JPH0665379A - Organic-surfactant-modified organopolysiloxane - Google Patents

Abstract

PURPOSE:To obtain a surfactant having an excellent performance as a foam stabilizer for the production of urethane foams by incorporating an organic surfactant substituent in the skeleton of an organopolysiloxane. CONSTITUTION:An organic-surfactant-modified organopolysiloxane having at least one Si-bonded organic surfactant substituent of the formula in the molecule (wherein R' is H, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or a hydrophilic group; R'' is H, a monovalent hydrocarbon group, an organic acid salt group, an inorganic acid salt group, an organic reactive group, an inorganic reactive group, or a hydrophilic group; (z) is 2-4; (m) is 2-6; and (n) is 1-500). It is useful as an emulsifier for cosmetics, mold releases, defoamers, textile processing agents, adhesives, anticlouding agents, lustering agents, water repellents, coating materials, resin additives, antistatic agents, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic surfactant-modified organopolysiloxane and a foam stabilizer for urethane foam characterized by containing the same.

[0002]

2. Description of the Related Art Polyether-modified organopolysiloxane is widely used as a foam stabilizer in the production of urethane foam, an emulsifier for cosmetics, an emulsifier for defoaming agents, an emulsifier for fiber treatment, etc. due to its unique interface characteristics. There is. However,
A silicone-based surfactant having further improved emulsifying properties has been desired. In particular, regarding the production of urethane foam, the use of CFCs has been limited due to global environmental problems such as ozone layer depletion due to CFCs, which has become a social problem in recent years. There is a great demand for technology conversion. Freon gas has been used because it has been recognized for its safety and heat insulation properties in addition to foaming during the production of urethane foam. Actually, by reducing the amount of freon gas, in addition to these effects, polyol and isocyanate, which are the raw materials for urethane, are used. , A compatibilizing action of substances that are difficult to dissolve, such as a catalyst,
Even important effects such as a viscosity lowering effect during the reaction are impaired. In the conventional polyether-modified organopolysiloxane, when the reduction of the CFC gas is 50 to 100%, there is a problem that not only the imparting of the compatibilizing action but also the foam stabilizing effect is insufficient due to the limit of the interfacial effect. there were.

[0003]

DISCLOSURE OF THE INVENTION The present invention aims to solve the above-mentioned drawbacks, and in particular, when used as a foam stabilizer in the production of urethane foam, a novel silicone-based interface having excellent performance. It is an object to provide an activator.

[0004]

Means for Solving the Problem and Its Action As a result of intensive studies, the present inventors have found that a novel organic surfactant-modified organopolysiloxane and, when it is used as a foam stabilizer in the production of urethane foam, The inventors have found that they have excellent performance and completed the present invention.

That is, the present invention relates to the following formula in which one molecule is directly bonded to a silicon atom.

[Chemical 4] (In the formula, R ′ is independently a hydrogen atom, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or an arbitrary substituent selected from a hydrophilic group, and R ″ is a hydrogen atom or a monovalent group. Arbitrary substituent selected from a hydrocarbon group, an organic acid group, an inorganic acid group, an organic reactive group, an inorganic reactive group, or a hydrophilic group, z is 2 to 4, m is 2 to 6, and n is 1 to 500)) and an organic surfactant-modified organopolysiloxane having at least one organic surfactant substituent.

The present invention is particularly

[Chemical 5] (In the formula, R is independently a hydrogen atom, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or an arbitrary substituent selected from a hydrophilic group;

[Chemical 6] (In the formula, R ′ is independently a hydrogen atom, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or an arbitrary substituent selected from a hydrophilic group, and R ″ is a hydrogen atom or a monovalent group. Arbitrary substituent selected from a hydrocarbon group, an organic acid group, an inorganic acid group, an organic reactive group, an inorganic reactive group, or a hydrophilic group, z is 2 to 4, m is 2 to 6, and n is 1 to An organic surfactant substituent represented by 500), A represents a group selected from R and Q, x is 0 to 100 and y is 0 to 100, provided that y is 0. Represents an organic surfactant-modified organopolysiloxane represented by the formula (A is Q).

In the above formula, R's are independently of each other a hydrogen atom, a monovalent hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group). Group, decyl group, dodecyl group,
Octadecyl group, eicosyl group, phenyl group, naphthyl group, benzyl group, phenylethyl group, tolyl group, xylyl group, cyclohexyl group, decyl group, dodecyl group, octadecyl group, polycaprolactone group, trifluoropropyl group, chloropropyl group, etc. ), An organic reactive group (for example, an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an acyl group, a mercapto group, a methacrylo group, an isocyanate group,
Ureido group, vinyl group, amide group, imide group, imino group, aldehyde group, nitro group, nitrile group, oxime group, azo group, hydrazone group, and hydrocarbon group to which these are bonded, etc. Methoxysilylethyl group, triethoxysilylethyl group, methyldimethoxysilylethyl group, etc.), hydrophilic group (for example, polyether group, glucose group, sulfate base, ammonium sulfonate group, carboxylate group, etc.) Although it is a substituent, a monovalent hydrocarbon group is preferable, and a methyl group is particularly preferable.

