JPH03115421A - Production of condensation resin dispersion and its use - Google Patents

Abstract

PURPOSE:To obtain a low-viscosity resin dispersion having good dispersion stability and suited for the production of a flame-retarding polyurethane by dispersing particles obtained by condensing a guanidine compound with an aldehyde in an organic isocyanate-reactive active hydrogen compound. CONSTITUTION:A particle dispersion obtained by condensing an aldehyde (A) (desirably formalin) with a guanidine compound (B) condensible with component (A) or a cocondensate of 40-100mol% guanidine compound with 60-0mol% aldehyde-condensible compound other than the guanidine compound (e.g. phenol) is dispersed in an organic isocyanate-reactive active hydrogen compound (C) (having at least two desirably 2-8 active hydrogen groups such as hydroxyls or aminos and a molecular weight per active hydrogen group of especially 400-2500, e.g. polyetherpolyol or polyesterpolyol) to obtain a condensation resin dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a condensed resin particle dispersion suitable for producing polyurethane and a method for producing the same.

[Prior Art] Conventionally, polyols for polyurethane raw materials are known as polymer polyols, graft polyols, and the like. This is a polymer in which an addition polymer is grafted onto the molecular chain of a polyol such as a polyether polyol or an unsaturated polyol, or an addition polymer or other polymer is simply dispersed in the polyol. . This type of polymer polyol can be produced by polymerizing vinyl monomers such as acrylonitrile or styrene in a liquid polyol, by simply dispersing a pre-produced polymer such as a vinyl polymer in a polyol, or by simply dispersing a pre-produced polymer such as a vinyl monomer in a polyol. Methods are known in which a polymer is then grafted onto a polyol. The polymer in such conventional polymer polyols is almost always a vinyl polymer, but as an exception, it is known that linear polyesters are dispersed therein.

It is also known to use an amino resin initial condensate as a polyurethane raw material. Since the amino resin initial condensate has hydroxyl groups such as methylol groups, polyurethane foam etc. can be obtained by reacting this with a polyisocyanate compound (for example, as disclosed in JP-A-53-1679).
Publication No. 8, etc.).

Furthermore, it is also known that a mixture of an etherified amino resin initial condensate, in which a portion of the methylol groups of the amino resin initial condensate is etherified, and a polyol used as a regular polyurethane raw material can be used as a raw material for producing polyurethane foam ( JP-A No. 52-153000), and a method of manufacturing by condensing such an amino resin initial condensate in a polyol has also been proposed (JP-A No. 54-101848).

[Problems to be Solved by the Invention] There are still various problems with the conventional polyurethane raw materials described above. First, so-called polymer polyols are suitable as raw materials for high-modulus polyurethane foams, etc., but they have the unresolved problem that they are not only ineffective in making polyurethane flame retardant, but also actually reduce the flame retardance.

On the other hand, polyols containing amino resin initial condensates are relatively low molecular weight polyols containing hydroxyl groups such as methylol groups, and do not have as high a molecular weight as the polymers in the above-mentioned polymer polyols. It is difficult to recognize it as a type of polymer polyol because it is difficult to exhibit the effect of increasing the elasticity of foam and its use is limited to rigid polyurethane foam.

On the other hand, it is also known to make polyurethane flame retardant by filling polyurethane with powder of cross-linked high molecular weight condensation resin as a filler, but it is difficult to stably disperse such a filler in polyol. It was difficult to achieve this, and the dispersion stability was inferior to that of so-called polymer polyols.

Furthermore, Japanese Patent Publication No. 57-14078 proposes a method for producing a dispersion of an aminoblast condensate by condensing a substance capable of forming an aminoblast in a polyhydroxy compound; A completely stable dispersion of particles was not obtained, and only resin particles with a high particle size were obtained. Furthermore, Japanese Patent Application Laid-open No. 122193/1983 describes a method of producing sedimentary particles and blending them with polyol or the like. However, in this case, the particle size is large and tends to settle in the polyol. In order to improve the dispersion stability of such condensed resin particles, it is necessary to reduce the particle size, but on the other hand, when the particle size is reduced, there is a problem that sedimentation becomes difficult (filtration separation becomes difficult).

The present invention solves the various problems with conventional polyols containing polymer components as raw materials for polyurethane as described above, and can be used as a raw material for producing flame-retardant polyurethane. The object of the present invention is to provide a method for producing a condensed resin particle dispersion that is favorable and has a low viscosity.

