KR101403258B1 - Phenol resin foam - Google Patents

Abstract

The present invention provides a phenol resin foam having excellent flame retardancy and fire resistance, good heat insulation performance, excellent mechanical properties, high pH compared to conventional products, and good corrosion resistance to a contact member. 1. A foam obtained by foaming and expanding a foamable phenolic resin molding material containing a resin, a foaming agent, a foam stabilizer, a curing agent and an inorganic filler, wherein the foaming agent contains a chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms, Wherein the inorganic filler is contained in an amount of 70 to 220 parts by mass based on 100 parts by mass of the phenol resin.

Description

{PHENOL RESIN FOAM}

The present invention relates to a phenolic resin foam, more particularly to a phenol resin foam having excellent flame retardancy and fire resistance, excellent heat insulation performance, excellent mechanical properties, high pH compared to conventional products, The present invention relates to a resin foam.

BACKGROUND ART Conventionally, phenol resin foams are used as insulating materials in industrial fields other than construction, in view of excellent heat insulation, flame retardancy, and fire resistance.

It is known that a phenol resin foam having an independent cell structure has an adiabatic performance with good temporal stability. As a method for producing a phenol resin foam having this independent cell structure, a method using a physical foaming means containing chloropropane (See, for example, Japanese Patent Application Laid-Open No. 5-87093).

On the other hand, a composition prepared by adding 62.5 to 200 parts by weight of aluminum hydroxide per 100 parts by weight of the acid-curing phenol resin to a composition containing an acid-curing phenol resin, a surfactant, a foaming agent and a curing agent as the non- A nonflammable resin foamed construction material is disclosed (for example, see JP-A-3-160038). This foamed construction material is excellent in flame retardancy and fire resistance because it contains a large amount of aluminum hydroxide. However, it is considered that a conventional foamed agent is used (the type of foaming agent is not described), and therefore, As a result, it is considered that the heat insulating performance is deteriorated and the thermal conductivity exceeds 0.035 W / m · K.

However, in the production of the phenolic resin foam, a method of foaming and curing a foamable phenolic resin molding material containing at least a phenol resin, a foaming agent and a curing agent is generally used, and as the curing agent, a curing agent such as sulfuric acid, Benzenesulfonic acid, toluenesulfonic acid, and xylenesulfonic acid. Therefore, the resulting phenolic resin foam contains the acid curing agent, and therefore, when wet by rain or the like, the acid curing agent is extracted with water. As a result, when the metal member is in contact with the phenol resin foam, or when the metal member is present in the vicinity of the foam, the metal member is liable to be corroded.

DISCLOSURE OF INVENTION

It is an object of the present invention to provide a phenol resin foam material having excellent flame retardancy and fire resistance, excellent heat insulation performance, excellent mechanical properties, high pH compared to conventional products, And to provide an image processing method and an image processing method.

The inventors of the present invention have conducted intensive studies to develop a phenolic resin foam having the above-mentioned properties. As a result, the present inventors have found that a foaming agent containing a chlorinated aliphatic hydrocarbon compound, preferably chloropropane, It has been found that the object can be achieved by using a specific amount of the inorganic filler, and the present invention has been completed on the basis of this point.

That is,

(1) A foam obtained by foam-curing a foamable phenolic resin molding material containing a phenol resin, a foaming agent, a foam stabilizer, a curing agent and an inorganic filler, wherein the foaming agent contains a chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms, Wherein the material contains the inorganic filler in an amount of 70 to 220 parts by mass based on 100 parts by mass of the phenol resin,

(2) The phenolic resin foam according to the above item (1), wherein the pH is 3.0 or more,

(3) The phenolic resin foam according to the above item (1) or (2), wherein the chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms is chloropropane,

(4) The foamable phenolic resin molding material as described in any one of (1) to (3) above, which contains 1 to 20 parts by mass of a foaming agent per 100 parts by mass of the phenol resin,

(5) The phenolic resin foam according to any one of the above items (1) to (4), wherein the inorganic filler is at least one selected from the group consisting of hydroxides, oxides,

(6) The phenolic resin foam according to the above item (5), wherein the inorganic filler contains aluminum hydroxide,

(7) The phenolic resin foam according to any one of (1) to (6) above, wherein the thermal conductivity is 0.035 W / mK or less,

(8) The phenolic resin foam according to any one of the above (1) to (7), which has a density of 80 to 250 kg / m 3,

(9) The phenolic resin foam according to any one of the above (1) to (8), wherein a face material is formed on at least one surface of the phenolic resin foam, and

(10) The phenolic resin according to the above item (9), wherein the face material is at least one selected from the group consisting of glass fiber nonwoven fabric, spunbonded nonwoven fabric, aluminum foil laminated nonwoven fabric, metal plate, metal foil, plywood, calcium silicate plate, gypsum board and woody cement board To provide a foam.

