JPH0446294B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a foaming phenolic resin composition suitable for producing a phenolic resin foam having excellent properties. This foam has excellent properties such as light weight, heat insulation, fire resistance, low smoke emission, and heat resistance. This foam is used as a fireproof and fireproof lightweight insulation material in the building materials field, including interior wall materials such as partition panels and clean room panels, curtain wall panels,
It is used for external wall materials such as metal siding, ceiling panels, roof base materials, underfloor insulation materials, fire doors, storm shutters, etc. In the field of cold and thermal insulation plants, it is used for methane, propane, butane tanks, LNG tanker tanks, and refrigeration. Cold insulation materials for warehouses and cold storage,
It is typically used as a heat insulating material for oil pipelines, heavy oil tanks, etc., but is not limited to these. [Prior Art] Conventionally, phenolic resin foams have excellent heat resistance, fire resistance, and low smoke emission properties that cannot be obtained with thermoplastic resin foams such as polystyrene, polyurethane, and polyethylene. Attention has been paid. However, the phenolic resin foam has a major drawback in that it is brittle due to its crosslinked structure, and this is due to the poor surface brittleness of the foam, which may cause it to crack or if it is self-adhered to the surface material. , the bond strength is weak, and large cracks occur under the interface with the surface material, the surface material peels off, and in some cases, the cell membrane becomes weak and thermal conductivity deteriorates. ing. Moreover, these problems cause various troubles during manufacturing and processing. Japanese Patent Publication No. 58-29814 and Japanese Patent Publication No. 58-56376 disclose the use of a block copolymer resin of orthocresol and phenol. In this method, an orthocresol resol or novolak is prepared in advance, and then a phenol is mixed with the resol made by reacting the same with phenol and an aldehyde, which is then used for the foam. Although this method has improved the surface brittleness of the foam to some extent, it has the following drawbacks.
In particular, phenolic foam requires surfactants, blowing agents, acidic curing catalysts, and flame retardants in order to meet the required properties, but foaming occurs in the coexistence of these additives. When manufacturing a body,
It is difficult to produce a foam using the above composition without causing fine cracks when left at room temperature. Furthermore, JP-A No. 56-67341 discloses a product containing polyethylene glycol;
This foam is obtained by stirring and mixing a composition whose main components are a resol-type phenolic resin, a foam stabilizer, a blowing agent, polyethylene glycol with a number average molecular weight of 800 to 2,500, and a phosphoric acid curing agent. be. Although the surface brittleness of this foam has been improved to some extent, it has drawbacks such as a marked increase in moisture permeability due to the addition of a water-absorbing resin and a deterioration in low smoke generation, so that it is not practically satisfactory. [Problems to be Solved by the Invention] The present invention has been made in view of the problems of the prior art, and the problems to be solved are the brittleness of the resin, which is a basic requirement for foams, as described above. It solves the disadvantages such as surface brittleness, cracks in the foam, large cracks that occur under the interface with the facing material, peeling of the facing material, and fine cracks that occur on the surface and inner surface of the foam when left at room temperature. To provide a foaming phenolic resin composition suitable for molding a phenolic resin foam, which has excellent properties such as light weight, heat insulation, fire resistance, low smoke emission, and heat resistance. [Means for Solving the Problems] In view of the problems of the prior art described above, the present inventors conducted intensive research as follows. A urea formaldehyde resin and a bisphenol A formaldehyde resin having substantially methylol groups at both ends were reacted with resorcin, respectively, and then mixed with a resol type phenol resin. A surfactant, a retardant, a foaming agent, and a curing catalyst are mixed with each resin composition, and the mixture is subjected to cream time for 70 minutes.
C. for about 150 seconds to obtain a foam. The surface brittleness (hereinafter sometimes abbreviated as flyability) of these foams was extremely small, ranging from 9 to 12%. On the other hand, I tried to make a foam in the same way as above by mixing urea formaldehyde resin with resol-type phenolic resin without reacting resorcinol, but I could not obtain a foam and could only obtain a rice cracker-like product with coarse cells. Nakatsuta. In addition, a similar operation was performed on bisphenol A formaldehyde resin without reacting with resorcin, but although a foam was obtained, the flyability was 25%.
This was a large value, and it was extremely fragile. Further, a resol-type orthocresol formaldehyde resin was reacted with resorcin, and then mixed with a resol-type phenol resin to obtain a foam in the same manner as described above. This foam had a very low flyability of 10%, and no cracking occurred even if it was left at room temperature for more than 30 days. On the other hand, a foam was obtained by mixing orthocresol formaldehyde resin with resol-type phenol resin without reacting resorcin and using the above method, but the flyability was a large value of 21% and it was brittle, so it was left at room temperature for 2 days. However, many fine cracks had occurred. Furthermore, a resol type orthocresol formaldehyde resin was prepared in advance, and phenol was mixed with the resol type resin prepared by reacting the same with phenol and formaldehyde, and a foam was obtained in the same manner as described above. This foam had a low flyability of 12%, but many fine cracks appeared when it was left at room temperature for 5 days. In addition, the same results as above were obtained with para-alkylphenol aldehyde resin. As mentioned above, the present inventors have discovered that urea aldehyde resins, which hardly react with resol-type phenolic resins within the short time of foaming and curing, bisphenol A aldehyde resins, which react slowly, and ortho- or para-alkyl phenolic aldehyde resins, are used as resorcinols. By pre-reacting, it easily and reliably bonds with resol type phenolic resin, has extremely low flyability, and does not crack at all even when left at room temperature. He came up with an invention. That is, the measures taken in the present invention are a urea aldehyde resin, a bisphenol A aldehyde resin, or a resin having 1 to 1 carbon atoms at the ortho or para position.
