JP5036021B2 - Phenolic resin foam - Google Patents

Description

  The present invention is a phenol resin foam. More specifically, it has excellent flame resistance and fire resistance, has good heat insulation performance, excellent mechanical properties, and has a higher pH than conventional products, and is suitable for contact members. The present invention relates to a phenol resin foam having good corrosion resistance.

  2. Description of the Related Art Conventionally, phenol resin foams are excellent in heat insulation, flame retardancy, fire resistance, and the like, and are therefore used as heat insulation materials in construction and other industrial fields.

  It is known that a phenol resin foam having an independent cell structure has a heat insulation performance with good stability over time. As a method for producing the phenol resin foam having an independent cell structure, physical foaming containing chloropropane is used. A method using means has been proposed (see, for example, Patent Document 1).

On the other hand, the composition containing an acid curable phenol resin, a surfactant, a foaming agent, and a curing agent as a non-combustible resin foam building material contains aluminum hydroxide in an amount of 62.5 to 100 parts by weight per 100 parts by weight of the acid curable phenol resin. A non-flammable resin foam building material produced by using 200 parts by weight added is disclosed (for example, see Patent Document 2).
Although this foamed building material contains a large amount of aluminum hydroxide, it is considered excellent in terms of flame resistance and fire resistance, but it seems that ordinary foaming agents are used (for the types of foaming agents, Therefore, it is difficult to form an independent cell structure, and as a result, the heat insulation performance is inferior, and the thermal conductivity is considered to exceed 0.035 W / m · K.

By the way, in the production of a phenol resin foam, generally, a method of foaming and curing a foamable phenol resin molding material containing at least a phenol resin, a foaming agent and a curing agent is used, and an acid curing agent, for example, Organic acids such as sulfuric acid, benzenesulfonic acid, toluenesulfonic acid and xylenesulfonic acid are used. Therefore, since the obtained phenol resin foam contains the acid curing agent, for example, when wet with rain, the acid curing agent is extracted with water. As a result, when a metal member is in contact with the phenol resin foam, or when a metal member is present in the vicinity of the foam, there is a problem that the metal member is susceptible to corrosion.
Japanese Patent Publication No. 5-87093 Japanese Patent Laid-Open No. 3-160038

  Under such circumstances, the present invention has excellent flame resistance and fire resistance, good heat insulation performance, excellent mechanical properties, and has a higher pH than conventional products. An object of the present invention is to provide a phenol resin foam having good corrosion resistance.

  As a result of intensive research to develop a phenol resin foam having the above-mentioned preferable properties, the present inventors have found that a chlorinated aliphatic hydrocarbon compound having a specific number of carbon atoms, preferably chloropropane, as a foaming agent. It was found that the object can be achieved by using a material containing a kind and using a specific amount of an inorganic filler, and the present invention has been completed based on this finding.

That is, the present invention
(1) A foam obtained by foam-curing a foamable phenol resin molding material containing a phenol resin, a foaming agent, a foam stabilizer, a curing agent and an inorganic filler, wherein the foaming agent is chlorine having 2 to 5 carbon atoms. It includes aliphatic hydrocarbon compounds, and the molding material is a phenol 100 parts by weight of the resin to the inorganic filler seen contains a proportion of 70 to 220 parts by weight, the thermal conductivity of the foam is 0.035W / m A phenolic resin foam characterized by being K or less ,
(2) The phenol resin foam as described in (1) above, wherein the pH is 3.0 or more,
(3) The phenol resin foam according to (1) or (2) above, wherein the chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms is chloropropanes,
(4) The phenolic resin foam according to any one of (1) to (3) above, wherein the foamable phenolic resin molding material contains 1 to 20 parts by mass of a foaming agent per 100 parts by mass of the phenolic resin,
(5) The phenol according to any one of (1) to (4) above, wherein the inorganic filler is at least one selected from metal hydroxides, oxides, carbonates, and metal powders. Resin foam,
(6) The phenol resin foam according to (5) above, wherein the inorganic filler contains aluminum hydroxide,
( 7 ) The phenol resin foam according to any one of (1) to ( 6 ), wherein the density is 80 to 250 kg / m ³ .
( 8 ) The phenolic resin foam according to any one of (1) to ( 7 ) above, wherein a face material is provided on at least one surface, and ( 9 ) the face material is a glass fiber nonwoven fabric, a span The phenol resin foam described in ( 8 ) above, which is at least one selected from a bond nonwoven fabric, an aluminum foil-clad nonwoven fabric, a metal plate, a metal foil, a plywood, a calcium silicate plate, a gypsum board, and a wood cement board. ,
Is to provide.

