JPH0582857B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Field of Application> The present invention relates to a microspherical resin composition composed of a resol resin and a thermoplastic resin, which is thermally reactive, exhibits extremely excellent adhesive properties when cured, and has excellent storage stability. It concerns the manufacturing method. <Prior art><Problems to be solved by the present invention> Resole resins are widely used as adhesives with excellent heat resistance and chemical resistance. Since the flexibility is poor, there is a problem in that the peel strength is low. On the other hand, although thermoplastic resins are flexible and have excellent peel strength, they are inferior in tensile strength and heat resistance, and both pose problems as so-called structural adhesives when used alone.
For this reason, compositions consisting of thermosetting resins and thermoplastic resins are considered preferable for structural adhesives used in aircraft, automobiles, and the like. In order to increase the adhesive strength of a composition consisting of a thermosetting resin and a thermoplastic resin, uniform and intimate mixing of both resins is considered to be an important element, and various mixing methods have been proposed. Conventionally known methods such as melt mixing method, solution mixing method, and mixing method during polymerization all have various problems and are not necessarily satisfactory.
Improvements were desired. For example, in the melt mixing method, a thermosetting resin and a thermoplastic resin are melt-mixed and extruded, but there is often a large difference in the softening temperature of the two resins, as well as a large difference in melt viscosity. Therefore, even melt extrusion is often difficult, and even if melt extrusion is possible, the degree of mixing is insufficient and the adhesive strength of the resulting composition is not necessarily satisfactory. In addition, in order to use the composition obtained by this method for powder applications, not only is a pulverization step required following the melt extrusion step, but the resulting powder shape is irregular and has poor fluidity, and handling is difficult. The problem was that it was difficult. On the other hand, the solution mixing method, which is most commonly used, has a high degree of mixing and can provide an adhesive with excellent adhesive strength. Since it is applied and dried, it not only causes environmental pollution due to solvent volatilization and economic problems due to unrecovered solvent, but also makes it difficult to provide a composition suitable for use in powder or solid form. Recently, The British
Polymer Journal, Vol15, March, 1983, (authors Christopher G. Demmer, Edward W.
The mixing method during polymerization published by Garnish, et al.
The resol resin is polymerized in the presence of a thermoplastic resin in an aqueous medium using an aqueous emulsion stabilizer, and the composition consisting of the resol resin and thermoplastic resin obtained by this method is solid or powder. It exists in the form of an aqueous emulsion that cannot be removed. Furthermore, in order to use it as an adhesive, it is necessary to dry the moisture in the area where the adhesive is applied, which requires time for adhesion, and there is a problem of foaming when the moisture evaporates. <Means for Solving the Problems> The present invention solves the above-mentioned conventional problems. That is, the first object of the present invention is to
An object of the present invention is to provide microspherical solid particles of a resin composition comprising a resol resin and a thermoplastic resin, and a method for producing the same. A second object of the present invention is to provide a microspherical resin composition that has thermal reactivity and exhibits excellent adhesive properties, and a method for producing the same. A third object of the present invention is to provide a microspherical resin composition that is solid and free of fusion and has excellent storage stability, and a method for producing the same. As a result of intensive research to solve these problems, the present inventors have found that the objective can be achieved by emulsion polymerization of resol resin in the presence of thermoplastic resin using inorganic salts as emulsion stabilizers. Heading, we arrived at the present invention. That is, the present invention provides a microorganism comprising a resol resin and a thermoplastic resin, whose surface is partially or entirely coated with an inorganic salt that is substantially insoluble in water, and whose particle size is 500 μm or less. Reacting a spherical resin composition, phenols and aldehydes in an aqueous medium in the presence of a substantially water-insoluble inorganic salt, a thermoplastic resin of 1 to 100 wt% based on the phenols, and a basic catalyst. A method for producing a microspherical resin composition whose surface is partially or entirely coated with a substantially water-insoluble inorganic salt and whose particle size is 500 μm or less. Hereinafter, the present invention will be explained in further detail. The thermoplastic resin referred to in the present invention may be any resin that can be dissolved in the phenols constituting the resol resin, such as polyethylene, polypropylene, polystyrene, AS,
Polyolefins such as ABS, polyvinyl acetal, and PMMA, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyacrylate, polyamides such as polycapramide, polyhexamethylene adipamide, polyundecanamide, and polylaurinamide, or their partial methoxymethyl Polyamides, copolymerized polyamides, polysulfones, polyphenylene sulfides, etc. are mentioned, and polyamides, polyvinyl acetals, etc. are particularly preferred. Partially methoxymethylated polyamide is one in which the hydrogen atoms bonded to the nitrogen atoms constituting the amide bonds are replaced with methoxymethyl groups, and the substitution rate is 20 to 50 mol%.
