JPS59196332A - Production of phenol foam - Google Patents

Abstract

PURPOSE:To produce a phenol foam of improved mechanical properties, by foaming by heating a mixture formed by adding specified two kinds of compounds, water and a foam stabilizer to a benzylic ether type phenolic resin. CONSTITUTION:A phenol foam is produced by foaming by heating a mixture comprising benzylic ether type phenolic resin, a polyisocyanate compound (e.g., polymethylenepolyphenyl isocyanate), an aromatic sulfonic acid compound (e.g., benzenesulfonic acid), water, a blowing agent (e.g., petroleum ether), and a foam stabilizer (e.g., alkylphenol/ethylene oxide adduct). It is possible to improve the deficiency of a phenol foam in mechanical properties without detriment to its inherent heat resistance, flame resistance and low smoke formation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a phenol 7 ohm using a benzylic ether type phenolic resin.

Although phenol foam has excellent properties such as heat resistance, flammability, and low smoke emission, it is extremely brittle and prone to flaking compared to other plastic foams such as urethane foam and polystyrene foam. Therefore, it is difficult to use. Furthermore, in addition to these physical property disadvantages, resol-type phenolic resins have problems with their own storage stability, and novolak-type phenolic resins are solid, making handling difficult. There has been no significant increase in the amount of phenol foam used to date.

On the other hand, benzylic ether type phenolic resin fJxW
The phenol foam used as a material has good storage stability as a phenol resin itself, but when a curing agent is added, it generates intense heat and turns into a resin with foaming.

The resulting foam has a very low density and is too brittle to be used as an insulating material. Regarding foams using benzylic ether type phenolic resins, a method of producing urethane foams by reacting with polyincyanate compounds is also known, for example, in Japanese Patent Publication No. 55-27093, but it is not flame-retardant and low smoke-emitting. etc. are quite inferior compared to phenol form.

The present invention uses a benzylic ether-type phenol resin that maintains the heat resistance, flame retardance, and low smoke emission properties that are the characteristics of phenol foam, while improving the poor mechanical properties that are its drawbacks and can be used in practical applications. It concerns phenolic forms.

That is, the present invention is a method for producing phenol foam, which is characterized by foaming and heating a liquid mixture consisting of a benzylic ether type phenol resin, a polyisocyanate compound, an aromatic sulfonic acid compound, a blowing agent, and a foam stabilizer. .

Since the phenol foam according to the present invention has a hard skin layer, it has good adhesion to surface materials, and can be used with various surface materials, which was not possible with conventional phenol foams made from resol type or novolac type phenol mIIW. Another advantage is that the laminate can be integrally molded by self-adhesion.

The benzylic ether type phenol resin used in the present invention is known from, for example, Japanese Patent Publication No. 47-50873, and is composed of phenol represented by the general formula %) and the following general formula R' CHO (R ' represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms) in a ratio of 1=1 to 1:3 in the presence of a metal salt catalyst. It is.

The foam stabilizer used in the present invention is a silicone-based nonionic surfactant and/or a nonionic surfactant, such as an ethylene oxide adduct of sorbitan fatty acid ester, alkylphenol, or the like.

The blowing agent used in the present invention is a low-boiling aliphatic hydrocarbon or its halide, and examples thereof include petroleum ether, n-hexane, n-hebutane, methylene chloride, and trichlorofluoromethane.

Aromatic sulfonic acid compounds used in the present invention include benzenesulfonic acid, toluenesulfonic acid, xylene sulfonic acid,
Representative examples include phenolsulfonic acid, phosphoric acid, sulfuric acid,
Inorganic acids such as hydrochloric acid can also be used in combination. The aromatic sulfonic acid compound is preferably used as an aqueous solution with an appropriate amount of water.

The polyisocyanate compound used in the present invention is polymethylene polyphenylisocyanate (so-called crude [4,4
'-diphenylmethane diisocyanate), tolylene diisocyanate, hexamethylene diisocyanate, etc. are preferred, but polyisocyanate compounds having terminal incyanate groups that are reaction products of polyincyanate and polyhydric alcohols such as glycol, glycerin, and trimethylolpropane, or A prepolymer type polyisocyanate compound having an incyanate group at the end obtained by reacting a polyisocyanate with a polyether-based or polyester-based polyol can also be used.