[Means for Solving the Problems] The present inventors have conducted various studies in order to find a condensed dispersion that has high flame retardancy, particularly low smoke generation, good dispersion stability, and low viscosity. Ta.

As a result, it is difficult to produce particles by condensing a guanidine compound alone or a dispersion containing 40 mol% or more of a guanidine compound with an organic isocyanate compound and a reactive active hydrogen compound and/or water or an organic solvent. It has been found that a condensed resin dispersion can be obtained that has low flammability, particularly low smoke generation during flame retardation, has fine particles of condensed resin stably dispersed in an active hydrogen compound, and has low viscosity.

That is, the present invention has been made to solve the above-mentioned problems, and uses a compound capable of condensation with aldehydes, which is composed of a guanidine compound having flame retardancy, particularly low smoke generation property when flame retardant. The present invention provides a condensation resin dispersion that is stably dispersed over a long period of time in an active hydrogen compound that is reactive with bound isocyanate particles of condensates or initial condensates produced by aldehydes.

One of the raw materials for forming the condensation resin according to the present invention is aldehydes. As the aldehydes, aliphatic, alicyclic, aromatic, and heterocyclic aldehyde compounds, other aldehydes, condensates thereof, and derivatives such as compounds capable of generating aldehydes can be used alone or in combination. Preferred aldehydes are aliphatic aldehydes having 4 or less carbon atoms and derivatives thereof, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
Examples include isobutyraldehyde, paraformaldehyde, paraacetaldehyde, and formaldehyde is preferred. These aldehydes can also be used dissolved in a solvent, and the preferred solvent is water, but the solvent is not limited to this. Particular preference is given to using an aqueous solution of formaldehyde, ie formalin.

Another raw material for forming the condensation resin is an aldehyde condensation compound, which basically requires two positions that can react with aldehydes (hereinafter referred to as reaction sites). The reactive site is typically a carbon atom to which hydrogen is bonded in an aromatic nucleus, or a nitrogen atom to which hydrogen is bonded to an amino group or an amide group. The reaction site of the aromatic nucleus is
The ortho-position or rose-position of the aromatic nucleus to which a hydroxyl group or amide group is bonded is particularly preferred, and phenols and aromatic amines that have two or more of these reactive sites, that is, do not have a substituent at this site, are particularly preferred. As the compound having an amino group or an amide group, a polyamine compound having two or more of these groups is basically preferable.

In the present invention, it is essential to use a guanidine compound as the aldehyde condensing compound. The guanidine compound can be used in combination with other aldehyde condensation compounds.

The ratio of the guanidine compound to the total amount of aldehyde condensable compounds is preferably 40 to 100 mol%, particularly 60 to 100 mol%. Examples of guanidine compounds include guanidine salts, dicyandiamide, aminoguanidine salts, and guanylurea salts. Examples of the salt include hydrochloride, phosphate, sulfamate, and carbonate.

Examples of aldehyde condensing compounds that can be used in combination with the guanidine compound include phenols, aromatic amines, polyamine compounds, and other compounds.

Examples of the above-mentioned phenols include phenol, cresol, xylenol, p-alkylphenol, p-phenylphenol, bisphenol A, resorcinol, etc., with phenol being particularly preferred, and examples of aromatic amines such as aniline, diamino Benzene, p-alkylaniline, N-substituted alkylaniline,
Examples include diphenylamine and diaminodiphenylmethane, with aniline being particularly preferred.

Since the amino group and amide group of aromatic amines are themselves reactive sites, they may be considered as a type of diamine compound, and reactive sites other than the amino group and amide group of the aromatic nucleus are It may be one. The aromatic compounds are not limited to the above two types, and aromatic hydrocarbons such as benzene and xylene and other compounds can also be used.

As the polyamine compound, compounds having basically two or more amino groups or amide groups are preferred, especially compounds having two or more amino groups, such as urea, thiourea, N
Preferred are ureas such as -substituted urea, melamine compounds such as melamine and N-alkyl substituted melamine, and s-triazines represented by guanamine compounds such as benzoguanamine and acetoguanamine. Among these, particularly preferred are urea, melamine, It is benzoguanamine.

Furthermore, as the aldehyde condensing compound, in addition to the above, ketone compounds known as raw materials for ketone resins may also be used.

Furthermore, the above aldehyde condensing compound can be used in combination with a compound having only one reactive site, or a compound that does not have aldehyde condensing ability but has two or more active sites, such as dialkanolamine, monoalkanolamine, aliphatic amine, etc. Good too.

