JPS60108441A - Production of foam particle of thermosetting resin - Google Patents

Abstract

PURPOSE:To obtain spherical foam particles having 60 microns -3mm. particle diameter stably with a high efficiency, by expanding a system solution consisting of precondensate of a phenol and/or an amino based compound and formaldehyde, a foaming agent, a foam stabilizer, and an acidic curing agent, and curing the expanded material. CONSTITUTION:A system solution of 1-6pH containing (A) 100pts.wt. precondensate of a phenol, e.g. phenol, and/or an amino based compound, e.g. melamine, with 1.1-2mol, based on one equivalent of -OH or -NH2, formaldehyde, (B) 5-25pts.wt. foaming agent, e.g. trichlorofluoroethane, (C) 0.5-5pts.wt. foam stabilizer, e.g. a silicone oil, and (D) 2-12pts.wt. acidic curing agent, e.g. phosphoric acid, is mixed with 100-900pts.wt. based on 100pts.wt. component (A) nonsolvent for the component (A), e.g. a silicone oil. The resultant mixture is then heated at the boiling point of the component (B) or below, stirred, gelatinized, expanded and cured at the boiling point of the component (B) or above to give the aimed resin foam particles having 60 microns -3mm. particle diameter and 0.1-0.8g/cm<3> bulk density.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing small spherical phenolic resin or amino resin foam particles having a particle size of 60 microns to 3 fi. The foam particles obtained by carrying out the present invention are useful as fillers for liquid thermosetting resins such as epoxy resins and phenol resins, cement, and flame retardants.

Conventionally, the production of thermosetting resin foam particles as a filler involves heating a system liquid containing a resol condensate, an acidic curing agent, a foaming agent, and a foam stabilizer to 60 to 70°C and spraying it into the atmosphere. I was getting it.

In this method, only fine foam particles having a particle size of 20 to 40 microns can be obtained, and it is difficult to make the particle sizes of the foam particles uniform. In addition, fillers with particle sizes of 0.1 to 3111+, which are obtained by mechanically crushing phenolic resin foams, are also known, but since they are not spherical, they have the disadvantage of a low filling rate.

The purpose of the present invention is to stably and efficiently obtain relatively large spherical foam particles having a particle diameter of 60 microns to 3 microns.

That is, the present invention provides: (4) Precondensate of phenols and/or amino compounds and formaldehyde) 0 foaming agent (C'1. Foam stabilizer 0, acidic curing agent (a) above, Q3), (The system solution containing 0 and 0 components is mixed with the non-solvent of the precondensate of component (4), and the precondensate is gelled at a temperature lower than the boiling point of the blowing agent (B) while stirring. After the precondensate has gelled, the system solution is heated to a temperature higher than the boiling point of the blowing agent (b) to foam and harden the precondensate, resulting in resin foaming. The present invention provides a method for producing thermosetting resin foam particles, which is characterized by obtaining body particles.

In the practice of the present invention, examples of the amino compound used as a raw material for the precondensate of the prisoner component include compounds having an amino group (-NH2) such as melamine, urea, ammeline, and ammelide.

In addition, phenols include phenol, cresol,
Examples include xylenol. These may be used alone or in combination of two or more.

When using a phenol compound and an amino compound together, the amine compound can be mixed with the phenol compound from the beginning, or the phenol compound can be condensed with formalin, and then the amino compound and formaldehyde can be added to this. They may be further mixed and condensed again. Alternatively, a precondensate of an amino compound which has been separately condensed may be mixed with a condensate of a phenol compound and formaldehyde.

Moreover, this mixture may be further condensed.

The precondensate contains 1.1 formaldehyde per equivalent of -OH of phenol or -NH2 of amino compound.
It is obtained by a condensation reaction at 60-iooC in the presence of ~2 mol of basic catalyst.

Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and aqueous ammonia. The obtained precondensate solution is neutralized with an acid and, if necessary, dehydrated under reduced pressure to prepare its resin solid content.

To the aqueous solution of the precondensate thus produced, (
B) Blending a foaming agent, a foam stabilizer, and (g) an acidic curing agent.
A system liquid with H of 1 to 6 is obtained.

The blowing agent (6) is preferably an organic solvent having a boiling point of 40 to 60°C, such as trichloromonofluoromethane, trichloromethane, trichlorotrifluoroethane (Freon 113), petroleum ether, and the like.

(Examples of the foam stabilizer Q include silicone oil or surfactants such as sodium dodecylbenzenesulfonate and alkylene polyether polyols.

