JP2002241530A - Resol-type phenolic resin compound for manufacturing phenolic foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resol-type phenolic resin compound which can manufacture a metal sandwich panel and a metal siding having high fire protection performance at a manufacturing speed not lowered from that of the case of using a conventional resin compound by using a conventional facility on an industrial scale. SOLUTION: The resol-type phenolic resin compound is manufactured by compounding a resol-type phenolic resin with a foam stabilizer, a foaming agent and a flame retardant, and it is used for manufacturing a metal sandwich panel or a metal siding by further adding a curing agent and mixing them to foam and cure. In the manufacturing, the resol-type phenolic resin of the raw material has an average molecular weight of 250-400 and a viscosity of <=1,200 mPa.s, and the flame retardant in an amount of 20-150 pts.wt. is added to 100 pts.wt. of the resol-type phenolic resin. It is preferable that, as the flame retardant, aluminum hydroxide and boric acid are compounded at a ratio of 0/10 to 10/0 by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol foam used for producing a metal panel or a metal siding excellent in fire resistance and heat resistance in which a metal plate is used as an image material and a foam is filled therein, with good productivity. The present invention relates to a resol-type phenolic resin compound for body production.

[0002]

2. Description of the Related Art Conventionally used metal sandwich panels and metal sidings include those using urethane foam, nullate foam or phenol foam. As such a metal sandwich panel or metal siding, it is necessary to produce a fire-retardant product with high productivity, and a resole-type phenol foam has recently been used as a foam resin satisfying such conditions. . Also, if necessary, resole type phenol foam,
A small amount of inorganic flame retardant aluminum hydroxide, magnesium hydroxide, boric acid, phosphorus flame retardant, organic flame retardant chlorine flame retardant, bromine flame retardant, etc. is added to assist the fire protection.

[0003]

In recent years, there has been a demand for further improvement in fire prevention performance due to changes in fire prevention standards.
In this case, a method is known in which a large amount of a flame retardant such as aluminum hydroxide or boric acid is added to enhance fire resistance. However, when a large amount of a flame retardant such as aluminum hydroxide or boric acid is added to the resole type phenolic resin used for conventional metal sandwich panels and metal siding, a resin compound is produced, and foaming and curing are attempted. There is a problem that the curing time is greatly lengthened, it is necessary to industrially reduce the operation speed, and in some cases, the foaming and curing are not performed.

[0004] Further, a resin compound to which a large amount of a flame retardant is added has a high viscosity, and when the mixed resin is conveyed through a pipe, problems such as the resin compound becoming difficult to flow or not flowing occur. In general, when the viscosity of the resin mixture exceeds 50,000 mPas, it becomes difficult for the resin compound to flow through the piping in equipment conventionally used for manufacturing metal sandwich panels and metal siding, and it may be difficult to stably manufacture the compound. . for that reason,
Significant remodeling of the equipment is required, such as increasing the pipe diameter and increasing the capacity of the pump.

SUMMARY OF THE INVENTION The present invention has been devised to solve such a problem, and is intended to reduce the production speed of a metal sandwich panel or metal siding having a high fire protection performance, similarly to the case of using a conventional resin compound. It is another object of the present invention to provide a resol-type phenol resin compound that can be industrially produced with conventional equipment.

[0006]

The resole type phenolic resin compound for producing a phenolic foam of the present invention has a mean molecular weight of 250 to 400 and a viscosity of 1200 m as a resol type phenolic resin raw material in order to achieve the object.
A foam stabilizer is used by adding a foam stabilizer and a foaming agent, and a flame retardant of 20 to 150 parts by weight based on 100 parts by weight of the resole type phenol resin, and further adding a curing agent. It was made. The resol-type phenol resin raw material preferably has a water content of 9% or less. Further, aluminum hydroxide and boric acid are used as flame retardants in a weight ratio of 0/10 to 10/0. It is preferable that the content be contained so as to be parts by weight.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A mixed resin compound using a resol type phenolic resin according to the present invention is discharged from a mixing head into an area defined by metal face plates 1 and 2, and foamed and cured to form a resin foam 3, It is sandwiched and used as the core material of the panel (see FIG. 1).

The metal face plates 1 and 2 have a thickness of 0.2 to 0.2 mm.
A 2.0 mm metal plate is used. Specifically, there are various surface-treated steel sheets, zinc-aluminized steel sheets, Cu-plated steel sheets, aluminum-plated steel sheets, aluminum sheets, painted aluminum sheets, and the like. A flat metal plate is generally used, but a metal plate having improved appearance and strength can be used by subjecting these metal plates to embossing or bending with a roll forming machine or the like. Further, the metal face plate 2 may be paper in which aluminum foil is bonded in place of the metal plate.