An alkylphenolaldehyde resin (hereinafter abbreviated as alkylphenolaldehyde resin) having one alkyl group of No. 4, which has methylol groups at both ends of the molecule and does not substantially contain methylol groups other than at both ends of the molecule. A cocondensation resin A containing 2% by weight or less of free resorcinols obtained by reacting a resin with 0.4 to 1.0 moles of resorcinols based on the moles of the methylol group, and 1.0 to 1.0% by weight of free resorcinols per mole of phenol. Resol type phenolic resin B, which is obtained by reacting 2.0 mol of aldehydes in the presence of a basic catalyst and has a number average molecular weight of 200 to 700, is mixed with a solid resin component weight ratio of A/B of 5/95. ~30/70
It was mixed so that The urea aldehyde resin, bisphenol A aldehyde resin, and alkylphenol aldehyde resin used in the present invention are thermosetting resins that have methylol groups at both ends of the molecular chain and do not substantially contain methylol groups other than at both ends of the molecule. Each of the resins includes urea, bisphenol A, alkylphenols and aldehydes, and alkali metal hydroxides,
It is obtained by addition condensation under known reaction conditions using a basic catalyst such as an alkaline earth metal oxide, hydroxide, ammonia, or an amine compound alone or in combination. Although not particularly limited, the number average molecular weight of the urea aldehyde resin is preferably
150-400, bisphenol A aldehyde resin is
400~800, alkylphenol aldehyde 200~
500 initial condensate. Here, as the alkylphenols, those having a structure having one alkyl group having 1 to 4 carbon atoms at the ortho or para position are preferably used, and specific examples include orthocresol, paracresol, paratertiary butyl Examples include phenol alone or as a mixture. The use of alkylphenols having a carbon number greater than 4 is undesirable because the reaction with resorcinols tends to be inhibited due to steric hindrance. Further, as aldehydes, formalin, paraformaldehyde, trioxane, etc. are preferably used alone or in mixtures, and the reaction molar ratio is urea, bisphenol A, alkylphenol
It is preferably 1.1 to 2.0 mol, more preferably 1.3 to 1.7 mol. Aldehydes are 2.0
If it is more than 1 molar, many methylol groups tend to attach to areas other than both ends of the molecular chain, so in the next step when reacting with resorcinols, resorcinols tend to attach to areas other than both ends of the molecular chain, resulting in crosslinking and free aldehyde. As a result, self-condensation of resorcinols progresses, resulting in a lack of resorcinols in the methylol groups at both ends, resulting in no condensation.
The effect of improving the surface brittleness of the foam and cracking when left at room temperature is reduced, and in some cases, it may gel when reacting with resorcinols. If the amount of aldehydes is less than 1.1 mol, the amount of methylol groups is small and the co-condensed resin A obtained by addition condensation of resorcinols and the resol-type phenol resin B cannot be sufficiently bonded, and cracks may occur when left at room temperature or foams may be formed. The effect of improving surface brittleness becomes smaller. The cocondensation resin A used in the present invention is prepared by adding resorcinols in an amount of 0.4 to 1.0 moles, preferably 0.6 to 0.8 moles, based on the moles of methylol groups at both ends of the molecular chain of the thermally effective resin. This is what I did. When the number of resorcinols is less than 0.4 moles relative to the number of moles of the methylol group, the amount of resorcinols that react with the methylol group is small, so
The resol type phenolic resin B cannot be sufficiently bonded to the resulting co-condensed resin A during foaming and curing, and the effect of improving the surface brittleness of the foam and cracking at room temperature is small. Moreover, if the number of moles is more than 1.0, a large amount of free resorcinols will be produced, and the effect of improving the surface brittleness of the foam will be reduced. Here, free resorcinols are co-condensed resin A
It is preferable that the amount is 2% by weight or less. 2
When the amount exceeds % by weight, the effect of improving the surface brittleness of the foam becomes small. The resorcinols used in the present invention include resorcinol, 5-methylresorcinol, 5-methylresorcinol, and 5-methylresorcinol.
-ethylresorcinol, 2 and 4-methylresorcinol, 2,5-dimethylresorcinol, 2-ethyl-5-methylresorcinol, 2
-ethyl-5-ethylresorcinol, 4,5-
Dimethylresorcinol, 2-methyl-5-ethylresorcinol, 5-propylresorcinol, 4-methyl-5-ethylresorcinol and the like are suitable, and these are used alone or in combination. Further, even if some of these resorcinols are oligomerized, the gist of the present invention does not change. The resol type phenolic resin B used in the present invention contains 1.0 to 2.0 mol of aldehydes per 1 mol of phenol, such as alkali metal hydroxides, alkaline earth metal oxides, hydroxides, amine compounds, etc. The reaction is carried out using a basic catalyst alone or in combination, preferably at 60 to 100°C, but not limited to, and if necessary, the catalyst is replaced with an inorganic or organic acid such as hydrochloric acid, p-toluenesulfonic acid, or acetic acid. It has a number average molecular weight of 200 to 700 and is obtained by neutralizing with water and dehydrating and concentrating it under reduced pressure. The reaction molar ratio of aldehydes is preferably 1.0 to 2.0 mol, more preferably 1.3 to 1.8 mol, per 1 mol of phenol. If the amount of aldehydes is less than 1.0 mol, there will be a shortage of methylol groups and the curing speed of resol type phenolic resin B will be extremely slow.