R'and R "in the Q group are selected in exactly the same manner as R above, but R'is particularly preferably an octyl group or a nonyl group, and R" is a hydrogen group or an ammonium sulfonate group. preferable.

Specific examples of the organosurfactant-modified organopolysiloxane of the present invention include the following, but of course the invention is not limited thereto.

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

The organic surfactant substituent portion of the present invention has a known chemical structure, and although its use as a surfactant has been known so far, it should be incorporated in the skeleton of the organopolysiloxane as in the present invention. Has been reported as an organosurfactant-modified organopolysiloxane which is a novel surfactant having both the low surface tension of the organopolysiloxane and the surfactant ability of the organic surfactant substituent portion of the present invention. Instead, it was first discovered in the present invention.

The organic surfactant-modified organopolysiloxane of the present invention exhibits particularly excellent interfacial properties when used in the production of urethane foam, and can be used as a foam stabilizer for high-quality urethane foam.

The organic surfactant-modified organopolysiloxane of the present invention can be used alone or as a mixture of two or more kinds, and other compounds (for example, polyether-modified organopolysiloxane, polydimethylsiloxane, nonionic surfactant) can be used. Activators, nonionic surfactants, cationic surfactants, amphoteric surfactants, polyether polyols, glycols, cellosolves, other solvents, etc.) can be used in combination.

Since the organic surfactant-modified organopolysiloxane of the present invention has excellent interfacial properties, it is used as a cosmetic, a release agent, a defoaming agent, a fiber treating agent, an adhesive, an antifogging agent, and a glossing agent. It can be widely used by being blended with a water repellent, a paint / resin additive, an antistatic agent, or the like, or as an emulsifier of these.

[0014]

EXAMPLES Next, the present invention will be explained based on examples, but the present invention is not limited to these.

Example 1 An allyl group-containing surfactant was placed in a 1,000 ml three-necked flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet.

[Chemical 14] 216 g, 300 g of toluene, and 10% methanol solution of chloroplatinic acid were added so that the amount of platinum was 20 ppm. To this mixture was added methylhydrogenpolysiloxane at a rate to maintain the temperature at 80-100 ° C.

[Chemical 15] 84 g was added slowly. The end of this reaction was determined by the AgNO ₃ test for SiH being negative. The reaction mixture was then neutralized with NaHCO ₃ , filtered and freed from the solvent on a rotary evaporator at 50 ° C./1 mmHg,
265 g of an organic surfactant-modified organopolysiloxane having a molecular weight of 5,700 represented by the following formula was obtained.

[Chemical 16]

Example 2 Allyl group-containing surfactant

[Chemical 17] 194g, Methyl hydrogen polysiloxane

[Chemical 18] The same operation as in Example 1 was carried out using 106 g, toluene 300 g, and platinum 20 ppm to obtain 269 g of an organic surfactant-modified organopolysiloxane having a molecular weight of 8,700 represented by the following formula.

[Chemical 19]

Example 3 Allyl group-containing surfactant

[Chemical 20] 269 g, methyl hydrogen polysiloxane

[Chemical 21] The same operation as in Example 1 was carried out using 31 g, 300 g of toluene, and 20 ppm of platinum to obtain 209 g of an organic surfactant-modified organopolysiloxane having a molecular weight of 1,500 represented by the following formula.

[Chemical formula 22]

Example 4 Allyl group-containing surfactant

[Chemical formula 23] 227g, methyl hydrogen polysiloxane

[Chemical formula 24] The same operation as in Example 1 was carried out using 73 g, 300 g of toluene, and 20 ppm of platinum to obtain 262 g of an organic surfactant-modified organopolysiloxane having a molecular weight of 5,800 represented by the following formula.

[Chemical 25]

Example 5 An allyl group-containing surfactant was placed in a 1,000 ml three-necked flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet.

[Chemical formula 26] 164 g, vinyltrimethoxysilane 31 g, toluene 300 g, and 10% methanol solution of chloroplatinic acid were added so that the platinum content was 20 ppm. To this mixture was added methylhydrogenpolysiloxane at a rate to maintain the temperature at 80-100 ° C.

