JPS61238833A - Phenolic resin foam - Google Patents

Abstract

PURPOSE:The titled foam excellent in nonbrittleness, heat insulation and low in friability, obtained by curing by expansion a composition comprising a liquid phenolic resin, a blowing agent, an acid curing agent, a foam stabilizer and a saccharide. CONSTITUTION:A composition is obtained by mixing 100pts.wt. (in terms of solid matter) resol phenolic resin of a viscosity at 25 deg.C of 500-200,000cP with 1-50pts.wt. blowing agent (e.g., methylene chloride), 3-100pts.wt. acid curing agent (e.g., p-toluenesulfonic acid), 0.3-10pts.wt. foam stabilizer (e.g., castor oil/ethylene oxide adduct) and 0.1-50pts.wt. polysaccharide (e.g., ribose). This composition is poured into a predetermined mold kept at 30-90 deg.C and cured by expansion under an applied pressure to obtain a phenolic resin foam.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a phenolic resin foam having particularly improved brittleness resistance and heat insulation performance, and more specifically to a phenolic resin foam using sugars. It is related to.

The phenolic resin foam according to the present invention is mainly used for architectural insulation materials such as exterior wall materials, interior wall materials, ceiling materials, roof base materials, floor base materials, and rain shutters, and industrial insulation materials such as storage tanks, refrigerated warehouses, and pipes. Although it is used as a material, it can also be used for various other purposes.

(Prior art) In recent years, phenolic resin foams have become popular because they have excellent properties such as heat resistance, fire resistance, and low smoke emission that cannot be obtained with thermoplastic resin foams such as polystyrene resin, polyurethane resin, and polyethylene resin. , its usefulness has received a lot of attention.

However, due to the inherent fragility of phenolic resin, the phenolic resin foam has poor surface brittleness (hereinafter referred to as 7 liability), and if it becomes powdered or self-adhesive to the surface material, the surface material may peel off. In addition, since the bubble membrane is weak and easily disintegrates, it has the disadvantage of poor insulation performance and a very large decline in insulation performance over time, and there is a strong demand for improvement. This is the current situation.

(Problems to be Solved by the Invention) The present invention has been made in view of the problems of the prior art as described above, and its purpose is to solve the major 7 liability problems of the phenolic resin foam in the prior art. To provide a phenolic resin foam that solves the drawbacks of low heat insulation performance or a decline in heat insulation performance over time, and also has excellent properties such as heat resistance, fire resistance, and low smoke emission without impairing it. It is to be.

(Means for Solving the Problems) In order to solve the above-mentioned drawbacks, the present inventors conducted intensive research and found that when monosaccharide is added when producing a phenolic resin foam, the above-mentioned It was discovered that the foam has a very low 7 liability and has excellent heat insulation performance with little deterioration over time, leading to the completion of the present invention.

That is, the present invention provides a phenolic resin foam obtained by foaming and curing a blended composition containing a liquid phenol resin, a blowing agent, an acidic curing agent, a foam stabilizer, and a saccharide as essential components, wherein the amount of the saccharide is It is characterized in that cL is 1 to 50 parts by weight based on 100 parts by weight of the phenol resin converted to solid resin content.

The saccharides used in the present invention include monosaccharides, trisaccharides, trisaccharides,
or polysaccharides etc. alone or in mixtures thereof, specifically ribose, xylose, arabinose, glucose,
Mannose, galactose, fructose, maltose, lactose, sucrose, molasses, raffinose, genteanose, stachyose, celluloses such as 0, M, O, Hl, O, starches such as constar △, potato starch, Arabic Examples include rubber and fructan. Especially sucrose, molasses, fructose,
Preferred examples include, but are not limited to, glucose, lactose, maltose, and gum arabic.

Further, the amount of the saccharide is a, 1 to 50 parts by weight per 100 parts by weight of the phenol resin converted to solid resin content,
If the amount is less than 0.01% by weight, the object of the present invention cannot be achieved and good flyability-1 insulation performance cannot be expected. On the other hand, if it exceeds 50% by weight, the curing properties will be significantly deteriorated.

Furthermore, methods for blending sugars in the present invention include a method in which they are mixed during or after the production of the liquid phenolic resin, and a method in which they are blended at the time of preparing the foamable resin composition. Any method may be used and is not particularly limited.