Curing becomes insufficient. On the other hand, if the amount is more than 2.0 mol, the crosslinking rate of the resin B becomes slow during foaming and curing, and cracks tend to occur when left at room temperature, which is not preferable. Here, regardless of whether the reaction molar ratio is low or high, cocondensation resin A has resorcinols attached to both ends of the molecular chain, so resol type phenol resin B
However, since resol type phenol resin B, which has a large mixing ratio, has the above-mentioned tendency, a good foam cannot be obtained. Further, the resol type phenol resin B having a number average molecular weight of 200 to 700 is preferably used. If the molecular weight is less than 200, the foaming speed during foaming and curing will be too fast, making it impossible to obtain uniform and fine cells, and
If it is higher than 700, the resin viscosity will increase, making it difficult to mix uniformly with other materials such as blowing agents and hardeners using ordinary foaming machines, and furthermore, the curing speed will be extremely low, making it difficult to produce a good foam. I can't get it. Also here, since the resol type phenol resin B, which has a larger mixing ratio than the co-condensed resin A, has this tendency, a good foam cannot be obtained. The foaming phenolic resin composition of the present invention comprises the co-condensed resin A and the resol type phenolic resin B.
The solid resin weight ratio of A/B is 5/95 to 30/70.
It is made by mixing so that A/B
If the weight ratio of the solid resin component is less than 5/95, the surface brittleness of the foam and the improvement in curing against cracking when left at room temperature will hardly be achieved. On the other hand, if it is larger than 30/70, the amount of co-condensed resin A will be too large, resulting in insufficient curing through crosslinking, resulting in increased flyability of the foam. Incidentally, various characteristic values of the co-condensed resin A and the resol type phenol resin B were determined by the following method. [Number of moles of methylol group]: Approximately 10 g of resin and approximately 20 g of phenol (containing 1% by weight of para-toluenesulfonic acid) in a 200 ml flask.
Weigh out the amount accurately, put it in, attach a condenser, and place it on an oil bath.
React at 115-120℃ for about 90 minutes. After cooling, water content was measured by the Karl Fischer method, and free formaldehyde was measured by the hydrochloric acid hydroxyamine method, which was determined by the following formula. Number of moles of methylol group = Mn/---/10 ^-2 (100-RW) x {10 ^-2 (P+R) (R
RW) −18×10 ^-2 [R×RF−(P+R)RF]/30 −10 ^-2 R(RW)−10 ^-2 P(RW)}/[18×R×10 ^-2 (10
0−RW)] However, P: Weight of added phenol (g) R: Weight of resin (g) RF: Free formaldehyde in resin (wt%) RW: Moisture in resin (wt%) PW: Moisture in added phenol (wt%) RRF: Free formaldehyde after reaction (wt%) RRW: Moisture after reaction (wt%): Resin number average molecular weight [number average molecular weight]: The number average molecular weight was obtained by measuring by vapor pressure method (resin number average molecular weight) using the following formula. Number average molecular weight = Mn/10 ^-2 (100 - RW) However: Number average molecular weight determined by vapor pressure method RW: Moisture in resin (% by weight) [Moisture]: Determined by Karl Fischer method. [Free formaldehyde]: Determined by the hydrochloric acid hydroxyamine method. [Free monomer]: Determined by gas chromatography using OV-17 (manufactured by Gas Chroma Industries) as a column except for urea. [Solid resin content]: The resin placed on aluminum foil was dried on a hot plate at 180°C for 60 minutes, and determined using the following formula. Solid resin content = Weight after drying/Sample weight x 100 (wt%) [Free resorcinols]: Determined by gas chromatography using OV-17 as a column. [Viscosity]: Determined using a BH type viscometer. The foam obtained from the foaming phenolic resin composition of the present invention is generally obtained by sufficiently mixing the foaming phenolic resin composition with a surfactant, a flame retardant, a blowing agent, and an acidic catalyst, and then foaming the mixture. Obtained by curing. The surfactant used here is not particularly limited, but polysiloxanes, polyoxyethylene sorbitan fatty acid esters, castor oil ethylene oxide adducts, alkylphenol ethylene oxide adducts, and the like are suitable. The flame retardant is not particularly limited, but tris-β-ethyl chlorophosphate, triphenyl phosphate, boric acid, guanidine phosphate, ammonium polyphosphate, and the like are preferably used. The blowing agent is not particularly limited, but commercially available low boiling point fluorocarbon blowing agents such as Freon 11 and Freon 113, butane,
Preferably used are aliphatic hydrocarbons such as pentane and hexane, and chemically reactive blowing agents such as baking soda that generate gases such as carbon dioxide when mixed with acids. Examples of acidic catalysts include, but are not limited to, paratoluenesulfonic acid, phenolsulfonic acid, xylenesulfonic acid, benzenesulfonic acid, resorcinsulfonic acid, metaxylenesulfonic acid, polymeric sulfonic acid, styrenesulfonic acid, and polystyrene. In addition to organic sulfonic acids such as sulfonic acid, inorganic acids such as phosphoric acid, sulfuric acid, oxalic acid, and hydrochloric acid are preferably used. Note that a foam neutralizer such as zinc powder, iron powder, or aluminum powder, or a filler such as aluminum hydroxide, talc, or alumina may be added to the foaming agent. The procedure for producing the foam includes a batch type high-speed stirring method, a continuous mixing method, a spray mixing method, etc., and there are no particular limitations on the operations. do not have. The mixture obtained by each of these operations can be molded by flowing it out onto an endless conveyor, by blowing it out in spots and foaming it partially, by foaming it under pressure in a mold, or by blowing it into a space of a certain size. It is used in a method to create a foam block by pouring it in, and a method to fill and foam while press-fitting it into a cavity. [Effect] Although the effect of the measures taken in the present invention is not clear, it is thought to be as follows. Urea aldehyde resin, bisphenol A aldehyde resin, and alkyl phenol aldehyde resin, which are raw materials for cocondensation resin A, have methylol groups substantially only at both ends, so that crosslinking does not substantially occur in the molecular chain, and each resin has a linear structure, so
It has the effect of imparting flexibility to the phenolic resin foam. Since each of the thermosetting resins has poor or low reactivity, resorcinols are produced by adding resorcinols in an amount that reacts with the methylol groups at both ends and bonding with the methylol groups. It has the effect of increasing the reactivity with resin B. Therefore, the cocondensation resin A reacts with the resol type phenolic resin B simply by mixing it easily and reliably within the short time of foam curing, imparts flexibility to the foam, and concomitantly improves the surface of the foam. Improves brittleness and prevents cracking. Furthermore, since the resol type phenol resin B is sufficiently crosslinked and rigidly bonded, it has the effect of increasing the strength of the uniform and fine cell membrane. Furthermore, keeping the free resorcinols below 2% by weight means that when the cocondensation resin A and the resol type phenolic resin B are mixed and foamed and cured, the free resorcinols are crosslinked with the resol type phenolic resin B. This has the effect of preventing a rigid configuration from occurring partially. [Example] Example 1 Production of co-condensed resin A: 200 kg of orthocresol and 47% formalin
Charge 142 kg into a reactor equipped with a reflux tube and a stirrer, and then add 20% aqueous sodium hydroxide solution while stirring.
