JP2006056960A - Resol type phenol resin emulsion and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resol type phenol resin emulsion that is readily dispersible in water in an arbitrary ratio, controls reactivity and adjusts a curing rate to a preferable level and to provide a method for simply producing the resol type phenol resin emulsion. <P>SOLUTION: The resol type phenol resin emulsion comprises a resol type phenol resin and a water-soluble polymer compound. The resol type phenol resin has 1-10 mol% ratio of a dimethylene ether group and/or a substituted dimethylene ether group to the whole bond groups of derived from aldehydes bonded to aromatic rings derived from phenols and has 70-90 mol% ratio of a methylene group and/or a substituted methylene group. The method for producing the same is provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resol type phenol resin emulsion and a method for producing the same.

  Phenolic resin is a typical thermosetting resin used in many fields. Phenol resins are broadly divided into novolak type phenol resins that are cured by heating with the addition of a curing agent such as hexamethylenetetramine, and resol type phenol resins that are cured by heating alone. It has been broken.

Among these phenol resins, resol type phenol resins having high hydrophilicity are often used without using hexamethylene tetramine in applications requiring ammonia-free.
Resol type phenol resin is reacted with phenols and aldehydes using an alkaline catalyst such as sodium hydroxide, aqueous ammonia, tertiary amine, alkaline earth metal oxide or hydroxide, sodium carbonate, etc. In addition to the methylol-type resol-type phenol resin obtained by this, there is a dimethylene ether-type resol-type phenol resin obtained by reacting with a divalent metal salt such as zinc acetate (see, for example, Patent Document 1). ).

  Since methylol type resol type phenolic resin has high reactivity, its curing speed is fast, and it may be difficult to apply to applications where it is desired to control the curing speed. On the other hand, the dimethylene ether type resol type phenol resin can impart flexibility to the cured product depending on the curing conditions, but has a problem that the curing rate is very slow.

  In order to appropriately control the curability, there is a method of adjusting the curability by mixing a methylol-type resol-type phenol resin and a dimethylene ether-type resol-type phenol resin. However, when a plurality of resins are used in combination, there is a problem that an extra mixing step is required and not only costs are disadvantageous but also quality management becomes complicated.

  Further, by resolating a novolac type phenol resin using a divalent metal salt catalyst, a dimethylene ether type resol type phenol resin having appropriate curability can be obtained. However, the dimethylene ether-type resol type phenolic resin made in this way has low hydrophilicity and is difficult to use as a dispersion such as an aqueous solution or emulsion like the methylol type resol type phenolic resin. . In applications where it is desired to use the resol type phenolic resin in liquid form, it is necessary to use a solvent. However, there is a problem that there is a risk of catching fire in addition to the problem of polluting the working environment and air.

Japanese Patent Laid-Open No. 05-148334.

  The present invention is a resol type phenol resin emulsion that can be dispersed in water at an arbitrary ratio, capable of controlling the reactivity and setting the curing rate to a desirable level in the use of the resol type phenol resin in a liquid form. And the method of manufacturing such a resol type phenol resin emulsion easily is provided.

(1) A resol type phenol resin emulsion containing a resol type phenol resin and a water-soluble polymer compound, wherein the resol type phenol resin binds aromatic rings derived from phenols. The ratio of the dimethylene ether group and / or the substituted dimethylene ether group is 1 to 10 mol% with respect to all the linking groups derived from the aldehydes, and the ratio of the methylene group and / or the substituted methylene group is 70 to Resol type phenol resin emulsion characterized by being 90 mol%.
(2) The resol type phenol resin according to (1), wherein the content of unreacted phenols and unreacted aldehydes is 2% by weight or less with respect to the entire resol type phenol resin. Phenol resin emulsion.
(3) The resol type phenol resin emulsion according to (1) or (2), wherein the resol type phenol resin has a number average molecular weight of 500 to 1200.
(4) A method for producing a resol type phenol resin emulsion according to any one of (1) to (3),
(A) a step of synthesizing a novolac type phenol resin by reacting a phenol and an aldehyde under an acidic catalyst,
(B) a step of synthesizing a resol type phenol resin by reacting the novolac type phenol resin and an aldehyde in the presence of a divalent metal salt; and
(C) a step of adding a water-soluble polymer compound during or after the synthesis of the resol type phenolic resin, and emulsifying the resol type phenolic resin,
A process for producing a resol-type phenolic resin emulsion, comprising:
(5) The method for producing a resol type phenol resin emulsion according to (4), wherein the acidic catalyst contains an organic phosphonic acid.
(6) The said organic phosphonic acid is a manufacturing method of the resol type phenol resin emulsion as described in (4) or (5) which is shown to the following general formula (I).
R-PO (OH) ₂ (I)
(R is a group containing a carbon atom and containing —COOH and / or —PO (OH) _2. )
(7) The method for producing a resol type phenol resin emulsion according to claim 4, wherein the acidic catalyst contains phosphoric acids.
(8) The method for producing a resol type phenol resin emulsion according to (7), wherein in the step (a), 0.2 mol or more of the phosphoric acid is used with respect to 1 mol of the phenol.
(9) The method for producing a resol type phenol resin emulsion according to claim 7 or 8, wherein the phosphoric acid contains phosphoric acid.
(10) The novolac type phenolic resin according to any one of (4) to (9), wherein the number average molecular weight is 300 to 1,000, and the degree of dispersion of the molecular weight distribution is 1.15 to 1.6. A method for producing a resol type phenol resin emulsion.
(11) The novolac-type phenol resin is a resol-type phenol resin according to any one of (4) to (10), wherein the contents of unreacted phenols and unreacted aldehydes are each 2% by weight or less. A method for producing an emulsion.

The resol type phenol resin emulsion of the present invention is a resol type phenol resin emulsion containing a resol type phenol resin and a water-soluble polymer compound, and the resol type phenol resin is derived from phenols. The ratio of the dimethylene ether group and / or the substituted dimethylene ether group is 1 to 10 mol% with respect to all the linking groups derived from the aldehydes that bind the aromatic rings to each other, and the methylene group and / or Or the ratio of a substituted methylene group is 70-90 mol%. The resol-type phenol resin emulsion of the present invention can control the reactivity even in the use of the resol-type phenol resin in a liquid form, can set the curing rate to a preferable level, and can be added to water at an arbitrary ratio. It has the dispersibility of.
And the manufacturing method of the resol type phenol resin emulsion of this invention can be applied preferably, in order to manufacture such a resol type phenol resin emulsion easily.