The polyisocyanate compound and the aromatic sulfonic acid compound are used at a (NGO)/(8(hH) equivalent ratio of 0.1-to, preferably 0.5-0.9. (herein referred to as (NGO)) is the gram equivalent of the incyanate group, and (80, H) is the gram equivalent of the sulfone group. is extremely brittle and has a low density, resulting in poor foam shrinkage after molding.If the (NGO)/(SOaH) equivalence ratio exceeds 1.0, the foam becomes extremely non-uniform and cannot be used for practical purposes. I can't get the body.

The polyisocyanate compound may be used in an amount of 1 to 50 parts by weight or 3 to 25 parts by weight per 100 parts by weight of the benzylic ether type phenolic resin.

The amount of the foam stabilizer used is preferably 1 to 5 parts by weight per 100 parts by weight of the benzylic ether type phenol resin.

In addition, in the present invention, as additives, polyhydric hydroxy compounds such as ethylene glycol, propylene glycol, glycerin, or polyoxyalkylene polyols M such as polyoxyethylene glycol are used as additives to further improve the mechanical properties of the foam. , polyoxyethylene glycol, or nitrogen-containing compounds such as jetanolamine, triethanolamine, diethanoltriamine, urea, etc. can also be added to further improve heat resistance, flame retardancy, and low smoke emission. In addition, it is also possible to add flame release agents, inorganic powders, etc. as appropriate.

The foam according to the invention is produced as follows.

Benzylic ether type phenol m fat! Mix the foaming agent, blowing agent and optionally other additives. next,
A polyisocyanate compound and an aromatic sulfonic acid compound are added to this mixed solution, mixed vigorously at room temperature, poured into a mold, and heated to 60 to 80°C to obtain a foam.

In this case, although it takes some time, a foam can be obtained without heating. It is also possible to mix the polyisocyanate compound and the curing agent in advance and add them to the above mixture.

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

Example 1 Before foam molding, a benzylic ether type phenol resin was synthesized by the following method.

Phenol 3579, paraformaldehyde 1741F
, 1.5 F of lead naphthenate, and 50 F of zinc naphthenate were stirred and mixed, reacted at 110 to 114°C for 3 hours, and then immediately dehydrated under reduced pressure, resulting in a viscosity of 50,000.
A benzylic ether type phenol resin with Cps (at 25°C) was obtained.

Example 2 1 oor of the benzylic ether type phenol resin obtained in Example 1, 3 parts of a foam stabilizer (Tween-40, manufactured by Kao Atlas Co., Ltd., and 25 parts of a foaming agent (Freon R-11, manufactured by Mitsui Fluorochemical Co., Ltd.) were added. Mix thoroughly and add hardening agent 7 to this.
0 t (p-)luenesulfonic acid 70% aqueous solution) and crude diphenylmethane diisocyanate4. (I
Add P (Millione) MR-200 (manufactured by Nippon Polyurethane Co., Ltd.) and use a lab mixer to mix 3000 to 400
After stirring vigorously for 15 seconds at 0 rpm, the mixture was placed in another mold for foaming.

The foam obtained after mixing the foam in a constant temperature bath at 60 to 80 °C for 30 to 60 minutes has no brittleness, no looseness, and no shrinkage.
The mechanical properties were also good.

Physical properties and flame retardancy test (ASTM-D-1692), smoke generation test (
JIS A-1! +21) results are shown in Table-IK.

Table 1 Note) Test was conducted using test piece 3Dx220x220+e+ according to JIS A-1321 (Fume generation test) K.

Examples 3 to 10 and Comparative Examples 1 to 3 Using the benzylic ether type phenolic resin described in Example 1, foams were synthesized in the same manner as in Example 2. The compounding recipe and molding results are shown in Table-2. (Numbers in the table represent parts by weight.) (1) Benzylic ether inkstone phenolic resin described in Example 1.