Examples of the liquid phenolic resin according to the present invention include phenol, cresols such as 〇- or m- or p-cresol, xylenols such as 3,4- or 3,5-xylenol, and pseudophenols such as p-tertiary phenol. Alkylphenols having the above alkyl groups, catechol,
For every 1 mole of phenols such as polyhydric phenols such as resorcinol, hyrogallol, bisphenol A, and bisphenol F, alone or as a mixture, add 18 to 40 moles of aldehydes such as formalin, paraformaldehyde, glyoxal, etc. alone or as a mixture. In the presence of an alkaline catalyst such as an alkali metal hydroxide, an alkaline earth metal oxide or hydroxide, amines, ammonia, etc. alone or in a mixture, preferably at 50 to 100°C, and then as necessary. The catalyst is neutralized with an inorganic or organic acid such as sulfuric acid or P-toluenesulfonic acid, and then dehydrated and concentrated under reduced pressure. Particularly preferably used are novolak-type phenolic resins produced using inorganic or organic acids such as hydrochloric acid, zinc acetate, citric acid, and l)-toluenesulfonic acid as catalysts, or divalent metal salts such as lead acetate. A mixed resin containing a benzyl ether type phenol resin produced using the above resol type phenol resin as a catalyst may also be used.

The blowing agents used in the present invention are not particularly limited to those described below, but include, for example, halogenated hydrocarbons such as methylene chloride, trichloromonofluoromethane, 1,1,2-tricloCl, etc. Gases such as carbon dioxide are generated by mixing fluorine-containing halogenated hydrocarbons such as IJ fluoroethane and 1,2-dichlorotetrafluoroethane, aliphatic hydrocarbons such as butane, pentane, and hexane, and even acids. Chemically reactive foaming agents such as heavy 1 etc. may be used alone or in mixtures, and the blending amount thereof is 1 to 50 parts by weight per 100 parts by weight of the phenol resin calculated as solid resin content.

The curing agent used in the present invention is not particularly limited to those mentioned below, but examples include EVA, halatoluenesulfonic acid, xylenesulfonic acid, metaxylenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid,
yN9me! JTux sulfonic acid, styrene sulfonic acid, etc.
In addition to organic sulfonic acids, inorganic acids such as phosphoric acid and sulfuric acid may be used alone or as a mixture, and the amount thereof is 5 to 100 parts by weight per 100 parts by weight of phenolic resin converted to solid resin content.
Parts by weight.

The foam stabilizer used in the present invention is not particularly limited to those described below, but includes, for example, polysiloxane, polyoxyethylene sorbitan fatty acid ester,
Castor oil ethylene oxide adducts, alkylphenol ethylene oxide adducts, etc. may be used singly or in mixtures thereof, and the blending amount thereof is 15 to 10 parts by weight per 100 parts by weight of the phenol resin calculated as solid resin content. Furthermore, commonly used additives such as curing accelerators, flame retardants, neutralizing agents, organic or inorganic fillers, or colorants can be used as required.

Next, in order to obtain the 7-Nol resin foam of the present invention, a foamable resin composition is prepared by appropriately selecting and blending each of the above components and mixing them uniformly, and then injected into a predetermined mold. to harden the foam. For example, flame retardants, neutralizers, organic or inorganic fillers, pigments, etc. are added as necessary to a phenolic resin system liquid that has been internally added with sugars and foam stabilizers, and then a predetermined amount of foaming agent and curing agent are added. The agents are sequentially or simultaneously added and mixed with stirring, and a predetermined IIK whose temperature has been adjusted in advance to 30 to 90° C. is injected and foamed and hardened under pressure to obtain the desired foam.

Examples of industrial mixing methods include a batch method using high-speed stirring, a continuous high-speed stirring method, a spray mixing method, and a 7a miss method.

Examples of the molding method include a method in which the foamable resin composition obtained by the above-mentioned mixing method is discharged onto an endless conveyor, a method in which the foaming resin composition is caused to flow out in spots and foamed partially, and a method in which the foamable resin composition is foamed under pressure in a mold. There are two methods: a method of making a foam block by inserting it into a space of a certain size, and a method of filling and foaming it while press-fitting it into a cavity.