Hereinafter, the resol type phenol resin emulsion of the present invention and a method for producing the resol type phenol resin emulsion (hereinafter sometimes simply referred to as “manufacturing method”) will be described.
The resol type phenol resin emulsion of the present invention (hereinafter sometimes referred to simply as “resole resin emulsion”) is a resol type phenol resin emulsion containing a resol type phenol resin and a water-soluble polymer compound. The resol-type phenolic resin is a dimethylene ether group and / or a substituted dimethylene ether group with respect to all linking groups derived from aldehydes bonding aromatic rings derived from phenols. The ratio is 1 to 10 mol%, and the ratio of methylene groups and / or substituted methylene groups is 70 to 90 mol%.
Further, the production method of the present invention is a method for producing a resol type phenol resin emulsion,
(A) a step of synthesizing a novolac-type phenol resin by reacting phenols and aldehydes under an acidic catalyst;
(B) a step of synthesizing a phenol resin by reacting the novolac-type phenol resin and an aldehyde under a divalent metal salt catalyst, and
(C) a step of adding a water-soluble polymer compound during or after the synthesis of the resol type phenolic resin, and emulsifying the resol type phenolic resin,
It is characterized by having.

First, the resol resin emulsion of the present invention will be described.
The resol resin emulsion of the present invention is obtained by mixing a resol type phenol resin obtained by reacting phenols and aldehydes with a water-soluble polymer compound.
Although it does not specifically limit as phenols used here, For example, cresol, such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, xylenol such as 3,5-xylenol, ethylphenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol, isopropylphenol, butylphenol, p-tert-butylphenol Alkylphenols such as butylphenol, p-tert-amylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, and the like, fluorophenols, chlorophenol, bromophenol, iodophenol, etc. Monovalent phenol substitution products such as genated phenol, p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol, and monovalent phenols such as 1-naphthol and 2-naphthol, resorcin, alkylresorcin, Examples thereof include polyphenols such as pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and dihydroxynaphthalene. These can be used alone or in combination of two or more.

  The aldehydes are not particularly limited, but examples include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde. Benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These can be used alone or in combination of two or more.

Further, the water-soluble polymer compound is not particularly limited, but what is generally called a protective colloid is preferable. For example, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamides, Examples thereof include starch, gelatin, casein, gum arabic, and polyethylene oxide.
Polyacrylamides are not particularly limited. For example, polyacrylamide, polymethacrylamide, polyacrylamide and a partial hydrolyzate of polymethacrylamide, a copolymer of acrylic amide and acrylic acid or methacrylic acid, vinyl Polymers containing acid amide groups in the molecule represented by poly (vinyl amide) copolymers, cationized polyacrylamides, amphoteric polyacrylamides, sulfomethyleneated polyacrylamides, urethanized polyvinyl alcohol, etc., or methylolated And methylol compounds of the above acid amides such as polyacrylamide. These can be used alone or in combination of two or more.

The resol type phenol resin used in the resol resin emulsion of the present invention is a dimethylene ether group and / or a substitution with respect to all bonding groups derived from aldehydes bonding aromatic rings derived from phenols. The proportion of dimethylene ether groups is 1 to 10 mol%, and the proportion of methylene groups and / or substituted methylene groups is 70 to 90 mol%.
Thereby, while being able to disperse | distribute to water in arbitrary ratios, it can be set as the resole resin emulsion which has preferable sclerosis | hardenability. When the ratio of the dimethylene ether group and / or the substituted dimethylene ether group is less than the above lower limit value, the effect of adjusting the curing rate may not be sufficient. Moreover, since the fall of a cure rate will become large when the said upper limit is exceeded, productivity may fall depending on a use.

  Although the molecular weight of the said resol type phenol resin is not specifically limited, It is preferable that a number average molecular weight is 500-1200. Thereby, it can be made low viscosity, having moderate curability.

  The amount of unreacted monomers contained in the resol type phenol resin is not particularly limited, but the content of unreacted phenols and unreacted aldehydes is preferably 2% by weight or less. Thereby, the working environment at the time of use can be improved. Moreover, the fall of the physical property of hardened | cured material, such as mechanical strength, can be suppressed.

In the resole resin emulsion of the present invention, the blending ratio of the water-soluble polymer compound is not particularly limited, but is 0.1 to 60% by weight based on the total components excluding moisture in the resole resin emulsion. It can be. More preferably, it is 0.3-30 weight%, Most preferably, it is 0.5-15 weight%.
In addition, the compounding quantity of water-soluble polymer can set the compounding quantity optimal suitably according to the kind of water-soluble polymer to add, the use of a resole resin emulsion, etc.

Next, the manufacturing method of this invention is demonstrated.
In the production method of the present invention, first,
(A) Phenols and aldehydes are reacted under an acidic catalyst to synthesize a novolak type phenol resin.

  As phenols and aldehydes used here, the same thing as what was demonstrated in the resole resin of the said invention can be illustrated.

Although it does not specifically limit as an acidic catalyst used at the said (a) process, For example, organic acids, such as inorganic acids, such as hydrochloric acid, a sulfuric acid, phosphoric acids, oxalic acid, p-toluenesulfonic acid, and organic phosphonic acid, can be used. .
Among these, it is preferable to use organic phosphonic acid as an acidic catalyst. Thereby, a novolak resin having a narrow molecular weight distribution can be obtained efficiently. Moreover, the amount of unreacted phenols and unreacted aldehydes contained in the novolak resin can be reduced.

The organic phosphonic acid is an organic compound containing a phosphonic acid group —PO (OH) ₂ , and any compound can be used. In order to produce a novolak resin with a low content of unreacted phenols, the following general formula is used. The organic phosphonic acid represented by (I) is preferred.
R-PO (OH) ₂ (I)
(R is a group containing a carbon atom and containing —COOH and / or —PO (OH) _2. )

The organic phosphonic acid represented by the general formula (I) is not particularly limited. Examples include acid N, N-diacetic acid, aminomethylphosphonic acid N, N-diacetic acid, 1-hydroxyethylidene-1,1′-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and the like.
Among these, aminotrismethylenephosphonic acid, 1-hydroxyethylidene-1,1′-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid, which are industrially mass-produced and inexpensive, are preferable.

When an organic phosphonic acid is used as the acidic catalyst, the amount added is not particularly limited, but is preferably 0.001 to 4 mol, more preferably 0.01 to 0.5 mol, per 1 mol of phenols.
Within the above range, the larger the amount of organic phosphonic acid added, the narrower the molecular weight distribution and the higher the effect of obtaining a novolak resin with a low content of unreacted phenols in high yield. When the addition amount exceeds the above upper limit, the effect does not change, and when it is less than the lower limit, the effect as a catalyst is substantially lost.