In the present invention, initial condensates of aldehyde condensable compounds and aldehydes, such as dimethylol urea, hexamethylol melamine, hexamethoxymethyl melamine, etc., can also be used as forming raw materials.

The active hydrogen-containing compound according to the present invention preferably has two or more active hydrogen groups capable of reacting with an organic isocyanate compound and is liquid at room temperature, particularly preferably one that can be used as a raw material for polyurethane.

These usually have very high boiling points or no boiling points (decompose without vaporization).

Examples of active hydrogen groups that are reactive with such organic isocyanate compounds include hydroxyl groups, -grade amino groups, and secondary amino groups, and in the present invention, at least two such active hydrogen groups are added per molecule. Above, preferably 2
~8, and the molecular weight per active hydrogen group is 100 to 10
00, preferably Zoo~3000, particularly preferably 4
Active hydrogen-containing compounds having a molecular weight of 00 to 2,500 are preferable, such as polyethers, polyesters, hydrocarbon polymers having hydroxyl groups at the ends, and so-called polymer polyols. Polyethers are particularly preferable, and among them, polyether polyols and hydroxyl groups of polyether polyols are preferable. Preferred examples include aminated polyethers in which part or all of the polyethers are substituted with primary or secondary amino groups, and mixtures thereof.

Examples of polyether polyols include polyether polyols made by adding alkylene oxide to polyhydroxy compounds such as polyhydric alcohols, amines, active hydrogen-containing compounds such as phosphoric acid, and polyether polyols made from other cyclic ether polymers. be. Specifically, glycol, glycerin, trimethylolpropane, pentaerythritol, and dextrose.

Sucrose and other polyhydric alcohols, jetanolamine, triethanolamine, other alkanolamines, bisphenol A.

Polymers made by adding ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, other alkylene oxides, and epoxides such as styrene oxide and glycidyl ether to phenol-formaldehyde condensates, other polyhydric phenols, ethylenediamine, diaminodiphenylmethane, and other amines. There are ether polyols and polyhydroxy polyols such as tetrahydrofuran polymers. Two or more of these can also be used in combination. The preferred polyether polyol is OH
A polyether polyol having a molecular weight per group of 300 to 2,500, particularly a molecular weight of 600 to 2,500 per OH group.
2000, polyether polyols having 2 to 8 hydroxyl groups are preferred.

As the aminated polyether, those obtained by aminating a polyether polyol with ammonia, and those obtained by hydrolyzing an isocyanate group-containing prepolymer obtained by reacting a polyether polyol and a polyisocyanate can be used. Although it is possible, the former is particularly preferred.

In addition, polyhydric alcohols of the same type as the above-mentioned active hydrogen-containing compounds but with a lower molecular weight than those mentioned above, esters containing hydroxyl groups such as polyhydroxy esters, etc. are used, and the polyhydric alcohols include the above-mentioned polyethers, polyesters,
Among those that can be used as an incubator for polyether polyols, liquid ones can also be used.

The ratio of the aldehyde condensable compound to the aldehyde in the reaction for producing condensed resin particles is not particularly limited as long as the ratio includes the ratio at which the condensed resin is theoretically produced. Even if unreacted aldehyde condensation compounds remain, they may be included in the produced dispersion as long as their proportion is not excessive (this is because unreacted aldehydes can be simultaneously removed during dehydration, etc.). 5 to 500 parts of aldehyde based on ioo parts by weight of aldehyde condensing compound
Parts by weight are used, especially 10 to 100 parts by weight.

The amount of dispersion of condensed resin particles in the active hydrogen-containing compound is
There is no particular restriction as long as the condensation resin particles are stably dispersed, but if the condensation resin particles are in excess, the dispersion stability will decrease and the viscosity will become high. The amount of each raw material to be charged is determined so that the amount of resin is preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less. There is no particular lower limit, but in order to exhibit the effect of the dispersion of the present invention in producing polyurethane, the amount of condensation resin should be at least 5 parts by weight per 100 parts by weight of the active hydrogen compound.
Preferably, about parts by weight are present.

The reaction is usually carried out by stirring and heating a dispersion medium containing the raw materials for the aldehyde condensation resin. The heating temperature is usually 180°C or lower, particularly 40 to 150°C. The size of the precipitated particles often depends on the raw material concentration, reaction temperature, stirring speed, reaction time, etc. In order to obtain smaller particles, it is preferable to appropriately adopt one or more of the following conditions: low raw material concentration, low reaction temperature, high stirring speed, short reaction time, etc.