Industrial Applicability According to the present invention, it is possible to provide a flame retardant resin composition which has excellent flame retardancy and fire resistance, is excellent in thermal insulation performance and excellent in mechanical properties by using a resin containing a chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms as a blowing agent and using a relatively large amount of inorganic filler , And a phenol resin foam having a higher pH than that of the conventional product and having good corrosion resistance against the contact member can be provided.

Carrying out the invention  Best form for

The phenolic resin foam of the present invention is obtained by foam-curing a foamable phenolic 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 phenol resin may be at least one selected from the group consisting of phenols such as phenol, cresol, xylenol, paraalkyl phenol, paraphenyl phenol, resorcin and the like, and aldehydes such as formaldehyde, paraformaldehyde, furfural, acetaldehyde, But is not limited to, a resol-type phenol resin obtained by adding a catalytic amount of an alkali such as potassium hydroxide, calcium hydroxide, trimethylamine, triethylamine, and the like. The ratio of the phenol and aldehyde 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 terms of molar ratio.

In the present invention, those containing a chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms are used as the foaming agent. The chlorinated aliphatic hydrocarbon compound having 2 to 5 carbon atoms is a chlorinated compound of a linear or branched aliphatic hydrocarbon having 2 to 5 carbon atoms, and the number of chlorine atom bonds is not particularly limited, but is preferably about 1 to 4 . 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 singly or in combination of two or more. Of these, chloropropanes such as propyl chloride and isopropyl chloride are preferable, and isopropyl chloride is particularly preferable.

The foam obtained by using such a chlorinated aliphatic hydrocarbon compound as the foaming agent has low initial thermal conductivity and good heat insulating performance.

The blowing agent used in the present invention is characterized in that it contains a chlorinated aliphatic hydrocarbon compound. The blowing agent used in the present invention may contain, for example, 1,1,1,3,3- Fluorinated hydrocarbon compounds (such as pentafluorobutane), fluorinated hydrocarbon compounds such as pentafluorobutane (substituted fluorocarbons), trichlorofluoromethane and trichlorotrifluoroethane, hydrocarbon compounds such as butane, pentane, hexane and heptane, , Air such as nitrogen, argon, or carbon dioxide gas, and the like can be suitably added in an appropriate amount. The amount thereof is preferably 0.1 to 20%, more preferably 0.5 to 15%, based on the chlorinated aliphatic hydrocarbon compound.

In the present invention, the amount of the foaming agent used is usually 1 to 20 parts by mass, preferably 5 to 10 parts by mass, per 100 parts by mass of the phenol resin.

The bubble stabilizer to be used in the present invention is preferably a nonionic surfactant such as polysiloxane-based, polyoxyethylene sorbitan fatty acid ester, and castor oil ethylene oxide adduct. These may be used singly or in combination of two or more.

In the present invention, as the curing agent, acid-curing agents such as inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, para toluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid and phenolsulfonic acid are used. Of these, benzenesulfonic acid, ethylbenzenesulfonic acid, para toluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid and phenolsulfonic acid are preferable, and paratoluenesulfonic acid and xylenesulfonic acid are particularly preferable.

In the present invention, one kind of these curing agents may be used alone, or two or more kinds thereof may be used in combination. The amount to be used varies depending on the kind of the curing agent, but 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. When the amount of the curing agent is within the above range, the function as a curing agent can be exerted well and the pH of the foam can be controlled to 3.0 or more. More preferably, the amount of the curing agent to be used is 10 to 20 parts by mass.

Examples of the inorganic filler in the present invention include hydroxide or oxide of a metal such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide or zinc oxide, metal powder such as zinc, calcium carbonate, magnesium carbonate, Barium, zinc carbonate, and the like. These inorganic fillers may be used singly or in combination of two or more kinds.

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

The amount of the inorganic filler to be used is selected in the range of 70 to 220 parts by mass based on 100 parts by mass of the phenol resin. When the amount of the inorganic filler is within the above range, it is possible to obtain a phenolic resin foam having excellent flame retardancy and fire resistance, good heat insulating performance, excellent mechanical properties, and a pH of not less than 3. The amount of the inorganic filler to be used is preferably 80 to 200 parts by mass, more preferably 80 to 180 parts by mass, from the viewpoint of the performance of the obtained phenol resin foam.

In the present invention, a plasticizer is used in accordance with the requirements for the following reasons.

It has been confirmed that the thermal conductivity of the plastic-based heat insulating material, including the phenolic resin foam, varies with time from the time of production. This is a phenomenon in which the gas in the bubbles diffuses out of the system, and the foaming agent permeates through the bubbles and is gradually replaced with air in the atmosphere. Therefore, also in the case of the phenolic resin foam, the thermal conductivity is increased over time, and the heat insulating performance deteriorates over time.

