JPS59170128A - Phenolic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for producing foam of high closed cell content leading to good insulation, by incorporating a foaming agent and an alkylenedimelamine in a phenol-formaldelyde resol resin. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of a phenol-formaldelyde resol resin with (B) 0.5-15(pref. 1-10)pts.wt. of an alkylenedimelamine Cpref. of 1-6C alkylene, especially ethylenedimelamine). Said composition can be made into a foam with a density of 20- 100kg/m<3> and a closed cell content of 70-98%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a phenolic resin composition. More specifically, the present invention relates to a phenolic resin composition suitable for producing a foam with a high heat insulation effect.

Phenol resin foam is manufactured from a resin composition whose main components are phenol pot formaldehyde resol resin and a blowing agent, and among organic resin foams,
Because it is the most flame-retardant foam and smokeless,
It is particularly useful as a heat insulating material for building materials. However, since the cells in general phenolic resin foam are basically open cells, they have poor insulation properties compared to foams with high insulation effects such as urethane resin foams, which are basically made up of closed cells. It has the disadvantage of being inferior.

Therefore, in order to obtain a phenolic resin foam with excellent heat insulating properties, it is necessary to produce a foam with a high closed cell ratio, and many studies have been conducted to achieve this objective.

For example, JP-A-53-59754 and JP-A-53-59754
Japanese Patent No. 61263 discloses a method for producing a phenolic resin foam using a resin composition in which a phenolic resin composition contains a surfactant having a specific structure, and an acid.

Also, JP-A-53-13669 and JP-A-57-9
Publication No. 1244 discloses a method for producing a phenolic resin foam, which comprises foaming under specific conditions.

Furthermore, British Patent Publication No. 2089812 discloses a phenolic resin foam produced from a phenolic resin composition containing powdered aluminum hydroxide.

The present invention provides a phenolic resin composition that is advantageous for producing a foam with a high closed cell ratio.

The present invention consists of a phenolic resin composition characterized by containing a phenol-formaldehyde resol resin, a blowing agent, and an alkylene dimelamine.

Next, the present invention will be explained in detail.

The present invention is a resin composition in which an alkylene dimelamine is added to a conventionally known phenolic resin composition for producing a phenolic resin foam.

In other words, for components other than alkylene dimelamine among the various components used in the phenolic resin composition of the present invention, various conventionally known materials and substances can be used.

For example, phenol Φ formaldehyde resol resin can be obtained by mixing phenol and formalin, subjecting the mixture to a heating reaction in the presence of an alkali catalyst, and then neutralizing the mixture with an acidic substance.

Generally, phenol and formalin have a molar ratio of 1:1,
2-l:2. Mix at a ratio of o (former: latter). Furthermore, the phenol-formaldehyde resol resin used has a viscosity of 500 to 20,000 cP, with those having a viscosity of 1,000 to 6,00 OcP being particularly preferred. Note that the pH of the resin is preferably in the range of 6 to 7.5.

Low boiling point fluorinated hydrocarbons (for example, Freon 11, Freon 113, Freon 114, all trade names) are generally used as blowing agents, but if they can be used for the production of phenolic resin foams, It is not particularly limited to the above.

The alkylene dimelamine used in the present invention has the formula [
■] : (In the formula, R represents a divalent hydrocarbon residue having 1 to 6 carbon atoms)
It is a compound represented by

The alkylene dimelamines represented by the above formula [I] are known compounds, and these compounds and methods for producing these compounds are described in U.S. Pat. No. 2,544,071.
It is stated in the specification of the issue.

Specific examples of the alkylene dimelamine represented by the above formula [I] include methylene dimelamine (R = methylene group), ethylene dimelamine (R = ethylene 7u), and rimethylene dimelamine (R = nitrimethylene). ), tetramethylene dimelamine (R=tetramethylene group), hexamethylene dimelamine (R=hexamethylene group), and the like. Among these, those in which R is an alkylene group having 1 to 4 carbon atoms, ie, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group, are preferable. A particularly preferred alkylene dimelamine is ethylene dimelamine.

The content of alkylene dimelamine in the phenolic resin composition of the present invention is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the phenol-formaldehyde resol resin. is preferred. A particularly preferred range of tLl' is 2 to 6 parts by weight. If the content of alkylene dimelamine is too low, the effect of its addition will not be sufficiently apparent, and if the content is too high, the curing reaction of the resin composition will be slow and the proportion of closed cells will tend to be low. There is. Moreover, other compounds such as melamine can also be used in combination with the alkylene dimelamine of the present invention.

The phenolic resin composition of the present invention can contain various known additives. Examples of such known additives include antifoam agents. Examples of antifoam agents include known antifoam agents made of silicone polymers.

Further, for foaming and curing the phenolic resin composition of the present invention, for example, a usual acidic curing agent can be used. Examples of the acidic curing agent include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; and organic acids such as phenolsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and xylenesulfonic acid. Further, the foam curing operation can be carried out according to known techniques.

