JPS58162656A - Polyol composition - Google Patents

Abstract

PURPOSE:To provide a polyol composition having suppressed tendency of the separation of the components and the abnormal viscosity increase of a polyol composition during storage, and having high storage stability, by compounding a sulfurcontaining anionic surface active agent to a mixture of a polymeric polyol and a low molecular weight active hydrogen compound, thereby increasing the mutual solubility of both components. CONSTITUTION:The objective polyol composition is prepared by mixing (A) a polymeric polyol such as polyether polyol, polyester polyol, etc. having a molecular weight of preferably 3,000-7,000 with (B) a low molecular weight active hydrogen compound such as low molecular weight polyol, polyamine, amino alcohol, etc., and (C) a sulfur-containing anionic surface active agent. The weight ratio of A:B is 100:(0.1-50), and the amount of the component (C) is 0.5-5wt%, preferably 0.8-3wt%, based on the whole composition. The component (C) is an anionic surface active agent of a sulfonic acid salt-type (e.g. alkylbenzenesulfonate) and/or sulfuric acid ester salt-type (e.g. polyoxyalkylene alkylsulfate salt).

Description

[Detailed description of the invention] The present invention relates to polyol compositions.

More specifically, the present invention relates to a polyol composition with good storage stability.

Conventionally, it has been known to produce polyurethane by reacting a high-molecular polyol and a low-molecular active hydrogen compound with an organic polyisocyanate, and methods for reacting these include (1) a method in which all components are simultaneously mixed and subjected to two reactions; (
2) A method of stepwise mixing and reaction, that is, a method in which a polymer polyol and a polyisocyanate are reacted to form a prepolymer, and then chain extension or crosslinking is performed using a low-molecular active hydrogen compound; There is a method in which a low-molecular active hydrogen compound is mixed in advance and reacted with a polyisocyanate. Among these methods, methods (1) and (2) do not pose a problem with the compatibility between the high molecular polyol and the low molecular active hydrogen compound, but in the method (3), the compatibility between the high molecular polyol and the low molecular active hydrogen compound is not a problem. Due to poor compatibility with molecularly active hydrogen compounds, they may separate,
There is a problem in that the viscosity of the mixture increases abnormally, resulting in loss of fluidity and significant loss of workability.

Under these circumstances, the inventors of the present invention have conducted extensive studies on polyol compositions with good storage stability, and as a result, have arrived at the present invention. That is, the present invention provides polymeric polyol (a)
This is a polyol composition characterized by containing a low-molecular active hydrogen compound (b) and a sulfur-containing anionic surfactant (e).

Examples of the sulfur-containing anionic surfactant used in the present invention include sulfonate type anionic surfactants and/or sulfate ester salt type anionic surfactants. Examples of the sulfonate salt type anionic surfactant and the sulfate salt type anionic surfactant (e) include the following compounds.

α] Sulfonate type anionic surfactant (1) Alkylbenzene sulfonate Alkylbenzene having one and/or a plurality of branched or straight chain alkyl groups, usually having 8 to 20 (preferably 10 to 18) carbon atoms Alkali metals (sodium, potassium, etc.) as salts such as sulfonates
, ammonium, and salts of amines (alkanolamines such as mono-, di-, and tri-ethanolamines, propatoolamines, etc.) (the same applies to the salts of the activators below), as well as alkaline earth metals (calcium, magnesium, etc.). (2) Sulfosuccinic acid ester salt Dialkyl sulfosuccinic acid ester salt: The alkyl group usually has 6 to 2 carbon atoms, and the alkyl group also contains a cycloalkyl group. (3) (Alkyl) naphthalene sulfonate and ( Formalin condensate of (alkyl) naphthalene sulfonate ((alkyl) naphthalene sulfonate refers to naphthalene sulfonate and alkylnaphthalene sulfonate.

The same description will be used below. ] Naphthalene sulfonic acid or a naphthalene sulfonic acid salt having one and/or a plurality of alkyl groups having usually 1 to 18 carbon atoms, and its formalin condensate (degree of condensation is usually 1 to 20, preferably 1 to 8), etc. 4) Alkanesulfonate Alkanesulfonate having an alkyl group, usually having 8 to 20 carbon atoms (5) α-olefin sulfonate Usually having 1 carbon number
Sulfonic acid sodium salts of α-olefins 5 to 18, etc. (6) Fatty acid amide sulfonates 2-Igen T (1, G, ), etc. (7) Lignosulfonates (sodium salts, etc.)
Petroleum sulfonates (sodium salts, etc.), etc. (8)
Alkyl Substituted Aryl Ether Sulfonate Among these sulfonate type anionic surfactants, the sulfonate type anionic surfactant described in section (2) is preferred.