As a cause of deterioration of the phenol resin foam over time, the phenomenon that the flexibility of the foam wall of the phenol resin foam deteriorates with time can be considered. Therefore, one of the means for suppressing deterioration of the phenol resin foam is to impart flexibility to the bubble wall. The addition of the plasticizer is intended to impart flexibility to the bubble wall of the foam, thereby suppressing deterioration of the heat insulating performance over time.

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

In particular, since the polyester polyol has a structure containing an ester bond and a hydroxyl group that are excellent in hydrophilicity and surfactant, it is excellent in compatibility with a hydrophilic phenol resin liquid and can be uniformly mixed with a phenol resin. Furthermore, by using the polyester polyol, it is possible to avoid the localization of bubbles, uniformly distribute bubbles throughout the foam, and easily produce a homogeneous phenol resin foam in quality.

In the present invention, the plasticizer is usually used in the range of 0.1 to 20 parts by mass based on 100 parts by mass of the phenol resin. When the amount of the plasticizer used is within the above range, the performance other than the obtained phenolic resin foam is not inhibited and the effect of imparting flexibility to the bubble wall is excellently exerted. The plasticizer is preferably used in an amount of 0.5 to 15 parts by mass, and more preferably 1 to 12 parts by mass.

In the present invention, urea to be used as desired can impart a phenolic resin foam having low initial thermal conductivity and strength, particularly low brittleness. This urea is used in an amount of usually 1 to 10 parts by mass, preferably 3 to 7 parts by mass, per 100 parts by mass of the above-mentioned phenol resin.

The foamable phenolic resin molding material may be obtained by, for example, adding and mixing the above-mentioned inorganic filler, foam stabilizer, plasticizer and urea to the above-mentioned phenol resin, adding to the mixture a foaming agent containing the chlorinated aliphatic hydrocarbon compound and a curing agent And then the mixture is supplied to a mixer and stirred.

Examples of the method for forming the phenolic resin foam using the foamable phenolic resin molding material prepared as described above include (1) a molding method in which the resin flows out onto the endless conveyor, (2) a method in which the foam is partially sprinkled (3) a method of pressurized foaming in a mold, (4) a method of making a foam block by injecting it into a large space, and (5) a method of charging and foaming while press fitting into a cavity.

In a preferred method, the foamable phenolic resin molding material is discharged onto a carrier moving continuously, and the discharged material is foamed via a heating zone and molded to produce a desired phenolic resin foam. Specifically, the foamable phenolic resin molding material is discharged onto the face material on the conveyor belt. Then, the face material is loaded on the upper surface of the molding material on the conveyor belt, and the resultant is introduced into the hardening furnace. In the curing furnace, the phenolic resin foam is adjusted to a predetermined thickness by pressing with another conveyor belt from above, and is foamed and cured under the conditions of about 60 to 100 DEG C for about 2 to 15 minutes. The phenol resin foam from the curing furnace is cut to a predetermined length.

The face material is not particularly limited and generally used are natural fibers, synthetic fibers such as polyester fibers and polyethylene fibers, nonwoven fabrics such as inorganic fibers such as glass fibers, paper, aluminum laminated nonwoven fabrics, metal plates, A metal plate, a metal plate, a plywood, a structural panel, a particle board, a hard board, a woody cement board, a flexible board, a pearlite board, a calcium silicate board, a magnesium carbonate board, a pulp Water hydrants such as cement board, seeding board, medium density fiber board, gypsum board, lath sheet, volcanic glass composite plate, natural stone, brick, tile, glass molded body, lightweight foam concrete molded body, cement mortar molded body, glass fiber reinforced cement molded body A molded article having a hydrated cement hydrate as a binder component is preferable. The face material may be formed on one side of the phenol resin foam or on both sides thereof. Further, in the case of forming on both surfaces, the face materials may be the same or different. Alternatively, the face material may be adhered later by using an adhesive.

The phenolic resin foam of the present invention usually has a pH of 3.0 or higher. If the pH is 3.0 or more, corrosion to the metal member which is in contact with the foam or the metal member which is present in the vicinity of the foam can be suppressed even if it is wetted. The pH is preferably 4.0 or more, particularly preferably 4.5 or more. The method of measuring the pH of the foam will be described in detail below.

In the phenolic resin foam of the present invention, the thermal conductivity is preferably 0.035 W / m · K or less, more preferably 0.030 W / m · K or less. If the thermal conductivity exceeds 0.035 W / m · K, the heat insulating performance of the phenolic resin foam becomes insufficient.

