JPH0717812B2 - Granular resole resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a thermosetting granular resol resin composition comprising a filler and a resole resin, which is excellent in moldability and storage stability, and a method for producing the same. .

<Prior art><Problems to be solved by the invention> Phenolic resin is obtained by reacting phenols and aldehydes in the presence of a basic catalyst with a resole resin obtained in the presence of an acidic catalyst. The resulting novolak resins are roughly classified. Since resole resin contains many methylol groups in the molecule, it is suitable for melt molding because it can be cured by heating without using a curing agent.

However, since the resole resin has extremely high reactivity, there is a problem that it is difficult to store it in a powder or granular form as it is, and it has been desired to produce a stable solid resole resin suitable for melt molding.

Therefore, various methods for producing a solid resol resin that are easy to handle and have good storage stability have been proposed. For example, Japanese Patent Publication Sho 53-
In the 42077 publication, a condensate obtained by reacting phenols and formaldehyde in the presence of an aliphatic amine such as ethylenediamine using a basic catalyst is added with a hydrophilic organic compound such as gelatin, casein or polyvinyl alcohol. To produce a granular or powdery resol resin, and in JP-A-52-141893, phenol, formaldehyde, and a basic catalyst such as ammonia are added to gum arabic, gatch gum, and hydroxyalkyl guar gum. Alternatively, a method for producing a granular resol resin by emulsion polymerization in the presence of a protective colloid such as partially hydrolyzed polyvinyl alcohol is disclosed.

However, in all of these methods, a hydrophilic organic compound is used as an emulsion stabilizer, and the resole resin obtained by these methods contains a hydrophilic organic polymer compound.
ing).

On the other hand, a composition comprising a filler and a phenol resin, which aims to improve the mechanical strength of the phenol resin, is known. However, the conventionally known method of producing a composition comprising a filler and a phenol resin is to mix a curing agent, a filler, a release agent, a pigment, etc. with a resole resin or a novolac resin with a hot roll mill, melt extrusion, Banbury mixer, etc. and then cool. Since it is crushed, there is a problem that it requires two steps of mixing the filler and crushing the composition composed of the filler and the phenol resin.

Japanese Unexamined Patent Publication (Kokai) No. 54-88995 discloses a method for producing a granular resol resin composition comprising a filler and a resole resin, which are capable of emulsion polymerization of phenol and formaldehyde in the presence of the filler.

According to this method, the step of compounding the filler and the step of crushing the composition of the filler and the resole resin described above are unnecessary, and the manufacturing process of the granular resole resin composition of the filler and the resole resin is extremely simplified. There is an advantage that However, even in this method, since the hydrophilic organic compound is used as the emulsion stabilizer, not only the properties of the molded article obtained by using this composition are deteriorated but also the above-mentioned problem of fusion during storage occurs. Still not resolved.

<Means for Solving Problems> The present invention solves the above conventional problems.

That is, the first object of the present invention is to provide a simple method for producing a granular resole resin composition comprising a filler and a resole resin which are easily cured by heating and have excellent mechanical strength.

A second object of the present invention is to provide a granular resol resin composition comprising a filler and a resole resin having excellent storage stability, and a simple method for producing the same.

As a result of earnest research to solve such problems, the present inventors can achieve the above object by producing a resole resin in the presence of a filler using a specific inorganic salt as an emulsion stabilizer. The inventors have found that and reached the present invention.

That is, the present invention comprises a filler and a resole resin,
The proportion of the filler is 20 to 200 wt% with respect to the phenols constituting the resol resin, and part or all of the surface is covered with a substantially water-insoluble inorganic salt containing a fluorine atom. And a granular resol resin composition characterized by reacting phenols and aldehydes in an aqueous medium in the presence of a basic catalyst, a filler and a substantially water-insoluble inorganic salt containing a fluorine atom. It is composed of a filler and a resole resin characterized in that the proportion of the filler is 20 to 20 relative to the phenols constituting the resole resin.
It is 0 wt% and is a method for producing a granular resole resin composition in which a part or all of the surface is coated with a substantially water-insoluble inorganic salt containing a fluorine atom.

Hereinafter, the present invention will be described in more detail.