■ Sulfate ester salt type anionic surfactant (1) Sulfate ester salt containing alkyl straight chain and/or branched sulfate ester of saturated and/or unsaturated alcohol with carbon number usually 6 to 20 (preferably 12 to 18) Salts, etc. (2) Pholioxyalkylene alkyl sulfate ester salts Alkylene oxides having 2 to 4 carbon atoms of linear and/or branched saturated and/or unsaturated alcohols having usually 6 to 20 carbon atoms (preferably 12 to 18 carbon atoms) (AO) adduct sulfate ester salt, etc. (3) Polyoxyalkylene alkylaryl ether sulfate salt AO adduct of alkylphenol or alkylnaphthol having at least one alkyl group having 8 to 12 carbon atoms (the number of moles of AO added is usually 2-50. Preferably 2-50.
20) Sulfate ester salts, etc. (4) Sulfate ester salts of higher fatty acid esters, carbon number 10
~20 saturated and/or unsaturated fatty acid monoglyceride sulfate ester salts, etc. (5) Higher fatty acid alkylolamide sulfate ester salts Saturated and/or unsaturated fatty acid monoglyceride sulfate ester salts with 10 to 20 carbon atoms, etc. (6) Sulfated parts, highly sulfated oils, sulfated fatty acid esters and sulfated fatty acid funnel oils, sulfated sodium salts of butyl oleate, sulfated sodium salts of oleic acid, etc. (7) Sulfated olefins with 12 to 18 carbon atoms Among these sulfate ester salt type anionic surfactants such as sulfated sodium salts of α-olefins, the sulfate ester salt type anionic surfactants described in sections (1) and (2) are preferred.

A sulfonate type anionic surfactant and a sulfate ester salt type anionic surfactant can be used together.

For the sulfonate salt type and sulfate ester salt type anionic surfactants, polymeric surfactants can also be used, but low molecular weight surfactants (for example, those with a molecular weight of usually 50
00 or less, preferably 8000 or less).

Details of sulfonate type anionic surfactants can be found in JP-A-56-125488, page 678, and details of alkyl-substituted arylether sulfonates can be found in JP-A-55-766H, pages 352-853. Details of the sulfate ester salt type anionic surfactants are also described on page 672 of JP-A-56-125487.

Low molecular weight active hydrogen compound (b) used in the present invention
Examples include low-molecular polyols (triethanolamine,
Ethylene glycol, 1,4-butanedi.

polyamines (tolylene diamine, xylylene diamine, diaminodiphenylmethane, hydrogenated diaminodiphenylmethane, methylene bis-70)
-Chloraniline, isophoronediamine, piperazine,
aminoethylpiperazine), aminoalcohol (monoethanolamine).

(e.g., jetanolamine) and mixtures of two or more of these. Among these, preferred are low-molecular polyols, and particularly preferred are ethylene glycol and 1,4-butanediAl? ...h3゜The polymer polyol (a) used in the present invention includes those conventionally used in the production of polyurethane. For example, the polyether polyol described in Japanese Patent Application No. 56-4505.

Examples include polyester polyols, polyether ester polyols, 9-polymer polyols, and mixtures of two or more of these. Among these polymer polyols, polyether polyols and polymer polyols are preferred, and polyether polyols are particularly preferred.

The OH value of polymeric polyols is wide-ranging (for example, 1O~5
00). When used for producing polyurethane For producing flexible polyurethane, the OH value is usually 10 to 100. Preferably 15-70.
Particularly preferably 20 to 4 degrees. For hard polyurethane, those having an OH value of 200 or more, preferably 400 or more are used. For semi-rigid polyurethane production, the OH value is usually 20 to 150. Preferably 25-10
I like 0 things.

In addition, for semi-rigid use, flexible polyurethane use (low Off
It can also be used in combination with hard (high OH value) and hard (high OH value). O
If the H number is less than 10, the viscosity will be high and the workability of polyurethane production will be poor, and if the OH number is more than 100, the temperature characteristics of the polyurethane will deteriorate.

Further, the molecular weight of the high molecular weight polyol is usually 1000 or more.

Preferably it is 3000-7000.