When using the said organic phosphonic acid, it is although it does not specifically limit as reaction conditions in the said (a) process, It is preferable that reaction temperature shall be 80-200 degreeC. More preferably, it is 100-160 degreeC.
When the reaction temperature is lower than the above lower limit, depending on the amount of water in the reaction system, the organic phosphonic acid may become highly viscous or solidified and the catalytic action may be reduced. When the above upper limit is exceeded, decomposition of the organic phosphonic acid or novolak resin may occur.

The water content in the reaction system is preferably 30% by weight or less. More preferably, it is 1 to 20% by weight. Here, the water includes water added at the time of charging, water contained in aldehydes and organic phosphonic acid, water derived from the raw material such as crystallization water of organic phosphonic acid, and condensed water generated during the reaction.
The water content is calculated by dividing the amount of water in the charged raw material and the amount of condensed water produced by the reaction as the amount of water in the reaction system, and dividing this by the total amount charged. Moreover, when making it react, distilling and removing water, it can calculate from the moisture content which reduced the part which distills.
The smaller the water content, the higher the effect of obtaining a high yield of novolak resin with a narrow molecular weight distribution and a small amount of unreacted phenols. The phosphonic acid becomes highly viscous or solidified, and the catalytic action is lowered. On the other hand, if it exceeds 30% by weight, the effect is hardly changed.

  There is no restriction | limiting in particular about reaction time, According to the kind of raw material, compounding molar ratio, the usage-amount and kind of a catalyst, and reaction conditions, it can select suitably.

By carrying out the reaction under such conditions, not only unreacted phenols but also low molecular weight components such as dinuclear components react selectively, so that novolak resins with a narrow molecular weight distribution can be efficiently used. Can get to.
The novolak resin can be synthesized even under conditions outside the above range, for example, under conditions where the temperature is less than the above lower limit value, or under conditions where the moisture content is greater than the above upper limit value. There is a tendency that a low molecular weight component such as a nuclear component is selectively reacted and a molecular weight distribution is widened.

  After completion of the reaction, neutralization or washing with water may be performed to remove the catalyst. Moreover, in order to remove water, an organic solvent, and also unreacted phenol as needed, atmospheric distillation, reduced pressure distillation, steam distillation, etc. can also be performed.

  Moreover, in the manufacturing method of this invention, it is preferable to use phosphoric acids as an acidic catalyst at the said (a) process. Thereby, the same effect as the case where organic phosphonic acid is used can be acquired.

  Here, as the phosphoric acid, a phosphoric acid compound that can be dissolved in water to form a phosphoric acid aqueous solution can be used, and is not particularly limited. For example, phosphoric acid (orthophosphoric acid), diphosphoric acid, triphosphoric acid, etc. In addition to linear polyphosphoric acid, cyclic polyphosphoric acid, diphosphorus pentoxide, phosphorous acid, hypophosphorous acid and the like, various phosphoric acid ester compounds can be mentioned. These can be used alone or in combination of two or more.

  Of these phosphoric acids, phosphoric acid is preferred. When phosphoric acid is used in the form of an aqueous solution, the concentration can be easily adjusted, and it can be obtained at low cost.

The concentration of phosphoric acid when using phosphoric acid in the form of a phosphoric acid aqueous solution is not particularly limited, but is preferably 20 to 99% by weight, more preferably 40 to 99% by weight with respect to the entire phosphoric acid aqueous solution. is there.
By setting the concentration of phosphoric acid in the phosphoric acid aqueous solution to the above lower limit or more, the reaction between phenols and aldehydes can be efficiently advanced.

The amount of the phosphoric acid used here is not particularly limited, but is preferably 0.2 mol or more, more preferably 0.2 to 1.0 mol, relative to 1 mol of phenols. Thereby, in the system which reacts phenols and aldehydes using phosphoric acids, distribution of the organic phase which has phenols as a main component and the aqueous phase which has phosphoric acid aqueous solution can be stabilized.
The amount of the phosphoric acid is more preferably 0.3 to 0.9 mol, and particularly preferably 0.4 to 0.8 mol with respect to 1 mol of the phenol. Thereby, the novolak resin with little content of unreacted phenols can be obtained efficiently.

  Increasing the amount of the phosphoric acid tends to increase the effect of obtaining a novolak resin with a low content of unreacted phenols in a high yield, but the amount exceeds the upper limit with respect to 1 mol of phenols. Even if is used, this effect may not be substantially changed, so it may not be economical. Moreover, if it is less than the said lower limit, since the phosphoric acid density | concentration in an aqueous phase will become low in order to distribute an organic phase and an aqueous phase stably, reaction rate will come to fall.

  When phosphoric acids are used as the acidic catalyst, the reaction conditions in the step (a) are not particularly limited, but the reaction temperature is preferably 40 to 150 ° C. More preferably, it is 90-140 degreeC. By making reaction temperature more than the said lower limit, reaction with phenols and aldehydes can be accelerated | stimulated and content of unreacted phenols can be reduced. Moreover, it can make phosphoric acid aqueous solution into a preferable viscosity, and can avoid that a catalytic action falls. On the other hand, the decomposition of the novolak resin can be suppressed by setting it to the upper limit value or less.

When phosphoric acids are used as the acidic catalyst, the water content in the reaction system is not particularly limited, but is preferably 1 to 40% by weight. More preferably, it is 1 to 30% by weight. The water content can be calculated in the same manner as in the case of using the organic phosphonic acid.
By carrying out the reaction preferably within this range for the water content, a novolak resin having a narrow molecular weight distribution and a low content of unreacted phenols can be obtained in a high yield.
By setting the water content in the reaction system within the above range, it is possible to suppress the increase in viscosity or consolidation of phosphoric acids and to suppress a decrease in the reaction rate. It is possible to efficiently proceed with the reaction.

Such reaction conditions are effective for selectively reacting not only unreacted phenols but also low molecular weight components such as dinuclear components, and can narrow the molecular weight distribution of the resulting novolak resin. .
That is, the reaction of unreacted phenols proceeds sufficiently even outside the range of the above reaction conditions, but for the selective reaction of a low molecular weight component such as a binuclear component, it is within the range of the above reaction conditions. It is effective to do.

  There is no restriction | limiting in particular about reaction time, According to the kind of starting material, compounding molar ratio, the usage-amount and kind of a catalyst, and reaction conditions, it can select suitably.