Preferably, the range is . In the present invention, the substantially water-insoluble inorganic salts have a solubility in water of 0.2 g/25°C.
Refers to the following inorganic salts, such as calcium fluoride, magnesium fluoride, strontium fluoride, calcium phosphate, magnesium phosphate, barium phosphate, aluminum phosphate, barium sulfate, calcium sulfate, zinc hydroxide, aluminum hydroxide, and hydroxide. Examples include iron, and calcium fluoride, magnesium fluoride, and strontium fluoride are particularly preferred. The microspherical resin composition according to the present invention is formed by coating the particle surfaces with the above-mentioned substantially water-insoluble inorganic salts, and embodiments thereof will be described below. FIG. 1 is a scanning electron micrograph showing an example of the structure of the microspherical resin composition of the present invention, in which extremely fine, substantially water-insoluble inorganic salts are deposited on the particle surface, covering the particle surface. There is. The coating of the substantially water-insoluble inorganic salts on the particle surface is effective when reacting phenols and aldehydes with a thermoplastic resin in the presence of a basic catalyst in an aqueous medium, as described below. It is formed by allowing water-insoluble inorganic salts to coexist with the coating material, and the desired coating amount can be obtained by appropriately changing the amount of the substantially water-insoluble inorganic salts added. The resin composition of the present invention coated with the substantially water-insoluble inorganic salt has a microspherical shape with a particle size of 500 μm or less, as shown in FIG. That is, in the resin composition of the present invention, each particle is microspherical, unlike conventional powder or granular ones, and no fusion of the particles is observed. As described above, the reason why the resin composition of the present invention has a microspherical shape and no fusion is observed is that the coating of substantially water-insoluble inorganic salts formed in the production method described below is formed during resin production and storage. It is presumed that this prevents particle fusion. Thus, the microspherical resin composition of the present invention having the above-mentioned structure has excellent storage stability because its surface is coated with a substantially water-insoluble inorganic salt, and particles do not melt for more than one year. In addition to being able to be stored without causing adhesion, since the particles are microspherical particles with a particle size of 500 μm or less, they are easy to handle during use such as molding. Next, a method for producing the microspherical resin composition 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 thermoplastic resin and a basic catalyst, substantially water-insoluble inorganic salts are allowed to coexist in the reaction system. .