(Function) Although the effects of the measures taken in the present invention are not clear, they are thought to be as follows.

Sugars improve the surface plasticity (stickiness) of the cell membrane that forms the foam.
It is thought to have the effect of increasing the temperature of the foam, and eliminates the brittleness of the bubble membrane caused by the inherent fragility of the phenolic resin in the foam, or the breakage of the membrane caused by that fragility. It is thought that this prevents the movement and release of the foaming gas, which has low conductivity.

(Examples) Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited in any way by these examples. In addition, parts and % in the examples represent parts by weight and % by weight.

Example-1 Phenol 5QQkg and concentration 47% formalin sabk
g was charged into a reaction vessel equipped with a stirrer, a reflux tube, and a thermometer.

Next, 30k19 of a 20% aqueous sodium hydroxide solution was added, the temperature was raised from room temperature to 90°C in about 60 minutes, and the reaction was continued at the same temperature for 75 minutes. The viscosity of the reactant is 50
ap/50°C.

The reaction mixture was then cooled to 40°C, 10% sulfuric acid aqueous solution was added to adjust pli to 6.5, and concentrated under reduced pressure at 60 wilt to give a viscosity of 18QOap at 25°C.

A resin 470 YU with a solid resin content of 81% (non-volatile content dried on a hot plate at 180° C. for 30 minutes) was obtained. 1 kg of sucrose a was dissolved in 1 ook kg of the obtained phenol resin, and OX-100 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and ethylene oxide adduct of mustard oil) was added as a foam stabilizer and 3 kg of ammonium polyphosphate as a flame retardant. The mixture is one liquid, Freon 113 as a foaming agent is liquid ■, and 67% phenol sulfone i! is a hardening agent. lI? i, l! :L, Pmu-21
Using a foaming machine (trade name, manufactured by Toho Kikai Co., Ltd.) for 0-phenol foaming,! Liquid/Liquid II/Liquid I-100 parts/25 parts/3
A foam of 18QOX900X25- was prepared using a decorative steel plate mixed at a ratio of 5 parts and heated to 70°C as a face material. The gel time at this time was 120 seconds. After this foam was left at room temperature for 4 days, the density (YXAM P5T4), flyability (MU8〒M-421), bond strength with the surface material (measurement method shown below), oxygen index (K from J 720
1) Thermal conductivity (hot wire method) was measured. Also, the thermal conductivity is
Measurements were also made after 30 days of standing.

Here, the bonding force with the facing material is determined by cutting out a 25 x 150 square foam with facing material, making a hole with a diameter of 5 cm at the end of the facing material, hooking a K spring scale there, and pulling it up so that the facing material is the same as the foam. The value indicated by the spring gauge when the material is peeled off from the material is expressed as the bonding force.

As shown in Table 1, the obtained foam has a good appearance, low liability, strong bonding strength with the face material, excellent heat insulation performance with little deterioration over time, and is also flame retardant. It was a very good product that did not affect the quality of the product.

Comparative example-1 A foam was produced according to Example 1 without adding sucrose.

As shown in Table 1, the obtained foam had a high 7 liability, a weak bonding force with the face material, and a very large deterioration of heat insulation performance over time.

Comparative Example-2 According to Example-1, 5 & 7 kg of sucrose were mixed,
A foam was created. The gel time at this time was 420 seconds, and curing was extremely slow. The resulting foam has a slightly higher liability of 7, as shown in Table 1.
The insulation performance showed a slight decline over time.

Examples 2 to 10 According to Example 1, foams were created by changing the amount and type of sugar. As shown in Tables 1 and 2, the obtained foam has a good appearance, low liability, strong bonding strength with the facing material, and excellent heat insulation performance with little deterioration over time.
Furthermore, it was extremely excellent without impairing flame retardancy.

Example 11 Orthocresol 50kl? , Phenol 250 Yu, 9
1 aykcy of 2% paraformaldehyde and 88 kg of water were charged into a reaction vessel equipped with a stirrer, a reflux tube, and a thermometer. Next, 9 was added to 7.5 of triethylamine and the mixture was heated to 10 from room temperature.
Raise the temperature in about 60 minutes until it reaches 0℃, and then raise it to 45℃ at the same temperature.
The reaction was allowed to continue for minutes. The reaction mixture was then cooled to 40°C, and a 40% aqueous solution of para-toluenesulfonic acid was added to adjust the pH.
8 and 60°C, am was conducted under reduced pressure of H9 to obtain 45 kg of resin with a viscosity of 2.0 OGap at 25°C and a solid resin content of 80%.