The phenolic resin foam is manufactured from a resol-type phenolic resin or a novolak-type phenolic resin, and the resin foam corresponding to the present invention is from a resol-type phenolic resin. The resol resin compound is prepared by adding a foaming agent, a foam stabilizer and the like to a resol-type phenol resin obtained by reacting phenol and formalin under an alkaline catalyst. A flame retardant is added to the resin compound as required according to the required fire protection performance.

[0010] The foaming agents to be added include volatile petroleum oils such as petroleum ether, naphtha, pentane and hexane; low boiling hydrocarbons such as methylene chloride, carbon tetrachloride, trichloroethane, fluorotrichloromethane and trifluorotrichloromethane. It is. Foam stabilizers to be added are polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene solibitan stearate,
Nonionic surfactants such as polyoxyethylene castor oil fatty acid ester and polyoxyethylene dimethyl silicon.

As the flame retardant added to the resin compound mainly composed of a resol type phenol resin as necessary, tris (tribromoneopentyl) phosphate, tetrabromobisphenol A, and organic flame retardants can be used.
Triphenyl phosphate, as inorganic flame retardants, aluminum phosphate, ammonium phosphate, aluminum hydroxide, magnesium hydroxide, boric acid, dihydrate gypsum and the like. As the flame retardant to be added to the resole type phenolic resin, an inorganic flame retardant is recommended rather than an organic flame retardant because of a problem of toxicity when a metal sandwich panel or a metal siding is incinerated and discarded. Aluminum hydroxide is preferred from the viewpoint of cost, and boric acid is preferred from the viewpoint of improving fire prevention performance.

The weight ratio of boric acid to aluminum hydroxide is 0
/ 10 to 10/0 parts by weight can be mixed and added, but the total amount is 10% by weight.
It should be 20-150 parts by weight for 0 parts by weight. In general, if the amount of the flame retardant is less than 20 parts by weight, the fire protection performance is low, and if it exceeds 150 parts by weight, the viscosity increases and it becomes difficult to feed, and, like the conventional resol-type phenol resin, the foam hardening time is increased. And become unsuitable for the production of metal sandwich panels and metal siding.

The resol type phenol foam is prepared by adding a curing agent such as an organic sulfonic acid such as phenolsulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid or benzenesulfonic acid to the prepared resol type phenol resin compound. It is manufactured by having

In the present invention, a foaming agent, a foaming agent, and a flame retardant are added to and mixed with a resole type phenolic resin to produce a resin compound, and a curing agent is added to the produced compound, followed by foaming and curing to form a phenol. In the method for producing a resin foam, the weight average molecular weight is 250 to 400,
A resol type phenol resin having a viscosity of 1200 mPas or less is used. The resole type phenolic resin used in the present invention is a prototype produced by the present invention and the like, but if the average molecular weight of the resin for preparing the resin compound is less than 250, the foaming curing reaction is too fast and the reaction speed is too high. It cannot be adjusted. When the average molecular weight exceeds 400, the viscosity increases, or when the molecular weight is 400 or less, the viscosity becomes 120.
If a resol-type phenolic resin exceeding 0 mPas is used, the viscosity of the resin compound will exceed 50,000 mPas, and it will be too high to make molding difficult.

When such a resol-type phenol resin is used, the flame-retardant is blended with 20 to 150 parts by weight with respect to 100 parts by weight of the present resole-type phenol resin, and the resol-type phenol resin is also mixed with a foam stabilizer and a foaming agent. The viscosity of the phenolic resin compound is kept low to 50,000 mPas or less, so that it does not become difficult to flow when being conveyed through a pipe, and the foaming and curing speed is almost the same as the conventional one.

The amount of water contained in the resole type phenolic resin of the present invention is desirably 9% or less.
%, The internal exothermic reaction occurring during the foaming curing reaction is suppressed in the resin compound system containing the flame retardant, so that the foaming curing speed is retarded, particularly the curing speed is retarded.

In the present invention, a predetermined amount of a flame retardant is added to the resin compound. Without the addition of a flame retardant, the foam hardening rate is high and cannot be used for the production of metal sandwich panels and metal siding. In general, if the foaming and curing time is 1 minute or less in a resin compound using a resol type phenol resin, it is difficult to control the foaming and curing, and it is not suitable for the production of metal sandwich panels and metal siding.