FIG. 1 is an example of an electron micrograph of a granular resole resin composition comprising the filler of the present invention and a resole resin. It can be observed that the granular resol resin composition of the present invention is particles independent of each other and that the surface of the particles is covered with the inorganic salt containing a fluorine atom.

The substantially water-insoluble inorganic salt containing a fluorine atom referred to in the present invention has a solubility in water at 25 ° C. of 0.2 g /
The following inorganic salts containing a fluorine atom are mentioned, and examples thereof include calcium fluoride, magnesium fluoride and strontium fluoride, and calcium fluoride is particularly preferable.

A granular resol resin composition comprising a filler and a resol resin according to the present invention has a particle surface coated with the above-mentioned substantially water-insoluble inorganic salt. The embodiment will be described below. .

The coating of the substantially water-insoluble inorganic salt containing a fluorine atom on the particle surface is performed by reacting phenols and aldehydes in an aqueous medium in the presence of a basic catalyst and a filler, as described later. At this time, it is formed by coexisting a substantially water-insoluble inorganic salt containing a fluorine atom, and its coating amount is a desired amount by appropriately changing the addition amount of the substantially water-insoluble inorganic salt. Can be adjusted to.

In the granular resole resin composition of the present invention, no fusion of particles is observed as illustrated in FIG. As described above, no fusion is observed in the granular resol resin composition of the present invention when the coating of the substantially water-insoluble inorganic salt containing a fluorine atom formed in the production method described later is performed during resin production. It is also presumed that it prevents fusion of particles during storage. Although some of these inorganic salts are taken in the inside of the particles, most of them are present on the surface.

Thus, since the surface of the granular resol resin composition of the present invention having the above structure is coated with a substantially water-insoluble inorganic salt containing a fluorine atom,
It has excellent storage stability and can be stored for over a year without fusion of particles, and it is easy to handle during use such as molding.

Examples of the filler used in the present invention include silicates such as calcium silicate, magnesium silicate and aluminum silicate, carbonates such as calcium carbonate and magnesium carbonate,
Antimony trioxide, titanium oxide, iron oxide, magnesium oxide, metal oxides such as aluminum oxide, sulfates such as barium sulfate, sulfides such as molybdenum disulfide, quartz, mica, glass, graphite, carbon black, talc, Kaolin and the like are preferable, and one or more of these can be used.

Next, a method for producing the granular resol resin composition of the present invention will be described.

First, the method of the present invention comprises reacting phenols and aldehydes in an aqueous medium in the presence of a basic catalyst, a filler and a substantially water-insoluble inorganic salt containing a fluorine atom. Phenols used here are phenol and phenol derivatives. Examples of the phenol derivative include m-alkylphenol, o-alkylphenol and p-alkylphenol substituted with an alkyl group having 1 to 9 carbon atoms, specifically, Examples include m-cresol, p-ter-butylphenol, o-propylphenol, resorcinol, bisphenol A, and halogenated phenol derivatives in which some or all of the hydrogen atoms of the benzene nucleus or alkyl groups thereof are replaced with chlorine or bromine. One or more of these are used. The phenols are not limited to these, and any other compound containing a phenolic hydroxyl group can be used. The aldehydes used in the present invention include
Examples include formaldehyde and furfural in any form of formalin or paraformaldehyde, and the molar ratio of aldehydes to phenols is 1 to
2, particularly 1.1 to 1.4 are preferable.

Preferred fillers used in the present invention include silicates, carbonates, metal oxides, sulfates, sulfides, quartz, mica, glass, graphite, carbon black, talc and kaolin as described above. However, it is preferable that the average particle size is about 100 μm or less.
The amount used is 20-200wt with respect to phenols.
%, Especially 50 to 150 wt%.

Further, as the basic catalyst used in the method of the present invention, a basic catalyst used in ordinary resol resin production can be used. For example, in addition to ammonium water, hexamethylenetetramine and dimethylamine, diethylenetriamine, polyethyleneimine and other fats can be used. Group amines and the like can be mentioned. The molar ratio of these basic catalysts to phenols is 0.02 to 0.
2 is preferred.