[Chemical 27] 105 g was added slowly. The end of this reaction was determined by the AgNO ₃ test for SiH being negative. Then, the reaction mixture was neutralized with NaHCO ₃ , filtered, and the solvent was removed by a rotary evaporator at 50 ° C./1 mmHg, and then an organic surfactant-modified organopolysiloxane having a molecular weight of 7,600 represented by the following formula: 267 g were obtained.

[Chemical 28]

Example 6 An allyl group-containing surfactant was placed in a 1,000 ml three-necked flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet.

[Chemical 29] 91 g, allyl polyalkylene glycol at one end

[Chemical 30] 91 g, allyl glycidyl ether 18 g, toluene 3
A 10% methanol solution of chloroplatinic acid was added so that the amount of platinum was 20 ppm. To this mixture was added methylhydrogenpolysiloxane at a rate to maintain the temperature at 80-100 ° C.

[Chemical 31] 98 g was added slowly. The end of this reaction was determined by the AgNO ₃ test for SiH being negative. The reaction mixture was then neutralized with NaHCO ₃ , filtered and freed from the solvent on a rotary evaporator at 50 ° C./1 mmHg,
266 g of an organic surfactant-modified organopolysiloxane having a molecular weight of 8,100 represented by the following formula was obtained.

[Chemical 32]

Examples 7-8 and Comparative Examples 1-2 Organic surfactant-modified organopolysiloxanes obtained in Examples 1 and 2 as foam stabilizers and the following formulas (1) and (2):

[Chemical 33]

[Chemical 34] The conventional polyether-modified organopolysiloxane represented by the following is used, and the resin premix is adjusted into a container by using polyether polyol, water, an amine catalyst, and Freon 11 according to the following Table-1, and the temperature in the container is adjusted. 2
Adjusted to 2 ° C. Next, using a turbine type agitator,
After premixing at 0 rpm for 60 seconds, MDI of 22 ° C was added, stirred for 10 seconds, and preliminarily adjusted to 40 ° C with 400
It was poured into a (W) × 400 (L) × 70 (H) mm aluminum mold to form a foam. About 20 seconds after the addition of MDI, the filling of the mold was completed to obtain a rigid polyurethane mold foam. This form is JIS K-
The physical properties of the foam were measured in accordance with 6401, and the state of the foam was investigated. O The results are shown in Table 1.

[Table 1] As is clear from Table 1, the present invention has excellent properties as a foam stabilizer, even though the amount of freon is as small as 1/2 to 1/4 or less as compared with the usual formulation of uretafoam. It can be seen that it has excellent interface characteristics.

[0022]

INDUSTRIAL APPLICABILITY The present invention relates to a novel organic surfactant-modified organopolysiloxane and a urethane foam using the same, and the novel organic surfactant-modified organopolysiloxane is used as a foam stabilizer in the production of urethane foam. When used, it has particularly excellent performance and excellent interfacial properties, so it is used as a cosmetic, a release agent, a defoaming agent, a fiber treatment agent, an adhesive, an antifogging agent, a glazing agent, and a water repellent. It can be widely used by blending it with an agent, a paint / resin additive, an antistatic agent, or as an emulsifier for these.

Claims (3)

[Claims] 1. The following formula in which one molecule is directly bonded to a silicon atom: (In the formula, R ′ is independently a hydrogen atom, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or an arbitrary substituent selected from a hydrophilic group, and R ″ is a hydrogen atom or a monovalent group. Arbitrary substituent selected from a hydrocarbon group, an organic acid group, an inorganic acid group, an organic reactive group, an inorganic reactive group, or a hydrophilic group, z is 2 to 4, m is 2 to 6, and n is 1 to An organic surfactant-modified organopolysiloxane having at least one organic surfactant substituent represented by the formula: 2. A general formula: (In the formula, R is independently a hydrogen atom, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or an arbitrary substituent selected from a hydrophilic group, and Q is a group represented by the following formula: (In the formula, R ′ is independently a hydrogen atom, a monovalent hydrocarbon group, an organic reactive group, an inorganic reactive group, or an arbitrary substituent selected from a hydrophilic group, and R ″ is a hydrogen atom or a monovalent group. Arbitrary substituent selected from a hydrocarbon group, an organic acid group, an inorganic acid group, an organic reactive group, an inorganic reactive group, or a hydrophilic group, z is 2 to 4, m is 2 to 6, and n is 1 to An organic surfactant substituent represented by 500), A represents a group selected from R and Q, x is 0 to 100 and y is 0 to 100, provided that y is 0. Is an organic surfactant-modified organopolysiloxane represented by A is Q) 3. A foam stabilizer for urethane foam, comprising the organic surfactant-modified organopolysiloxane according to claim 1.