[0018]

EXAMPLES Example 1 Molecular weight (Mv) 300, water content 8%, viscosity 900 mPa
4 parts by weight of methylene chloride as a foaming agent, 3 parts by weight of a silicon-based nonionic surfactant as a foam stabilizer, and 40 parts by weight of aluminum hydroxide as a flame retardant, in 100 parts by weight of resole type phenolic resin A (25 ° C.) Parts and 40 parts by weight of boric acid as a flame retardant were added and mixed to prepare a resin compound. The viscosity of the prepared resin compound was measured. Further, 25 parts by weight of a phenolsulfonic acid as a curing agent was added to the prepared resin compound, mixed and stirred, poured into a mold adjusted to 70 ° C., and the time until the foam foamed and cured was measured.

Example 2 Molecular weight (Mv) 250, water content 8%, viscosity 700 Pas
(25 ° C.) 100 parts by weight of resol type phenol resin B, 4 parts by weight of methylene chloride as a foaming agent, 3 parts by weight of a silicone-based nonionic surfactant as a foam stabilizer, and 70 parts by weight of aluminum hydroxide as a flame retardant Then, 70 parts by weight of boric acid as a flame retardant were added and mixed to prepare a resin compound. The viscosity of the prepared resin compound was measured. Further, 25 parts by weight of phenolsulfonic acid as a curing agent was added to the prepared resin compound, mixed, stirred, and poured into a mold adjusted to 70 ° C.
The time required for the foam to foam and harden was measured.

Comparative Example 1 Molecular weight (Mv) 800, water content 14%, viscosity 3000 m
Pas (25 ° C) resol type phenolic resin C100
4 parts by weight of methylene chloride as a foaming agent, 3 parts by weight of a silicone-based nonionic surfactant as a foam stabilizer, 40 parts by weight of aluminum hydroxide as a flame retardant, and 40 parts by weight of boric acid as a flame retardant
A resin compound was prepared by adding and mixing parts by weight. The viscosity of the prepared resin compound was measured. Further, phenolsulfonic acid as a curing agent was added to the prepared resin compound.
5 parts by weight of the mixture were mixed, stirred, and charged in a mold adjusted to 70 ° C., and the time until the foam foamed and hardened was measured.

Comparative Example 2 Molecular weight (Mv) 1200, water content 16%, viscosity 4500
mPas (25 ° C) resol type phenolic resin D10
0 parts by weight, 4 parts by weight of a blowing agent methylene chloride, 3 parts by weight of a silicone-based nonionic surfactant as a foam stabilizer, 40 parts by weight of aluminum hydroxide as a flame retardant, and 4 parts by weight of boric acid as a flame retardant
0 parts by weight were added and mixed to prepare a resin compound. The viscosity of the prepared resin compound was measured. Further, 25 parts by weight of a phenolsulfonic acid as a curing agent was added to the prepared resin compound, mixed and stirred, poured into a mold adjusted to 70 ° C., and the time until the foam foamed and cured was measured.

Comparative Example 3 Molecular weight (Mv) 300, water content 8%, viscosity 900 mPa
s (25 ° C.) 100 parts by weight of resol type phenolic resin A, 4 parts by weight of methylene chloride as a foaming agent, 3 parts by weight of a silicone-based nonionic surfactant as a foam stabilizer, and 80 parts by weight of aluminum hydroxide as a flame retardant Parts, and 80 parts by weight of boric acid as a flame retardant were added and mixed to prepare a resin compound. The viscosity of the prepared resin compound was measured. Further, 3 parts by weight of a phenolsulfonic acid as a curing agent was added to the prepared resin compound, mixed, stirred, poured into a mold adjusted to 70 ° C., and the time until the foam foamed and cured was measured.

Comparative Example 4 Molecular weight (Mv) 300, water content 8%, viscosity 900 mPa
To 100 parts by weight of the resol type phenolic resin A (25 ° C.), 4 parts by weight of methylene chloride as a foaming agent and 3 parts by weight of a silicone-based nonionic surfactant as a foam stabilizer were added and mixed. A compound was made. The viscosity of the prepared resin compound was measured. Further, 25 parts by weight of phenolsulfonic acid as a curing agent was added to the prepared resin compound, mixed, stirred, and charged into a mold adjusted to 70 ° C.
The time required for the foam to foam and harden was measured.

Comparative Example 5 Molecular weight (Mv) 800, water content 14%, viscosity 3000 m
Pas (25 ° C) resol type phenolic resin C100
4 parts by weight of methylene chloride as a foaming agent and 3 parts by weight of a silicon-based nonionic surfactant as a foam stabilizer were added to
A resin compound was prepared without adding a flame retardant. This resin compound corresponds to a resin compound used in the production of conventional metal sandwich panels and metal siding. The viscosity of the prepared resin compound was measured. Further, 25 parts by weight of phenolsulfonic acid as a curing agent was added to the prepared resin compound, and the mixture was stirred.
It was put into a mold adjusted to 0 ° C., and the time until the foam foamed and hardened was measured.