After adding 24Kg and raising the temperature from room temperature to 90℃ in about 60 minutes, and continuing the reaction at the same temperature for 90 minutes,
It was cooled to obtain an orthocresol resin. This resin contains 3.2% by weight of free forsocresol (hereinafter referred to as 3.2%).
It is abbreviated as ), free formaldehyde 0%, moisture
39%, number average molecular weight 417, number of moles of methylol group
It was 1.2 mol. 57 kg (0.8 moles) of resorcin was added to the resin, and the temperature was raised from room temperature to 80°C in about 30 minutes.
The reaction was continued for 30 minutes at the same temperature. Then cool to 40℃ and add 40% para-toluenesulfonic acid to pH 6.5.
Concentrate under reduced pressure of 60 mmHg. 25℃
Viscosity at 8000 cp, solid resin content 75%, free orthocresol 3.1%, free resorcin Trace,
A co-condensation resin A having 0% free formaldehyde, 15% water and a number average molecular weight of 522 was obtained. Production of resol type phenolic resin B: 200 kg of phenol and 204 kg of formalin with a concentration of 47% were placed in a reflux tube and a reactor equipped with a stirrer, and while stirring, 20 kg of a 20% aqueous sodium hydroxide solution was added, and the temperature was raised from room temperature to 90°C. After about 60 minutes, the reaction was continued at the same temperature for 120 minutes, cooled to below 40℃, and 40% para-toluenesulfonic acid was added.
Adjust the pH to 6.5, concentrate under 60mmHg vacuum,
Viscosity at 25℃ 5000 cp, solid resin content 78%, free phenol 5.8%, free formaldehyde 0.4
%, water content 13.4%, and number average molecular weight 460, resol type phenol resin B was obtained. 20 g of the obtained co-condensed resin A and 80 g of resol type phenolic resin B (weight ratio of solid resin content of A/B =
19/81) in a cup and mix well, then add 1.5 g of SH-193 (manufactured by Toray Silicone) as a foam stabilizer, 7 g of ammonium polyphosphate and 7 g of aluminum hydroxide as flame retardants, and Freon 113 (Asahi Glass Co., Ltd.) as a foaming agent. 18g of the solution was added and stirred for 30 seconds using a homodisper with a rotational speed of 3000 rpm, and the liquid temperature was adjusted to 20°C. Then 65% as a curing catalyst adjusted to 20℃
Add 20g of phenolsulfonic acid aqueous solution, stir for 20 seconds using the homodisper, and immediately use kraft paper as the top and bottom materials and heat to 80°C.
The mixture was injected into a mold of 1.0 mm in diameter, kept in a constant temperature bath at 80° C. for 5 minutes, and then removed from the mold to obtain a foam with a cream time of 30 seconds and a gel time of 120 seconds. After leaving this foam at room temperature for 10 days, the density, surface brittleness, bonding strength with the face material, flame retardant class 2 test, and thermal conductivity were measured using JISA9514, ASTM421, the measurement method shown below, JIS1321, and the hot wire method, respectively. In addition, the appearance of the foam was observed every day for 30 days or more after production. Here, the bonding force with the facing material is determined by cutting out a 25 x 150 mm foam with a facing material,
A 5 mm hole is made at the end of the surface material, a spring balance is hung there and pulled up, and the value indicated by the spring balance when the surface material is peeled off from the foam is expressed as the bonding force. The obtained foam has a density of 0.042 g/cm ³ , a flyability of 9%, a bond strength with the face material of 280 g, a thermal conductivity of 0.020 Kcal/m・hr・℃, high flame retardancy, and a good appearance. It has excellent surface brittleness, with little powder falling off even when rubbed strongly with fingers, and has strong bonding strength with the surface material, even after 30 days or more, unlike conventional phenolic resin foam (see Comparative Example 5). The foam was excellent in that there were no large cracks that occurred below the interface with the surface material, and no fine cracks occurred on the surface or inner surface of the foam when left at room temperature. Example 2 A foam was produced in the same manner as in Example 1, except that the co-condensed resin A of Example 1 was replaced with a co-condensed resin obtained by changing the amount of resorcin to 35 kg (0.5 moles). I got it. The obtained foam was tested in the same manner as in Example 1, and the results were as shown in Table 1. The obtained co-condensed resin had a viscosity of 6700 cp at 25°C, a solid resin content of 75%, free orthocresol 3.1%, free resorcinol trace, free formaldehyde 0%, water 14.2%, and a number average molecular weight of 485.
