JPH02214716A - Composition for phenolic resin composite - Google Patents

Abstract

PURPOSE:To obtain the title composition of high curing rate, self-tack to the substrate, flame retardancy, and thermal insulation by using, as essential components, a benzylic ether type, liquid phenolic resin of a specific viscosity, a polyisocyanate and an inorganic foaming agent. CONSTITUTION:The subject composition comprises (A) a benzylic ether type of liquid phenolic resin of 1 to 50 poise in viscosity at 25 deg.C (preferably containing 7 to 50wt.% of dicarboxylic ester), (B) a polyisocyanate (preferably diphenylmethane diisocyanate, polymethylene-polyphenylisocyanate) and particles of inorganic foaming agent (such as pearlite, of 0.10 to 0.50 bulk density, 0.2 to 7mm particle sizes) as essential components.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is applicable to phenolic resin composites that have a fast curing speed, good self-adhesion to adherends, good flame retardancy, and good heat insulation properties. The present invention relates to a composition in which the present invention is applied.

[Conventional technology]

Although phenolic resin foams have excellent properties such as flame retardancy and low smoke emission, they have the disadvantages of slow foam formation (and poor self-adhesion to adherends).

In order to increase the production rate of phenolic resin foam and improve its self-adhesion to adherends, attempts have been made to obtain foam using a benzylic ether type liquid phenolic resin and polyisocyanate in combination with a blowing agent. However, it has the drawback that flame retardancy and low smoke generation properties are extremely low.

[Problem to be solved by the invention]

The present inventors have conducted various studies on methods for improving the production rate of phenolic resin foam, flame retardancy, low smoke emission, heat insulation, self-adhesiveness to adherends, etc. of the foam, and as a result, they have developed the present invention. This is what we have come to complete.

[Means to solve the problem]

The present invention is characterized in that a phenolic resin composite is produced using as essential components a benzylic ether type liquid phenol resin having a viscosity of 1 to 50 voids/25°C, polyisocyanate, and inorganic foam particles.

The benzylic ether type phenol tree of the present invention is a mixture of phenols and aldehydes, and the PM in the system is adjusted to 4 to 7 using a naphthenate or a divalent metal salt and/or hydroxide as a catalyst. It is obtained by doing.

Phenols include phenol and bisphenol A
1, alkylphenols such as cresol and xylenol, and mixtures thereof. As the aldehyde, formalin, paraformaldehyde, trioxane that generates formaldehyde, or a mixture thereof may be used. Phenols and aldehydes are converted into lead naphthenate, zinc naphthenate, cobalt naphthenate,
Naphthenic acid salts such as manganese naphthenate, salts of divalent metals such as zinc acetate and cobalt acetate, and hydroxides of divalent metals such as barium hydroxide are used as catalysts to reduce the amount of P in the system.
Adjusting H to 4 to 7 and proceeding with the reaction. As the reaction progresses, the addition reaction of aldehydes to phenols proceeds, and as the number of methylol groups increases, the molecular weight increases. Further, as the reaction time is prolonged, the methylol group is converted to a benzylic ether group and a methylene group, which is accompanied by an increase in the molecular weight.

Since the obtained benzylic ether type phenol resin has a high viscosity, a solvent that does not react with the polyol is added and mixed to form a low-viscosity liquid that is easy to handle.

Ketones, hydrocarbons, esters, or mixtures thereof are used as solvents, but dicarboxylic acid esters are particularly preferred.Dicarboxylic acid esters include dimethyl succinate, dimethyl glutarate, dimethyl adipate, etc. 7 The present inventors have found that dicarboxylic acid esters, used alone or in combination, have superior flame retardancy and low smoke emission properties for phenolic resin composites, and have less off-odor than other agents. I found it.

The benzylic ether type liquid phenol resin in the present invention is thus obtained and has a viscosity of 1 to 50 poise/
It is a liquid resin at 25°C. When the viscosity exceeds 50 poise/25° C., the workability of mixing with polyisocyanate and inorganic foam particles deteriorates. When the viscosity is less than 1 poise/25° C., flame retardancy and low smoke generation properties decrease due to an increase in the amount of solvent contained. In particular, when a dicarboxylic acid ester is used as a solvent, the content of the dicarboxylic acid ester is desirably 7 to 50% by weight.