As a result of measuring the viscosity of the prepared resin compound, Example 1 was 11000 mPas, and Example 2 was 4
7000 mPas, Comparative Example 1 has 140000 mPas,
Comparative Example 2 was 200,000 mPas, and Comparative Example 3 was 5500
0 mPsa, Comparative Example 4 was 600 mPas, Comparative Example 5 was 1
800 mPas. Examples 1 and 2 and Comparative Examples 4 and 5
Although the viscosity of the resin compound was suppressed to 50,000 mPas or less, Comparative Examples 1, 2, and 3 showed that the viscosity of the resin compound exceeded 50,000 mPas, and in the equipment conventionally used for the production of metal sandwich panels and metal siding, the piping It became difficult for the resin compound to flow, making production difficult.

Further, a hardening agent is added to the prepared resin compound, mixed, stirred, and poured into a mold controlled at 700 ° C.
As a result of measuring the time until the foam foams and hardens,
Example 1 was 2 minutes and 40 seconds, Example 2 was 3 minutes and 20 seconds, Comparative Example 1 was 5 minutes and 20 seconds, Comparative Example 2 was not able to be measured due to uneven mixing, Comparative Example 3 was 5 minutes, and Comparative Example 4 Is 50 seconds, Comparative Example 5
Was 2 minutes and 30 seconds. In Examples 1 and 2, the foam hardening time was almost the same as that of Comparative Example 5 corresponding to the resin compound used for the production of the conventional metal-metal sandwich panel and metal siding. Comparative Examples 1, 2, and 3 have a long foam hardening time or are not measurable, and Comparative Example 4 has a short foam hardening time, which makes it difficult to control foam hardening, and is suitable for manufacturing metal sandwich panels and metal siding. I can't say that.

Table 1 summarizes the measurement results of the viscosity and the foam hardening time of the resin compound using the resol type phenol resin of the present invention. From the above, Examples 1 and 2 have the same foaming and curing time as Comparative Example 5 conventionally performed,
The viscosity of the resin compound is kept low. Further, although no measurement examples are shown, Examples 1 and 2 have excellent fire resistance and heat resistance because a flame retardant is added.

[0028]

[0029]

As described above, by using the resole type phenol resin as specified in the present invention and adjusting the addition amount of the flame retardant, the viscosity of the resin compound for producing a foam is low. Suppressed, the foam hardening time is the same as the conventional resin compound, and combined with the fact that the flame retardant is added, the metal sandwich panel and metal siding with high fire protection performance use the conventional resin compound Similarly, it can be manufactured industrially with conventional equipment.

[Brief description of the drawings]

FIG. 1 shows a cross-sectional structure of a metal sandwich panel

[Explanation of symbols]

 1, 2: metal face plate, 3: resin foam

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuaki Nakata 7-1 Takayashinmachi, Ichikawa City, Chiba Prefecture Nisshin Steel R & D Co., Ltd. (72) Inventor Takashi Hashiba 1021 Tomizukacho, Isesaki City, Gunma Prefecture (72) Inventor, etc.Takada et al. 1021 Tomizuka-cho, Isesaki-shi, Gunma F-term (reference) 4F074 AA60 AB01 AB05 AC20 AC33 AG10 BA39 BA40 BA43 BA44 BA75 BB01 BB03 BB06 BC02 DA18 DA20 DA54 DA59 4J002 AE052 CC031 CH052 CP032 DE146 DK006 EA017 EB027 ED027 FD136 FD202 FD327

Claims (3)

[Claims] 1. A resol-type phenolic resin is prepared by mixing a foam stabilizer, a foaming agent, and a flame retardant, and a curing agent is added and mixed, and foamed and cured to be used in the production of a metal sandwich panel or metal siding. A resol-type phenolic resin compound, wherein the raw material resol-type phenolic resin has an average molecular weight of 250 to 400 and a viscosity of:
A resol type phenolic resin compound for producing a phenol foam, which has a flame retardant content of 1200 mPas or less and 20 to 150 parts by weight based on 100 parts by weight of the resol type phenol resin. 2. The resol-type phenolic resin compound for producing a phenol foam according to claim 1, wherein the water content of the resol-type phenolic resin as a raw material is 9% or less. 3. The resol type for producing a phenol foam according to claim 1, wherein the flame retardants are aluminum hydroxide and boric acid, and the mixing ratio thereof is 0/10 to 10/0 parts by weight. Phenolic resin compound.