It was from. Example 3 Production of resol type phenolic resin C: 200 kg of phenol and 204 kg of formalin with a concentration of 47% were charged into a reactor equipped with a reflux tube and a stirrer, and while stirring, 10 kg of a 20% aqueous sodium hydroxide solution was added, and the mixture was heated from room temperature to room temperature. Raise the temperature to 90℃ in about 60 minutes, continue the reaction at the same temperature for 140 minutes, cool it to below 40℃, add 40% para-toluenesulfonic acid,
Adjust the pH to 6.5 and concentrate under a reduced pressure of 60 mmHg.
Viscosity at ℃ 2500 cp, solid resin content 81%, free phenol 8.2%, free formaldehyde 0.9%,
Lysol type phenol resin C having a water content of 9.8% and a number average molecular weight of 230 was obtained. 20 g of co-condensed resin A of Example 1 and 80 g of resol type phenolic resin C (weight ratio of solid resin content of A/C = 18/82) were taken into a cup and mixed well, and then 1.5 g of SH-193 was added as a foam stabilizer. g, 7 g of ammonium polyphosphate, 7 g of aluminum hydroxide as a flame retardant, and 10 g of Freon 113 as a foaming agent, and the rotation speed was increased.
The mixture was stirred for 30 seconds using a homodisper at 3000 rpm, and the liquid temperature was adjusted to 20°C. Next, 20g of 65% phenolsulfonic acid aqueous solution as a curing catalyst adjusted to 20℃
was added, stirred for 20 seconds using the homodisper, and immediately used kraft paper as the upper and lower surface materials to obtain a foam in the same manner as in Example 1. The obtained foam was tested in the same manner as in Example 1, and the results were as shown in Table 1. Example 4 Production of resol type phenolic resin D: 200 kg of phenol and 231 kg of formalin with a concentration of 47% were charged into a reactor equipped with a reflux tube and a stirrer, and while stirring,
Next, 20 kg of 20% sodium hydroxide aqueous solution was added and the temperature was raised from room temperature to 100°C in about 60 minutes.
After continuing the reaction for 100 minutes at the same temperature, it was concentrated under a reduced pressure of 60 mmHg, and the viscosity at 25°C was 4500 cp.
Opalescent resol type phenolic resin D with solid resin content 75%, free phenol 2.5%, free formaldehyde 0.3%, water 18.2%, number average molecular weight 650.
I got it. 20 g of the co-condensed resin A of Example 1 and 80 g of the resol type phenolic resin D (weight ratio of solid resin content of A/D = 20/80) were taken into a cup and mixed well, and then SH-193 was added as a foam stabilizer. 1.5g, 7g of ammonium polyphosphate as a flame retardant, 7g of aluminum hydroxide,
Add 30g of Freon 113 as a foaming agent and increase the rotation speed.
The mixture was stirred for 60 seconds using a homodisper at 3000 rpm.
After that, the liquid temperature was adjusted to 30℃ due to the high viscosity.
Next, 60 g of a 65% phenolsulfonic acid aqueous solution as a curing catalyst adjusted to 30°C was added, stirred for 30 seconds using the homodisper, and immediately the upper and lower surfaces were made of kraft paper, and a foam was obtained in the same manner as in Example 1. . The resulting solid foam was tested in the same manner as in Example 1, and the results were as shown in Table 1. Comparative Example 1 In place of the co-condensation resin A of Example 1, Example 1
Add 40% para-toluenesulfonic acid to the orthocresol resin obtained in , adjust the pH to 6.5, and
A resin obtained by concentration under reduced pressure of Hg and having a viscosity of 5000 cp at 25°C, a solid resin content of 80%, free orthocresol 3.0%, free formaldehyde 0%, moisture 12.4%, and a number average molecular weight of 422 was used. A foam was obtained in the same manner as in Example 1 except for this. The obtained foam was tested in the same manner as in Example 1, and the results showed that the flyability was very poor.
In addition, many fine cracks were formed on the surface and inner surface of the foam on the second day after being left at room temperature. Other results were as shown in Table 2. Comparative Example 2 200 kg of orthocresol and 76 kg of 92% paraformaldehyde were placed in a reflux tube and a reactor equipped with a stirrer, and while stirring, 3.7 kg of 50% aqueous sodium hydroxide solution was added and the temperature was raised from room temperature to 90°C. The reaction was continued for 110 minutes at the same temperature, then cooled, and 100 kg of phenol and 45 kg of 92% paraformaldehyde were added and heated at 90°C.
The reaction was continued for 130 minutes. Then cooled to 40℃,
Add acetic acid to adjust the pH to 6.5, and check the viscosity at 25℃.
A resin of 24000 cp, solid resin content 79%, free orthocresol 0.9%, free phenol 8.7%, free formaldehyde 0.1%, and water 13.0% was obtained. 90g of the resin, 10g of phenol, L- as a foam stabilizer
Take 1.5 g of 5340 (Nippon Unica), 7 g of ammonium polyphosphate as a flame retardant, 7 g of aluminum hydroxide, and 18 g of Freon 113 as a blowing agent.
The mixture was stirred for 30 seconds using a homodisper with a rotational speed of 3000 rpm, and the liquid temperature was adjusted to 20°C. Next, 1/1 of 67% xylene sulfonic acid aqueous solution and 67% para-toluene sulfonic acid aqueous solution as a curing catalyst adjusted to 20 ° C.