The polyisocyanate liquid in the present invention is an aliphatic, alicyclic, or aromatic polyisocyanate having a small amount (both of which have two or more isocyanate groups, and is preferably diphenylmethane diisocyanate or polymethylene polyphenylisocyanate alone or in a mixture. The proportion of polyisocyanate used is 50 to 200 parts by weight per 100 parts by weight of phenol resin.

The inorganic foamed particles used in the present invention are pearlite, vermiculite, obsidian, shirasu balloons, etc., and their bulk specific gravity is 0.01~(L5G, particle size 0.2~7cm is preferable. For the total amount of 100 parts by weight of rick ether type liquid phenol resin and polyisocyanate,
The inorganic foam particles are mixed in an amount of 100 to 500 parts by weight.

A phenol resin composite composition is obtained by mixing the components, such as a benzylic ether type liquid phenol resin, a polyisocyanate, and inorganic foam particles, as they are in a mixer. At this time, it is also possible to use conventionally known blowing agents, flame retardants, and surfactants.

The obtained phenolic resin composite composition is cured at a temperature of 0° C. or higher to produce a phenolic resin composite. At this time, as curing rate regulators, various aliphatic or aromatic amines may be used in combination to improve the curing rate, and various acidic substances may be used in order to decrease the curing rate.

(Function) The present invention uses a benzylic ether type liquid phenol resin with a viscosity of 1 to 50 poise/25°C, a polyisocyanate,
and inorganic foamed granules as essential ingredients.

A phenolic resin composite composition is obtained in which a mixture of a benzylic ether type liquid phenolic resin and a polyisocyanate is present on the surface of low-density inorganic foamed particles, and this is
It is cured using a mold, continuous heating machine, etc. to produce a lightweight phenolic resin composite with a face material or as a single unit. Further, this phenolic resin composite composition can also be used as various caulking materials at construction sites.

The benzylic ether type liquid phenol resin present on the surface of the inorganic foam particles quickly reacts with the polyisocyanate to form a strong cured resin that provides the strength of the composite and simultaneously completes adhesion to the adherend. . The combined use of inorganic foam particles reduces the density of the composite, improves flame retardancy, low smoke emission, and heat insulation properties.

The viscosity of benzylic ether type liquid phenolic resin is 1
~50voices/25°C is required. As mentioned above, good properties and workability cannot be obtained outside this range.The solvent for reducing the viscosity of the benzylic ether type liquid phenol resin is particularly preferably a dicarboxylic acid ester. %, exhibits excellent behavior particularly in terms of workability, flame retardancy, and low smoke emission.

(Thus, the composition for a phenolic resin composite of the present invention has excellent properties in terms of workability, productivity, flame retardancy, low smoke emission, adhesion to adherends, etc.).

(Example) Next, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples. All %J indicates "part by weight J" and "% by weight".

Example 1 1000 parts of phenol, 1250 parts of 37% formalin,
Five parts of 24% zinc naphthenate were charged to a four-loaf flask equipped with a reflux condenser and a stirrer.

The pH was 5.8.The system was heated to 75-80℃ at 90℃.
After holding for a minute, the reaction was carried out at 97 to 100°C for 2 hours. Then, while removing water and unreacted phenol,
A temperature of 40°C was reached. The reaction was continued for 20 minutes at the same temperature.
Next, the inside of the system was cooled to 120° C. and maintained at the same temperature for 30 minutes. After this, 400 parts of dimethyl glutarate was added and mixed,
The mixture was cooled to room temperature to obtain 1,670 parts of a benzylic ether type liquid phenol resin having a viscosity of 25 voids/25° C. and a dimethyl glutarate content of 24%.

Example 2 1000 parts of phenol, 590 parts of paraformaldehyde, and 3 parts of zinc acetate were charged into a four-loaf flask equipped with a reflux condenser and a stirrer.

The pH was 5.5.Next, the inside of the system was heated to 75-80℃
After holding for a minute, the reaction was carried out at 110 to 150°C for 2 hours. Next, the system was heated to 140°C while removing water and unreacted phenol. Next, the system was cooled, 550 parts of dimethyl succinate was added and mixed, cooled to room temperature, and the viscosity was 10 poise/25°C. Benzylic ether type liquid phenol tree Jl1169 with acid dimethyl content 33%
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Comparative Example 1 1000 parts of phenol, 590 parts of paraformaldehyde, and 3 parts of zinc acetate were charged into a four-loaf flask equipped with a reflux condenser and a stirrer.