The second method for producing the dispersion of the present invention is to carry out the condensation reaction to obtain the aldehyde condensation resin in the presence of a surfactant and to obtain a dispersion using water and/or an organic solvent as a dispersion medium. This is a method of replacing the dispersion medium in which the dispersion medium of the product, that is, the medium of the condensation reaction, is replaced with an active hydrogen-containing compound.

In this second method, an active hydrogen-containing compound may be used in combination with water and/or an organic solvent as a dispersion medium.

The difference from the first method is that an active hydrogen-containing compound is added after the aldehyde condensation resin particles are precipitated. In the second method, water and organic solvent may be removed before (or after) the active hydrogen compound is added. In the former case, water and organic solvent are usually removed by heating and/or It is preferable to remove water and organic solvents by vaporizing them under reduced pressure.In the latter case, the water and organic solvents can be removed by heating and/or vaporizing under reduced pressure as described above, as well as by solid-liquid separation such as filtration. Separation means can be employed. In this case, the aldehyde condensation resin particles may be made into a dry powder.Also, if the active hydrogen compound is contained in the dispersion medium, it may be made into a highly concentrated slurry. In order to obtain particles with high dispersion stability, the particles need to be sufficiently small, so even if water and other solvents are removed first, they can be removed by heating and/or reduced pressure. Vaporization is preferred since such fine particles are often difficult to filter out.

The organic solvent used as a dispersion medium outside the waterside is preferably an organic solvent having a boiling point lower than that of the oil-containing hydrogen compound. This is because separation of the organic solvent and the oil-containing hydrogen compound is preferably performed by vaporizing the former. As mentioned above, many oil-containing hydrogen compounds have extremely high boiling points or have no boiling point and are stable even at extremely high temperatures. Therefore, as the organic solvent, an organic solvent having a boiling point of 250°C or lower, particularly 180°C or lower is preferable. Water and organic solvents can be removed by heating to a temperature higher than their boiling point and vaporizing them under normal pressure. More preferably, it is carried out under reduced pressure by heating to a temperature higher than the boiling point.

Examples of organic solvents include aliphatic hydrocarbons such as pentane, cyclohexane, and hexene, aromatic hydrocarbons such as benzene, toluene, and xylene, alcohols such as methanol, ethanol, isopropanol, butanol, cyclohexanol, and benzyl alcohol, and isopropyl. ether, tetrahydrofuran, benzyl ethyl ether,
Ethers such as acetal and anizole, ketones such as acetone, methyl ethyl ketone and acetophenone, esters such as ethyl acetate and butyl acetate, chlorobenzene,
Halogen compounds such as chloroform, dichloroethane, 1,1.2-)lichlorotrifluoroethane, nitro compounds such as nitrobenzene, nitrile compounds such as acetonitrile and benzonitrile, amine compounds such as triethylamine, tributylamine, dimethylaniline, N, N
Amide compounds such as '-dimethylformamide and N-methylpyrrolidone, sulfur compounds such as dimethyl sulfoxide and sulfolane, and the like can be used alone or in combination if necessary. The aldehyde condensing compound and aldehydes or their initial condensates can be reacted as they are in an organic solvent, but since they are highly compatible with water in the initial condensation state, a combination system of water and an organic solvent is preferable. .

In order to allow the condensation reaction to proceed at a relatively low temperature, an acid such as hydrochloric acid or acetic acid, or a base such as NaOH or triethylamine may be used as a catalyst. In addition, in order to increase the stability of the condensation resin particles, 100 parts by weight or less of an oil-containing hydrogen compound, such as a part of polyol or aminopolyol, which will be replaced with a dispersion medium later during the condensation reaction, is added to 100 parts by weight of the condensation resin. It is also effective to keep it. Furthermore, the reaction can be carried out in the presence of various additives such as a curing agent such as hexamethylenetetramine, a dispersion stabilizer, and a coloring agent.

In addition, the ratio of aldehydes and aldehyde condensing compounds,
The amount of surfactant added and the ratio of the amount of condensed resin particles after dispersion medium replacement to the amount of oil-containing hydrogen compound are the same as in the first method.

[Effect]

The mechanism by which a condensed resin dispersion with good dispersion stability (and low viscosity) can be produced in the present invention is not necessarily clear, but it is important to note that the condensed resin particles are fine and uniform, and that they basically do not react with polyols. It can be assumed that this is because there are many particles that exist independently.