25 g of the mixture was added and stirred for 20 seconds using the homodisper. Immediately, the upper and lower surfaces were made of kraft paper, and a foaming agent was obtained in the same manner as in Example 1. The obtained foam was tested in the same manner as in Example 1, and the flyability was improved to some extent, but many fine cracks appeared on the surface and inner surface of the foam after 5 days of being left at room temperature. It was hot.
Other results were as shown in Table 2. Comparative Example 3 Foaming was carried out in the same manner as in Example 1, except that in place of the co-condensed resin A of Example 1, a co-condensed resin obtained by changing the amount of resorcin to 14 kg (0.2 moles) was used. I got a body. The obtained foam was tested in the same manner as in Example 1, and the results were as shown in Table 2. The obtained co-condensed resin had a viscosity of 5000 cp at 25°C, a solid resin content of 75%, free orthocresol 3.2%, free resorcinol trace, free formaldehyde 0%, water 13.5%, and a number average molecular weight of 440.
It was from. Comparative Example 4 Example 1 except that the amount of resorcin was changed to 99 kg (1.4 moles) and a co-condensed resin containing 3.4% by weight of free resorcin was used in place of the co-condensed resin A of Example 1. A foam was obtained in the same manner. The obtained foam was tested in the same manner as in Example 1, and the results were as shown in Table 2. The resulting co-condensed resin had a viscosity of 16,000 cp at 25°C, a solid resin content of 74%, free orthocresol 2.4%, free resorcinol 3.4%, free formaldehyde 0%, water 15.9%, and a number average molecular weight of 560. It was from. Comparative Example 5 100g of resol type phenolic resin B of Example 1,
1.5g of SH-193 as a foam stabilizer, 7g of ammonium polyphosphate and 7g of aluminum hydroxide as flame retardants.
g, and 19 g of Freon 113 as a foaming agent were taken in a cup, using a homodisper with a rotation speed of 3000 rpm.
The mixture was stirred for 30 seconds and the liquid temperature was adjusted to 20°C. then 20
20 g of a 65% phenolsulfonic acid aqueous solution as a curing catalyst adjusted to a temperature of 0.degree. The obtained foam was tested in the same manner as in Example 1, and the results showed that the flyability was very poor.
Also, large cracks occurred at the interface with the face material. Other results were as shown in Table 2. Example 5 Production of co-condensation resin E: 500 kg of paratertiary butylphenol and 92 kg
% paraformaldehyde and 102 kg of water were charged into a reactor equipped with a reflux tube and a stirrer, and the mixture was heated to 40 kg while stirring.
The temperature was raised to 90°C in minutes to dissolve the paraformaldehyde, and then cooled to below 40°C. Next, 60 kg of 20% potassium hydroxide aqueous solution was added while stirring.
The temperature was raised from room temperature to 100°C in about 60 minutes, the reaction was continued at the same temperature for 90 minutes, and then cooled to obtain a paratertiary butylphenol resin. This resin contains free paratertiary butyl phenol 4.0
%, free formaldehyde 0%, water 31%, number average molecular weight 375, and number of moles of methylol group 1.8 moles. The main component of the resin is 5-methylresorcinol.
260 kg (0.8 moles) of SAR (Nagoya Yukagaku Kogyo) was added, the temperature was raised from room temperature to 70°C in about 30 minutes, and the reaction was continued at the same temperature for 50 minutes. Then 40℃
Cool to 60mmHg and add 40% acetic acid to adjust pH to 6.5.
Viscosity at 25℃ after concentration under reduced pressure
10200 cp, solid resin content 76%, free paratertiary butyl phenol 3.9%, free resorcinol
Trace, free formaldehyde 0%, moisture 14.2
% and a number average molecular weight of 554 was obtained. Production of resol type phenolic resin F: 500 kg of phenol and 92% paraformaldehyde
278 kg, 148 kg of water, a reflux tube, and a reactor equipped with a stirrer were charged, and the temperature was raised to 90°C in 40 minutes while stirring, and after dissolving the paraformaldehyde, it was cooled to below 40°C. Next, 12.5 kg of triethylamine was added with stirring, the temperature was raised from room temperature to 90°C in about 60 minutes, and the reaction was continued at the same temperature for 120 minutes.
Cool to below 40℃, add 40% acetic acid to adjust the pH to 6.5, and concentrate under 70mmHg vacuum. Viscosity at 25℃: 3900cp, solid resin content: 80%, free phenol: 6.1%, free formaldehyde: 0.5 %, moisture 15
% and a number average molecular weight of 390, resol type phenolic resin F was obtained. A mixture of 100 kg of the obtained co-condensed resin E and 364 kg of resol type phenolic resin (weight ratio of solid resin component of E/F = 18/82), and SH-193 as a foam stabilizer.
6.7Kg, ammonium polyphosphate 31Kg as a flame retardant, and aluminum hydroxide 31Kg are mixed into one liquid, Freon 113 as a foaming agent is mixed as a liquid,
A 75% para-toluenesulfonic acid aqueous solution as a curing catalyst was used as a liquid, and the temperature was adjusted to 20°C using a PA-210 phenol foam foaming machine (Toho Kikai). 100 parts by weight/18 parts by weight/20 Width is the underside material pre-heated to 50℃, mixed in proportions of parts by weight and run on a belt conveyor.
Apply it to 900mm of kraft paper and heat it to a temperature of 60℃, so that by the end of the cream time, the top material, aluminum kraft paper, is pasted to the opposite side where the bottom material was pasted. The material was then introduced into a belt-type heating and pressurizing device for uniform foaming at 80°C, and after curing was completed, it was cut to a length of 1800 mm to obtain an inner wall insulation material for a house measuring 180 x 900 x 25 mm. The obtained foam was tested in the same manner as in Example 1, and the results were as shown in Table 1. Example 6 In Example 5, a mixture of cocondensation resin E50 kg and resol type phenolic resin F594 kg (weight ratio of solid resin component of E/F = 8/92), and SH- as a foam stabilizer were used.