The phenols used here are phenol and phenol derivatives, and examples of the phenol derivatives include m-alkylphenol substituted with an alkyl group having 1 to 9 carbon atoms, O-alkylphenol, P-alkylphenol, Specifically, m-cresol, p-ter-butylphenol, O-propylphenol, resorcinol,
Examples thereof include bisphenol A and halogenated phenol derivatives in which a part or all of the benzene nucleus or hydrogen atom of an alkyl group is substituted with chlorine or bromine, and one or more of these may be used. Note that the phenols are not limited to these, and any other compound containing a phenolic hydroxyl group can be used. Further, examples of the aldehydes used in the present invention include formaldehyde in any form such as formalin or paraformaldehyde, as well as furfural, and the molar ratio of the aldehydes to the phenols is 1 to 2, preferably 1.1 to 1.4. It is. As mentioned above, the substantially water-insoluble inorganic salts are preferably calcium fluoride, magnesium fluoride, strontium fluoride, etc., and the amount thereof is 0.2 to 10 wt%, preferably 0.5 to 3.5 wt%, based on the phenols. It is. In addition, in order to add substantially water-insoluble inorganic salts, the substantially water-insoluble inorganic salts may be directly added as described above, or the substantially water-insoluble inorganic salts added during the reaction may be added directly. Two or more types of water-soluble inorganic salts may be added so as to produce the following. That is, for example, instead of the fluorine compounds of calcium, magnesium, and strontium, one of the water-soluble inorganic salts is at least one selected from the group consisting of sodium fluoride, potassium fluoride, and ammonium fluoride, and calcium, At least one selected from the group consisting of chlorides, sulfates, and nitrates of magnesium and strontium may be added to generate fluorine compounds of calcium, magnesium, and strontium during the reaction. As mentioned above, the thermoplastic resin used in the present invention is preferably a polyamide such as polycapramide, polyhexamethylene adipamide, polyundecanamide, polylaurinamide, etc., and the amount thereof is determined based on the phenols constituting the resol resin. Against 1~
100wt%, preferably 10-90wt%, especially 20
~70wt% is preferred. If it is less than 1wt%, the peel strength of the adhesive layer will be significantly weakened, and if it is more than 100wt%, it will be difficult to form microspherical particles. Furthermore, as the basic catalyst used in the method of the present invention, basic catalysts commonly used in the production of resol resins can be used, such as aqueous ammonia, hexamethylenetetramine, and alkyl amines such as dimethylamine, diethyltriamine, and polyethyleneimine. etc. The molar ratio of these basic catalysts to the phenols is preferably 0.02 to 0.2. The reaction of the present invention is carried out in an aqueous medium, and in this case, the amount of water charged is preferably such that the solid content concentration of the resin is, for example, 30 to 70 wt%, preferably 50 to 60 wt%. The reaction of the present invention is
For example, the temperature is gradually increased under stirring at a heating rate of 0.5 to 1.5°C/min, preferably 0.8 to 1.2°C/min, and the reaction temperature is 70 to 90°C, preferably 83 to 87°C.
React for 60-150 minutes, preferably 80-110 minutes.
After reacting in this manner, the reactants are cooled to 40° C. or lower to obtain a stable solid aqueous emulsion of a resin composition consisting of a resol resin and a thermoplastic resin. Next, after separating the solid and liquid from this aqueous emulsion using a conventional method such as filtration or centrifugation, washing and drying the emulsion results in particle sizes of 500 μm or less whose surfaces are coated with substantially insoluble inorganic salts. A solid microspherical resin composition of the present invention 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 a batch method. In the method of the present invention, when phenols and aldehydes are reacted in an aqueous medium in the presence of a substantially water-insoluble inorganic salt, a thermoplastic resin, and a basic catalyst, a flame retardant such as phosphorus is optionally added. ,
Various additives such as fillers such as talc or foaming agents may be present. The resin composition obtained by the method of the present invention as described above is smooth, non-fused microspherical solid particles, and as described above, has excellent stability, good flow characteristics, and moldability. Excellent. Furthermore, the microspherical resin composition produced by the method of the present invention has good reactivity and a fast gelation rate, can be molded in a short time, and has good performance and quality of molded products. Furthermore, the microspherical 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 has a smaller particle size distribution than the granular resin composition produced by the conventional method. They tend to be narrow. The microspherical resin composition of the present invention is normally used as a moldable solid resin composition, but the aqueous emulsion of the solid resin composition obtained after the above-mentioned reaction can also be used as an adhesive or the like. The microspherical resin composition comprising the resol resin and thermoplastic resin of the present invention may optionally contain a thermoplastic resin, a thermosetting resin, a flame retardant, a blowing agent, a reinforcing agent,