The foam obtained by foaming and curing the phenolic resin composition of the present invention has a high closed cell ratio (volume ratio of closed cells in the cells contained in the foam) despite being a phenolic resin foam. There are certain characteristics. Typical foams obtained from the phenolic resin composition of the present invention include:
Mention may be made of foams with a density of 20-100 kg/m' and a closed cell content of 70-98%. Note that a closed cell refers to a cell in which a unit cell (bubble) in a foam has a completely independent wall and is substantially completely isolated from adjacent cells by a cell membrane.

This closed cell ratio is, for example, ASTM-D-285
It can be measured according to the provisions of 6.

Examples and comparative examples of the present invention are shown below. The phenol-formaldehyde resol resin (resol resin) used in the following examples and comparative examples was prepared by mixing phenol and formalin at a molar ratio of 1:1.9, adding sodium hydroxide as a catalyst, and then , 90
The viscosity obtained by reacting at ℃ for 1.5 hours and neutralizing with hydrochloric acid was 2,
000cP, pH 6.5.

[Example 1] Funol, □Resol resin 100 parts by weight Silicone surfactant 2 parts by weight Foaming agent (Freon 11
3) 15 parts by weight ethylene dimelamine
3 parts by weight Hydrochloric acid 6.5 parts by weight A surfactant, a blowing agent and ethylene dimelamine were added to the above resol resin, and hydrochloric acid was added to the mixture with stirring. After stirring for about 30 seconds.

This was placed in a foaming container and foamed in an oven at 70°C.

The density of the resulting foam was 44'kCg/m' and the closed cell ratio was 91%. In addition, the thermal conductivity (K value) of this foam was 0.0180 K when measured one day later.
c a l / m h 'O. This thermal conductivity is a value measured according to JIS-A-1412.

The lower the thermal conductivity, the higher the insulation properties.

Further, the change over time in the thermal conductivity of the above foam is as follows.

``Kyo''``L'' K I K ca
l m h '01st 0.01
80 30 days 0.0175 60 days 0.0185 In other words, it can be seen that a foam with little change in heat insulation effect over time was obtained.

[Example 2] Phenol 7, 5 resol resin 100 parts by weight Silicone surfactant 2 parts by weight Foaming agent (Freon 11
3) 12 parts by weight ethylene dimelamine
2 parts by weight Melamine 2 parts by weight Phenolsulfonic acid (l: 19 compound with ethylene glycol) 15 parts by weight A surfactant, a blowing agent and ethylene dimelamine were added to the above resol resin, and to this mixture was added phenolsulfonic acid. Acid was added under stirring. After stirring for about 30 seconds, the mixture was placed in a foaming container and foamed in an oven at 70°C.

The resulting foam had a density of 41 kg/m3 and a closed cell ratio of 80%. In addition, the thermal conductivity of this foam (
K value) was 0.0210 K cal when measured one day later.
/ m h'cte was there.

[Comparative Example 1] Phenol, 5-group acid compounded resol resin 100 parts by weight Silicone surfactant 2 parts by weight Foaming agent (Freon 11
3) 15 parts by weight hydrochloric acid
A surfactant and a blowing agent were added to 6.5 parts by weight of the above resol resin, and hydrochloric acid was added to the mixture with stirring.

After stirring for about 30 seconds, put this into a foaming container and
Foaming was carried out in an oven at °C.

The resulting foam had a density of 51 kg/rn' and a closed cell ratio of 5%. In addition, the thermal conductivity of this foam (
K value) was 0.0340K cal when measured one day later.
/ m h 'C.

[Comparative Example 2] Phenolic tree and composite resol resin 100 parts by weight Silicone surfactant 2 parts by weight Blowing agent (Freon 11
．． 3) 15 parts by weight melamine
4 parts by weight Hydrochloric acid 6 parts by weight A surfactant, a blowing agent, and melamine were added to the resol resin described above, and hydrochloric acid was added to the mixture with stirring. After stirring for about 30 seconds, put this into a foaming container.
Foaming was carried out in an oven at 70°C.

The density of the obtained foam was 54 kg/m'', and the closed cell ratio was 76%.The thermal conductivity (K value) of this foam was 0.0187 K when measured one day later. c.
al/m h'C, and its change over time is as follows, and it was found that the heat insulating effect of this foam decreases over time.

E 11K K ca 1 m h ℃1
Day
0.018.730 days 0.0200 60 days 0.0302 Patent applicant: Ube Industries Co., Ltd. Agent Patent attorney: Yasuo Yanagawa

Claims (1)

[Scope of Claims] (1) A phenolic resin composition containing a phenol Q formaldehyde resol resin, a blowing agent, and an alkylene dimelamine. 2゜The content of alkylene dimelamine is 0.5 parts by weight per 100 parts by weight of phenol/formaldehyde resol resin.
The phenolic resin composition according to claim 1, wherein the amount is 15 parts by weight. 3゜The content of alkylene dimelamine is 1 to 1 per 100 parts by weight of phenol/formaldehyde resol resin.
The phenolic resin composition according to claim 2, characterized in that the amount is 0 parts by weight. 4゜Alkylene group of alkylene dimelamine has 1 or more carbon atoms
The phenolic resin composition according to any one of claims 1 to 2, wherein the phenolic resin composition is an alkylene group of 6. 5. The phenolic resin composition according to claim 4, wherein the 5° alkylene dimelamine is ethylene dimelamine.