  According to the present invention, by using a foaming agent containing a chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms and using a relatively large amount of inorganic filler, it has excellent flame resistance and fire resistance. In addition, it is possible to provide a phenolic resin foam that has good heat insulation performance, excellent mechanical properties, has a higher pH than conventional products, and has good corrosion resistance to contact members.

  The phenol resin foam of the present invention is obtained by foam-curing a foamable phenol resin molding material containing a phenol resin, a foaming agent, a foam stabilizer, a curing agent, an inorganic filler, and, if desired, a plasticizer and urea.

  The phenolic resin comprises phenols such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcin, and modified products thereof, and aldehydes such as formaldehyde, paraformaldehyde, furfural, acetaldehyde, sodium hydroxide, potassium hydroxide, water. A resol type phenol resin obtained by adding a catalytic amount of alkali such as calcium oxide, trimethylamine, triethylamine, and the like is preferable, but is not limited thereto. The ratio of the phenols and aldehydes to be used is not particularly limited, but is usually about 1: 1.5 to 1: 3.0, preferably 1: 1.8 to 1: 2.5 in molar ratio.

  In the present invention, as the foaming agent, one containing a chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms is used. The chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms is a chlorinated product of linear or branched aliphatic hydrocarbon having 2 to 5 carbon atoms, and the number of bonds of chlorine atoms is not particularly limited. However, about 1-4 are preferable. Examples of such chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, and the like. These may be used alone or in combination of two or more. Among these, chloropropanes such as propyl chloride and isopropyl chloride are preferable, and isopropyl chloride is particularly preferable.

  By using such a chlorinated aliphatic hydrocarbon compound as a foaming agent, the obtained foam has low initial thermal conductivity and good heat insulation performance.

  The foaming agent used in the present invention is characterized by containing a chlorinated aliphatic hydrocarbon compound. However, as long as the performance and physical properties of the phenol resin foam of the present invention are not impaired, for example, 1,1, Fluorinated hydrocarbon compounds such as 1,3,3-pentafluorobutane (alternative chlorofluorocarbons), salt fluorinated hydrocarbon compounds such as trichloromonofluoromethane and trichlorotrifluoroethane, hydrocarbons such as butane, pentane, hexane and heptane It is possible to add an appropriate amount and an appropriate amount of a system compound, an ether compound such as isopropyl ether, a gas such as nitrogen, argon or carbon dioxide, air or the like. The amount is preferably 0.1 to 20%, more preferably 0.5 to 15%, based on the chlorinated aliphatic hydrocarbon compound.

  In this invention, the usage-amount of the said foaming agent is 1-20 mass parts normally with respect to 100 mass parts of above-mentioned phenol resins, Preferably it is 5-10 mass parts.

  Preferred examples of the foam stabilizer used in the present invention include nonionic surfactants such as polysiloxanes, polyoxyethylene sorbitan fatty acid esters, and castor oil ethylene oxide adducts. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the present invention, as the curing agent, acid curing agents such as inorganic acids such as sulfuric acid and phosphoric acid, benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid, phenolsulfonic acid, etc. Organic acids are used. Among these, benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid and phenolsulfonic acid are preferable, and paratoluenesulfonic acid and xylenesulfonic acid are particularly preferable.

  In this invention, these hardening | curing agents may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of use is usually in the range of 5 to 25 parts by mass, preferably 7 to 20 parts by mass per 100 parts by mass of the phenol resin, although it depends on the type of curing agent. If the usage-amount of this hardening | curing agent exists in said range, while being able to exhibit the function as a hardening | curing agent favorably, the pH of a foam can be controlled to 3.0 or more. The more preferable usage-amount of a hardening | curing agent is 10-20 mass parts.

  Examples of the inorganic filler in the present invention include metal hydroxides and oxides such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide, and zinc oxide, metal powder such as zinc, calcium carbonate, and magnesium carbonate. Further, metal carbonates such as barium carbonate and zinc carbonate can be contained. These inorganic fillers may be used alone or in combination of two or more.