  After completion of the reaction, neutralization or washing with water may be performed to remove the catalyst. Moreover, in order to remove water, an organic solvent, and also unreacted phenol as needed, atmospheric distillation, reduced pressure distillation, steam distillation, etc. can also be performed.

When organic phosphonic acid or phosphoric acid is used as a catalyst in the above step (a), in addition to these catalysts, usually in the production of novolak resins such as oxalic acid, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, etc. The acidic catalyst to be used can also be used in combination.
The combined use of these acidic catalysts is effective for accelerating the reaction particularly when a high molecular weight component higher than the tetranuclear component is required, and is an effective means for controlling the molecular weight distribution.

As described above, the novolak resin obtained in the step (a) may be obtained by reacting phenols and aldehydes using organic phosphonic acid or phosphoric acid as a catalyst. Although it is preferable, other than this, it can also obtain by making it react using a well-known acidic catalyst.
At this time, the addition amount of the acidic catalyst is not particularly limited, but is preferably 0.001 to 0.1 mol, more preferably 0.005 to 0.05 mol, with respect to 1 mol of phenols. .
In addition, the reaction conditions at this time can usually be reacted under reflux conditions with easy temperature control. There is no restriction | limiting in particular about reaction time, What is necessary is just to determine suitably according to the kind of starting material, a compounding molar ratio, the usage-amount and kind of a catalyst, and reaction conditions.
In this case, the amount of unreacted phenols or dinuclear components contained in the obtained resin may increase, or the molecular weight distribution may be widened. Methods such as vacuum distillation, steam distillation, recrystallization, solvent extraction, water washing and fractionation can be applied.
As an example of a method for removing low nuclear components, unreacted phenols can be removed under reduced pressure conditions of 170 ° C. and 500 Pa, and dinuclear components can be removed under reduced pressure conditions of 250 ° C. and 100 Pa. it can.

  The reaction method of the above phenols and aldehydes is not particularly limited. In order to suppress this, it is possible to apply a method in which phenols and an acidic catalyst are mixed and then aldehydes are sequentially added and reacted therewith.

Although it does not specifically limit as molecular weight of the novolak resin obtained at the said (a) process, It is preferable that a number average molecular weight is 300-1000 and the dispersion degree of molecular weight distribution is 1.15-1.6. More preferably, the number average molecular weight is 500 to 800, and the dispersity is 1.2 to 1.5.
By using such a novolak resin, it is possible to prevent the viscosity of the reaction system from excessively increasing in the step (b). Moreover, the dimethylene ether bond of the ratio preferable for a resole resin can be produced | generated.

Further, the contents of unreacted phenols and unreacted aldehydes contained in the novolak resin synthesized by the step (a) are not particularly limited, but each is preferably 2% by weight or less.
Thereby, the resol resin with little content of unreacted phenols and unreacted aldehydes can be obtained efficiently.

Although there is no particular limitation on the method of setting the content of unreacted phenols and unreacted aldehydes contained in the novolak resin synthesized in the step (a) to the upper limit or less, an organic phosphonic acid can be used as an acidic catalyst. Alternatively, when phosphoric acids are used, the reaction can be made generally lower than the above upper limit value by reaction. Furthermore, if necessary, unreacted phenols and unreacted aldehydes can be removed by combining atmospheric distillation, reduced pressure distillation, steam distillation and the like.
In addition, when an acid catalyst other than organic phosphonic acid or phosphoric acid is used, unreacted phenols and unreacted aldehydes may be removed by atmospheric distillation, vacuum distillation, etc. after synthesizing a novolak type phenol resin. it can.

The reaction molar ratio of the phenols and aldehydes used in the step (a) is not particularly limited. However, when organic phosphonic acid is used as the acidic catalyst, the molar ratio of the aldehydes (F ₁ ) to the phenols (P) ( F ₁ / P) is preferably 0.5 to 0.95, more preferably 0.5 to 0.85, and particularly preferably 0.6 to 0.8.
The reaction molar ratio when phosphoric acids are used as the acidic catalyst is not particularly limited, but is preferably 0.1 to 1.0, more preferably 0.3 to 0.9, and particularly preferably 0.00. 4 to 0.8.
In addition, the reaction molar ratio when using an acid catalyst other than organic phosphonic acid or phosphoric acid is not particularly limited, but is preferably 0.3 to 0.85, and more preferably 0.4 to 0.8. It is.
Thereby, the novolak-type phenol resin which has said property can be obtained efficiently.
If the reaction molar ratio is smaller than the above lower limit, the content of unreacted phenols tends to increase, and it is difficult to obtain a product having a low content of unreacted phenols even when this is converted to a resole resin. There is. On the other hand, when the above upper limit is exceeded, in the step of converting the novolak resin to a resole resin, there is a case where the viscosity increases or gelation occurs depending on reaction conditions.

  In addition, when using organic phosphonic acid or phosphoric acid as an acidic catalyst, after completion | finish of reaction, these can be removed or collect | recovered by water washing. The washing method, removal or recovery method is not particularly limited, and the organic phosphonic acid or phosphoric acid recovered by washing or the like may be used again as a catalyst, or may be neutralized with an alkaline substance.

Next, in the production method of the present invention,
(B) The novolac resin and aldehyde are reacted in the presence of a divalent metal salt to synthesize a resole resin.

  Although it does not specifically limit as aldehydes used at the said (b) process, The same thing as what is used at the said (a) process can be illustrated.

Although the amount of aldehydes used in the step (b) is not particularly limited, unreacted phenols remaining in the phenol resin may be removed in the step (a). Including the case, the aldehydes (F ₁ ) used in the step (a) and the aldehydes (F ₂ ) used in the step (b) with respect to the phenols (P) used in the step (a) The molar ratio [(F ₁ + F ₂ ) / P] is preferably 0.7 to 3.0, and more preferably 0.8 to 2.5.
When this molar ratio is less than the above lower limit, resol resinification in the step (b) may be insufficient, and when the upper limit is exceeded, a large amount of unreacted aldehyde may remain.

  Although it does not specifically limit as a bivalent metal salt used at the said (b) process, As a bivalent metal, iron, cobalt, nickel, chromium, manganese, zinc, copper, calcium, magnesium, barium etc. are mentioned, for example. . Examples of the divalent metal salt include halides and oxides in addition to organic salts such as acetate. Specifically, zinc acetate, manganese acetate, magnesium oxide, or the like can be used.

