JPS6289740A - Phenolic resin composition and flame-resistive phenolic resin foam made therefrom - Google Patents

Abstract

PURPOSE:A composition that is obtained by adding aluminum hydroxide and a nonionic surface active agent to a resol-type phenolic resin, thus giving foamed products having uniformly fine closed cells, much improved flame retardancy and low thermal conductivity. CONSTITUTION:(A) 100pts.wt. of a resol-type phenolic resin are combined with (B) 10-200pts.wt. of aluminum hydroxide as a flame retarder, and (C) 0.1-10pts. wt. of a nonionic surfactant of 12-16 HLB. As component C, are used polyoxyalkylene higher fatty acid ester or its phenol-modified product, or polyoxyalkylene sorbitol higher fatty acid ester. The resultant composition gives foamed products containing 10-70wt% of component B, and having 20-300kg/m<3> density and 0-80% cell content.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a phenolic resin composition, a flame-resistant phenolic resin foam formed from this composition, and a method for producing the same.

(Prior art) Phenolic resin foam is produced by adding -m to a resol-type phenolic resin obtained by addition-condensing phenols and aldehydes using an alkali catalyst, a blowing agent, a surfactant as a foam stabilizer, and acid curing. It is obtained by foaming and curing a resin composition formed by uniformly blending the agents at room temperature or by heating.

Such phenolic resin foams have superior heat resistance and flame resistance compared to urethane foams and polystyrene foams, and furthermore, they do not emit smoke or toxic gases when burned, making them suitable for building materials. It is used as a construction material for furniture, fittings, etc., and as an industrial material.

However, in recent years, the demand for flame resistance or non-combustibility as building materials and industrial materials has increased significantly, and it has become difficult to meet these demands using conventionally known phenolic resin foams. Moreover, its thermal conductivity is high. In particular, for phenolic resin foams with a high closed cell ratio, Ministry of Construction Notification No. 137 of 1982
A large-scale test such as the model box test specified in No. 2 causes the foam to explode, so that it does not meet the flame resistance or non-combustibility conditions.

(Object of the Invention) The present invention was made to solve the above-mentioned problems in conventional phenolic resin foams, and includes a phenolic resin composition for producing a phenolic resin foam with excellent flame resistance. It is an object of the present invention to provide a flame-resistant phenolic resin foam formed from such a phenolic resin composition and a method for producing the same. .

(Structure of the Invention) The present invention provides a phenolic resin composition for producing a heat-resistant phenolic resin foam containing a resol-type phenolic resin, a blowing agent, a surfactant, an acid curing agent, and a flame retardant. For 100 parts by weight of resin, (al) 10 to 20 parts of aluminum hydroxide as a flame retardant.
0 parts by weight and 0.1 to 10 parts by weight of a nonionic surfactant with an HLB of 12 to 16 as a (bl surfactant).

In addition, the flame-resistant phenolic resin foam according to the present invention contains 10-70% by weight of aluminum hydroxide as a flame-retardant, has a density of 20-300 kg/m'', and has a closed cell ratio of 0-80%. It is characterized by

Furthermore, such a flame-resistant phenolic resin foam is a phenolic resin composition for producing a heat-resistant phenolic resin foam containing a resol-type phenolic resin, a blowing agent, a surfactant, an acid curing agent, and a flame retardant according to the present invention. per 100 parts by weight of resol type phenolic resin, fa) 10 to 20 parts of aluminum hydroxide as a flame retardant.
It can be obtained by foaming and curing a phenolic resin composition containing 0 parts by weight and 0.1 to 10 parts by weight of a nonionic surfactant with an HLB of 12 to 16 as a (bl surfactant).

First, the phenolic resin composition according to the present invention for producing a flame-resistant phenolic resin foam will be explained.

In the phenolic resin composition according to the present invention, the aluminum hydroxide used as the flame retardant preferably has an average particle size in the range of 10 to 100 μm, and is in the range of 10 to 100 parts by weight per 100 parts by weight of the resol type phenolic resin.
It is blended in an amount of 200 parts by weight, preferably 30 to 150 parts by weight.

If this amount is less than 10 parts by weight with respect to 100 parts by weight of resol type phenolic resin, the flame resistance of the phenolic resin foam obtained by foaming and curing this composition will be insufficient; If it exceeds this, the strength of the foam will deteriorate and the viscosity of the resin composition will increase, making it difficult to foam and harden.
This is because the resulting foam has a higher density and a higher thermal conductivity.

Moreover, in the phenolic resin composition according to the present invention,
HL is used as a foam stabilizer for foaming and curing a resin composition to stably obtain a foam having fine closed cells.
A nonionic surfactant with B in the range of 12 to 16 is used.