Furthermore, although the mechanism by which the present invention achieves high flame retardancy and low smoke generation is not necessarily clear, the particles are fine. High nitrogen content in the molecule. Melting point is relatively low (
, and thermal decomposition is likely to occur.

A compound capable of reacting with aldehydes and aldehydes react at room temperature to heating or under pressure. Reactions at relatively low temperatures tend to generate methylol group-containing compounds and low molecular weight condensates to which aldehydes are added, while at relatively high temperatures, methylene crosslinks and dimethylene ether bonds due to dehydration reactions of methylol groups, etc. tend to occur. it is conceivable that. Of course, the compounds produced are not related only to the reaction temperature (they vary depending on the charging ratio of each constituent unit, the presence of additives such as catalysts, pH, etc.). However, if only the reaction temperature is considered, the present invention It is preferable to carry out the reaction at a relatively low temperature in the first stage of the reaction and at a relatively high temperature in the latter stage of the reaction.In particular, the relatively high temperature in the latter stage of the reaction is necessary to carry out the condensation reaction of hydroxyalkyl groups such as methylol groups. Therefore, it is preferable to carry out the reaction at a temperature of about 80°C or lower in the first stage of the reaction, and at a temperature of about 10°C higher than the first stage in the latter stage, and at a temperature of about 60°C or higher. Upper limit temperature in the latter stage of the reaction is preferably a temperature at which side reactions other than the decomposition of oil-containing hydrogen compounds and the formation reaction of condensation resins are unlikely to occur, and is preferably 80 to 150°C when water is used as a solvent, and 80 to 150°C under normal pressure.
The temperature is preferably about 00°C, and in the case of an organic solvent or a system in which water and an organic solvent coexist, the temperature is preferably about 80 to 200°C. The presence of an acid or base catalyst allows the condensation reaction to proceed at relatively low temperatures.

The condensation resin produced at this time is thought to be similar or the same as the cured products of conventionally known condensation thermosetting resins such as phenol resins, urea resins, and melamine resins, and the production reaction is also It is also considered that they are similar or the same. For example, when formaldehyde is used as the aldehyde, the aldehyde condensable compound and formaldehyde undergo addition condensation in the initial stage of the reaction, thereby producing various methylol group-containing compounds. The above-mentioned initial condensate, which is one of the forming raw materials of the present invention, is
This corresponds to a methylol group-added compound at this stage. After this, the methylol group becomes a methylene group due to dehydration condensation of the methylol group-containing compound, etc., and it is considered that the methylol group becomes a methylene group and condenses to become a three-dimensionally crosslinked insoluble and infusible condensation resin.

When the aldehyde condensation compound, aldehydes, or their initial condensation products have affinity with the organic solvent, the initial condensation reaction proceeds uniformly, and condensed particles are then precipitated. In addition, if there is no affinity with the organic solvent, the reaction proceeds in an emulsified state from the initial condensation reaction stage, and the condensation resin is precipitated as it is.

In the present invention, the reaction for producing a condensed resin in water and/or an organic solvent is basically completed before the dispersion medium is replaced with an oil-containing hydrogen compound. , can be determined from the fact that the methylol group generated at the beginning of the reaction is converted to a methylene group and the hydroxyl value becomes smaller.In other words,
To explain using an example in which a polyol is used as an oil-containing hydrogen compound to replace the dispersion medium, when comparing the hydroxyl value of the polyol and the obtained dispersion, if the hydroxyl value of the dispersion increases, crosslinking is insufficient. It is thought that there is a methylol group for this reason, and if the hydroxyl value is the same or lower, sufficient crosslinking is considered to have occurred.

It is not preferable that the oil-containing hydrogen compound used as a raw material for polyurethane contains a relatively large amount of water. Therefore,
The water initially used as a dispersion medium needs to be removed when it is replaced with an oil-containing hydrogen compound such as a polyol. Water can usually be removed by heating or under reduced pressure,
At the same time, organic solvents can also be removed. Therefore, by adding an oil-containing hydrogen compound to a dispersion containing water and/or an organic solvent as a dispersion medium in which condensation resin particles have precipitated, and removing water and/or the organic solvent under heating and/or reduced pressure, , the dispersion medium is replaced with an oil-containing hydrogen compound.

Alternatively, water and/or organic solvent, etc. may be removed first, the residue may be dried and powdered, and then this powder may be mixed and dispersed in the oil-containing hydrogen compound.