The addition amount of the divalent metal salt in the step (b) is not particularly limited, but is usually 0.0001 to 0.5 mol, preferably 0.001 with respect to 1 mol of the phenols used in the step (a). -0.05 mol.
When the addition amount of the divalent metal salt is less than the above lower limit value, the action as a catalyst may not be sufficient. On the other hand, when the upper limit value is exceeded, the curability of the resulting resol resin may be affected.

  The amount of unreacted monomers contained in the resol resin obtained in the step (b) is not particularly limited, but the content of unreacted phenols and unreacted aldehydes is 2% by weight or less, respectively. Is preferred.

Although there is no particular limitation on the method of setting the content of unreacted phenols and unreacted aldehydes in the resole resin to 2% by weight or less, respectively, in step (a), the content of unreacted phenols and unreacted aldehydes It is preferable to synthesize a novolak resin having a small amount, preferably a novolak resin having an unreacted phenol content and an unreacted aldehyde content of 2% by weight or less, and synthesize a resol resin based on this. Thereby, a resol resin in which the contents of unreacted phenols and unreacted aldehydes are each 2% by weight or less can be obtained without causing problems such as excessive high molecular weight and gelation.
In addition to the above, if necessary, a conventionally known process or method for removing unreacted phenols and unreacted aldehydes may be used in combination.

In the step (a), after synthesizing a novolak resin from a phenol and an aldehyde using an organic phosphonic acid or phosphoric acid as a catalyst, and further synthesizing a resole resin from the product and the aldehyde. The reason why a resol resin having a reduced content of unreacted phenols and unreacted aldehydes can be considered as follows.
Organic phosphonic acids and phosphoric acids are very water-soluble. Phenols and aldehydes have relatively low solubility in water, and novolak resins have the property of further decreasing solubility in water as the molecular weight increases. For this reason, at the start of the reaction, the phase is separated into an aqueous phase containing a large amount of organic phosphonic acid or phosphoric acid as a catalyst and an organic phase composed of phenols with almost no catalyst. And the reaction of phenols and aldehydes eluted in the aqueous phase proceeds preferentially, and as a result, the content of unreacted phenols is reduced. Furthermore, since the reaction of increasing the molecular weight is difficult to occur, a novolak resin having a small content of unreacted phenols and a narrow molecular weight distribution can be obtained.

  Next, using the obtained novolak resin as a raw material, a resol resin having a desired molecular weight is obtained by adding a necessary amount of aldehydes to form a resole resin, thereby reducing the content of unreacted phenols and unreacted aldehydes. Can be manufactured.

  The resol resin obtained by the production method of the present invention has a dimethylene ether group and / or a substituted dimethylene ether group with respect to all linking groups derived from aldehydes bonding aromatic rings derived from phenols. The proportion is preferably 1 to 10 mol%, and the proportion of methylene group and / or substituted methylene group is preferably 70 to 90 mol%. By setting it within the above range, a resol resin having preferable curability can be obtained.

Although it does not specifically limit as a method to make the ratio of each said coupling group in the said range with respect to all the coupling groups derived from aldehydes, In the said (b) process of the manufacturing method of this invention, ie, said (a) process. By synthesizing a resol resin using a divalent metal salt as a catalyst using the obtained novolak resin as a raw material, an alkyl ether bridge in which a methylol group and / or a substituted methylol group are condensed, that is, a dimethylene ether group and / or Substituted dimethylene ether groups can be generated at a suitable ratio, whereby the resol resin of the present invention can be obtained.
The ratio of the dimethylene ether group and / or the substituted dimethylene ether group is adjusted by the reaction time, the amount of catalyst added, the amount of water in the reaction system, the reaction molar ratio (F / P), etc. in the step (b). be able to.

  The dimethylene ether group and / or the substituted dimethylene ether group in the resole resin molecule thus obtained has a feature that the reactivity is smaller than that of the methylene group and / or the substituted methylene group. Therefore, by adjusting the ratio of these bonding groups in the molecule, it is possible to obtain a resole resin having the desired reactivity and curing speed, and a resole resin emulsion obtained by emulsifying the resole resin is used. By appropriately optimizing according to the application, it can be suitably used in each application.

  Next, in the production method of the present invention, (c) during or after the synthesis of the resol type phenol resin, a water-soluble polymer is added to make the resol type phenol resin into an emulsion.

In the production method of the present invention, a method for adding a water-soluble polymer to the resol-type phenol resin synthesized in the step (b) and emulsifying it is not particularly limited, but examples thereof include the following methods. It is done.
(A) A novolac-type phenol resin and aldehydes are reacted halfway in the presence of a divalent metal salt catalyst, then a water-soluble polymer compound is added, and the reaction is further continued. An emulsion of resol type phenolic resin is obtained.
(B) A novolac-type phenol resin and aldehydes are reacted in the presence of a divalent metal salt catalyst, and after completion of the reaction, a water-soluble polymer compound is added and mixed uniformly. A turbid liquid is obtained.

In the production method of the present invention, examples of the water-soluble polymer compound used in the step (c) include the same compounds as those described in the resol resin emulsion of the present invention.
Although the form using these water-soluble polymer compounds is not particularly limited, for example, a water-soluble polymer previously prepared as an aqueous solution may be added, or these water-soluble polymers are dissolved in the reaction system. If time can be secured, it can be added in the form of powder.

In the production method of the present invention, the addition amount of the water-soluble polymer compound used in the step (c) is not particularly limited, but usually, with respect to the entire component excluding moisture in the final resol resin emulsion. 0.1 to 60% by weight is used. More preferably, it is 0.3-30 weight%, Most preferably, it is 0.5-15 weight%.
In addition, the compounding quantity of water-soluble polymer can set the compounding quantity optimal suitably according to the kind of water-soluble polymer to add, the use of a resole resin emulsion, etc.

Moreover, when obtaining a resole resin emulsion, a dispersion | distribution adjuvant can also be used together as needed other than the said water-soluble polymer compound.
Here, the dispersing aid is not particularly limited, but generally, surfactants, chelating agents, protective colloids can be used, for example, anionic, cationic, nonionic, zwitterionic surfactants. Agent, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, tragacanth gum, casein, gelatin, gluten, polyvinyl methyl ether, polyvinyl pyrrolidone, styrene maleic anhydride copolymer, Examples thereof include protective colloid materials such as polyacrylic acid and polyethylene glycol. These dispersing aids can be selected depending on the type of the divalent metal salt catalyst, the use of the resol resin emulsion, and the like. The timing of addition may be before or after the addition of the water-soluble polymer, or may be simultaneous.