(2) Examples of acidic curing agents include 5-mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, and organic acids such as halatoluenesulfonic acid, formic acid and xylenesulfonic acid.

Each component in the system liquid is (5 to 25 parts by weight of a foam leveling agent, 0.5 to 5 parts by weight of a foam stabilizer, 0 acidic curing agent 2-1
The proportion is 2 parts by weight.

This system liquid is mixed with a non-solvent that does not dissolve the precondensate (4) to obtain a dispersion of the precondensate.

Mixing is performed at a temperature below the boiling point of the blowing agent in the system solution.

At this time, it is also possible to incorporate a protective colloid agent such as polyvinyl alcohol, polyvinylpyrrolidone, or CMC into the mixed solution.

In addition, dyes such as Subiron Red 2W (product name manufactured by Hodogaya Chemical Co., Ltd.) and Solvent Yellow 56 (product name
Oil Yellow GG-8. Orient Chemical), Solvent Orange 72 (trade name: Diamond Resin Brown A1, manufactured by Mitsubishi Chemical Industries), 6-Solvent Blue 35 (trade name: Oil Blue IN, manufactured by Orient Chemical), etc., can be blended into resin particles that harden the dye. and dyed resin spherical particles are obtained.

The dye should be added in an amount of 0.001 to 1 per 100 parts by weight of the precondensate.
Used in parts by weight.

Nonsolvents such as silicone oil are also immiscible with water, and the amount is io per 100 parts by weight of the precondensate.

It is used in a proportion of ~900 parts by weight.

After dispersing the system solution in a non-solvent, it is heated at a temperature lower than the boiling point of the blowing agent until the precondensate gels. After gelation is completed, the temperature of the reaction system is heated to a temperature higher than the boiling point of the blowing agent, for example, 60 to 80° C., to complete foaming and hardening of the precondensate, and to precipitate foam particles in a nonsolvent.

Then, the foam particles are separated by filtration, washed with water, and dried to obtain foam particles as a commercial product.

The foam particles have an average particle size of 60μ to 3μ,
The bulk density is 0.1 to o, sy/d. The particle size and bulk density of the foam particles are influenced by the type and amount of the foam stabilizer, foaming agent, reaction time, etc. It also depends on the stirring conditions.

The resin foam particles are useful as fillers for polyamides, epoxy resins, phenolic resins, unsaturated polyester resins, etc., flame retardants, and fillers for cement, and the dyed resin particles are useful as colorants.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Melamine 63
01 and 37% formalin 1215f were added, and then caustic soda was added to adjust the pH of the liquid to 11.5.

Then, a condensation reaction was carried out at 80°C until the cloudy point reached 62°C (water miscibility: 110).

The obtained solution was dehydrated under reduced pressure at 50°C to reduce the concentration of the precondensate to 7.
It was increased to 0% by weight.

This 70% precondensation aqueous solution 1432 was placed in another reaction vessel, and a surfactant "Neoperex 25" (trade name) 2F manufactured by Kao Soap was added thereto. After mixing, trichlorotrifluoroethane (boiling point 47. 6℃) mix 2f,
Furthermore, 50% sulfuric acid 42 was added to obtain a system liquid.

This system liquid was poured into 40°C silicone oil "YF-33" (trade name) 5001 made by Toshiba Silicone ■, under stirring, and heated to 40°C while the resin particles were being dispersed.
After heating for 10 minutes to effect gelation, the reactor was transferred to a 70°C water bath and heated at the same temperature for 30 minutes to complete foaming and curing.

The foam particles were then filtered, washed with water, and dried to obtain 1301 spherical foam particles having an average particle diameter of iooμ and a bulk density of 0.3 f/cf/l.

Example 2 Phenol 5 in a stainless steel flask equipped with a condenser
649,37% formalin 972f and hydroxide)
After adding IJum 201 and reacting at 80° C. for 2 hours, hydrochloric acid was added to neutralize it.

Then, this was dehydrated under reduced pressure at 50° C. to obtain an aqueous solution having a precondensate concentration of 80% by weight.

To 125f of this precondensate aqueous solution, Toshiba Silicone ■
Silicone surfactant "5H-1'13" 9- (trade name) 22 was mixed well, then trichlorotrifluoroethane (Freon-113) 2f was mixed, and then
A system liquid was obtained by adding 6 tons of 0% sulfuric acid.

Silicone oil heated to 40℃ is added to this system liquid.
001 was added under stirring and heated at 40°C for 7 minutes to gel the precondensate, then placed the flask in a 70°C water bath and heated at 70°C for 30 minutes to complete the foaming and curing reaction. I let it happen.