  The inorganic filler is mainly used to obtain a phenol resin foam having improved flame retardancy and fire resistance. From this viewpoint, aluminum hydroxide is particularly preferable as the inorganic filler.

  The usage-amount of the said inorganic filler is selected in the range of 70-220 mass parts with respect to 100 mass parts of the above-mentioned phenol resins. If the amount of the inorganic filler used is in the above range, a phenol resin foam having excellent flame retardancy and fire resistance, good heat insulation performance, excellent mechanical properties, and a high pH of 3 or higher is obtained. Can do. From the viewpoint of the performance of the obtained phenol resin foam, the amount of the inorganic filler used is preferably 80 to 200 parts by mass, more preferably 80 to 180 parts by mass.

  In the present invention, a plasticizer is optionally used for the following reasons.

  It has been confirmed that the thermal conductivity of a plastic heat insulating material such as a phenol resin foam changes over time from the time of manufacture. This is due to the diffusion of the gas inside the bubble to the outside of the system, and is a phenomenon in which the foaming agent permeates the bubble film and is gradually replaced with air in the atmosphere. Therefore, the phenol resin foam also has a phenomenon in which its thermal conductivity increases with time and the heat insulation performance deteriorates with time.

  As one of the causes of the deterioration of the phenol resin foam over time, a phenomenon in which the flexibility of the cell walls of the phenol resin foam deteriorates with time can be considered. Therefore, as one of means for suppressing deterioration of the phenol resin foam, it is possible to give flexibility to the cell walls. The addition of the plasticizer is performed in order to impart flexibility to the cell walls of the foam and to suppress deterioration over time of the heat insulation performance.

  The plasticizer is not particularly limited, and known plasticizers conventionally used in phenol resin foams such as triphenyl phosphate, dimethyl terephthalate, dimethyl isophthalate, and the like can be used. Furthermore, a polyester polyol can also be used.

  In particular, the polyester polyol has a structure including an ester bond and a hydroxyl group that are hydrophilic and excellent in surface activity, and thus has a good compatibility with the hydrophilic phenol resin liquid and can be uniformly mixed with the phenol resin. . Moreover, by using this polyester polyol, it is a preferable plasticizer that avoids uneven distribution of bubbles, distributes the bubbles uniformly throughout the foam, and easily produces a phenol resin foam that is homogeneous in quality.

  In the present invention, the plasticizer is generally used in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the phenol resin. When the amount of the plasticizer used is in the above range, the effect of imparting flexibility to the cell wall is satisfactorily exhibited without impairing other performances of the obtained phenol resin foam. The preferable use amount of the plasticizer is 0.5 to 15 parts by mass, and more preferably 1 to 12 parts by mass.

  In the present invention, the urea used as desired can provide a phenol resin foam having a low initial thermal conductivity and a strength, particularly a low brittleness. The amount of urea used is usually 1 to 10 parts by mass, preferably 3 to 7 parts by mass with respect to 100 parts by mass of the phenol resin.

  The foamable phenolic resin molding material is, for example, the above-mentioned phenol resin mixed with the inorganic filler, foam stabilizer, further plasticizer and urea, and the mixture with the chlorinated aliphatic hydrocarbon. After adding the foaming agent and hardening | curing agent containing a compound, this can be prepared by supplying this to a mixer and stirring.

  As a method of forming a phenol resin foam using the foamable phenol resin molding material thus prepared, for example, (1) a molding method for flowing out onto an endless conveyor, (2) a portion that is caused to flow out in a spot manner (3) a method of foaming under pressure in a mold, (4) a method of making a foam block by putting it in a large space, (5) a method of filling and foaming while press-fitting into a cavity, etc. Can be mentioned.

  As a preferable method, the foamable phenol resin molding material is discharged onto a continuously moving carrier, and the discharged material is foamed through a heating zone and molded to produce a desired phenol resin foam. To do. Specifically, the foamable phenol resin molding material is discharged onto a face material on a conveyor belt. Next, a face material is placed on the upper surface of the molding material on the conveyor belt and enters a curing furnace. In the curing furnace, the material is pressed from above with another conveyor belt, the phenolic resin foam is adjusted to a predetermined thickness, and foamed and cured under conditions of about 60 to 100 ° C. for about 2 to 15 minutes. The phenol resin foam exiting the curing furnace is cut into a predetermined length.