As the substantially water-insoluble inorganic salt containing a fluorine atom used in the present invention, as described above, calcium fluoride, magnesium fluoride and strontium fluoride are preferable, and calcium fluoride is particularly preferable. The amount used is 0.2-10 wt% relative to phenols, especially 0.5-
3.5 wt% is preferred. In addition, in order to add the above-mentioned substantially water-insoluble inorganic salts, the above-mentioned substantially water-insoluble inorganic salts may be directly added. You may add 2 or more types of water-soluble inorganic salts so that inorganic salts may be produced. That is, for example, instead of the fluorine compound of calcium, magnesium, strontium, at least one selected from the group consisting of sodium fluoride, potassium fluoride, and ammonium fluoride as one of the water-soluble inorganic salts and calcium, magnesium strontium as the other It is also possible to add at least one selected from the group consisting of chlorides, sulfates and nitrates to produce a fluorine compound of calcium, magnesium and strontium during the reaction.

The reaction of the method of the present invention is carried out in an aqueous medium. In this case, as the charged amount of water, for example, the solid content concentration of the resin is 30 to
It is desirable to set it to 70 wt%, preferably 50 to 60 wt%.

The granular resol resin composition of the present invention is produced, for example, as follows.

Phenols, aldehydes, fillers, basic catalysts and the above inorganic salts in an aqueous medium are stirred and the temperature rising rate is 0.5 to 1.5.
The temperature is gradually raised at a rate of 0.8 to 1.2 ° C / min, and the reaction is performed at a reaction temperature of 70 to 90 ° C, preferably 83 to 87 ° C for 60 to 150 minutes, preferably 80 to 110 minutes. After the reaction in this way, the reaction product is cooled to 40 ° C. or lower to obtain a stable solid modified resol aqueous emulsion.

Then, this aqueous emulsion is separated into solid and liquid by a conventional method such as filtration or centrifugation, washed, and dried to form a granular material whose surface is coated with a substantially insoluble inorganic salt containing a fluorine atom. A resol resin composition is obtained.

The method of the present invention can be carried out by either a continuous method or a batch method, but is usually carried out by the batch method.

As described above, the granular resol resin composition obtained by the method of the present invention is dry and non-fusing particles, and as described above, has excellent stability, good flow characteristics, and excellent moldability. There is. Further, the granular resol resin composition prepared by the method of the present invention has good reactivity, a high gelation rate, can be molded in a short time, and has excellent performance and quality of the molded product. Furthermore, the granular resole resin composition obtained by the method of the present invention has a particle size of 500 μm or less, most of which is 100 μm or less, and the particle size distribution is extremely sharp. It is acknowledged that it is an excellent method.

In the method of the present invention, when reacting phenols and aldehydes in an aqueous medium in the presence of a basic catalyst, a filler and a substantially water-insoluble inorganic salt containing a fluorine atom, if necessary, Various additives such as flame retardants such as phosphorus and foaming agents can be made to coexist.

The granular resol resin composition of the present invention is usually used as a moldable solid resol resin composition, but it can also be used as an adhesive or the like as an aqueous emulsion of the solid resol resin composition obtained after the above reaction.

The granular resol resin composition of the present invention contains a thermoplastic resin, a thermosetting resin, a flame retardant, a foaming agent, a reinforcing agent, if necessary.
Fillers, extenders, leveling agents, flow control agents, stabilizers, antistatic agents, electrical conductors or dyes and pigments can be included.

Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, rubber-modified polystyrene, AS,
ABS, polyvinyl chloride, polymethylmethacrylate, polyolefin such as ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyester such as polyarylate, polycaprolactam, polyamide such as polyhexamethylene adipamide, Examples thereof include polysulfone and polyphenylene sulfide.

Examples of the thermosetting resin include melamine resin, urea resin, furan resin, alkyd resin, unsaturated polyester resin and the like.

Examples of the flame retardant include halogen compounds such as decabromodiphenyl ether, and inorganic and organic phosphorus compounds.

Examples of the reinforcing agent, filler, extender and the like include glass fiber, asbestos fiber, carbon fiber, metal fiber, quartz, mica, asbestos, carion, aluminum oxide, silica, aluminum hydroxide and antimony trioxide. Other additives include titanium oxide, iron oxide,
Aluminum powder, iron powder, metal soap, carbon black,
Wood flour, paper, etc. can be mentioned.