The present invention is characterized in that most of the condensation reaction is completed before the dispersion medium is replaced, but when water is removed, some unreacted components may be condensed and dehydrated. Also,
Since the oil-containing hydrogen compound is added after the condensation reaction to replace the dispersion medium, the condensation reaction no longer proceeds in the active hydrogen compound, and grafting of the condensation resin to the active hydrogen compound basically does not occur. It is safe to assume that there is no such thing. However, if a portion of an oil-containing hydrogen compound is added to improve dispersibility during the condensation reaction in water and/or an organic solvent, there is a possibility that a graft reaction may occur.

The solid condensed resin particle dispersion of the present invention obtained as described above is a white or colored translucent or opaque viscous liquid, and its viscosity is determined by the viscosity of the above-mentioned oleaginous hydrogen compound used and the condensation system in the dispersion. Although it varies depending on the proportion and type of resin, a resin having a viscosity of 50,000 cps or less at 25° C. is usually suitable for use as a raw material for polyurethane. Of course, even if the viscosity is higher than this, it may be possible to use it by diluting it with other self-active hydrogen compounds.

It is thought that most of the condensation resin is dispersed in the synthetically active hydrogen compound.

The particle size of the fully crosslinked condensed resin particles of the present invention is 0.0
It is preferably within the range of 1 to 5μ, particularly preferably 0.1 to 5μ.
It is within the range of 2μ. If it exceeds 5μ, it tends to settle in oil-containing hydrogen compounds such as polyols.

In the present invention, in the case of a dispersion using a self-active hydrogen compound containing an aromatic nucleus, an amino group, or an amide group, a particularly good dispersion state can be obtained because it has good affinity with the condensation resin.

The condensed resin particle dispersion according to the present invention is preferably one that does not undergo separation for at least about 60 days when left standing, but of course it is not limited to this period. The reason why the product of the present invention has such a low viscosity and excellent dispersion stability is that although the effect of the condensation reaction is not necessarily clear, the diameter of the condensed resin particles is fine and uniform, so it is fundamentally different from polyol. Since there are many particles that do not react and exist independently, it can be assumed that this is due to the presence of surfactant.

The hydroxyl value of the condensed resin particle dispersion of the present invention is mainly related to the hydroxyl value of the self-active hydrogen compound.

The reason for this is that the condensation resin of the present invention is sufficiently crosslinked and has almost no functional groups containing hydroxyl groups such as methylol groups, and is dispersed in proportion to the resin particle content in the dispersion. It is lower than the hydroxyl value of the self-active hydrogen compound that is the medium. Therefore, the hydroxyl value of the dispersion of the present invention is preferably 1.2 times or less, particularly preferably equal to or less than the hydroxyl value of the self-active hydrogen compound. The hydroxyl value of the self-active hydrogen compound in the present invention is usually 800.
The following are preferred. Molecular weight per acid group is 300-25
In the case of 00 high molecular weight polyol, the hydroxyl value is about 22~
It is 190. However, when a hydroxyl group-containing compound such as a phenolic compound is used as the aldehyde condensing compound, the hydroxyl value of the dispersion may be higher than the hydroxyl value of the self-active hydrogen compound.

Incidentally, in the case of known polyols containing amino resin initial condensates, if the hydroxyl value of the polyol used is higher than that of the amino resin initial condensate, the hydroxyl value of the dispersion polyol will be lower than that of the original polyol, but dimethylol urea The hydroxyl value of polymethylolmelamine, etc. is approximately 600.
When a substance with a higher hydroxyl value than the above is used as a constituent component of an amino resin initial condensate, a dispersion using a polyol with a low hydroxyl value (i.e., high molecular weight) may have a hydroxyl value much higher than the hydroxyl value of the polyol. It has a hydroxyl value.

The dispersion of the present invention described above is particularly suitable for use as part or all of the self-active hydrogen compound as the main raw material in polyurethane production. Furthermore, the dispersion of the present invention containing a relatively low molecular weight self-active hydrogen compound can be used as part or all of the active hydrogen compound-based raw material in polyurethane production. The dispersion of the present invention is superior to conventional polymer polyols and ordinary polyols in that it can improve flame retardancy. The dispersion of the present invention using phenols, ureas, melamines, guanamines, and guanidines as condensation resin forming raw materials is particularly effective in improving the flame retardancy of polyurethane. The dispersion of the invention is also particularly suitable for the production of polyurethane foams and can be used in the same way as conventional polymer polyols to obtain high performance polyurethane foams.