A residential inner wall insulation material was obtained in the same manner as in Example 5, except that a mixture of 9.7 kg of 193 and 31 kg of ammonium polyphosphate and 31 kg of aluminum hydroxide as flame retardants was used as a single liquid. The obtained foam was tested in the same manner as in Example 1, and the results were as shown in Table 1. Example 7 In Example 5, a mixture (E/F
weight ratio of small resin component = 25/75), as a foam stabilizer,
A residential inner wall insulation material was obtained in the same manner as in Example 5, except that a mixture of 8.7 kg of SH-193 and 31 kg of ammonium polyphosphate and 31 kg of aluminum hydroxide as flame retardants was used as a single liquid. The resulting foam was tested in the same manner as in Example 1. The results were as shown in Table 1. Example 8 Production of co-condensation resin G: 200 kg of bisphenol A and 47% formalin
101Kg was charged into a reactor equipped with a reflux tube and a stirrer, and while stirring, 24% of a 20% aqueous sodium hydroxide solution was added.
Kg was added, the temperature was raised from room temperature to 100°C in about 60 minutes, the reaction was continued at the same temperature for 60 minutes, and then cooled to obtain a bisphenol A aldehyde resin. This resin has 6.2% free bisphenol A, 0% free formaldehyde, 38% moisture, and a number average molecular weight of
620, the number of moles of methylol group was 2.0 moles. Add 72 kg (0.8 moles) of resorcin to the resin, raise the temperature from room temperature to 70°C in about 30 minutes,
The reaction was continued for 45 minutes at the same temperature, and then concentrated under a reduced pressure of 60 mmHg.
18000cp, solid resin content 7.4%, free bisphenol
A cocondensation resin G having A6.2%, free resorcin trace, free formaldehyde 0%, water 18.2%, and number average molecular weight 780 was obtained. A mixture of 100 kg of the co-condensed resin G and 854 kg of resol type phenolic resin B of Example 1 (weight ratio of solid resin component of G/B = 10/90), SH- as a blowing agent
The liquid was a mixture of 14.3 kg of 193, 67 kg of boric acid as a flame retardant, and 67 kg of guanidine phosphate, the liquid was a 7:3 mixture of Freon 113 and Freon 11 as a blowing agent, and 70% xylene was used as a curing catalyst. Using a sulfonic acid aqueous solution as a liquid, mix liquid/liquid/liquid adjusted to 20°C in a ratio of 100 parts by weight/25 parts by weight/22 parts by weight using a PA-210 phenol fluor foaming machine, and heat to 70°C. A hose was inserted into the space of a 1800 x 900 x 25 mm mold with heated decorative iron plates as the facing material, foaming was carried out, and the material was cured for 7 minutes to obtain a partition insulation material. The obtained foam was cut out and tested in the same manner as in Example 1. As a result, the density was 0.042 g/cm ³ , the flyability was 7.4%, the bonding strength with the face material was 220 g,
It has a thermal conductivity of 0.020Kcal/m・hr・℃, is highly flame retardant, has a good appearance, has excellent surface brittleness, and does not shed a lot of powder even when rubbed vigorously with your fingers, and has a strong bond with the surface material. Even after 30 days or more, no large cracks appeared under the interface with the foam, and the foam was very good with no small cracks on the surface or inside surface. Example 9 Partition insulation was made in the same manner as in Example 8, except that instead of co-condensation resin G in Example 8, a co-condensation resin obtained by changing the amount of resorcin to 36 kg (0.5 moles) was used. I got the material. The obtained foam was cut out and tested in the same manner as in Example 1, and the results were as shown in Table 1. The obtained co-condensed resin had a viscosity of 17,900 cp at 30°C, solid resin content of 74%, free bisphenol A of 6.1%, free resorcinol trace, free formaldehyde of 0%, moisture of 17.8%, and number average molecular weight. It was from 725. Example 10 A mixture (G/
Weight ratio of solid resin component of B = 22/78), as a foam stabilizer
6.5Kg of SH-193 and 31Kg of boric acid as a flame retardant.
A partition heat insulating material was obtained in the same manner as in Example 8, except that a mixture of 31 kg of guanidine phosphate was used as the liquid. The obtained foam was cut out and tested in the same manner as in Example 1, and the results were as shown in Table 1. Comparative Example 6 The bisphenol A aldehyde resin obtained in Example 8 was concentrated under a reduced pressure of 60 mmHg, and the viscosity at 30°C was 11000 cp, solid resin content 76%, free bisphenol A 6.2%, and free formaldehyde 0. %,
Resin H having a water content of 16.0% and a number average molecular weight of 628 was obtained. A mixture of 100 kg of the resin H and 336 kg of resol type phenolic resin B of Example 1 (weight ratio of solid resin component of H/B = 22/78), and 6.5 kg of SH-193 as a foam stabilizer.
A partition heat insulating material was obtained in the same manner as in Example 8, except that a mixture of 31 Kg of boric acid and 31 Kg of guanidine phosphate as a flame retardant was used as a liquid. The obtained foam was cut out and tested in the same manner as in Example 1. As a result, the flyability was very poor, and many fine cracks appeared on the surface and inner surface of the foam after being left at room temperature for two days. It was hot.
