JPS6151019A - Fine spherical resol resin particle and its production - Google Patents

Abstract

PURPOSE:To obtain fine spherical resol particles excellent in flow property, moldability and storage stability, by reacting a phenol with an aldehyde in an aqueous medium in the presence of both of a basic catalyst and a water-insoluble inorganic salt. CONSTITUTION:The reaction of a phenol with an aldehyde in an aqueous medium in the presence of a basic catalyst, is performed by adding a substantially water-insoluble inorganic salt to the reaction system to obtain fine spherical resol resin particles each of which is surface-treated partially or entirely with the water-insoluble inorganic salt and has a particle diameter <=500mu. Said water-insoluble inorganic salt comprises at least one selected from the group consisting of calcium fluoride, magnesium fluoride and strontium fluoride and is used in an amount of preferably 0.2-10wt% based on the phenol.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to microspherical solid resol resin particles having thermal reactivity and excellent storage stability, and a method for producing the same.

<Prior art> Resol resin (membrane phenolic resin) is produced by combining phenols such as phenol and cresol with aldehydes such as formaldehyde and acetaldehyde and a basic catalyst such as aqueous ammonia, organic amine, and sodium hydroxide. It is a resin obtained by polycondensation in the presence of.

Novolac resins (two-step phenolic resins) usually use a crosslinking agent such as hexamethylenetetramine as a curing agent during heat curing, whereas resol resins contain many methylol groups in their molecules, so no curing agent is used. It can be heat-cured alone without using it. In this way, since resol resin has extremely high reactivity8, the solid content is usually 50 to 60%.
It was manufactured as a water or methanol solution of about 1.5% and was stored as a solution, making it difficult to remove it from the solution as a stable solid in the form of a single grain or powder. Various proposals have been made to plan the production of resol resin9, for example,
No. 077 discloses that a hydrophilic substance such as gelatin, casein, or polyvinyl alcohol is added to a condensate obtained by reacting phenols and formaldehyde using a basic catalyst in the presence of a nitrogen-containing compound such as ethylenediamine. A method for producing resol resin in the form of one grain or powder by adding and reacting organic compounds is also disclosed in JP-A-52-14.
No. 1893 discloses the production of granular resol resin by emulsion polymerization of phenol, formaldehyde, and a basic catalyst such as ammonia in the presence of a protective colloid such as gum arabic, gum gafti, hydroxyalkyl guar gum, or partially hydrolyzed polyvinyl alcohol. A method is disclosed.

However, all of these methods use hydrophilic organic polymer compounds as emulsion stabilizers;
Since the resol resins obtained by these methods contain hydrophilic organic polymer compounds, the performance of molded products obtained from them decreases, and the resin particles may fuse (Sin) during storage.
It has the disadvantage of causing a lot of damage (tering).

In order to eliminate such drawbacks, Unexamined Patent Publication E1g57-17
Publication No. 7011 discloses that phenols and a large excess of formaldehyde (8 to 10
Disclosed is a method for producing fine-grained solid thermosetting phenolic fats by reacting them with 2 times the molar amount.

However, resins produced by this method have poor flow characteristics and therefore poor moldability.

It also has the disadvantage of slow curing speed.

<Problems to be Solved by the Invention> In view of the above circumstances, the present inventors have conducted intensive studies on the development of microspherical solid resol resins with excellent properties, and as a result, have found that phenols and aldehydes are During emulsion polymerization, by coexisting with substantially water-soluble inorganic salts, emulsion polymerization can be carried out extremely stably.

Furthermore, it has been found that microspherical solid resol resin particles having excellent resin properties can be produced.

The present invention was made based on this knowledge,
The purpose is to provide microspherical resol resin particles having a particle size of 500 μm or less and a method for producing the same. - Another object of the present invention is to provide microspherical resol resin particles with excellent storage stability and a method for producing the same.

Another object of the present invention is to provide microspherical resol resin particles having good flow characteristics and thermal reactivity and good moldability, and a method for producing the same.

Still another object of the present invention is to provide a microspherical resol resin and a method for producing the same, which can produce a molded product with excellent performance and quality without deteriorating the performance of the molded product.