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

Example 1 200 g of phenol, 200 g of 37 wt% formalin, 200 g of talc having an average particle size of 10 μm, 70 g of water, 18 g of hexamethylenetetramine, and 8.4 g of calcium chloride were charged into the three-necked flask of Example 1 while stirring. 5.8 g of potassium fluoride was added to this solution with stirring, the temperature was raised to 85 ° C. in 60 minutes, and the mixture was reacted at the same temperature for 90 minutes to obtain an emulsion of the granular resin composition.

Next, the flask contents were lowered to 30 ° C., 0.5 water was added, the supernatant was removed, and the lower layer granulated resin composition was washed with water and air dried. Then, this is depressurized (5m
mHg or less) at 50 to 60 ° C. to obtain a granular resol resin composition composed of talc having an average particle size of about 100 μm and a resol resin. The surface of these particles was covered with fine particles of calcium fluoride as shown in FIG.

Example 2 The same treatment as in Example 1 was carried out except that 200 g of kaolin having an average particle size of about 10 μm was added instead of talc, and the average particle size was about 10
A granular resin composition consisting of 0 μm kaolin and a resole resin was obtained. The surface of these particles was covered with fine particles of calcium fluoride as shown in FIG.

Example 3 The same treatment as in Example 1 was carried out except that 200 g of TiO ₂ having an average particle size of about 2 μm was added instead of talc, and an average particle size of about 80 μm.
m granular TiO ₂ and a resol resin were obtained.

The surface of these particles was covered with fine particles of calcium fluoride as shown in FIG.

Comparative Example 1 It was synthesized according to the method described in JP-A-54-88995.
That is, 200 g of phenol, 200 g of TiO _{2 having} an average particle size of about 2 μm, 200 g of 37 wt% formalin, 18 g of hexamethylenetetramine, 120 g of water and 4 g of gum arabic were put into a three-necked flask of 1 with stirring, and the mixture was heated to 85 ° C. for 60 minutes. Raise the temperature to 90 at the same temperature
The reaction was carried out for a minute to obtain an emulsion of the resin composition. When the post-treatment was carried out in the same manner as in Example 1, some particles of the resin composition were fused during the drying to form a lump having a diameter of about 5 mm.

This lump was crushed to obtain a powdery resin composition.

Comparative Example 2 200 g of resole resin powder (Gunei Kagaku / PS-2173) and 200 g of talc having an average particle size of about 10 μm were kneaded with a hot roll and pulverized to produce a resin composition in a powder state having an average particle size of about 100 μm. .

Next, the resin compositions obtained in Examples 1, 2, and 3 and Comparative Examples 1 and ² were press-molded at a mold temperature of 160 ° C. and a molding pressure of 150 kg / cm ² for 10 minutes to obtain test pieces for measuring physical properties. Molded. Table 1 shows the measured values of physical properties.

The resin composition of the present invention not only does not cause fusion, but also has excellent physical properties.

<Effects of the Invention> The granular resole resin composition comprising the filler of the present invention and the resole resin does not cause fusion due to the surface being covered with the inorganic salt containing a fluorine atom, and is extremely excellent in storage stability. In addition to being manufactured, it is manufactured without using a hydrophilic protective colloid, so that it has excellent thermal stability during melt molding and various physical properties of the resulting molded product.

In addition, since the production method of the present invention produces a granular resole resin composition comprising a filler and a resole resin in a polymerization step, it requires more treatment steps than conventionally known production methods. It is greatly shortened and has a large economic effect.

[Brief description of drawings]

FIG. 1 is an electron micrograph (magnification: 3000 times) showing an example of the particle structure of the granular resol resin composition of the present invention.

Claims (2)

[Claims] 1. A filler and a resole resin, wherein the proportion of the filler is relative to phenols constituting the resole resin.
A granular resol resin composition having a content of 20 to 200 wt% and a part or all of the surface coated with a substantially water-insoluble inorganic salt containing a fluorine atom. 2. A filler characterized by reacting phenols and aldehydes in an aqueous medium in the presence of a basic catalyst, a filler and a substantially water-insoluble inorganic salt containing a fluorine atom. And the resol resin, and the proportion of the filler is 20% with respect to the phenols constituting the resol resin.
A method for producing a granular resol resin composition, the content of which is about 200 wt% and whose surface is partially or wholly coated with a substantially water-insoluble inorganic salt containing a fluorine atom.