Other results were as shown in Table 2. Comparative Example 7 100g of resol type phenolic resin B of Example 1,
A mixture of 1.5 g of SH-193 as a foam stabilizer, 7 g of boric acid and 7 g of guanidine phosphate as a flame retardant was used as a liquid, and a 7:3 mixture of Freon 113 and Freon 11 as a foaming agent was used as a liquid and hardened. A 70% xylene sulfonic acid aqueous solution as a catalyst is used as a liquid,
Using PA-210 phenol fluor foaming machine, 20
100 parts by weight of liquid/liquid/liquid adjusted to ℃/25
They were mixed at a ratio of parts by weight/22 parts by weight, and a partition heat insulating material was obtained in the same manner as in Example 8. The obtained foam was cut out and tested in the same manner as in Example 1. As a result, the flyability was very poor and large cracks were generated under the interface with the face material. Other results were as shown in Table 2. Example 11 Production of co-condensation resin (): 500 kg of urea and 904 g of formalin with a concentration of 47% were charged into a reactor equipped with a reflux tube and a stirrer, and while stirring, 10 kg of 25% ammonia water was added, and the mixture was heated from room temperature to room temperature.
The temperature was raised to 90°C for about 60 minutes, the reaction was continued at the same temperature for 35 minutes, and then cooled to obtain a urea aldehyde resin. This resin contains 0.3% free formaldehyde,
The water content was 42%, the number average molecular weight was 300, and the number of moles of methylol groups was 1.7. The main component of the resin is 5-methylresorcinol.
Add 347g (0.6 moles) of SAR and
The temperature was raised to ℃ in about 30 minutes, and the reaction was continued at the same temperature for 30 minutes. After that, it was cooled to 40℃, 20% sulfuric acid was added to adjust the pH to 6.5, and it was concentrated under a reduced pressure of 60mmHg, and the viscosity at 25℃ was 7000cp, solid resin content
A co-condensation resin () with 76% free resorcin trace, 0% free formaldehyde, 13.2% water, and number average molecular weight 490 was obtained. A mixture of 100 kg of the co-condensed resin () and 552 kg of resol type phenolic resin B of Example 1 (weight ratio of solid resin component of /B = 15/85), 9.8 kg of L-5340 (Nippon Unica) as a foam stabilizer. , and guanidine phosphate 65Kg as flame retardant, aluminum hydroxide
A mixture of 33 kg was made into a liquid, Freon 113 as a blowing agent was made into a liquid, and a 75% aqueous solution of para-toluenesulfonic acid was made into a liquid as a curing catalyst, and the temperature was adjusted to 20℃ using a PA-210 phenol fluor foaming machine. 100 parts by weight of liquid/liquid/liquid/20 parts by weight/20
Mix the parts by weight and insert a hose into the space of a 1800 x 900 x 25 mm mold with a facing material made of decorative iron plate heated to 70℃ to foam, cure for 7 minutes, and create a partition insulation material. Obtained. The obtained foam was cut out and tested in the same manner as in Example 1. As a result, the density was 0.043 g/cm ³ , the flyability was 9.8%, the bonding strength with the face material was 230 g,
Thermal conductivity is 0.020Kcal/m・hr・℃, highly flame retardant,
The appearance was also good, and the foam had good surface brittleness with little powder falling, no bonding strength with the face material, and no small cracks on the surface or inner surface of the foam. Example 12 Instead of the co-condensation resin () of Example 11, 5-
The amount of SAR whose main component is methylresoricin is 578
A partition-cut heat material was obtained in the same manner as in Example 11, except that a co-condensed resin obtained by changing the amount to 1.0 g (1.0 moles) was used. The obtained foam was cut out and tested in the same manner as in Example 1, and the results were as shown in Table 1. The obtained co-condensed resin had a viscosity of 10,200 cp at 25°C, a solid resin content of 76%, and a free resorcin content.
Trace, 0% free formaldehyde, moisture 14.4
% and number average molecular weight of 511. Comparative Example 8 Instead of the co-condensation resin () of Example 11, the urea aldehyde resin obtained in Example 11 was cooled to 40°C, 20% sulfuric acid was added, the pH was adjusted to 6.5, and the mixture was heated under reduced pressure of 60 mmHg. The viscosity at 25℃ is 4800cp.
Solid resin content 78%, free formaldehyde 0.2%,
An attempt was made to obtain a partition insulation material in the same manner as in Example 11, except that a resin with a moisture content of 11.9% and a number average molecular weight of 310 was used, but the foam could not be obtained, and the foam was replaced with a rice cracker-like material with coarse cells. I couldn't help it.

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〔Effect of the invention〕

If the phenolic resin composition for foaming of the present invention is used, the basic requirements for foams, such as surface brittleness due to the brittleness of the resin, cracks in the foam, large cracks that occur under the interface with the facing material, and An excellent phenolic resin that can eliminate defects such as peeling and minute cracks that occur on the surface and inner surface of foam when left at room temperature, and also has the characteristics of lightweight, heat insulation, fire resistance, low smoke emission, and heat resistance. This has the effect of producing a foam.

Claims (1)

[Scope of Claims] 1 Urea aldehyde resin, bisphenol A aldehyde resin, or alkylphenol aldehyde resin having one alkyl group having 1 to 4 carbon atoms at the ortho or para position, which has methylol groups at both ends of the molecule. 2% by weight or less of free resorcinols, which is obtained by reacting a resin that has 0.4 to 1.0 moles of resorcinols based on the number of moles of the methylol groups to a resin that does not substantially contain methylol groups other than at both ends of the molecule. co-condensation resin A, which is obtained by reacting 1.0 to 2.0 mol of aldehydes per 1 mol of phenol in the presence of a basic catalyst, and a resol type phenolic resin B having a number average molecular weight of 200 to 700, A/B solid resin weight ratio is 5/95 to 30/70
A phenolic resin composition for foaming, which is characterized by being mixed so as to have the following properties.