<Means for Solving the Problems> However, the features of the present invention that achieve such objects are as follows: 1. Part or all of the surface is coated with an inorganic salt that is substantially insoluble in water, and the particle size is When reacting phenols and aldehydes in microspherical resol resin particles with a size of 500 μ or less and an aqueous medium in the presence of a basic catalyst,
The reaction system is made to coexist with an inorganic salt that is substantially insoluble in water, and the reaction is carried out to form microspheres with a particle size of 500 μm or less whose surface is partially or entirely coated with an inorganic salt that is substantially insoluble in water. The objective is to generate resol resin particles.

The present invention will be further explained in detail below.

The substantially water-insoluble inorganic salts referred to in the present invention are 25
Refers to inorganic salts having a solubility in water of 0.2 g/β or less at ℃.1 For example, calcium fluoride.

Magnesium fluoride, strontium fluoride, calcium phosphate, magnesium phosphate, barium phosphate, aluminum phosphate, barium sulfate, calcium sulfate, zinc hydroxide, aluminum hydroxide.

Examples include iron hydroxide, especially calcium fluoride.

Magnesium fluoride and strontium fluoride are preferred.

The microspherical resol resin particles according to the present invention are formed by coating the resin surface with the above-mentioned substantially water-insoluble inorganic salts, and one embodiment thereof will be described below.

Figure 1 (tag, tb) is a scanning electron micrograph showing an example of the microspherical resol resin particle structure of the present invention.
Very fine, substantially water-insoluble inorganic salts are deposited on the particle surface and cover the surface of each particle. The coating of the particle surface with this substantially water-insoluble inorganic salt is carried out as described below (
When phenols and aldehydes are reacted in an aqueous medium in the presence of a basic catalyst, substantially water-insoluble inorganic salts are allowed to coexist. A desired HH effect can be obtained by appropriately changing the amount added and the like.

The resol resin particles of the present invention coated with the substantially water-insoluble inorganic salt are shown in FIG. 1(a).

As shown in tb), the particles exhibit a microspherical shape with a particle size of 500 μm or less. That is, the resol resin particles of the present invention are different from conventional powder or granular particles.

Each particle is microspherical, and no fusion of particles is observed.In this way, the resol resin particles of the present invention exhibit a microspherical shape,
It is presumed that the reason why no fusion is observed is that the substantially water-insoluble non-salt coating material, which is formed in the production method described below, prevents the particles from fusion during resin production and storage.

Thus, since the resol resin particles of the present invention having the above-mentioned structure have their surfaces coated with substantially water-insoluble inorganic salts, they have excellent storage stability and can last for more than one year. It can be stored without causing A-arrival, and FL
Since they are microspherical particles with a diameter of 500 μm or less, they are easy to handle during molding and other uses.

Next, a method for producing the microspherical resol resin particles of the present invention will be explained.

First, in the method of the present invention, when phenols and aldehydes are reacted in an aqueous medium in the presence of a basic catalyst, a substantially water-insoluble inorganic salt is allowed to coexist in the reaction system. The phenols used here are phenol and phenol F4, and the phenol derivatives include m-alkylphenol substituted with an alkyl group having 1 to 9 carbon atoms, ○-alkylphenol, P
-alkylphenol, specifically m-cresol,
Examples include pwter-butylphenol, O-probyrfuninol, resorcinol, bisphenol A, and halogenated phenol derivatives in which part or all of the hydrogen atoms of the benzene nucleus or alkyl group of these are imitated with chlorine or bromine. One or more of these are used. Note that the phenols are not limited to these, and any other compound containing a phenolic hydroxyl group can be used.

In addition, 8 aldehydes used in the present invention:=.

For example, formaldehyde in any form such as formalin or formaldehyde and furfural are used, and the molar ratio of aldehydes to phenols is 1 to 2.
．． Preferably it is 1.1 to 1.4.

In addition, as the basic conspiracy used in the method of the present invention, 1
Basic catalysts commonly used in the production of resol resins can be used, including aqueous ammonia, hexamethylenetetramine, and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The molar ratio of these basic catalysts to phenols is 0.02
~0.2 is preferred.