The above phenolic resin 1100ky, BH- as a foam stabilizer
195 (product name, manufactured by Toray Silicone Co., Ltd.) t5 to 9
, a mixture of talc 5 and 9 as a neutralizing agent and filler! liquid, Freon 113 as a foaming agent as liquid (■), 80% xylene sulfonic acid aqueous solution as a hardening agent as liquid (■), 70
% sucrose aqueous solution with N? IIL, using a Henschel mixer, I liquid / ■ liquid / ■ liquid / W liquid - 100 parts by weight / 16 parts by weight /
Mixed at a ratio of 54 parts by weight/41 parts by weight (an amount of 3 parts by weight of sucrose per 100 parts by weight of phenol resin converted to solid resin content), 1800 x 90 using an aluminum plate as a face material.
A 0 x 40 wm foam was made. The gel time at this time was 110 seconds. As shown in Table 3, the obtained foam has a good appearance, low liability, strong bonding strength with the face material, excellent heat insulation performance that shows little deterioration over time, and has excellent flammability. It was an extremely good product that did not damage the product.

Comparative Example 3 According to Example 11, a resin and a foam were produced without adding an aqueous sucrose solution. As shown in Table 3, the obtained foam had a weak bonding force with the face material having a large liability, and its heat insulating performance deteriorated significantly over time.

Examples 12 to 16 According to Example 11, resins and foams were created by changing the type and amount of sugar. As shown in Table 3, the obtained foam has a good appearance, low liability, strong bonding strength with the facing material, and excellent heat insulation performance with little deterioration over time. It was an extremely good product that did not impair flammability.

Example 17 20 to 9 p-tert-butylphenol, 280 kg of phenol, 280 kg of 47% formalin, 2 o of sucrose
kg (an amount equivalent to 4 parts by weight of sucrose i per 100 parts by weight of phenol resin converted to solid resin content, calculated from the yield) was charged into a reaction vessel equipped with a stirrer, a reflux tube, and a thermometer. Next, 30 g of a 20% barium hydroxide aqueous solution was added, the temperature was raised from room temperature to 80° C. in about 50 minutes, and the reaction was continued at the same temperature for 3 hours. Cool to 40°C, adjust the pH to 45 by adding 50% acetic acid aqueous solution, and concentrate under reduced pressure of 60 μHt.
Viscosity at 5℃ 10,000'P% Solid resin content 83%
7 kg of resin A was obtained.

To the above phenolic resin IQQkg, 8H-1951,5
) A mixture of C9 is used as one liquid, and 70 tons of blowing agent 11
/ Freon 113 Maro 50 / 5 G% mixture as a layer liquid, 7
0% para-toluenesulfonic acid aqueous solution is used as m liquid, P m-
Using a 2107 Nord foaming machine, mix at a ratio of 100 parts, 720 parts, and 725 parts of 1 liquid/ul/m liquid, and heat at 70°C.
A foam was created using heated glass paper as a face material. The resulting foam has a density a, asbt/, J, -y
Liability - 12%, bond strength with facing material 520 f.

It had very excellent physical properties such as thermal conductivity α017 koal/gIhHr, C (after 4 days), 1018 kcal/m Hr, 'C (after 50 days), and oxygen index 40.

(Effects of the Invention) The phenolic resin foam according to the present invention greatly improves flyability and adhesive strength with surface materials, so it has good workability during construction and heat conduction over time. It has excellent insulation performance with little reduction in thermal insulation rate, so construction costs can be reduced.

Furthermore, it has the advantage of not having excellent properties such as heat resistance, fire resistance, and low smoke generation.

Claims (1)

[Claims] 1. A phenolic resin foam obtained by foaming and curing a composition containing a liquid phenol resin, a blowing agent, an acidic curing agent, a foam stabilizer, and a saccharide as essential components, wherein the amount of the saccharide is equal to that of the solid resin. A phenolic resin foam, characterized in that the amount is 0.1 to 50 parts by weight based on 100 parts by weight of the phenol resin.