The polyols used as basic raw materials for polyurethane include -
For boat fishing, use a high molecular weight polyol with a molecular weight of 300 to 3000 per hydroxyl group, especially a molecular weight of 6 per hydroxyl group.
Polyether polyols having a molecular weight of 00 to 2,500 and 2 to 8 hydroxyl groups in the molecule are used, and polyols having a lower molecular weight than the above are used for rigid polyurethane foams. Therefore, when the condensed resin dispersion of the present invention is used as part of the raw material for polyurethane, the above-mentioned conventionally used high molecular weight polyols are suitable as other polyols to be used in combination.

In the production of polyurethane, a crosslinking agent consisting of a relatively low molecular weight oil-containing hydrogen-containing compound containing two or more active hydrogens such as polyhydric alcohol, alkanolamine, polyamine, etc. is used in addition to the basic raw materials of polyol and polyisocyanate compound. may be done. In particular, the condensed resin particle dispersion of the present invention obtained using a low molecular weight polyol as a raw material can be used as part or all of the crosslinking agent.

The use of blowing agents is usually necessary in the production of polyurethane foams. As the blowing agent when using the dispersion of the present invention, water, trichlorofluoromethane, dichlorodifluoromethane, methylene chloride, or other halogenated hydrocarbons are used. Furthermore, as a foam stabilizer, which is a necessary component in most cases in the production of polyurethane foam, poly(dialkylsilanes), polyoxyalkylene chain-containing silanes, and other organosilicon compounds are suitable, but fluorosurfactants may be used.

Catalysts are usually used in the production of foam or non-foam polyurethanes, and various tertiary amines, other amine compounds, organotin compounds, etc. are used alone or in combination as catalysts. In addition, various additives such as stabilizers, fillers, reinforcing agents, colorants, mold release agents, crosslinking agents, chain extenders, and flame retardants can be used as raw materials for the foam or non-foam polyurethane.

As the polyisocyanate compound, which is another basic raw material for polyurethane, aromatic, aliphatic, alicyclic, and heterocyclic compounds having at least two isocyanate groups can be used alone or in combination. In particular, it is preferable to use aromatic polyisocyanate compounds. Specific polyisocyanate compounds include, for example, tolylene diisocyanate (TDI), diphenylmethane isocyanate (MDI), polymethylene polyphenylisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like. . Polyisocyanate-1 compounds can also be modified with various methods or compounds.
It can be used as a modified polyisocyanate compound, and it can also be used as a blocked isocyanate compound blocked with various compounds. The method for producing polyurethane using these raw materials is not particularly limited, and methods such as the one-shot method, prepolymer method, and RIM method can be used, for example.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Example 1 In a 5I2 reactor, 2250 parts of polyoxypropylene oxyethylene triol with a molecular weight of 5000 (the same applies below weight parts), 375 parts of melamine powder, and dicyandiamide (D
CD) 375 parts, 35% formaldehyde aqueous solution 100
0 part was charged and reacted at 100℃ for 4 hours, then at 150℃
Dehydration was performed under reduced pressure to obtain a milky white viscous polyol dispersion.

The viscosity was 2200 cp (same as below 25°C).

Furthermore, it was found that the solid content in the polyol was stably dispersed for more than two months as it was. The ratio of propylene oxide and ethylene oxide in the polyol used was 85:15 (weight ratio).

Example 2 2250 parts of the same polyol as in Example 1 was added to a 5-flood reactor;
Melamine powder 160 parts, guanidine sulfamate 59 parts
0 parts, 650 parts of a 35% formaldehyde aqueous solution were charged, reacted at 100°C for 4 hours, and then dehydrated under reduced pressure at 150°C to obtain a milky white viscous polyol dispersion. The viscosity is 2
It was 500 cp.

The solids in the polyol remain stably dispersed for more than two months as they are.

Example 3 Same polyol 2250 as in (Example 1) in a reactor at 5°C.
1, 750 parts of dicyandiamide, and 1150 parts of a 35% formaldehyde aqueous solution were charged and reacted at 100°C for 4 hours, followed by dehydration under reduced pressure at 150°C to obtain a milky white viscous polyol dispersion.

The viscosity was 25QOcp.

The solids in the polyol remain stably dispersed for more than two months as they are.

Example 4 Same polyol 2100 as in (Example 1) in 5-flood reactor
parts, 147 parts of melamine, 753 parts of guanidine phosphate, 3
Add 600 parts of 5% formaldehyde aqueous solution and heat to 100°C.
The mixture was reacted for 4 hours, and then dehydrated under reduced pressure at 150°C to obtain a milky white viscous polyol dispersion. Viscosity is 3500
It was cp.