Fillers, extenders, leveling agents, flow regulators, stabilizers,
Additives such as antistatic agents, electrically conductive agents, dyes and pigments can be added. Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, rubber-modified polystyrene, AS, ABS, polyvinyl chloride, polymethyl methacrylate, polyolefins such as ethylene-vinyl acetate copolymers, polyethylene terephthalate, polybutylene terephthalate, Examples include polyesters such as polycarbonate and polyarylate, polyamides such as polycaprolactam and polyhexamethylene adipamide, polysulfone, and polyphenylene sulfide. Examples of thermosetting resins include melamine resins, urea 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, carbon fibers, metal fibers, quartz, mica, asbestos, kaolin, aluminum oxide, silica, aluminum hydroxide, and antimony trioxide. Other additives include titanium oxide, iron oxide, aluminum powder, iron powder, metal soap, carbon black, wood powder,
Examples include paper. <Examples> Hereinafter, the present invention will be specifically explained using examples. Example 1 80 g of phenol and 20 g of nylon 6 (Unitika Co., Ltd. A1030BRL) chips were added to a 500 ml three-necked flask with stirring, and the mixture was heated and dissolved at 85°C. Next, 4.2g of calcium chloride, 2.9g of potassium fluoride
After stirring for 10 minutes, add 7.2 g of hexamethylenetetramine, 80 g of 37wt% formalin, and 60 g of water.
was added, heated to 85℃ over 40 minutes, and heated to 85℃ at the same temperature.
The mixture was reacted for a minute to obtain a composition consisting of nylon 6 and resol resin. Next, the flask contents were allowed to cool to 30°C,
After adding 0.5 ml 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 heated for 50 minutes under reduced pressure (5 mmHg or less).
It was dried at ~60°C to obtain microspherical resin composition particles with an average particle size of about 50 μm (Resin A). When the surface of this particle was observed using an electron microscope, a shape very similar to that shown in FIG. 1 was observed. Examples 2 to 5 Among the reaction conditions of Example 1, Example 1 except that the amounts used of phenol, nylon 6 (A1030BRL), 37wt% formalin, potassium fluoride, calcium chloride, and hexamethylene diamine were changed as shown in Table 1. A microspherical resin composition having an average particle size of about 40 μm was obtained by processing in the same manner as above. The resulting resin compositions are referred to as resins B, C, D, and E, respectively. When the surfaces of these particles were observed using an electron microscope, a shape very similar to that shown in FIG. 1 was observed.

[Table] Examples 6 to 8 Among the reaction conditions of Example 1, partially methoxymethylated nylon 6 (Unitika Co., Ltd.) was used.
8-Type Nylon, methoxymethylation rate 31 mol%), and the reaction was carried out under the conditions of Example 1 with the amount charged as shown in Table 2.
A resin composition in the form of microspheres of 40 μm was obtained. These are called resins F, G, and H, respectively. When the surfaces of these particles were observed using an electron microscope, a shape very similar to that shown in FIG. 1 was observed.

[Table] Comparative example 1 200g of phenol, 200g of 37wt% formalin,
140g of water, 18g of hexamethylenetetramine, and 8.4g of calcium chloride were poured into a three-necked flask (No. 3) while stirring to make a homogeneous solution. After adding 5.8g of potassium fluoride, the temperature was raised to 85℃ over 60 minutes. The mixture was warmed up and stirring was continued at the same temperature for 80 minutes. After the reaction is complete,
When the contents were cooled to 40°C, a solid microspherical resol resin was produced. This was separated by filtration, washed with water, and dried to obtain a microspherical resol resin with an average particle size of about 50 μm. When the surface of this particle was observed using an electron microscope, a shape very similar to that shown in FIG. 1 was observed (Resin I). Comparative example 2 The British Polymer Journal, vol 15
An aqueous emulsion of nylon-resol resin was obtained according to the method described in March 1983. That is, 80 g of phenol, 0.3 g of ethyl cellulose, and 20 g of nylon 6 (Unitika Co., Ltd. A1030BRL) are added to the three-necked flask in Step 1, heated to 80° C., and stirred until the nylon is completely dissolved. Next, 2.5g of polyvinyl acetate (mw125000),
sodium carboxymethyl cellulose 2.5g, nonylphenol/ethylene oxide adduct 4.7g
Then, 110g of 37wt% formalin was added, and the pH was adjusted to 7 to 8 with 27wt% ammonia water.
