JPS61243A - Preparation of phenolic resin foam - Google Patents

Abstract

PURPOSE:To obtain the titled foam having excellent mechanical properties, flame resistance, and heat resistance by compounding a liquid phenolic resin of resol type, an acid curing agent, a foam stabilizer, a foaming agent, and a specified inorganic powder. CONSTITUTION:100pts.wt. gypsum such as calcined alpha-gypsum is mixed with 10- 500pts.wt. inorganic compound containing water of crystallization such as Al (OH)3 to give inorganic powders having a particle size of 325 mesh or smaller. Then an acid curing agent (e.g. an inorganic or organic acid) is added to a premix obtained by mixing 100pts.wt. liquid phenolic resin of resol type which is obtained by the polycondensation of a phenol and an aldehyde in the presence of a basic catalyst and has a viscosity of 500-1,500cP (at 25 deg.C), a foam stabilizer (e.g. a silicone surface active agent), a foaming agent (e.g. a halogenated hydrocarbon), and 10-500pts.wt. inorganic powders aforementioned, and is mixed by stirring to give the titled phenolic resin foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a phenolic resin foam, and more specifically, the present invention relates to a method for producing a phenolic resin foam.
This invention relates to a method for producing a highly expanded phenolic resin foam, and its purpose is to provide a method for producing a phenolic resin foam that has particularly excellent mechanical properties, flame resistance, and heat resistance. .

Conventionally, one liquid resol type phenolic resin foam was
Usually, liquid resol-type phenolic resin is obtained by reacting phenol salts such as phenol, cresol, xylenol, and catechol with altehydes such as formaldehyde and acetaldehyde in the presence of a basic catalyst, along with foam stabilizers, blowing agents, and curing agents. It is manufactured by mixing and foaming and curing. The phenolic resin foam obtained by this method has superior properties such as flame resistance and heat resistance compared to other plastic foams, and has recently attracted attention as an insoluble heat insulating material for chemical plants, building materials, etc. There is.

However, when the 7-enol resin foam obtained by the above method is exposed to flame, a carbonized layer is easily formed and the smoke and flammability are very low, but the cell structure of the foam is completely carbonized. However, it has the drawback that it turns into ash and the bubble skeleton collapses, making it a completely non-combustible insulation material. It doesn't have good performance for 6.

In order to improve the above-mentioned drawbacks of phenolic resin foam, a method of adding inorganic fillers has been proposed, but this affects the phenol resin's ka Jji combination and foaming process, inhibits the curing reaction, and reduces the strength of the foam. This is remarkable, and the viscosity of the resin foam molding material composition during foaming increases significantly.
It is extremely difficult to mold a foam that has extremely poor flowability and has a strength that can be used for practical purposes.

In view of the above-mentioned circumstances, this inventor has found that the foam has excellent mechanical properties, and even when exposed to flame, the cell structure of the foam does not turn into ash, and the cell structure does not collapse. As a result of intensive research to develop a method for economically producing foam, we have developed a method for foaming and curing liquid resol-type phenolic resin in the presence of an inorganic powder consisting of gypsum and an inorganic compound containing water of crystallization. The inventors have discovered that an economical inorganic powder-rich, highly foamed phenolic resin foam with excellent mechanical properties and flame resistance can be obtained by this method, and based on this knowledge, the present invention has been completed.

The liquid resol type phenolic resin used in this product is a liquid phenolic resin obtained by a polycondensation reaction between phenols such as phenol and cresol and aldehydes such as polyaldehyde and acetaldehyde in the presence of a basic catalyst. It is manufactured by a known manufacturing method. Liquid resol type resins can be used as appropriate, but from the viewpoint of operability in producing foams, the temperature at 25°C
A viscosity of about 500 to 1500 cps is suitable.

The acidic curing agent used in this invention includes conventionally known acids such as non-acid acids such as sulfuric acid and phosphoric acid, organic acids such as luenesulfonic acid and phenolsulfonic acid, and mixtures of these inorganic acids and organic acids. use.

As the foam stabilizer, conventionally known foam stabilizers such as silicone surfactants, sorbitashi fatty acid esters, nonionic surfactants such as polyoxyethylene alkylphenyl ethers can be used, and these can also be used in combination. .

As blowing agents, low boiling volatile organic compounds such as aliphatic hydrocarbons and their derivatives are used.

In particular, halogenated hydrocarbons are preferred from the viewpoint of heat insulation performance and foam appearance.

The gypsum constituting the inorganic powder used in this invention is preferably gypsum that sets and hardens through a water utilization reaction in anhydrite, calcined gypsum (hemihydrate ceracola), etc., and A-type furnace gypsum is preferred. This gypsum has a considerable economic advantage in that it allows the use of by-product ceracola obtained as a by-product in the production of phosphoric acid, allowing for the reuse of chemical industry by-products.