The solids in the polyol remain stably dispersed for more than two months as they are.

Example 5 The same polyol 2250 as in (Example 1) was added to the 5β reactor.
210 parts of melamine, 281 parts of dicyandiamide, 259 parts of guanidine sulfamate, and 1140 parts of a 35% formaldehyde aqueous solution were charged, reacted at 100°C for 4 hours, and then dehydrated under reduced pressure at 150°C to obtain a milky white viscous polyol dispersion. Ta.

The viscosity was 2300 cp.

The solids in the polyol remain stably dispersed for more than two months as they are.

Comparative Example 1 The same polyol 2250 as in (Example 1) was added to a 5β reactor.
750 parts of melamine and 1000 parts of a 35% formaldehyde aqueous solution were charged and reacted at 100°C for 4 hours.
Dehydration was carried out under reduced pressure at 0°C to obtain a milky white viscous polyol dispersion. The viscosity was 2500 cp.

The solids in the polyol remain stably dispersed for more than two months as they are.

Comparative Example 2 Acrylonitrile was polymerized with azobisisobutyronitrile (AIBN) in oxypropylene/oxyethylene triol having a molecular weight of 5000 to obtain a yellow viscous polyol dispersion with a polymer concentration of 20%.

The viscosity was 2800 cp.

Tetrakis (
2-chloroethyl) ethylene diphosphate (trade name T
1-101) or a halogen-containing softener such as tri-2-chloroethyl phosphate (TCEP) was added and mixed with stirring to obtain a uniform polyol dispersion.

Comparative Example 3 A white viscous polyol dispersion with a polymer concentration of 20% was obtained by polymerizing 6 parts of acrylonitrile and 14 parts of styrene monomer to 80 parts of oxypropylene/oxyethylene triol having a molecular weight of 5000 in the above polyol using AIEN as an initiator. Obtained.

The viscosity was 2500 cp.

TH-101 per 100 parts of the obtained polyol composition
8 parts of the mixture were added and mixed with stirring to obtain a uniform polyol dispersion.

Example 6 [Foam manufacturing method] 100 parts by weight of polyol dispersion, 4 parts by weight of water, DABC
O33-LV O, 3 parts by weight, N-methylmorpholine 0
．． After stirring and mixing a mixture of 3 parts by weight of silicone foam stabilizer, 2 parts of silicone foam stabilizer, and 0.2 parts by weight of stannus octoate (T-9) tolylene diisocyanate (T-80) to an index of 105, a 350 mm opening x Pour into a 100n+mt mold (mold temperature 40℃) and heat in a 180℃ oven for 1 hour.
Cure was performed for 2 minutes.

The combustion test results of the obtained urethane foam are summarized in Table 1.

[Effects of the Invention] The present invention relates to a polyol composition in which particles of an aldehyde condensation resin are dispersed in a polyol, and has excellent effects such as flame retardancy. Alternatively, the effect of low smoke generation was observed by containing 40 mol% or more in the initial condensate.

Claims (1)

[Claims] 1. A dispersion medium of a particle dispersion in which condensed particles are precipitated from an aqueous solution of a guanidine compound capable of condensing with aldehydes and aldehydes, or an initial condensate thereof, is reactive with an organic isocyanate compound. A method for producing a condensed resin dispersion obtained by substitution with an active hydrogen compound. 2. 40-100 mol% of guanidine-based compounds and 60-0 mol% of non-guanidine-based aldehyde-condensable compounds
The dispersion according to claim 1, characterized in that the dispersion is co-condensed with the following. 3. The dispersion according to claim 1, wherein the aldehyde is formaldehyde. 4. Claim 1, characterized in that the active hydrogen compound reactive with organic isocyanates has a molecular weight of 250 or more and has two or more hydroxyl groups and/or amino groups in the molecular chain. Condensed resin dispersion. 5. The condensed resin dispersion according to claim 4, wherein the active hydrogen compound having reactivity with an organic isocyanate is a polyether polyol. 6. The condensed resin dispersion according to claim 4, wherein the active hydrogen compound having reactivity with an organic isocyanate is a polyester polyol. 7. A method for producing polyurethane using an active hydrogen compound and a polyisocyanate compound as basic raw materials,
A method for producing polyurethane and/or polyurea, characterized in that part or all of the active hydrogen compound or, if necessary, part or all of the crosslinking agent is a condensed resin dispersion produced by the method of claim 1. . 8. The method according to claim 7, wherein the polyurethane or polyurea is a foam.