In the method for producing a resol resin emulsion of the present invention, the reaction apparatus used in the above steps (a) to (c) is not particularly limited, but can be carried out using a normal reaction kettle.
In particular, even in the step (c), forced stirring by a so-called emulsifier such as a homodisper, a homomixer, a homogenizer, or a wet pulverizer is not required. However, if necessary, the above-described emulsification apparatus may be used in combination.

As explained above, in the method for producing a resol resin emulsion of the present invention,
(A) a step of synthesizing a novolac-type phenol resin by reacting phenols and aldehydes under an acidic catalyst;
(B) a step of synthesizing a resol type phenolic resin by reacting the novolac type phenolic resin and an aldehyde under a divalent metal salt catalyst; and
(C) a step of emulsifying the resol-type phenol resin by adding a water-soluble polymer compound during or after the synthesis of the resol-type phenol resin;
It is characterized by having.
In this way, a novolak resin is synthesized in the step (a) and converted into a resole resin in the presence of a divalent metal salt in the step (b), whereby a predetermined proportion of dimethylene ether groups and / or A resol resin into which a substituted dimethylene ether group is introduced can be obtained. The resol resin thus obtained has preferable curability.
Here, in particular, in the step (a), novolak resin having a narrow molecular weight distribution and a low content of unreacted phenols and unreacted aldehydes by using organic phosphonic acid or phosphoric acid as an acidic catalyst. Can be obtained efficiently. And by making this a resol resin, in addition to the above effects, it is possible to obtain a resol resin having a low content of unreacted phenols and unreacted aldehydes. (C) In addition to the said effect, the resol resin emulsion with little content of an unreacted monomer can be manufactured by emulsifying by a process.

  The resole resin emulsion thus obtained is easier to adjust the reactivity than conventional methylol-type resole resins and emulsions using dimethylene ether-type resole resins. In addition, the curing speed can be optimized. In addition, the organic solvent is not used and the content of unreacted monomer is small, so it is not only excellent in workability and safety and health, but also in the amount of unreacted monomer in the waste liquid discharged during use. Therefore, the load on the environment can be reduced. Furthermore, when processing such waste liquid, there is also an advantage that expensive processing equipment such as activated sludge is not required.

In the present invention, the number average molecular weight and the degree of dispersion of the novolak resin and the resol resin are calculated based on a calibration curve prepared using a polystyrene standard substance by gel permeation chromatography (GPC) measurement. GPC measurement was performed under the conditions of using tetrahydrofuran as an elution solvent, a flow rate of 1.0 ml / min, and a column temperature of 40 ° C.
The device
1) Body: "HLC-8020" manufactured by TOSOH
2) Detector: “UV-8011” manufactured by TOSOH with wavelength set to 280 nm
3) Analytical column: “SHODEX KF-802, KF-803, KF-805” manufactured by Showa Denko KK
Were used respectively.

In the present invention, the ratio of the bonding group of the resole resin is measured according to the 1H-NMR method.
The resol resin was treated with acetic anhydride in a pyridine catalyst to acetylate the methylol group, and 1H-NMR of the acetylated product was measured. Based on the acetone peak (2.04 ppm), the methylene group (about 3.8 ppm), the dimethylene ether group (about 4.5 ppm), and the methylol group (about 5.0 ppm) were used. The ratio of the linking group was calculated from the ratio of the value of 1/2 for the group and methylol group and 1/4 for the dimethylene ether group. As a device, “JNM-AL300” (frequency 300 MHz) manufactured by JEOL Ltd. was used. In addition, although the said measuring method is a case where phenol and formaldehyde are used as a raw material of a phenol resin, even when using phenols and aldehydes other than this, it can measure on the same principle fundamentally.
In addition, the content of unreacted phenols in the novolak resin and the resol resin is measured by an internal standard method using 3,5-xylenol as an internal standard in accordance with JIS K 0114. The content of unreacted aldehydes is measured by the hydroxylamine hydrochloride method in the case of formaldehyde, for example.

  Hereinafter, the present invention will be described in detail with reference to examples. “Parts” and “%” described here all indicate “parts by weight” and “% by weight”.

Example 1
In a three-necked flask equipped with a stirrer and a thermometer, 1000 parts of 1-hydroxyethylidene-1,1′-diphosphonic acid 60% aqueous solution (manufactured by Lion, “Feriox 115”) was charged, and the temperature was raised to 120 ° C. Concentration was performed under normal pressure until the concentration reached 85%. Then, after adding 1000 parts of phenol and heating up to 100 degreeC, 650 parts of 37% formaldehyde (molar ratio F1 / P = 0.75) was added sequentially over 2 hours. Thereafter, 500 parts of pure water was added and mixed, and then the temperature was lowered to 60 ° C. to remove the catalyst. In order to remove the residual catalyst, water washing was performed twice to add and remove 1000 parts of pure water, followed by distillation under reduced pressure at 15000 Pa, and the water content in the flask was equal to the total amount of reaction product and water content. Thus, the novolac resin A was obtained by adjusting the weight ratio to 10%.
Next, after neutralizing with calcium hydroxide to bring the pH of the reaction system to 5.5, 6 parts of zinc acetate and 103 parts of 92% paraformaldehyde ([(F1 + F2) / P] = 1.05) were added. The mixture was heated to 100 ° C. and refluxed for 1 hour to obtain resole resin A.
After the reaction, vacuum distillation was performed at 15000 Pa, and the water content in the flask was adjusted to 10% by weight with respect to the total amount of the reaction product and the water content. Then, 670 parts of polyacrylamide (Arakawa Chemical Industries, "Polystron 117", 15% aqueous solution) was added, and 1150 parts of water was added and stirred for 1 hour to obtain a resol type phenol resin emulsion A. It was.

