JPS60177014A - Composition for phenolic resin foam - Google Patents

Abstract

PURPOSE:The titled composition keeping flame retardance, etc., having improved mechanical properties, obtained by blending a benzilic ether type phenolic resin with a polyisocyanate compound, a blowing agent, etc. and an aromatic sulfonic acid compound as a curing agent. CONSTITUTION:(A) A benzilic ether type phenolic resin is blended with (B) a polyisocyanate compound (preferably tolylene diisocyanate, etc.), (C) an aromatic sulfonic acid compound (e.g., benzenesulfonic acid, etc.) as a curing agent, (D) water, (E) a blowing agent (e.g., n-hexane, etc.), and (F) a foam adjustor (e.g., silicone nonionic surface active agent, etc.), to give the desired composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin foam composition suitable for forming a phenol foam using a benzylic ether type phenolic resin.

Although phenol 7ohm has excellent properties such as heat resistance, flame retardance, and low smoke emission, it is extremely brittle and resistant to leakage compared to other plastic foams such as urethane foam and polystyrene foam. It is difficult to use because of the Furthermore, in addition to these physical property disadvantages, resol-type phenolic resins have problems with the storage stability of the resin itself, and novolac-type phenolic resins have their own disadvantages, such as being inconvenient to handle because they are solids. However, to date there has been no significant increase in the amount of phenol foam used.

On the other hand, in the case of phenol foam made from a benzylic ether type phenol resin, the phenol resin itself has good storage stability, but when a curing agent is added, it generates intense heat and turns into a resin with foaming.

The 7 ohm formed has a very low density and cannot be used as brittle insulation. Regarding 7 ohms using benzylic ether type phenol resin, there is also a method of producing urethane foam by reacting with a polyisocyanate compound, for example, in Japanese Patent Publication No. 55-27093, but it is not flame retardant and has low smoke emission. Its properties are considerably inferior to those of phenol form.

Tree 31 Light is heat resistance, which is a characteristic of phenolic foam.
The present invention relates to a composition for a benzylic ether type phenolic resin foam that can be used practically and has flame retardancy and low smoke emission properties while improving its poor mechanical properties.

More specifically, the present invention relates to a composition for a phenolic resin foam comprising a benzylic ether type phenolic resin, a polyisocyanate compound, an aromatic sulfonic acid compound, water, a blowing agent, and a foam stabilizer.

The phenolic foam formed from the composition of the present invention has a hard skin layer and does not have any slipping properties. I! It has good adhesion to surface materials, and has the advantage of being able to integrally form laminates with various surface materials through self-adhesion, which was not possible with conventional 7-enol 7-ohm materials made from resol type or novolac type phenolic resins. have.

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 1'l'CHO (R' is hydrogen (representing an 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.

The polyincyanate compound used in the present invention is polymethylene polyphenyl isocyanate (so-called crude 4.4
'-diphenylmethane diisocyanate), tolylene diisocyanate, hexamethylene diisocyanate, etc. are preferred, but polyinocyanate compounds having a terminal isocyanate group that are a reaction product of polyisocyanate and a polyhydric alcohol such as glycol, glycerin, or trimethylolpropane, or A prepolymer type polyisocyanate compound having an isocyanate group at the end obtained by reacting a polyisocyanate with a polyether-based or polyester-based polyol can also be used.

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

Aromatic sulfonic acid compounds used in the present invention include benzenesulfonic acid, toluenesulfonic acid, xylene sulfonic acid,
Typical examples include phenolsulfonic acid, but phosphoric acid, sulfuric acid,
Non-alcoholic acids such as hydrochloric acid can also be used in combination. The aromatic sulfonic acid compound can be used as a powder or dissolved in an organic or inorganic solvent capable of dissolving the compound, but it is preferable to use it as an aqueous solution with an appropriate amount of water.

The polyisocyanate compound and the aromatic sulfonic acid compound are used in an equivalent ratio of [NC0)/[80,H] of 0.1 to 1.0, preferably 0.3 to 0.9. ([NCO] here refers to the Durham equivalent of an isocyanate group, and [80,H] refers to the Durham equivalent of a sulfone group.) [NCO]7(80,H) equivalent ratio 0. If it is less than 1, the resulting foam is very brittle, has low blindness, and has a large foam shrinkage after molding. [NCO]/(80,H) equivalent ratio is 1.0
If it exceeds this range, the foam will be extremely non-uniform and no practical foam will be obtained.

The addition of water to the invention can be accomplished in any way, such as by using the aromatic sulfonic acid as an aqueous solution, as described above. The water seal is a benzylic ether type phenol, (H, 0% NGO) equivalent ratio is at least 0.5 or more, preferably 4 to 45 parts by weight, [HzO:]/[NCO] member ratio is at least 1.0
If it is above, it works effectively. Excessive water exceeding 1,001,111 parts causes stagnation, while water below 0.1 part by weight makes it impossible to control foaming. If the [HaO)/[Nco] equivalent ratio is less than 0.5, the resulting 7 ohm material has weak mechanical properties and is poor in heat resistance and flame retardancy.