Further, when used for producing polyurethane, among the polymer polyols, preferred are those having primary OH at the terminal. The terminal primary OH content is usually 20% or more, preferably 30% or more, and particularly preferably 40 to 80%. The terminal primary OH-containing polymer polyols include those containing an oxyethylene chain at the terminal (chip type, balanced type, lantum type), and the content thereof is usually 5 to 40% by weight, preferably 1% by weight.
It is 0 to 30% by weight. By using a polyol having a terminal oxyethylene chain content within the above range, polyurethane can be prepared by, for example, the Reaxicon injection molding method (R
Molded using IM method). When cured, a molded product with good initial strength upon demolding can be obtained, and a molded product with good physical properties can be obtained.

If the content of terminal oxyethylene chains is less than 5%, the initial strength during demolding is low and problems such as breakage of the molded product are likely to occur. If it exceeds 40%, the appearance of the polymer polyol becomes poor (turbidity and ) The water resistance and moisture resistance of the molded product become extremely poor.

In the polyol group and acid compound of the present invention, a surfactant (e
) content in the composition [total of (a), (b) and (e)]
During.

It is usually 0.5 to 5% by weight, preferably 0.8 to 3% by weight. If the content is less than 0.5% by weight, high molecular polyol (
The compatibility between a) and the low-molecular active hydrogen compound (b) is insufficient, and if the amount exceeds 5% by weight, adverse effects such as deterioration of physical properties will occur when polyurethane is produced using the polyol composition.

When used for producing polyurethane, the amount of the low-molecular active hydrogen compound (b) is usually 0.1 to 50 parts, preferably 15 to 40 parts, based on 100 parts of (a) on a weight basis.

When (+1) is a low-molecular polyol, it is usually 10 to 50 parts, preferably 1 to 40 parts per 100 parts of (a), and when (+1) is a polyamine or amino alcohol, the weight is less than the above. The proportion is usually 0.1 to 20 parts, preferably 05 to 10 parts per 100 parts of (a).

Also, the equivalent ratio of (a) and (b) is (a) to 1 equivalent (
b) is usually 0.05 to 30 equivalents, preferably 0.2 to 25
It is equivalent. When (h) is a low molecular polyol (a) 1
(b) is usually 6 to 30 equivalents, preferably 1 equivalent
0 to 25 equivalents, and in the case of polyamine or amino alcohol Ω, (b) is usually 003 to 1 equivalent for (a).
The method of incorporating (b) and (e) into (a) in an amount of 5 equivalents, preferably 0.1 to 8 equivalents is not particularly limited as long as they can be mixed uniformly. For example, ■ mix (a) and (c) and then mix (b); ■ mix (b) and (1) and then mix (a);
), ■ Mix (a) and (b) and then (
e) method of mixing.

■Methods such as mixing (a), (b), and (C) are mentioned.

Preferred is method (2). It is also possible to prepare a concentrate by mixing ((+) with a small amount of (a) and/or (b) in advance and adding it to the other ingredients. Mixing can be done at room temperature or heated ( The temperature may be generally 40 to 150°C (preferably 70 to 180°C).

The polyol composition of the present invention is useful for producing polyurethane. As the organic polyisocyanate used in the production of polyurethane, those conventionally used in the production of polyurethane can be used. For example, the patent application in 1983-
Those described in the specification of No. 4505 can be used. Specifically, aliphatic polyisocyanates, cyclic polyisocyanates, aromatic polyisocyanates, mixtures of two or more thereof, crude products thereof (crude polyisocyanates such as crude TDI, crude MDI, modified polyisocyanates such as liquid MDI (Carposiimide modified.

It can also be used as a free isocyanate-containing prepolymer obtained by reacting an excess polyisocyanate (TDI, MDI, etc.) with a trihydrocarbylphosphate-modified polyol, or it can be used in combination (for example, modified It is also possible to use a combination of polyisocyanate and prepolymer.

The content of free isocyanate groups in the above modified polyisocyanates and prepolymers is usually 10 to 80%, preferably 15 to 30%, particularly preferably 20v80%.

Among the organic polyisocyanates (A), preferred are modified polyisocyanates, and particularly preferred are carposiimide-modified MDI, prepolymers of MDI and polyol, and mixtures thereof.

When producing polyurethane using the polyol composition of the present invention, a foam is produced by performing a reaction in the presence of a blowing agent [water and/or a halogen-substituted aliphatic hydrocarbon blowing agent (such as Freon-11)]. Alternatively, elastomers, sealants, sheets, etc. may be produced without using a blowing agent.