As the substantially water-insoluble inorganic salts that are allowed to coexist when the phenols and aldehydes are reacted in the presence of a basic catalyst, calcium fluoride, magnesium fluoride, strontium fluoride, etc. are preferably used as described above. , the process has a content of 0.2 to 10 wt% relative to phenols,
Preferably it is 0.5 to 3.5 wt%. In addition, in order to add substantially water-insoluble inorganic salts, the substantially water-insoluble inorganic salts may be directly added as described above,
In addition, two or more water-soluble inorganic salts may be added such that substantially water-insoluble inorganic salts are produced during the reaction, i.e., water-soluble At least one selected from the group consisting of sodium fluoride, potassium fluoride, and ammonium fluoride on one side of the inorganic salts and calcium on the other side.

Chlorides and sulfates of magnesium and strontium.

At least one member selected from the group consisting of nitrates is added during the reaction to produce calcium and magnesium.

It is also possible to generate a fluorine compound of strontium.

The reaction of the method of the invention is carried out in an aqueous medium.

In this case, the amount of water to be charged is 1. For example, the solid content concentration of the resin is 30 to 70 wt%, preferably 50 to 60 wt%.
%.

The reaction was carried out at a temperature increase rate of 0.5 to 1.5°C/min under stirring.
.

The temperature is gradually increased, preferably at a rate of 0.8 to 1.2°C/min, and the reaction temperature is 70 to 90°C.
~87°C for 60-150 minutes, preferably 80-110 minutes
Let it react for a minute. After reacting in this manner, one reactant is cooled to 40° C. or lower to obtain a stable aqueous emulsion of solid resol.

Next, this aqueous emulsion is divided into solid and liquid parts according to a conventional method such as filtration or centrifugal separation, and then washed and dried to obtain a particle size of 500 ml, the surface of which is coated with substantially insoluble inorganic salts.
Solid, microspherical resol resin particles of the present invention with a size of less than μ are obtained.

Although the method of the present invention can be carried out by either a continuous method or a punch method, 9 it is usually carried out by a punch method.

As described above, the resol resin particles obtained by the method of the present invention are smooth microspherical patterned particles with no melting and waxing, and as described above (in addition to being highly stable),
Good flow properties and poor formability. Furthermore, the microspherical resol resin particles obtained by the method of the present invention have good reactivity, a high gelation rate, can be molded in a short time, and the performance and quality of the molded product are also good. Furthermore, the microspherical resol resin particles obtained by the method of the present invention have a particle size of 5.
00μ or less, and most of them are 100μ or less.

The particle size distribution is extremely sharp compared to the granular resol resin produced by the conventional method, and this confirms that the emulsion stabilization method of the present invention is an extremely superior method.

The microspherical resol resin particles of the present invention are generally used as moldable solid resol resins.

The aqueous emulsion of the solid resol obtained after the above-mentioned reaction can also be used as is for adhesives and the like.

In addition, the resol resin particles of the present invention can be applied to all fields in which ordinary phenolic resins are used, such as products and binders. It can also be used in combination or in a blend with other rice-rich molecules such as polyvinyl formal, nylon, etc.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 200 g of phenol, 37% in 12 Mitsuro flasks
200 g of formalin, 70 g of water, 18 g of hexamethylenetetramine, and 8.4 g of calcium chloride are poured into a uniform layer while stirring. It was a long night, and I had one child on this night! $
Add 4 h of a 10% solution of sodium fluoride under 60
The temperature was raised to 85° C. for 900 minutes at the same temperature to obtain an emulsion of microspherical resol resin.