  The face material is not particularly limited and is generally natural fiber, synthetic fiber such as polyester fiber or polyethylene fiber, non-woven fabric such as inorganic fiber such as glass fiber, paper, aluminum foil-clad nonwoven fabric, metal plate, metal Foil is used, but glass fiber nonwoven fabric, spunbond nonwoven fabric, aluminum foil tension nonwoven fabric, metal plate, metal foil, plywood, structural panel, particle board, hard board, wood cement board, flexible board, perlite board, silica Calcium oxide board, magnesium carbonate board, pulp cement board, shizing board, medium density fiber board, gypsum board, lath sheet, volcanic glass composite board, natural stone, brick, tile, glass molding, lightweight cellular concrete molding, cement Mortar molded products, glass fiber reinforced cement molded products, etc. Molded body curable cement hydrate as a binder component are preferred. This face material may be provided on one side of the phenol resin foam or may be provided on both sides. Moreover, when providing in both surfaces, a face material may be the same and may differ. In addition, a face material may be attached later using an adhesive.

  The phenol resin foam of the present invention usually has a pH of 3.0 or higher. If pH is 3.0 or more, even if it gets wet in rain, the corrosion with respect to the metal member which contacts this foam, or the metal member which exists in the vicinity of a foam can be suppressed. A preferable pH is 4.0 or more, and 4.5 or more is particularly preferable. The method for measuring the pH of the foam will be described in detail later.

  In the phenol resin foam of this invention, it is preferable that heat conductivity is 0.035 W / m * K or less, More preferably, heat conductivity is 0.030 W / m * K or less. When this thermal conductivity exceeds 0.035 W / m · K, the heat insulating performance of the phenol resin foam becomes insufficient.

Further, the density is about 80 to 250 kg / m ³ , the average bubble diameter is about 5 to 400 μm, and the void area ratio in the cross-sectional area of the foam is preferably 5% or less. Furthermore, the pores are substantially free of pores, and the closed cell ratio is usually 85% or more, preferably 90% or more.

  In addition, the measuring method of the said property of a phenol resin foam is explained in full detail later.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the physical property of the phenol resin foam obtained in each example was measured according to the method shown below.

(1) Density Measured according to JIS A 9511: 2003, 5.6 density.

(2) Thermal conductivity Using a 300 mm square phenolic resin foam sample, set to a low temperature plate of 10 ° C. and a high temperature plate of 30 ° C., and according to the heat flow meter method of JIS A 1412-2: 1999, the thermal conductivity measuring device HC- 074 304 (manufactured by Eiko Seiki Co., Ltd.) was used for measurement. The initial thermal conductivity is the thermal conductivity after leaving the phenolic resin foam sample in a 70 ° C. atmosphere for 4 days.

(3) Corrosion prevention property A phenol resin foam sample of the same size was placed on a 300 mm square zinc iron plate (thickness 1 mm plating coverage 120 g / m ² ), and fixed so as not to slip. Then, it was installed in an accelerated environment of 40 ° C. and 100% RH, and the corrosivity of the contact surface with the sample of the galvanized iron plate after standing for 24 weeks was visually evaluated.

(4) pH
Weigh 0.5 g of a phenol resin foam sample micronized to 250 μm (60 mesh) or less with a mortar or the like into a 200 ml conical stoppered flask, add 100 ml of pure water, and seal tightly. The mixture was stirred for 7 days at room temperature (23 ± 5 ° C.) using a magnetic stirrer and then measured with a pH meter.

(5) Closed cell ratio Measured according to ASTM D2856.

(6) Fire resistance Using a fire resistance test furnace with a heating area of 70 cm x 70 cm, based on performance evaluation based on the provisions of Article 2, Item 7 (Fireproof Structure) of the Building Standard Law,
Heating temperature curve T = 345log ₁₀ (8t + 1) +20
[T: average furnace temperature (° C), t: elapsed time (minutes)]
The heated surface was heated according to the above, and the elapsed time and the back surface temperature were measured. A back surface temperature of 140 ° C. or lower was determined to be acceptable.