(Example 2)
In a three-necked flask, 1500 parts of a 1% -hydroxyethylidene-1,1′-diphosphonic acid 60% aqueous solution (“Ferox 115” manufactured by Lion Corporation) was added and subjected to atmospheric distillation to a concentration of 80%. The temperature was raised to 100 ° C., and 230 parts of 92% paraformaldehyde was sequentially added over 1 hour. Furthermore, atmospheric distillation was performed, the temperature was raised to 130 ° C., and the water content in the reaction system was adjusted to 6%. Thereafter, the temperature was maintained at 130 ° C., the water content was kept constant at about 6%, and 81 parts of a 37% formaldehyde aqueous solution (F1 / P = 0.75) were sequentially added over 1 hour while performing atmospheric distillation. Thereafter, the reaction is carried out at 140 ° C. for 1 hour, 2000 parts of pure water is added, and the water washing step for removing the aqueous phase separated from the resin is performed three times, followed by distillation under reduced pressure, and the amount of water in the flask is determined as a reaction product. The novolac resin B was obtained by adjusting the weight ratio to 10% with respect to the total amount of the product and water.
Next, the reaction system was neutralized with sodium hydroxide to adjust the pH to 5.2, and then 15 parts of zinc acetate and 138 parts of 92% paraformaldehyde ([(F1 + F2) / P] = 1.15) were added. The mixture was heated to 100 ° C. and refluxed for 1 hour to obtain resole resin B.
After the reaction, 860 parts of polyacrylamide (Arakawa Chemical Industries, “Polystron 117”, 15% aqueous solution) was added, 950 parts of water was added and stirred for 1 hour, and an emulsion of resol type phenolic resin B was obtained.

(Example 3)
In a three-necked flask, 1000 parts of phenol and 1000 parts of 85% phosphoric acid aqueous solution (corresponding to 0.82 moles per mole of phenol) were heated, heated to 100 ° C., and 500 parts of 37% formaldehyde aqueous solution over 2 hours. Are added in succession, and atmospheric distillation is performed. The water content in the reaction system is set to 10%, the temperature is raised to 110 ° C., and the water content is kept constant at about 10%. 60 parts of an aqueous formaldehyde solution (F1 / P = 0.65) was sequentially added over 1 hour, and the reaction was further performed while refluxing for 1 hour. Thereafter, in order to remove the residual catalyst, 2000 parts of pure water was added and mixed, and the aqueous phase separated from the resin phase was removed. After performing such a water washing step three times, vacuum distillation is performed, and the water content in the flask is adjusted so that the weight ratio is 10% with respect to the total amount of the reaction product and the water content. Got.
Next, after neutralizing with triethylamine to adjust the pH to 5.4, 6 parts of zinc acetate and 105 parts of 92% paraformaldehyde ([(F1 + F2) / P] = 0.95) were added and heated to 100 ° C. Then, a reflux reaction was performed for 1 hour to obtain a resole resin C.
Thereafter, 740 parts of polyacrylamide (Arakawa Chemical Industries, "Polystron 117", 15% aqueous solution) was added, and 700 parts of water was added to obtain an emulsion C of a resol type phenol resin.

Example 4
A three-necked flask was charged with 1000 parts of phenol and 429 parts of 85% phosphoric acid aqueous solution (corresponding to 0.35 mol per mole of phenol), heated to 100 ° C., and 570 parts of 37% formaldehyde aqueous solution over 2 hours. Are added in succession, and atmospheric distillation is performed. The water content in the reaction system is set to 10%, the temperature is raised to 110 ° C., and the water content is kept constant at about 10%. 80 parts of an aqueous formaldehyde solution (F1 / P = 0.75) was sequentially added over 1 hour, and further reacted for 1 hour under reflux. Thereafter, in order to remove the residual catalyst, 2000 parts of pure water was added and mixed, and the aqueous phase separated from the resin phase was removed. After performing such a water washing step three times, vacuum distillation was performed, and the water content in the flask was adjusted so as to be 10% by weight with respect to the total amount of the reaction product and the water content. Got.
Next, after neutralizing with calcium hydroxide to adjust the pH to 5.9, 12 parts of zinc acetate and 173 parts of 92% paraformaldehyde ([(F1 + F2) / P] = 1.25) were added at 100 ° C. And the reflux reaction was carried out for 1 hour and 30 minutes to obtain Resole Resin D.
After the reaction, vacuum distillation was performed at 15000 Pa, and the water content in the flask was adjusted to 15% by weight with respect to the total amount of the reaction product and the water content. Thereafter, 850 parts of polyacrylamide (Arakawa Chemical Industries, “Polystron 117”, 15% aqueous solution) was added, and 900 parts of water was added to obtain an emulsion D of a resol type phenolic resin.

(Example 5)
1000 parts of phenol and 20 parts of oxalic acid were added to a three-necked flask, the temperature was raised to 100 ° C., 450 parts of a 37% formaldehyde aqueous solution (F1 / P = 0.52) was added successively over 1 hour, and the mixture was further refluxed for 1 hour. After the reaction, dehydration was performed under normal pressure dehydration, the temperature was raised to 150 ° C., and the liquid temperature was 160 ° C., the degree of vacuum was 6000 Pa, and there was no distillate. Next, water vapor was introduced into the resin having a liquid temperature of 160 ° C. and a reduced pressure of 55000 Pa, and then the liquid temperature was maintained at 150 to 160 ° C. and the reduced pressure was maintained at 53,000 to 70000 Pa for 3 hours. Thereafter, the temperature is lowered to 100 ° C., and adjustment is made by adding pure water so that the water content in the flask is 10% by weight with respect to the total amount of the reaction product and the water content in order to avoid an increase in viscosity. Novolak resin E was obtained.
Next, after adding 10 parts of zinc acetate and 150 parts of 92% paraformaldehyde ([(F1 + F2) / P] = 0.95), the mixture was heated to 100 ° C. and refluxed for 2 hours to obtain resole resin E. It was.
Then, 800 parts of polyacrylamide (Arakawa Chemical Industries, "Polystron 117", 15% aqueous solution) was added, and 350 parts of water was added to obtain an emulsion E of a resol type phenol resin.

(Comparative Example 1)
In a three-necked flask, 1000 parts of phenol, 1035 parts of 37% formaldehyde (F / P = 1.20) and 10 parts of calcium hydroxide as a catalyst were added and reacted at 80 ° C. for 2 hours. Next, it is neutralized with sulfuric acid to pH 5.0, and this is subjected to vacuum distillation at 15000 Pa, and the water content in the flask is adjusted to 10% by weight with respect to the total amount of the reaction product and the water content. Resole resin (methylol type resole resin) F was obtained.
Next, 1000 parts of polyacrylamide (Arakawa Chemical Industries, "Polystron 117", 15% aqueous solution) is added, 500 parts of water is added, and the mixture is stirred for 1 hour. Got.

(Comparative Example 2)
In a three-neck flask, 1000 parts of phenol, 590 parts of 92% paraformaldehyde (F / P = 1.70), and 15 parts of zinc acetate as a catalyst were added and reacted under reflux conditions for 6 hours. Subsequently, pure water is added, and the water content in the flask is adjusted to 20% by weight with respect to the total amount of the reaction product and the water content, and a resol resin (dimethylene ether type resole resin) G is prepared. Obtained.
Next, 1000 parts of polyacrylamide (Arakawa Chemical Industries, “Polystron 117”, 15% aqueous solution) was added, 850 parts of water was added, and the mixture was stirred for 1 hour. Got.