The flask contents were then cooled to 30°C and 0.5
After adding 73 cm of water, the supernatant liquid was removed, and the microspheroidal resin particles in the lower layer were washed with water and air-dried.Next, this was dried at 50 to 60°C under reduced pressure (5 mmHε or less). Microspherical resin particles with an average particle size of about 50 μm were obtained. (
Resin A) Example 2 17! Phenol 200F in a Mitsuro flask, 3
7% formalin 257g, 28% ammonia water 64.
Add 2g while stirring to make a uniform liquid, and reduce to this volume. Potassium fluoride at night5. ag, calcium chloride8.
Calcium fluoride dispersion 54, 28 prepared separately from 4g of calcium fluoride and 40g of water was added under stirring, and 87g of calcium fluoride was added in 40 minutes.
℃ and reacted for 85 minutes at the same temperature.
Post-treatment was carried out in the same manner as in Example 1, and the average particle size was approximately 70μ.
Microspherical resol resin particles were obtained. (Resin B) Example 3 190 phenol instead of 200 g of raw material phenol
The reaction and post-treatment were carried out in the same manner as in Example 1, except that a mixture of 10 g of Pwter-butylphenol and 10 g of Pwter-butylphenol was used to obtain microspherical Resono C resin particles with an average particle size of about 50 μm. (Resin C) Example 4 The reaction and post-treatment were carried out in the same manner as in Example 1, except that 718 g of diethylene triamine was used instead of 18 g of hexamethylenetetramine as a basic catalyst, and the average particle size was about 4.
A microspherical resol resin with a diameter of 0μ was obtained. (Resin D) Example 5 Bisphenol 2 instead of 200g of raw material phenol
The reaction and post-treatment were carried out in the same manner as in Example 1, except that 00g was used, to obtain microspherical resol resin particles with an average particle size of about 80μ. (Resin E) Comparative Example 1 A particulate resol resin was produced with reference to the method described in JP-A-52-141893.

That is, in place of the calcium fluoride dispersion of inorganic salts in Example 2, 40 g of a 10 wt % gum arabic aqueous solution was used as the 8m colloid, and the reaction and post-treatment were carried out in the same manner as in Example 2. Some of the resin particles were fused to form a lump with a diameter of about 5 mm. This lump was crushed to obtain microspherical resin. (Resin F) Comparative Example 2 A microspherical phenol resin was produced with reference to the method of Takashi in Japanese Patent Application Laid-Open No. 57-177011.

That is, 37% formalin 4 was added to a 2β Mitsuro flask.
05g of 35% hydrochloric acid, and 881g of water were added, and to this was added a mixed aqueous solution of 62.5B of 50g of phenol, 8.4g of 37% formalin, and 4.1g of water. After stirring for 20 seconds, the mixture was allowed to stand still for 60 minutes. The mixture was heated to 80°C over 60 minutes with occasional stirring, stirred at the same temperature for 30 minutes, and then the contents were cooled to 30°C and filtered.

After washing with water and drying, fine particulate Funinol resin having an average particle size of about 30 μm was obtained. (Resin G) Reference Example 1 The flow characteristics of the resins A-G obtained in Examples 1 to 5 and Comparative Examples 1 to 2 above were measured in accordance with JIS K-6911, and the gel flow characteristics on a 150°C hot plate were measured. Table 1 shows the results of measuring the curing time.

Table 1 As is clear from Table 1, Comparative Resin G has an unmeasurable gelation time, slow curing speed, and poor flow characteristics, whereas Resins A to E of the present invention have poor flow properties. Both have good flow properties and thermal reactivity.

In addition, when the above resins A to G were left in a thermostatic chamber at 30°C and 85% relative humidity for one month and changes in the properties of the resins were investigated, it was found that the particles of resin F melted and solidified, but , other resins A-E of the present invention, and comparative resin C were spherical with a minute Ej and had free-flowing properties.

<Effects of the Invention> As stated above, the surface of the microspherical resol resin particles of the present invention is substantially coated with water-soluble inorganic salts, so that storage stability is improved. Particles can be stored for long periods without deterioration. Since the reeds are microspherical solid particles with a particle diameter of 500 μm or less, they are easy to handle during use, unlike conventional solutions or powders.

In addition, since the method of the present invention involves coexisting inorganic salts that are substantially insoluble in water in the reaction system,
Not only can it be stably produced as microspherical solid particles of 0 μ or less, but also microspherical solid particles with a sharper particle size distribution can be obtained compared to granular resol resin produced by conventional methods. . Moreover, the microspherical resol resin particles obtained by the method of the present invention do not deteriorate the performance of molded products unlike the above-mentioned resol resin containing a hydrophilic organic polymer compound, and can produce molded products with excellent performance and quality. can be obtained.

Furthermore, the microspherical resol resin particles obtained by the method of the present invention have good flow characteristics and good moldability, and also have a fast gelation rate and good reactivity, and can be molded in a short time. It also has the characteristics of 9+h, and the effects of the present invention in terms of production are extremely significant, and its industrial significance is extremely large.