Inorganic compounds containing water of crystallization constituting the inorganic powder used in this invention include aluminum hydroxide, calcium hydroxide, boric acid, calcium carbonate, kaolin clay, borax, zinc borate, etc. In particular, aluminum hydroxide and borax each have a It is a crystal water-containing compound having an amount of bound water per crystal mole of 47%, and is suitable because it has the effect of absorbing a large amount of heat when crystal water is violently dehydrated and decomposed during heating.

The particle size of the inorganic powder does not significantly affect the foaming properties and physical properties, and the inorganic powder used in this invention has a particle size as small as 200 to 325 mesh.
25 meshes or less is preferable.

The mixing ratio of the inorganic powder containing gypsum and the inorganic compound containing water of crystallization used in this invention is preferably 10 to 5"00 parts by weight of the inorganic compound containing water of crystallization per 100 parts by weight of gypsum.
If the amount of gypsum exceeds this range, the reluctance to solubility will decrease, and if the amount is less than this range, the viscosity of the resin foam molding material composition will increase, resulting in a decrease in foaming properties and a decrease in the mechanical properties of the produced phenolic resin foam.

The inorganic powder consisting of gypsum and an inorganic compound containing water of crystallization used in this invention is preferably contained in a proportion of 20 to 120 parts by weight, particularly preferably 65 to 80 parts by weight, per 100 parts by weight of the phenolic resin. If the amount is less than 20 parts by weight, the flame resistance will be insufficient, and if it is more than 120 parts by weight, the mechanical strength of the foam will decrease.

When producing an inorganic powder-rich phenolic resin foam according to the present invention, the inorganic powder mixed at a predetermined mixing ratio may be mixed in advance with the phenolic resin.
Alternatively, each component may be mixed at the same time.

According to this invention, the gypsum constituting the inorganic powder condenses and hardens by reacting with water generated during the condensation polymerization reaction of the resol type phenolic resin. The inorganic powder used in this invention has a resol type phenolic resin foam composition, and the inorganic powder used in this invention has a resol type phenolic resin foam composition. The inorganic powder can be used as a liquid resol type phenolic resin foaming composition because it does not adversely affect the condensation polymerization reaction and foaming hardening process, nor does it impair fluidity and operability during foaming due to increased viscosity. This makes it possible to obtain a highly foamed phenolic resin foam that is highly filled with inorganic powder and has excellent mechanical properties.

According to Jakimei, the above-mentioned effects of using an inorganic powder made by blending gypsum with an inorganic compound containing water of crystallization make it possible to fill a high amount of inorganic powder and reduce manufacturing costs. It is possible to significantly reduce the amount of heat generated when turned off, improve flame resistance and heat resistance, and furthermore, it is ti-free! The gypsum that forms the solid powder condenses and hardens with the water generated during the condensation reaction of the resol type phenolic resin.
It becomes a compound containing water of crystallization, and this hydrite/K has the same characteristic action as an inorganic compound containing water of crystallization in an inorganic powder, that is, it dehydrates and decomposes when heated to produce a nonflammable substance, and at the same time absorbs a large amount of heat. The metal body has the effect of suppressing the temperature rise of the phenolic resin foam and promoting nonflammability.

The effects of the above-mentioned inorganic powder consisting of gypsum and water-of-crystalline inorganic compounds are to prevent the phenolic resin foam from ashing and collapse of the cell skeleton, and to increase flame resistance and heat resistance. That is, according to the present invention, high filling of inorganic powder consisting of gypsum and a crystal-containing inorganic compound,
Due to the synergistic effect of the generation of nonflammable substances through dehydration and decomposition and the endothermic action, it is possible to economically produce a phenolic resin foam having extremely excellent flame resistance.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

The parts in each Example and Comparative Example are by weight unless otherwise specified.

Example (1) Liquid resol type phenolic resin (viscosity 1200Cp
100 parts of Fl (25°C), 3 parts of Towin 80 (Kao Atlas@Ko, nonionic surfactant) and 5IIj
93 (manufactured by Toshi Silineen@, silicone surfactant)
[15 parts, trichlorotrifluoroethane 15 parts calcined gypsum (α-type hemihydrous gypsum) 100 parts and aluminum hydroxide powder Hysilite H-43M (manufactured by Showa Light Metal ■, 32
After adding 40 parts of an inorganic powder consisting of 100 parts (5 mesh or less) and stirring for about 2 minutes to prepare a premix, a total of 25 parts of phenol sulfonic acid (70% active ingredient) was added and mixed with stirring to form a phenol resin foam. I got a body.

After leaving this foam at room temperature for 24 hours, )XSA 95
As a result of measuring the physical properties based on 14, the density was 38 kg/
, l, and the soil shrinkage strength was 1.0 Kyf/crl. In addition, this foam was heated using a Bunsen burner flame (900 to 100
0° C.) for 60 seconds, no ashing or collapse of the cell skeleton was observed in this foam.

Comparative Example In Example (1), 25 parts of 7-enol sulfonic acid (active ingredient 70%) was added to the premix liquid prepared by adding 40 parts of Hysilite H-43M without gypsum as an inorganic powder and stirred. A phenolic resin foam was obtained by mixing.