About the novolak resin obtained in the Example, the amount of unreacted phenol (%), the amount of unreacted formaldehyde (%), the molecular weight, and the degree of dispersion of the molecular weight distribution were measured.
Moreover, about the resol resin obtained by the Example and the comparative example, the unreacted phenol amount (%), the unreacted formaldehyde amount (%), the ratio of the bonding group, and the gelation time (second) were measured.
Furthermore, the unreacted phenol amount (%), the unreacted formaldehyde amount (%), and the gelation time (second) were measured for the resol resin emulsions obtained in Examples and Comparative Examples.
The measured values of unreacted phenol and unreacted formaldehyde in the novolak resin, resol resin, and resole resin emulsion are each converted to the content in the resin solid content.

  The properties of the resol type phenolic resins obtained in the examples and comparative examples were evaluated. The results are shown in Table 1.

Evaluation method (1) Molecular weight and dispersion degree of molecular weight distribution of novolak resin The number average molecular weight and dispersion degree were calculated based on a calibration curve prepared using a polystyrene standard substance by gel permeation chromatography (GPC) measurement. GPC measurement was performed under the conditions of using tetrahydrofuran as an elution solvent, a flow rate of 1.0 ml / min, and a column temperature of 40 ° C. The following equipment was used.
1) Body: "HLC-8020" manufactured by TOSOH
2) Detector: “UV-8011” manufactured by TOSOH with wavelength set to 280 nm
3) Analytical column: “SHODEX KF-802, KF-803, KF-805” manufactured by Showa Denko KK

(2) Content of unreacted phenol in novolak resin and resol resin Based on JIS K 0114, it was measured by an internal standard method using 3,5-xylenol as an internal standard.

(3) Content of unreacted formaldehyde in novolak resin, resole resin, and resole resin emulsion Measured by hydroxylamine hydrochloride method.

(4) Ratio of binding group of resole resin The resole resin was treated with acetic anhydride in a pyridine catalyst to acetylate the methylol group, and 1H-NMR of the acetylated product was measured. Based on the acetone peak (2.04 ppm), the methylene group (about 3.8 ppm), the dimethylene ether group (about 4.5 ppm), and the methylol group (about 5.0 ppm) were used. The ratio of the linking group was calculated from the ratio of the value of 1/2 for the group and methylol group and 1/4 for the dimethylene ether group. As a device, “JNM-AL300” (frequency 300 MHz) manufactured by JEOL Ltd. was used.

(5) Gelation time Based on JIS K6909, it measured with a 150 degreeC hotplate using 2 ml of resole resin and resole resin emulsion.

In all of Examples 1 to 5, the ratio of the dimethylene ether group and / or the substituted dimethylene ether group is 1 with respect to the total bonding group derived from aldehydes bonding aromatic rings derived from phenols. The resol resin emulsion of the present invention containing a resol-type phenolic resin having a proportion of methylene groups and / or substituted methylene groups of 70 to 90 mol% and a water-soluble polymer compound. The gelation time, which is a measure of the curing speed, is longer than that of the methylol-type resole resin emulsion of Comparative Example 1, and shorter than that of the dimethylene ether-type resole resin emulsion of Comparative Example 2, which is preferable. It was able to be of a standard level.
Moreover, the resole resin emulsion with little content of unreacted phenols and unreacted aldehydes was able to be obtained.

  The resol type phenol resin emulsion obtained by the production method of the present invention is useful as, for example, an adhesive, a water-based paint, a binder for inorganic fibers such as rock wool and glass fibers, an organic fiber such as pulp, and a latex compounding agent. It is excellent in workability, environmental pollution, and price.

Claims (11)

A resol-type phenol resin emulsion containing a resol-type phenol resin and a water-soluble polymer compound, wherein the resol-type phenol resin is bonded to aldehydes bonded with aromatic rings derived from phenols. The ratio of the dimethylene ether group and / or the substituted dimethylene ether group is 1 to 10 mol%, and the ratio of the methylene group and / or the substituted methylene group is 70 to 90 mol% with respect to all the derived bonding groups. A resol-type phenolic resin emulsion characterized by The resol-type phenol resin milk according to claim 1, wherein the resol-type phenol resin has a content of unreacted phenols and unreacted aldehydes of 2% by weight or less based on the whole resol-type phenol resin. Muddy liquid. The resol type phenol resin emulsion according to claim 1 or 2, wherein the resol type phenol resin has a number average molecular weight of 500 to 1200. It is a manufacturing method of the resol type phenol resin emulsion in any one of Claims 1 thru | or 3,
(A) a step of synthesizing a novolac type phenol resin by reacting a phenol and an aldehyde under an acidic catalyst,
(B) a step of synthesizing a resol type phenol resin by reacting the novolac type phenol resin and an aldehyde in the presence of a divalent metal salt; and
(C) a step of adding a water-soluble polymer compound during or after the synthesis of the resol type phenolic resin, and emulsifying the resol type phenolic resin,
A process for producing a resol type phenol resin emulsion characterized by comprising: The method for producing a resol type phenol resin emulsion according to claim 4, wherein the acidic catalyst contains an organic phosphonic acid. The method for producing a resol type phenol resin emulsion according to claim 4 or 5, wherein the organic phosphonic acid is represented by the following general formula (I).
R-PO (OH) ₂ (I)
(R is a group containing a carbon atom and containing —COOH and / or —PO (OH) _2. ) The method for producing a resol type phenol resin emulsion according to claim 4, wherein the acidic catalyst contains phosphoric acids. The method for producing a resol type phenol resin emulsion according to claim 7, wherein in the step (a), 0.2 mol or more of the phosphoric acid is used with respect to 1 mol of the phenol. The method for producing a resol type phenol resin emulsion according to claim 7 or 8, wherein the phosphoric acid contains phosphoric acid. The resol type phenolic resin milk according to any one of claims 4 to 9, wherein the novolac type phenolic resin has a number average molecular weight of 300 to 1,000 and a dispersity of a molecular weight distribution of 1.15 to 1.6. A method for producing a suspension. The said novolak-type phenol resin has a content of unreacted phenols and unreacted aldehydes of 2% by weight or less, respectively. Production of a resol-type phenol resin emulsion according to any one of claims 4 to 10. Method.