Example 1
Resol-type phenolic resin containing 3 parts by mass of a silicone surfactant [manufactured by Asahi Organic Materials Co., Ltd., trade name “PF-336”, phenol to formaldehyde molar ratio 1: 2.0, viscosity 3800 mPa · s / 25 ° C. , Moisture 11.5% by mass] 103 parts by mass of aluminum hydroxide [Sumitomo Chemical Co., Ltd., trade name “C31”] 100 parts by mass, calcium carbonate 2 parts by mass, and isopropyl chloride 8 as a foaming agent. Mass parts and 15 parts by mass of xylene sulfonic acid as a curing agent were supplied to a pin mixer and mixed by stirring to prepare a foamable phenol resin molding material.
Next, this molding material is discharged onto a 0.5 mm-thick Galvalume steel plate (JIS G 3321), and then the same 0.5 mm-thick Galvalume steel plate is placed thereon and placed in a dryer at 80 ° C. Foamed and molded for a minute, a phenol resin foam having a thickness of 50 mm, a length of 900 cm, a width of 900 cm and a density of 100 kg / m ³ was produced. The physical properties of this foam are shown in Table 1.

Example 2
In Example 1, the phenol resin foam was obtained like Example 1 except having changed the quantity of aluminum hydroxide into 85 mass parts. The physical properties of this foam are shown in Table 1.

Example 3
In Example 1, the phenol resin foam was obtained like Example 1 except having changed the quantity of aluminum hydroxide into 170 mass parts. The physical properties of this foam are shown in Table 1.

Example 4
In Example 1, a phenol resin foam was obtained in the same manner as in Example 1 except that 8 parts by mass of a mixture of isopropyl chloride: pentane mass ratio = 95: 5 was used as the foaming agent. The physical properties of this foam are shown in Table 1.

Example 5
In Example 1, a phenol resin foam was obtained in the same manner as in Example 1 except that the density of the foam was 125 kg / m ³ . The physical properties of this foam are shown in Table 1.

Example 6
In Example 1, a phenol resin foam was obtained in the same manner as in Example 1 except that the density of the foam was 150 kg / m ³ . The physical properties of this foam are shown in Table 1.

Comparative Example 1
In Example 1, the phenol resin foam was obtained like Example 1 except having changed the quantity of aluminum hydroxide into 60 mass parts. The physical properties of this foam are shown in Table 1.

Comparative Example 2
In Example 1, the phenol resin foam was obtained like Example 1 except having changed the quantity of aluminum hydroxide into 250 mass parts. The physical properties of this foam are shown in Table 1.

  The phenolic resin foam of the present invention uses a material containing a chlorinated aliphatic hydrocarbon compound as a foaming agent and has a relatively large amount of inorganic filler, thereby having excellent flame resistance and fire resistance, and heat insulation performance. In addition, the mechanical properties are excellent, the pH is higher than that of the conventional product, and the contact member has a good corrosion resistance. The phenolic resin foam of the present invention is suitably used as a fireproof heat insulating material in the construction and other industrial fields.

Claims (9)

A foam obtained by foam-curing a foamable phenol resin molding material containing a phenol resin, a foaming agent, a foam stabilizer, a curing agent, and an inorganic filler, wherein the foaming agent has 2 to 5 carbon atoms. includes a hydrocarbon compound, and the molding material is, relative to 100 parts by weight of phenolic resin, the saw including an inorganic filler in a proportion of 70 to 220 parts by weight, the thermal conductivity of the foam below 0.035W / m · K The phenolic resin foam characterized by being.   The phenol resin foam according to claim 1, wherein the pH is 3.0 or more.   The phenol resin foam according to claim 1 or 2, wherein the chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms is chloropropanes.   The phenol resin foam according to any one of claims 1 to 3, wherein the foamable phenol resin molding material contains 1 to 20 parts by mass of a foaming agent per 100 parts by mass of the phenol resin.   The phenol resin foam according to any one of claims 1 to 4, wherein the inorganic filler is at least one selected from metal hydroxides, oxides, carbonates, and metal powders.   The phenol resin foam according to claim 5, wherein the inorganic filler contains aluminum hydroxide. The phenol resin foam according to any one of claims 1 to 6 , which has a density of 80 to 250 kg / m ³ . The phenol resin foam according to any one of claims 1 to 7 , wherein a face material is provided on at least one surface. Surface material, glass fiber nonwoven fabric, spunbonded nonwoven fabric, an aluminum-foil-clad nonwoven fabric, a metal plate, metal foil, plywood, a calcium silicate board, according to claim at least one selected from among gypsum board and wood-cement board 8 The phenolic resin foam described in 1.