Further, if necessary, the reaction can be carried out in the presence of a catalyst (such as a tertiary amine, an organic tin compound, an organic lead compound, etc.), a silicone foam stabilizer, or other auxiliary agents.

The polyurethane manufacturing method can be applied using either the conventional one-shot method or the prepolymer method.

In producing polyurethane, the ratio (equivalent ratio) of active hydrogen components such as polyol compositions and organic polyisocyanates is usually active hydrogen-containing groups (OH, NH2, NH, etc.): m, po group = (0,8: 1.2) For manufacturing! 3. It is particularly useful for molding using the RIM method. RIM
The polyurethane molded product can be produced by a conventional method.

For example, a catalyst, if necessary a blowing agent (water or Freon 11), a pigment, and a foam stabilizer are added to the polyol composition of the present invention containing a low-molecular active hydrogen compound and mixed uniformly to form a solution A, and a solution B is Prepare organic polyisocyanate in advance and fill it into the A and B liquid tanks of a high-pressure foaming machine. The injection nozzle of the high-pressure foaming machine and the injection port of the mold are connected in advance, and liquids A and B are mixed with a mixing head and injected into a closed mold, and after curing, the mixture is molded.

Methods other than the RIM method, such as molding other than the RIM method (open mold molding, vinyl chloride body and limb molding method, vacuum molding, etc.)
cold cure and hot cure), slab method,
Current construction, spray method, injection.

It can also be applied to various methods such as coating and impregnation.

The polyol composition of the present invention can also contain a blowing agent, a catalyst and other auxiliary agents if necessary. These may be the same as those described in JP-A-56-67829. The blowing agent is water and/or
Alternatively, a halogen-substituted aliphatic hydrocarbon blowing agent may be mentioned. Examples of the catalyst include tertiary amine catalysts, organic acid salts thereof, and organometallic catalysts (tin-based catalysts, mercury acetate, cobalt organic naphthenate, etc.). Other auxiliary agents include foam stabilizers.

Examples include colorants and stabilizers. The amount of blowing agent in the polyol composition is usually 0 to 20% by weight, preferably 0 to 20% by weight.
The amount of 7% by weight catalyst is usually 0-3% by weight! Preferably 0.5 to 2% by weight.The amount of other auxiliary agents is usually 0.about.10% by weight, preferably 0.1 to 2% by weight.

The polyol composition containing the specific anionic surfactant of the present invention has good compatibility between the high-molecular polyol and the low-molecular active hydrogen compound, and has good compositional properties. The use of this composition, for example for the production of polyurethane, therefore improves workability by eliminating the need to prepare formulations each time.

The polyol composition of the present invention is used not only for producing polyurethane, but also for producing polyurethane.
It is useful for applications in which a high molecular weight polyol and a low molecular weight active hydrogen compound are used in combination, for example, for the production of other synthetic resins (such as polyester resins) and as brake fluid compositions.

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 A polyoxypropylene polyoxyethylene derivative of propylene glycol (terminal polyoxyethylene chain 20% by weight) having a hydroxyl value of 28 was used as a polymeric polyol.

24 four-loaf flasks with stirrer and thermometer.

1000 g of the above polymeric polyol was charged, and then 2-ethyl hexylsulfosuccinate sodium salt t
Add 5g (1.24%) and finally add 190g of ethylene glycol. The mixture was heated to 80 to 120° C. with stirring under a nitrogen atmosphere to obtain a uniform polyol composition. After that, cool to room temperature, put soybean into each 10cc test tube, seal it, and heat it to 0°C925°C.
Leave it in a constant temperature bath at 940°C, check the appearance and 0H-
The presence or absence of separation of polymer polio-J and ethylene glycol was investigated by V measurement.

Example 2 In the same manner as in Example 1, 1205 g of a homogeneous solution of 1000 g of a polymer polyol, 15 Ll of 2-ethylhexylsulfoconolate Estefle sodium salt, and 190 g of ethylene glycol was prepared, and then DABCOHLV (Sankyo Airp O Duck Co., Ltd.) was prepared. Manufactured by Triethylene Shea I :/
(7) 38% dipropylene glycol solution) 155
1 to VL-Black #2ooo (black toner manufactured by Fuji Shiki Co., Ltd., 25% polyoxypropylene glycol dispersion of carbon black) 40FI was added, stirred under a nitrogen atmosphere, the temperature was below 30°C, and 1lu of Daiflon (Daikin Industries, Ltd.) was added. manufactured by Freon 11) 50f and DTD (
dibutyl tin dilaure) ) 0.8 (l) was added and stirred to obtain a uniformly dispersed polyol composition. Then, 1ω
The sample was placed in a Ce test tube in a constant temperature bath at 0°C, 925°C, and 940°C, and the presence or absence of separation of the polymer polyol and ethylene glycol was examined by checking the appearance and measuring 0H-V.