The blowing agent used in the present invention is a low-boiling aliphatic hydrocarbon or its halide, such as petroleum ether, n-hexane, n-hebutane, methylene chloride, trichlorhydric
An example is lomethane.

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

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, as an additive, polyhydric hydroxy compounds such as ethylene glycol, propylene glycol, glycerin, or polyoxyalkylene polyols such as polyoxyethylene glycol can be used as additives. It is also possible to add polyoxybu-tetrapyrene glycol or nitrogen-containing compounds, such as jetanolamine, triethanolamine, jetanoltriamine, urea, etc., to further improve heat resistance, flame retardancy, and low smoke emission. , flame retardants, inorganic powders, etc. can be added as appropriate.

An example of producing a foam formed from the composition of the present invention will be described below.

A benzylic ether type phenolic resin, a foam stabilizer, a blowing agent, and optionally other additives are mixed. next,
A polyisocyanate compound and an aromatic sulfonic acid compound are added to this liquid mixture, 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 even 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 by examples and comparative examples.

Example 1 Prior to foam molding, a benzylic ether type phenolic resin was synthesized by the following method.

Phenol 5579. Paraformaldehyde 174t
, 1.5f of lead naphthenate, and 3.0f of zinc naphthenate were stirred and mixed, reacted at 110 to 114°C for 5 hours, and then immediately dehydrated under reduced pressure, resulting in a viscosity of 30,000c.
A benzylic ether type phenol resin (total water content: 2.0% by weight) of ps (at 25° C.) was obtained.

Example 2 100 f of benzylic ether type phenolic resin obtained in Example 1, 5 f of foam stabilizer (Tween-40: manufactured by Kao Atlas Co., Ltd.), 25 t of foaming agent (Freon Ru 11:
(manufactured by Mitsui Flo-Shike 2 Cal Co., Ltd.) was thoroughly mixed with the curing agent yotcp-) (970% aqueous solution of luenesulfone) and crude diphenylmethane diisocytonate. Of (Mirio-Ki-) MR-200: manufactured by Nippon Polyurethane Co., Ltd.) was added and heated to 3000 to 4000 using a lab mixer.
After vigorous stirring at pm for 15 seconds, the mixture was poured into another mold and foamed.

([NGO]/[5oA) (:] 0.1, (H*
0)/21) Foam in [NGO] 60-8
The foam obtained after heating in a constant temperature phase at 0° C. for 30 to 60 minutes had good brittleness, looseness, no shrinkage, and good mechanical properties.

Physical properties and flame retardancy test (A8TM-n-1692), smoke generation test (JIS
A-1321) results! ! -1.

Table-1 Note) According to JI8 A-1521C5 @ smoke test),
The test was conducted using a test piece of 30 x 220 x 220 m.

Examples 3 to 1O 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 2I. (Numbers in the table represent parts by weight.) (1) Benzylic ether type phenolic resin described in Example tic.

(fiT-401 foam stabilizer Tween-40 manufactured by Kao Atlas Co., Ltd.

(3) 8H-1911 foam stabilizer Toshi Silicone 8H-19
Manufactured by Silicone Co., Ltd. 5° East.

(4) PBG-400t polyolefin diethylenediol. Nirasan PEG-400, manufactured by NOF.

(5) Aromatic sulfonic acid compound 1p-toluenesulfonic acid 70% aqueous solution.

(6) Tolylene diisocyanate) IT-80, manufactured by Nippon Polyurethane Co., Ltd.

(20 parts by weight of aromatic sulfonic acid compound of η(5) 5 parts by weight of decaphosphoric acid (85% aqueous solution).

As described above, in Examples 2 to 10, good foams were obtained that were free from brittleness, looseness, and shrinkage.

Example 11 Adhesion Kv of the phenol foam according to the present invention to the facing material
In order to show that IE was maintained, the adhesive strength between the K-liner paper and the mild steel plate was measured by a 90 degree peel IIs test. For comparison, Table 3 shows the results of the same procedure for phenol foam obtained from resol type phenolic resin.

Table-3 (1) Mild steel plate: JI8 G-31418PCC-8B
(2) Phenol 940F, 57% Forlin 1460
f.

A resol type phenol resin obtained by reaction with 24 tons of sodium hydroxide was used. Viscosity 9.500 cps (20
℃), moisture 12.5%.

The adhesive strength of the phenol foam made by this Tj K to the surface material was 6 to 9 times higher than that of the phenol foam made using a resol type phenolic resin.

Hodogaya Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. A phenolic resin foam composition comprising a benzylic ether type phenolic resin, a polyinocyanate compound, an aromatic sulfonic acid compound, water, a blowing agent, and a foam stabilizer.