[Brief Description of the Drawings] Figure 1 (al, (bl) are electron micrographs (magnification: 300x) showing an example of the microspherical resol resin particle structure of the present invention. Patent applicant: Unitika Co., Ltd. Correct; (spontaneous) 1. Indication of the case Japanese Patent Application No. 150399/1982 2. Name of the invention: Microspherical resol resin particles and its manufacturing method 3. Person making the amendment Relationship with the case Patent applicant address Higashi, Amagasaki City, Hyogo Prefecture Honmachi 1-50 54
1 Address 4-68 Kitakyutabe-cho, Higashi-ku, Osaka @Place name
Uni Jinriki Company Patent Department Tel: 06-281-5258 (dial-in) 4. Detailed explanation of the invention of the specification subject to amendment ♂ and brief explanation of the drawings column 5. Contents of the amendment (11. "Water-soluble" in line 4 of page 6 is corrected to "insoluble in water." (2) "When causing" in line 8 of page 7 of the specification is corrected to "when causing." (3) "Coating with salts" on page 9, line 8 of the specification is corrected to "coating with salts." (4) "It is possible," on page 14, line 10 of the specification is corrected to "possible." (5) On page 14 of the specification, lines 10 to 14, "phenol can be..." is corrected to the following sentence. The resol resin particles may optionally contain one or more additives such as a thermoplastic resin, a thermosetting resin, a flame retardant, a blowing agent, a reinforcing agent, a filler, an extender, an electroconductive agent, or a facial cleanser. It can be used in combination with the above. Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, rubber-modified polystyrene, A
S, ABS, polyolefins such as polyvinyl chloride, polymethyl methacrylate, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate. Polyesters such as polyarylates, polyamides such as polycaprolactam, polyhexamethylene adipamide,
Examples include polysulfone and polyphnynylene sulfide. Examples of thermosetting resins include melamine resins, urine resins, furan resins, alkyd resins, and unsaturated polyester resins. Examples of flame retardants include halogen compounds such as decabromodiphenyl ether, inorganic and organic phosphorus compounds, and the like. Examples of reinforcing agents, fillers, extenders, etc. include glass fibers, asbestos fibers, and carbon fibers. Metal Fiber 1 Examples include quartz, mica, asbestos, kaolin, talc, aluminum oxide, silica, aluminum hydroxide, and altimony dioxide. Other additives include titanium oxide, iron oxide, aluminum powder, iron powder, metal stone, carbon blank, wood powder 5 paper, and the like. (6) Specification page 20, lines 11-12 r C $3
00 times)
3000 times).”

Claims (7)

[Claims] (1) Microspherical resol resin particles characterized in that part or all of the surface is coated with a substantially water-insoluble inorganic salt, and the particle size is 500 μm or less. (2) The microspherical resol according to claim 1, wherein the substantially water-insoluble inorganic salt is at least one selected from the group consisting of calcium fluoride, magnesium fluoride, and strontium fluoride. resin particles. (3) A surface characterized in that when phenols and aldehydes are reacted in an aqueous medium in the presence of a basic catalyst, a substantially water-insoluble inorganic salt is allowed to coexist in the reaction system. A method for producing microspherical rezone resin particles, some or all of which are coated with a substantially water-insoluble inorganic salt and have a particle size of 500 μm or less. (4) The microspherical resol resin according to claim 3, wherein the substantially water-insoluble inorganic salt is at least one selected from the group consisting of calcium fluoride, magnesium fluoride, and strontium fluoride. Method of manufacturing particles. (5) Microspheres according to claim 4, in which at least one selected from the group consisting of calcium fluoride, magnesium fluoride, and strontium fluoride coexists in an amount of 0.2 to 10 wt% relative to the phenol. Method for producing resol resin particles. (6) A patent claim in which at least one member selected from the group consisting of calcium fluoride, magnesium fluoride, and strontium fluoride is precipitated in a reaction system using two or more water-soluble inorganic salts. A method for producing microspherical resol resin particles according to item 4 or 5. (7) The water-soluble inorganic salt is selected from the group consisting of at least one selected from the group consisting of sodium fluoride, potassium fluoride, and ammonium fluoride, and chlorides, sulfates, and nitrates of calcium, magnesium, and strontium. 7. The method for producing microspherical resol resin particles according to claim 6, which is at least one type of microspherical resol resin particles.