(2) T-40s foam stabilizer Tween-40 manufactured by Kao Atlas Co., Ltd.

(!I) 81-1-193 as a foam stabilizer and silicone 5
T (-193° East, manufactured by Silicone Co., Ltd.)

(4) PEG-400s polyoxyethylene diol.

Nirasan PEG-400, manufactured by NOF.

(5) Aromatic sulfonic acid compound 5p-toluenesulfonic acid 70% aqueous solution.

(6) Tolylene dicyanate 5T-80, manufactured by Nippon Polyurethane Co., Ltd.

(7) 20 parts by weight of the aromatic sulfonic acid compound of (5), 5 parts by weight of phosphoric acid (85% aqueous solution).

As described above, in Examples 2 to 10, good foams without brittleness, looseness, and shrinkage were obtained.

Example 11 In order to demonstrate that the phenol foam according to the present invention has excellent adhesion to face materials, the adhesive strength with K-liner paper and mild steel plate was measured by a 90 degree peel test. For comparison, Table 3 shows the results of the same test for phenol foam obtained from resol type phenolic resin.

Table-3 (1) Mild steel plate: JIS G-51418PCC-8B
(2) A resol-type phenolic resin obtained by the reaction of 940 phenol, 146°I of 37% formalin, and 242% sodium hydroxide was used. Viscosity 9,500 cps
(20°C), moisture 12.5%.

The adhesion strength of the phenol foam according to the present invention to the surface material was 6 to 9 times higher than that of the phenol foam using a resol type phenol resin.

Hodogaya Chemical Industry Co., Ltd. Procedural Amendment (Voluntary) May 27, 1980 Dear Commissioner of the Japan Patent Office 1, Indication of Case 1988 Patent II! No. 69970 No. 2, Name of the invention N-adic method of phenol form 3, Relationship with the case of the person making the amendment Patent applicant Postal code 105 Address No. 4-2, Toranomon-chome, Minato-ku, Tokyo Procedural amendment (2)° July 40, 1980, Mr. Commissioner of the Japan Patent Office], Indication of the case 1988 Weight: '1 Application No. 69970 2, Name of the invention 'Jm method 3 of phenolphumeme, Relationship with the person making the amendment' case Patent l1IQ Person Postal code 105 Address 4-2 Toranomon-chome, Minato-ku, Tokyo Name
Title (531) Hodogaya Chemical Industry Co., Ltd. 4. Subject of amendment Feature Bj of the description, scope of claims and details of the invention 5. Contents of amendment (1) Procedural amendment submitted on May 27, 1988 book('!
'12a9J No. 4) Claims section of the specification.

"As per the attached sheet" (2) In the Detailed Description of the Invention section of the same book, insert "Water," on page 3, line 4, after "Sulfonic acid compound."

(3) Quantity meter, page 3, lines 7 to 8 [Because it has a hard skin layer] should be corrected as follows: "Because it has a hard skin layer and does not have a drop-off property," (4) Same as Between the first and second lines of page 5 of I-cho, it is written that ``Water used in the present invention may be added by any method, such as by using aromatic sulfonic acid as an aqueous solution as described above.'' It is also achieved by

Water star is benzylic ether type phenolic resin 100
It is effective to add 0.1 to 100 parts by weight, preferably 4 to 45 parts by weight of CO to 1 part of i. Excessive water in excess of 100[i parts] causes a drop in pressure, while water below 0.1 parts by weight makes foaming control impossible. ” is inserted.

Hodogaya Chemical Co., Ltd. Toku a'r 31+1 Range 1, foaming and heating of a mixed liquid consisting of a benzylic ether type phenol resin, a polyisocyanate compound, an aromatic sulfonic acid compound, water, a foaming agent, and a foam stabilizer. A method for producing a phenolphimeme, characterized by:

Claims (1)

[Claims] 1. A method for producing phenol foam, which comprises foaming and heating a liquid mixture consisting of a benzylic ether type phenol resin, a polyisocyanate compound, an aromatic sulfonic acid compound, a foaming agent, and a foam stabilizer.