Comparative Example 1 1,000 g of the polymer polyol used in Example 1 and 190 g of ethylene glycol were stirred at room temperature under a nitrogen atmosphere, and the white dispersion was poured into a TOOCC test tube and sealed. The sample was placed in a constant temperature bath at 25°C and 940°C, and the presence or absence of separation of the polymer polyol and ethylene glycol was examined by checking the appearance and measuring 0H-V.

Comparative Example 2 High molecular polyol 1000f used in Example 1, ethylene glycol 190f, DABCO88LV15f,
0.89% of VL-Liquid was added one after another, and the mixture was stirred at room temperature under a nitrogen atmosphere until the whole was homogeneous. Thereafter, it was placed in a 1 OOCC test tube in a constant temperature bath at O'C, 25°C, and 40'C, and the presence or absence of separation of the polymer polyol and ethylene glycol was examined by checking the appearance and measuring 0H-V.

(Summary) Examples 1 to 2 above. The results of testing the oral storage stability of the polyol compositions prepared in Comparative Examples 1 and 2 are shown in Tables 1 and 2. Table 1 Oral storage stability of polyol compositions (appearance check) Showa r74≠J! 1/day Indication of the case of Haruki Shimada, Commissioner of the Japan Patent Office, 1957 patent a% 45037 No. 2, Name of the invention Polyol composition 3. Regarding the subject specifications of number 6 and ll11 positive, see JP-A-55-76668 No. 352-35.
Details of the sulfate ester salt type anionic surfactant are described on page 3 and on page 672 of Japanese Patent Application Laid-open No. 125487/1987.

Low molecular weight active hydrogen compound (b) used in the present invention
Examples include low-molecular polyols (triethanolamine,
ethylene glycol, 1,4-butanedio)roudethylene glycol, trimethylolpropane, glycerin, etc.), polyamines (tolylene diamine, xylylene diamine, diaminodiphenylmethane, hydrogenated diaminodiphenylmethane).

Examples include methylenebis-〇-chloroaniline, isophoronediamine, piperazine, aminoethylpiperazine, etc.), amino alcohols (monoethanolamine, jetanolamine, etc.), and mixtures of two or more of these. Among these, preferred are low-molecular polyols, and particularly preferred are ethylene glycol and 1.4-butanediol.

Claims (1)

[Scope of Claims] 1. A polyol composition characterized in that a high molecular polyol (a) contains a low molecular active hydrogen compound (11) and a sulfur-containing anionic surfactant (e). 2. The composition according to claim 1, wherein the sulfur-containing anionic surfactant is a sulfonate salt type anionic surfactant and/or a sulfate salt type anionic surfactant. 8. The composition according to claim 1 or 2, containing 05 to 5% by weight of (C). 4. Sulfonate type anionic surfactants include alkylbenzene sulfonates, sulfosuccinate ester salts, (alkyl)naphthalene sulfonates and their formalin condensates, alkanesulfonates, α-olefin sulfonates, fatty acid amide sulfonic acids The composition according to any one of claims 1 to 8, which is a compound selected from the group consisting of salts and lignin sulfonates. 5. The sulfate ester salt type anionic surfactant is an alkyl sulfate ester salt, a polyoxyalkylene alkyl sulfate ester salt, a polyoxyalkylene alkylaryl ether sulfate ester salt, a sulfate ester salt of a higher fatty acid ester, a higher fatty acid alkylolamide sulfate ester salt, The composition according to any one of claims 1 to 4, which is a compound selected from the group consisting of sulfated moieties, highly sulfated oils, sulfated fatty acid esters, and sulfated olefins. 6. (a) and (b) (7) Weight ratio is (a):
(b) The composition according to any one of claims 1 to 5, wherein -too: o, 1 to 50. 7. The composition according to any one of claims 1 to 6, wherein the polyol composition is a polyol composition for producing polyurethane.