The foam particles were then filtered, washed, and dried to obtain 1102 spherical foam particles having an average particle diameter of 2.5 m+ and a bulk density of 0.5 f/al.

Example 3 In a reaction vessel equipped with a cooler, melamine 518f1 urea 1241.37% formalin 1000F and Nippon Gosei Kagakubu Polyvinyl Alcohol Gosenol T-33 were added.
0'' (trade name) 16f was added, and then a 48% aqueous solution of caustic soda was added to adjust the pH of the liquid to 11.5, and the mixture was heated to 80°C to carry out a precondensation reaction to obtain an aqueous solution with a cloudy point of 60°C.

10- This was dehydrated at 50°C to obtain an aqueous precondensate solution with a solid content of 70%.

Toshiba silicone ■ 142f of this precondensate aqueous solution
Thoroughly mix the silicone surfactant "5H-193'" (trade name) 21, then mix 2r of trichlorotrifluoroethane (Freon-zta), and then add 4f of 50% sulfuric acid to make the system liquid. Obtained.

Liquid paraffin heated to 40°C was added to this system liquid.
After adding 00f with stirring and heating at 40°C for 7 minutes to gel the precondensate, place the flask in a 70°C water bath and heat at 70°C for 30 minutes to complete the foaming and curing reaction. I let it happen.

The foam particles were then filtered, washed and dried to obtain 13 spherical foam particles with an average particle size of 200μ and a bulk density of 52/-.
I got it.

Example 4 A 48% aqueous solution of caustic soda was added to a mixed solution of urea 3001 and 37% formalin 810f, and the pH was adjusted to 9.

Then, a 30-molecule condensation reaction was carried out at 80° C. with stirring.

Then, formic acid was added so that the pH of the aqueous solution became 4.2, to obtain a resin liquid with a cloudy point of 60°C. Thereafter, after neutralizing with hydrochloric acid, this was dehydrated under reduced pressure at 50° C. to obtain an aqueous solution having a precondensate concentration of 80% by weight.

To 1 toop of the aqueous solution of this precondensate, 2 t of sodium dodecylbenzenesulfonate was thoroughly mixed, and then 2 f of trichlorotrifluoroethane (Freon-113) was mixed.
Furthermore, 0.52% of 50% sulfuric acid was added to obtain a system liquid.

Silicone oil heated to 40℃ is added to this system liquid.
002 was added under stirring and heated at 40°C for 7 minutes to gel the precondensate, then placed the flask in a 70°C water bath and heated at 70°C for 30 minutes to complete the foaming and curing reaction. I let it happen.

The foam particles were then filtered, washed, and dried to obtain 9Of spherical foam particles having an average particle size of 250μ, a bulk density o, and 4y/ctA.

Example 5 In a reaction vessel equipped with a cooler, melamine 5181, urea 124f, 37% formalin 1000f and Nippon Gohsei's handmade polyvinyl alcohol Gosenol T-33 were placed.
0'' (trade name) 16f was added, and then a 48% aqueous solution of caustic soda was added to adjust the pH of the liquid to 11.5, and the mixture was heated to 80°C to carry out a precondensation reaction to obtain an aqueous solution with a cloudy point of 60°C. This was neutralized with hydrochloric acid and then dehydrated under reduced pressure to a solid concentration of 70%.

143 tons of this pre-condensed resin aqueous solution was placed in another reaction vessel, and added to it was dyed "Subiron Red Q, 05" manufactured by Hodogaya Chemical Co., Ltd.
f. Surfactant “Neoperex 25” manufactured by Kao Soap■
(Product Name) 21F was added, and after mixing, 2 t of trichlorotrifluoroethane was mixed, and 4 v of 50% sulfuric acid was further blended to obtain a system liquid.

This system liquid was poured into 500f of silicone oil "YF-33" (trade name) manufactured by Toshiba Silicone ■ at 40℃ under stirring, and heated at 40℃ for 10 minutes while stirring to disperse the resin particles. After gelation was carried out, the reactor was transferred to a water bath at 70°C and heated at the same temperature for 30 minutes to complete foaming and curing.

The foam particles were filtered, washed with water, and dried to obtain red spherical foam particles 1302 having an average particle size of 300 μm and a bulk density of 0.4 f/ey/l.

Example 6 In a reaction vessel equipped with a condenser, cresol (containing 60% metacresol) 648f and 37% formalin 97
2v, then 232 ml of caustic soda, and heated to 80°C.
After heating at the same temperature and reacting for 2 hours, hydrochloric acid was added to neutralize and dehydrated under reduced pressure at 50°C to reduce the solid content of the precondensate to 8.
It was concentrated to 0% by weight.

