) * The number such that the alkylene oxide residue accounts for about 30% to about 100% by weight of the polyether substituent R * The number is such that it accounts for about 0% to about 70% by weight of the alkylene oxide residues of; R 1 is a C1-C10 alkyl group or a C2-C11 alkanoyl group, preferably a methyl group or an acetyl group). Claim 5 A surfactant composition according to any one of claims 1 to 4, wherein one or more of the silicone surfactant compound (A) has the following formula (I): M * D x D" y M * (I)(here, M * is (CH3)3SiO 1 / 2 or (CH3)2R * SiO 1 / 2 It represents; D is (CH3)2SiO 2 / 2 It represents;D" is (CH3)R * SiO 2 / 2 It represents; x is 0 to 200; y is 2 or greater; x+y is 10 to 250; the ratio of x to y is 2 to 50, and R * is the same or different -C n H 2n A polyether substituent independently selected from O-group-starting polyether substituents, where n is 2 to 10, and substituent R * It has a number average molecular weight of 200 daltons to 6000 daltons and is independently terminated by an alkoxy group or an acryl group, preferably a methoxy group or an acetoxy group). Claim 6 A surfactant composition according to any one of claims 1 to 5, wherein the component (B) is an alkanic acid or alkenic acid having 4 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 9 to 20 carbon atoms. Claim 7 A surfactant composition according to any one of claims 1 to 6, wherein the component (B) is a branched alkane acid, more preferably a branched alkane acid having 5 to 24 carbon atoms. Claim 8 A surfactant composition according to any one of claims 1 to 7, wherein the component (B) is a branched alkyl monocarboxylic acid having 5 to 20 carbon atoms, containing one or more quaternary carbon atoms, preferably containing a quaternary carbon atom at the α position of a carboxylic acid group. Claim 9 A surfactant composition according to any one of claims 1 to 8, wherein the amount of component (B) in the silicone surfactant composition is 1.0 to 10 weight%, preferably 1.5 to 8 weight%, and more preferably 2.5 to 7 weight% based on the total weight of components (A), (B), and (C) of the silicone surfactant composition. Claim 10 A surfactant composition according to any one of claims 1 to 9, wherein the sum of components (A) and (B) is 20% by weight or more of the total weight of the composition, preferably 25% by weight or more of the total weight of the composition, more preferably 30% by weight or more of the total weight of the composition, and even more preferably 35% by weight or more of the total weight of components (A), (B) and (C) of the silicone surfactant composition. Claim 11 A surfactant composition according to any one of claims 1 to 10, wherein the diluent (C) is completely miscible with the components (A) and (B), wherein the diluent (C) is water; a monoalcohol, a diol or a polyol; a monoether, a diether or a polyether; an aliphatic and aromatic hydrocarbon and a halogenated hydrocarbon, in particular a partially halogenated or perhalogenated alkane and a partially halogenated or perhalogenated alkylated phenyl compound; a ketone, an amide, a nitrile, a sulfoxide, an organocarbonate, or a combination of two or more of these, preferably an ethylene glycol ether or a propylene glycol ether, specifically a dipropylene glycol. Claim 12 A surfactant composition according to any one of claims 1 to 11, wherein the diluent (C) is ethylene glycol ether or propylene glycol ether, particularly dipropylene glycol. Claim 13 A surfactant composition according to any one of claims 1 to 12, wherein the composition comprises one or more diluents (C), and the amount of said diluent is 20% by weight or more, more preferably 35% by weight or more, more preferably 50% by weight or more, even more preferably 65% ​​by weight or more, much more preferably 75% by weight or more, and most preferably 85% by weight or more, based on the total weight of said surfactant composition. Claim 14 In any one of claims 1 to 13, the silicone surfactant compound (A) has the following formula (I) M * D x D" y M * (I)(here, M * , D and D” are as defined above, x is 45 to 90, preferably 55 to 80; y is 2 to 10, preferably 3 to 9; x+y is 50 to 90, preferably 55 to 85, and the ratio of x to y is 5 to 20, preferably 7 to 15); and the silicone surfactant compound (A) comprises one or more polyether substituents R selected from a group (iii) having the structure of formula (II''') below and a group (iv) having the structure of formula (II''') below * It consists of including (iii) -C n'" H 2n'" O(C2H4O) a'" (C3H6O) b'" R 4 (II''')(wherein, n''' is 2 to 4, preferably 3; a''' is a number such that the ethylene oxide residue occupies 30 to 60 weight percent of the alkylene oxide residue of the polyether substituent; b''' is a number such that the propylene oxide residue occupies 40 to 70 weight percent of the alkylene oxide residue of the polyether; R 4 (represents a methoxy group, acetoxy group, or butoxyl group) (iv) -C n"" H 2n"" O(C2H4O) a"" (C3H6O) b"" R 5 (II'''')(wherein n'''' is 2 to 4, preferably 3; a'''' is a number such that the ethylene oxide residue occupies 30% to 100% by weight of the alkylene oxide residue of the polyether substituent; b'''' is a number such that the propylene oxide residue occupies 0 to 70% by weight or less of the alkylene oxide residue of the polyether; R 5 represents a methoxy group, an acetoxy group, or a butoxyl group); the organic acid (B) is an alkyl carboxylic acid having 5 to 24 carbon atoms, preferably a branched alkyl carboxylic acid having 5 to 24 carbon atoms, more preferably selected from the group consisting of C8-neoalkasan, C9-neoalkasan, C10-neoalkasan, C11-neoalkasan, C12-neoalkasan, C13-neoalkasan, and C14-neoalkasan, most preferably a neodecanoic acid; and the composition is optionally composed of a diluent (C), wherein the diluent (C) is preferably a glycol ether, most preferably a dipropylene glycol, a surfactant composition. Claim 15 A surfactant composition according to any one of claims 1 to 12 and 14, wherein the composition comprises, based on the total weight of the surfactant composition, 20 to 80 weight% of a silicone surfactant compound (A), 1 to 8 weight% of a carboxylic acid (B), and 12 to 79 weight% of a diluent (C), wherein the sum of the components (A), (B) and (C) is 95 weight% or more, preferably 100 weight%, of the surfactant composition. Claim 16 A surfactant composition according to any one of claims 1 to 10 and claim 14, wherein the sum of components (A) and (B) is 100% by weight of the total weight of the composition. Claim 17 Use in the manufacture of polyurethane foam, particularly flexible polyurethane foam, of a surfactant composition according to any one of claims 1 to 16. Claim 18 A method for manufacturing a polyurethane foam, comprising the step of combining a surfactant composition according to any one of claims 1 to 16 with at least one isocyanate and at least one polyol. Claim 19 A polyurethane foam-forming composition comprising (a) one or more polyols; (b) one or more polyisocyanates; (c) one or more catalysts; (d) water; (e) a silicone surfactant composition of any one of claims 1 to 16; and (f) optionally additional additives and auxiliary compounds. Claim 20 Polyurethane foam formed from the composition of claim 19.

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