The temperature was raised to 80°C for 30 minutes, and the reaction was carried out at the same temperature for 80 minutes to obtain an aqueous emulsion of nylon 6-resol resin (Resin J). In order to compare the adhesive strength of the obtained resins, Resins A to I were applied to the adhesive strength test piece by electrostatic coating, and Resin J was applied to the test piece at 80°C.
After drying for 30 minutes, the adhesive strength was measured by pressing at 180° C. and 4 kg/cm ² for 10 minutes. The results are shown in Table 3.

[Table] Since the resin composition obtained in Comparative Example 2 is in a solid state and cannot be taken out, it takes time to apply the adhesive and dry it. Furthermore, the adhesive strength is not ranked among the highest. <Effects of the Invention> The resin composition of the present invention comprising a resol resin and a thermoplastic resin can not only be taken out in the form of solid particles, but also has excellent storage stability without fusion between particles. Furthermore, the resin composition of the present invention has a uniform particle size of 500 μm or less, and is easy to handle. Furthermore, the resin composition of the present invention has excellent thermosetting properties as well as excellent adhesive properties. Utilizing these features, the microspherical resin composition of the present invention can be used not only in all fields where ordinary phenolic resins are used, such as laminates and binders, but also in solid structural adhesives, especially for aircraft and automobiles. It is useful as a drug.

[Brief explanation of the drawing]

FIG. 1 is a scanning electron micrograph (magnification: 3000) showing an example of the structure of the microspherical resin composition of the present invention.
times).

Claims (1)

[Claims] 1. A resol resin and a thermoplastic resin of 1 to 100 wt% based on the phenols constituting the resol resin, and a part or all of the surface is coated with an inorganic salt that is substantially insoluble in water. and the particle size is
A microspherical resin composition characterized by having a particle size of 500 μm or less. 2. The microspherical resin composition according to claim 1, wherein the thermoplastic resin is soluble in the phenols constituting the resol resin. 3. The microspherical resin composition according to claim 1 or 2, wherein the thermoplastic resin is polyamide. 4. The microspherical resin composition according to claim 3, wherein the polyamide is at least one selected from the group consisting of polycapramide, polyhexamethylene adipamide, polyundecanamide, and polylaurinamide. 5. The microorganism according to any one of claims 1 to 4, wherein the substantially water-insoluble inorganic salt is at least one selected from the group consisting of calcium fluoride, magnesium fluoride, and strontium fluoride. Spherical resin composition. 6. Phenols and aldehydes are reacted in an aqueous medium in the presence of a substantially water-insoluble inorganic salt, a thermoplastic resin of 1 to 100 wt% relative to the phenols, and a basic catalyst. ,
A method for producing a microspherical resin composition whose surface is partially or entirely coated with a substantially water-insoluble inorganic salt and whose particle size is 500 μm or less. 7. The manufacturing method according to claim 6, wherein the thermoplastic resin is a thermoplastic resin soluble in the phenols constituting the resol resin. 8. The manufacturing method according to claim 6 or 7, wherein the thermoplastic resin is polyamide. 9. The manufacturing method according to claim 8, wherein the polyamide is at least one polyamide selected from the group consisting of polycapramide, polyhexamethylene adipamide, polyundecanamide, and polylaurinamide. 10. The production method according to any one of claims 6 to 9, wherein the substantially water-insoluble inorganic salt is at least one selected from the group consisting of calcium fluoride, magnesium fluoride, and strontium fluoride. .