To this precondensation resin aqueous solution, Toshiba Silicone ■
Silicone surfactant “5H-193” (product name)
22 was mixed well, then 2r of trichlorotrifluoroethane (Freon-11a) was mixed, and then 50% sulfuric acid 4
Add f to obtain a system liquid.

Add 50 ml of silicone oil heated to 40°C to this system liquid.
0t was added under stirring and heated at 40°C for 8 minutes to gel the precondensate, and then immersed 7lar 14 = Sco in an aqueous solution at 70°C and heated at 70°C for 30 minutes. Completed foaming and curing.

The foam particles were then filtered, washed, and dried to obtain 909 spherical foam particles with an average particle size of 220 μm and a bulk density of 0.45 t/al.

Example 7 In a reactor equipped with a cooler, melamine 126v phenol 564f, 37% formalin 121st and Nippon Gosei Kagaku's polyvinyl alcohol "Gosenol T-33" were placed.
0" (trade name) 16v, then add 40f of 48% caustic soda aqueous solution to adjust the pH of the liquid to 11.5, and then
The mixture was heated to 0.degree. C. and a preliminary cotton-combination reaction was carried out at the same temperature for 1 hour.

Then, after neutralizing the precondensate aqueous solution with hydrochloric acid, the temperature was increased to 50°C.
The solution was dehydrated under reduced pressure to concentrate the resin solid content in the solution to 70% by weight.

This precondensate aqueous ffL1009 is mixed with Toshiba silicone
Thoroughly mix 2g of silicone surfactant "S'[(-193" (trade name) manufactured by Manufacturer), then mix 4r of trichlorotrifluoroethane (Freon-113), and then add 6v of 50% sulfuric acid to prepare the system. Get the liquid.

Add 50 ml of silicone oil heated to 40°C to this system liquid.
After 0 t was added under stirring and heated at 40°C for 7 minutes to gel the precondensate, the flask was placed in a 70°C water bath and heated at 70°C for 30 minutes to complete the foaming and curing reaction. I let it happen.

The foam particles were then filtered, washed, and dried to obtain 901 spherical foam particles having an average particle size of 1.2 sieves and a bulk density of 0.5 y/-.

Example 8 In a reactor equipped with a cooler, urea 60f and phenol 5
642 and 37% formalin 11349 were added, and a 48% caustic soda aqueous solution 409 was added to carry out a 60-molecule condensation reaction at 80° C. with stirring.

Then, after neutralizing by adding hydrochloric acid, dehydration was carried out under reduced pressure at 50° C. to make the resin concentration of the precondensate solution 75% by weight.

A silicone surfactant "5H-193" (trade name) manufactured by Toshiba Silicone ■ was thoroughly mixed with 100 tons of an aqueous solution of this precondensate, and then trichlorotrifluoroethane (
Freon-1ta) is mixed with 4f, and then 50% sulfuric acid 2
A system liquid was obtained by adding t.

Add 50 ml of silicone oil heated to 40°C to this system liquid.
After adding 0f with stirring and heating at 40°C for 7 minutes to gel the precondensate, the flask was placed in an aqueous solution at 70°C and heated at 70°C for 30 minutes to complete the foaming and curing reaction. I let it happen.

The foam particles were then filtered, washed and dried to obtain 9Of spherical foam particles having an average particle diameter of 1.0 square meters and a bulk density of 0.4 f/ctI.

Patent applicant Yuka Melamine Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Patent Attorney Masahisa Nagatani =17-

Claims (1)

[Claims] 1), (A), precondensate of formaldehyde with phenols and/or amino compounds Q3) 0 foaming agent (O9) 0 foam stabilizer, acidic curing agent (A+, (B) ), (0) and the system solution containing the components (0 and After the precondensate gels, the temperature of the system solution is heated to a temperature higher than the boiling point of the blowing agent (B) to foam and harden the precondensate, resulting in resin foaming. A method for producing thermosetting resin foam particles characterized by obtaining body particles. 2) The zero foam particles have a particle size of 60 microns to 3 ma and a bulk density of 0.1 to 0.8 f/cIi. 3) The manufacturing method according to claim 1, characterized in that the non-solvent of the pre-synthesized product is silicone oil or liquid paraffin.
Manufacturing method described in section. 4) The manufacturing method according to claim 1, wherein the blowing agent is trichlorotrioleoethane.