Examples of the nonionic surfactant include polyoxyalkylene higher alcohol ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene higher fatty acid ester, phenol modified product of polyoxyalkylene higher fatty acid ester, and polyoxyalkylene sorbitan higher fatty acid ester. are used, but in particular,
Polyoxyalkylene higher fatty acid esters, phenol modified products of polyoxyalkylene higher fatty acid esters, and polyoxyalkylene sorbitan higher fatty acid esters are preferably used. In the above, preferred examples of higher fatty acids include capric acid, lauric acid, myristic acid, stearic acid, aragic acid, montanic acid, oleic acid, linoleic acid, riluic acid, soybean oil, and castor oil. , but not limited to these.

For example, preferred specific examples of the nonionic surfactant include polyoxyethylene castor oil ester, a phenolic compound of polyoxyethylene castor oil ester, and polyoxyethylene sorbitan stearate, more preferably 16 moles of ethylene oxide. Mention may be made of added sorbitan monostearate.

In the present invention, these nonionic surfactants need to have an HLB in the range of 12 to 16,
It is preferably in the range of 13 to 15.5, particularly 14 to 15. That is, the nonionic surfactant is 12
When the phenolic resin foam has an HLB in the range of ~16, the resulting phenolic resin foam has a closed cell ratio within a predetermined range of 80% or less and has excellent heat insulation properties, but when the HLB is smaller than 12. The closed cell ratio of the phenolic resin foam formed from the resin composition is increased to produce the above-mentioned barge, and when the ratio is larger than 16, the cells are changed into open cells when foamed and cured. Therefore, the heat insulation properties and water resistance are reduced.

In the present invention, such a nonionic surfactant is usually used for 100 parts by weight of the resol type phenolic resin.
It is blended in a range of 0.1 to 10 cells, and thus has a closed cell ratio of 80% or less and a density of 20 to 30%.
0 kg/m' can be obtained. Here, it is assumed that the closed cell ratio is measured by the measurement method specified in ASTM 1940. When the amount of the nonionic surfactant is less than 0.001 parts by weight per 100 parts by weight of the resol type phenolic resin, the resulting foam will not have a fine and uniform closed cell structure, and therefore will have poor heat insulation properties. On the other hand, if the amount is more than 1 part by 10 weight, the closed cell ratio will be too high, resulting in the formation of barges when exposed to flame, and the strength of the foam will also be poor. Particularly preferably, the nonionic surfactant is 1% per 100 parts by weight of the resol type phenolic resin.
It is blended in a range of 4 parts by weight.

Furthermore, the closed cell ratio of the phenolic resin foam of the present invention is 8.
It is necessary that it is 0% or less, preferably 60% or less. When it exceeds 60%, there is no practical problem, but some barges will occur, and when it exceeds 80%,
The barge becomes violent and exhibits dangerous flammability.

The resol type phenolic resin used in the resin composition according to the present invention can be obtained by a conventional method already known. For example, phenols and aldehydes are mixed at a phenol/aldehyde ratio of 1.1 to 1.8. It can be obtained by condensing an alkali metal hydroxide, an alkaline earth metal hydroxide, or a mono- to trivalent amine compound as a catalyst, neutralizing this with an appropriate acid, and dehydrating it under reduced pressure. Usually, its solid content concentration is 60-90% by weight, and its viscosity at 25°C is 1000-10000 cp.
It is s. Although not limited in any way, as the phenol, for example, phenol, cresol, xylenol, etc. are preferably used, and as the aldehyde, for example, formalin is preferably used.

As the blowing agent, hydrocarbons such as propane, butane, pentane, and hexane, and fluorinated hydrocarbons such as Freon 1), Freon 1) 2, Freon 1) 3, and Freon 120 are preferably used. The blending amount of these blowing agents is usually 1 to 30 parts by weight per 100 parts by weight of the resol type phenolic resin.
Parts by weight range.

Further, as the acid curing agent, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as benzenesulfonic acid, toluenesulfonic acid, and phenolsulfonic acid are used. The blending amount is based on 100 parts by weight of resol type phenolic resin.
Usually, it is in the range of 1 to 40 parts by weight.

The above-mentioned resol type phenolic resin composition according to the present invention can be obtained by adding a blowing agent, a surfactant, an acid curing agent, and aluminum hydroxide to a resol type phenolic resin and uniformly mixing them according to a conventional method. is possible,
The flame-resistant phenolic resin foam according to the present invention can be obtained by foaming such a composition at room temperature or by heating according to a conventional method. Note that foaming may be carried out using a mold or continuously using a double conveyor.

The flame-resistant phenolic resin foam according to the present invention contains 10 to 70% by weight of aluminum hydroxide as a flame retardant, and has a closed cell ratio of 0 to 80%. In a phenolic resin foam, when the aluminum hydroxide content is less than 10% by weight, the flame resistance is insufficient, as mentioned above, and on the other hand, when it exceeds 70% by weight, the strength of the foam is insufficient. This is because it also has high thermal conductivity. Also,
The closed cell ratio is in the range of 0 to 80%. Closed cell ratio is 8
When it exceeds 0%, a barge occurs. Furthermore, the water absorption rate is often 15% or less.