The pH of the system was 5.5.
After holding for a minute, the reaction was carried out at 110-150°C for 2 hours. Next, the system was heated to 140°C while removing water and unreacted phenol. 50 parts of isophorone was added and mixed, and the mixture was cooled to room temperature. 1190 parts of a .2% benzylic ether type liquid phenol resin were obtained.

Comparative Example 2 Too many parts of phenol, 590 parts of paraformaldehyde, and 3 parts of zinc acetate were charged into a four-hole flask equipped with a reflux condenser and a stirrer.

The pH of the system was 5.5.
After holding for a minute, the reaction was carried out at 110 to 150°C for 2 hours. Next, while removing water and unreacted phenol, the system was brought to 140°C and cooled down, 1300 parts of a petroleum solvent was added and mixed, and the mixture was cooled to room temperature and had a viscosity of 0.
112,440 parts of benzylic ether type liquid phenol tree with 3 voids/25° C. and a petroleum solvent content of 53% was obtained.

Comparative Example 3 1000 parts of phenol, 1380 parts of 37% formalin,
20 parts of sodium hydroxide was charged to a four-loaf flask equipped with a reflux condenser and a stirrer.

Then, the temperature was gradually raised and the reaction was carried out at 80 to 85°C for 3 hours. After neutralization by adding 70 parts of 50% lactic acid, a dehydration reaction was carried out under vacuum until the nonvolatile content reached 80%.
Poise 725℃ resol type liquid phenolic resin 138
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100 parts of each of the benzylic ether type liquid phenol resins obtained in Examples 1 and 2 and Comparative Example 1.2, and 130 parts of polyisocyanate containing diphenylmethane diisocyanate as the main component, bales and bulk specific gravity 0.20, grain power 0 After mixing 400 parts of perlite of .6 to 1.2 m/m in a mixer for 2 minutes, the composite composition was added to and filled into a 250 m x 250 mm x 250 aluminum mold. Then, after heating and curing at 50° C. for 10 minutes and 20 minutes, respectively, the molds were cut to obtain a phenol resin composite.

711,100 parts of the resol-type liquid phenol tree obtained in Comparative Example 3, surfactant "Kao Choke S-120J2"
10 parts of the foaming agent "Freon 113J" and 67% of the hardening agent.
After stirring and mixing 15 parts of an aqueous phenol sulfonic acid solution using a homodisper at a rotational speed of 5000 Fpm for 20 seconds, this mixture was poured into the aluminum mold. The mixture was then cured by heating at 50° C. for 10 minutes and 20 minutes separately, and then removed from the mold to obtain a phenol resin foam.

Next, 100% of each benzylic ether type liquid phenol resin obtained in Examples 1 and 2 and Comparative Examples 1 and 2
After mixing 120 parts of polyisocyanate mainly composed of k" diphenylmethane diisocyanate and 600 parts of perlite with a bulk density of 0.15 and a particle size of 0.4 to 0.8 m1 m in a mixer for 1 minute, this composite material was mixed, respectively. Separately, fill it in a continuous heating machine with a female fuel on the top and an iron plate on the bottom.
Exterior sizing was obtained by heating at 0° C. for 10 minutes and 20 minutes separately.

Resol type liquid phenol 1 obtained in Comparative Example 3
000 parts of surfactant "Kao τsan S-120J Violet", 5 parts, foaming agent "Freon 113" 9 parts, and curing agent 67% phenol sulfonic acid aqueous solution 15 parts were mixed in an injection foaming machine to form the above continuous heating material. and heated separately for 10 minutes and 20 minutes to obtain exterior sizing.

Table 1 shows the physical properties of these composites and foams.

〔Effect of the invention〕

When the composite material of the present invention is used, the composite material can be cured quickly, and is suitable as a composition material for a heat insulating material that is good as a building material.

Claims (2)

[Claims] (1) A composition for a phenolic resin composite comprising a benzylic ether type liquid phenol resin having a viscosity of 1 to 50 poise/25°C, a polyisocyanate, and inorganic foamed granules as essential components. (2) The composition for a phenolic resin composite according to claim 1, wherein the benzylic ether type liquid phenol resin contains 7 to 50% by weight of dicarboxylic acid ester.