As a result of testing this foam in the same manner as in Example +13, no ashing or collapse of the cell skeleton was observed in this foam, but the density was 41 kg/W? , compressive strength is α7
With Klf/cd, the fluidity of the resin foam molding material composition was extremely poor.

Example (2) In Example (1), calcined gypsum 100 was used as the inorganic powder.
A mixture of 70 parts of 17 parts of Hysilite H-43M and 20 parts of trichlorotrifluoroethane was stirred and mixed, and the mixture was foamed and cured to obtain a phenol resin foam.

This foam was tested in the same manner as in Example (1), and the density was 40 Kp/m' and the compressive strength was 1.1 F, 9 f/c.
However, no ashing or collapse of the cell skeleton was observed in this foam.

Example (6) Liquid resol type phenolic resin (viscosity 800 cps
(25°C)) 100 parts to 80 and 5) 119
3 3 parts each, [lL 1 part, calcined gypsum (α type semi-hydrated plaster)
After adding 55 parts of inorganic powder consisting of 100 parts and 250 parts of Hysilite H-43M and 10 parts of trichlorotrifluoroethane and stirring to prepare a premix,
25 parts of phenolsulfonic acid (70% active ingredient) was added and mixed with stirring to obtain a phenol resin foam. This foam was tested in the same manner as Example (υ), and the density was 49.5.
Kg/d, compressive strength was 1°5 K9f/-, and no ashing or collapse of cell skeleton was observed in this foam.

Example (4) In Example (3), 100 parts of calcined gypsum (α-type Hanhydrite) and Hysilite H-43M were used as inorganic powders.
25 parts of phenolsulfonic acid (70% active ingredient) was added to a premix liquid prepared by adding 100 parts of 11 parts of the mixture and 20 parts of trichlorotrifluoroethane, and the mixture was stirred to obtain a phenol resin foam.

As a result of testing this foam in the same manner as in Example (1), the density was 52 to 97 and 1.35 hours f/l:rA, and no ashing or collapse of the cell skeleton was observed in this foam. It was very bad.

Example (5) In Example (5), 100 parts of calcined gypsum (Q-type Hanhydrite) and Hysilite l-43M were used as inorganic powders.
A phenol resin foam was obtained by adding 25 parts of phenol sulfonic acid (70% active ingredient) to a premix solution prepared by adding 80 parts of 20 parts of 20 parts and 17 parts of trichlorotrifluoroethane and stirring and mixing.

This foam was tested in the same manner as in Example 11, and the density was 48 Kp/d and the compressive strength was 1.45 Kyf/cr/l.
No ashing or collapse of the cell skeleton was observed in this foam.

Example (6) In Example (3), a premix prepared by adding 80 parts of 100 parts of calcined gypsum (α-type hemihydrate) and 25 parts of borax as inorganic powder and 20 parts of trichlorotrifluoroethane. 30 parts of liquid niphenolsulfonic acid (70% active ingredient) was added and mixed with stirring to obtain a phenol resin foam.

As a result of testing this foam in the same manner as in Example (1), the density was 51 to 9/-, the compressive strength was 1.5 Kpf/-,
No ashing or collapse of the cell skeleton was observed in this foam.

As described above, according to the present invention, the foam has excellent mechanical properties, the cell structure of the foam does not turn into ash when exposed to flames, and the cell structure does not collapse. It is possible to economically produce a phenolic resin foam with excellent properties.

Patent applicant NICHIAS Co., Ltd. Procedural amendment (spontaneous) 1 Indication of the case Patent application No. 1983-121291 2 Name of the invention Process for producing phenolic resin foam 3 Person making the amendment Relationship with the case Patent applicant name NICHIA Su Co., Ltd. Company 4 Agent address: Marunouchi Building, 752nd Ward, 2-4-1 Marunouchi, Chiyoda-ku, Tokyo 100 Contents of amendment No. 1987-121291 ``Molding'' on page 3 of the specification, lines 13-14 Correct it to "formation," and correct "the inventors" in line 15 to "the inventors."

2 On page 10, line 2, ``East'' is corrected to ``11.-re''.

Claims (3)

[Claims] (1) In a method for producing a phenolic resin foam from a liquid resol type phenolic resin, an acidic curing agent, a foam stabilizer, and a foaming agent, foaming and curing is performed in the presence of an inorganic powder consisting of gypsum and an inorganic compound containing water of crystallization. A method for producing a characteristic phenolic resin foam. (2) A phenolic resin according to claim 1, characterized in that the mixing ratio of gypsum and an inorganic compound containing water of crystallization in the inorganic powder is 100 to 500 parts by weight of the latter to 100 parts by weight of the former. Method of manufacturing foam. (3) The method for producing a phenolic resin foam according to claim 1, characterized in that the inorganic powder is blended in a range of 20 to 120 parts by weight with respect to 100 parts by weight of the phenolic resin.