(Effects of the Invention) As described above, the resol type phenolic resin composition of the present invention contains aluminum hydroxide as a flame retardant, and has HLB or a nonionic surfactant within a predetermined range as a bubble stabilizer. By foaming and curing such a resin composition, the closed cells are fine and uniform, and the closed cell ratio is 80% or less,
It is possible to obtain a phenolic resin foam with significantly improved flame resistance compared to conventional phenolic resin foams. Therefore, the phenolic resin foam according to the present invention does not cause barges even in large-scale tests such as model box tests.
Moreover, the thermal conductivity is low.

(Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 Resol type phenolic resin 1 with methylol index 0.85
00 parts by weight and polyoxyethylene sorbitan monostearate (16 moles of ethylene oxide added, HLB=1
4.9) and 1 part by weight were sufficiently stirred and mixed at 25°C. Next, this mixture and aluminum hydroxide (average particle size 45μ
, 70 parts by weight of attached water (10% by weight),
To this were added a premix of 12 parts by weight of Freon (registered trademark) R1)3 as a blowing agent and 10 parts by weight of boric acid, and 12 parts by weight of phenolsulfonic acid as an acidic curing agent, and the mixture was heated at a temperature of 90°C. A foam was produced by heating for 10 minutes.

The phenolic resin foam thus obtained (density 6
5 kg/m", thickness 45 cranes), according to the flame retardancy test specified in Ministry of Construction Notification No. 1372 of 1981 and JIS A.
Thermal conductivity was measured in accordance with 1412. The results are shown in the table.

Examples 2 to 7 and Comparative Examples 1 to 9 A phenolic resin foam was prepared in the same manner as in Example 1, except that the amount of aluminum hydroxide and the type and amount of surfactant were shown in the table. It was manufactured and various physical properties were measured. The results are shown in the table.

Patent applicant Mitsui Petrochemical Industries Co., Ltd. agent Patent attorney Ittsu Makino Departmental procedural amendment (method) % formula % 2. Name of the invention Phenolic resin composition and flame-resistant phenolic resin foam formed from this composition 3 , Relationship to the case of the person making the amendment Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name
Mitsui Petrochemical Industries Co., Ltd. 4, Agent address: 1-8-3 Shinmachi, Nishi-ku, Osaka-shi 5. Date of amendment order: October 8, 1985 (Delivery date: October 28, 1985) 6. Subject of amendment: Column I for the title of the invention in the specification! '1 - Contents of the amendment (1) The name of the invention in the specification is corrected to "phenol resin composition and flame-resistant phenol resin foam formed from this composition."

that's all

Claims (9)

[Claims] (1) In a phenolic resin composition for producing a flame-resistant phenolic resin foam containing a resol-type phenolic resin, a blowing agent, a surfactant, an acid curing agent, and a flame retardant, for 100 parts by weight of the resol-type phenolic resin, A phenolic resin composition characterized by containing (a) 10 to 200 parts by weight of aluminum hydroxide as a flame retardant and (b) 0.1 to 10 parts by weight of a nonionic surfactant with an HLB of 12 to 16 as a surfactant. thing. (2) The phenol resin composition according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene higher fatty acid ester. (3) The phenol resin composition according to claim 1, wherein the nonionic surfactant is a phenol-modified product of polyoxyalkylene higher fatty acid ester. (4) The phenol resin composition according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene sorbitan higher fatty acid ester. (5) A flame-resistant phenolic resin foam containing a flame retardant, which contains 10 to 70% by weight of aluminum hydroxide as a flame retardant and has a density of 20 to 300 kg/m^
3 and a closed cell ratio of 0 to 80%. (6) A phenolic resin composition for producing a flame-resistant phenolic resin foam containing a resol-type phenolic resin, a blowing agent, a surfactant, an acid curing agent, and a flame retardant, the composition comprising 100 parts by weight of a resol-type phenolic resin. For foaming a phenolic resin composition containing (a) 10 to 200 parts by weight of aluminum hydroxide as a flame retardant and (b) 0.1 to 10 parts by weight of a nonionic surfactant with an HLB of 12 to 16 as a surfactant. A method for producing a phenolic resin foam, which comprises curing the foam. (7) The method for producing a phenolic resin foam according to claim 6, wherein the nonionic surfactant is a polyoxyalkylene higher fatty acid ester. (8) The phenol resin composition according to claim 6, wherein the nonionic surfactant is a phenol-modified product of polyoxyalkylene higher fatty acid ester. (9) The method for producing a phenolic resin foam according to claim 6, wherein the nonionic surfactant is a polyoxyalkylene sorbitan higher fatty acid ester.