It is preferable that the density is about 80 to 250 kg / m 3, the average cell diameter is about 5 to 400 μm, and the area ratio of the voids to the cross-sectional area of the foam is 5% or less. In addition, since there is substantially no hole in the bubble wall, the closed cell ratio is usually 85% or more, preferably 90% or more.

The method for measuring the properties of the phenolic resin foam will be described in detail later.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

The physical properties of the phenolic resin foam obtained in each example were measured according to the following methods.

(1) Density

It was measured according to JIS A 9511: 2003, 5.6 density.

(2) Thermal conductivity

A phenol resin foam sample having a width of 300 mm and a thickness of 10 캜 and a high temperature plate of 30 캜 was used and a thermoconductivity measuring device HC-074 304 Ltd.). The initial thermal conductivity is the thermal conductivity after the sample of the phenolic resin foam is allowed to stand in a 70 ° C atmosphere for 4 days.

(3) Corrosion resistance

A sample of a phenolic resin foam sample of the same size was loaded on a zinc steel plate (thickness of 1 mm plating adhered amount of 120 g / m 2) having a size of 300 mm in width and 300 mm in thickness and fixed without shifting the test piece under a promoting environment of 40 ° C and 100% RH And the corrosion of the contact surface with the sample of the zinc iron plate after being left for 24 weeks was visually evaluated.

(4) pH

0.5 g of a foamed phenol resin sample that has been pulverized to 250 μm (60 mesh) or less in a mortar or the like is weighed into a 200-ml plug-equipped Erlenmeyer flask, and 100 ml of pure water is added thereto to seal the plug. 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) Independent air bubble rate

ASTM D2856.

(6) Fire resistance

A fire resistance test furnace with a heating area of 70 cm x 70 cm was used to evaluate the performance of the fire resistance test according to the performance evaluation based on the provisions of Article 2 (7) (refractory structure)

Heating temperature curve T = 345 log ₁₀ (8t + 1) + 20

[T: average temperature (° C), t: elapsed time (minute)]

, And the elapsed time and the backside temperature were measured. The backside temperature was determined to be below 140 캜.

Example 1

A phenol / formaldehyde molar ratio of 1: 2.0, a viscosity of 3800 mPa 占 퐏 / 25 占 폚, and a moisture content of 11.5% by mass, manufactured by Asahi Organic Materials Industry Co., Ltd., trade name: PF- , 100 parts by mass of aluminum hydroxide (trade name " C31 ", manufactured by Sumitomo Chemical Co., Ltd.) as an inorganic filler, 2 parts by mass of calcium carbonate, 8 parts by mass of isopropyl chloride as a foaming agent, 15 parts by mass of xylene sulfonic acid 15 Mass part was fed to a pin mixer and mixed with stirring to prepare a foamable phenolic resin molding material.

Next, the molding material was discharged by a galvalume steel sheet (JIS G 3321) having a thickness of 0.5 mm, and then a galvalume steel sheet having the same thickness of 0.5 mm was placed thereon. The galvannealed steel sheet was placed in a drier at 80 DEG C and foamed for 20 minutes, A phenol resin foam having a thickness of 50 mm, a length of 900 cm and a width of 900 cm and a density of 100 kg / m 3 was produced. Table 1 shows the physical properties of the foam.

Example 2

A phenol resin foam was obtained in the same manner as in Example 1 except that the amount of aluminum hydroxide was changed to 85 parts by mass in Example 1. Table 1 shows the physical properties of the foam.

Example 3

In Example 1, a phenol resin foam was obtained in the same manner as in Example 1 except that the amount of aluminum hydroxide was changed to 170 parts by mass. Table 1 shows the physical properties of the foam.

Example 4

A phenol resin foam was obtained in the same manner as in Example 1 except that in Example 1, 8 parts by mass of a mixture of isopropyl chloride: pentane in a mass ratio of 95: 5 was used as a blowing agent. Table 1 shows the physical properties of the foam.

Example 5

A phenol resin foam was obtained in the same manner as in Example 1 except that the density of the foam was changed to 125 kg / m 3 in Example 1. Table 1 shows the physical properties of the foam.

Example 6

A phenolic resin foam was obtained in the same manner as in Example 1 except that the density of the foam was changed to 150 kg / m 3. Table 1 shows the physical properties of the foam.

Comparative Example 1

A phenol resin foam was obtained in the same manner as in Example 1 except that the amount of aluminum hydroxide was changed to 60 parts by mass in Example 1. Table 1 shows the physical properties of the foam.

Comparative Example 2

A phenol resin foam was obtained in the same manner as in Example 1 except that the amount of aluminum hydroxide was changed to 250 parts by mass in Example 1. Table 1 shows the physical properties of the foam.

The phenolic resin foam of the present invention is excellent in mechanical properties and has excellent fire retardancy and fire resistance by using a resin containing a chlorinated aliphatic hydrocarbon compound as a foaming agent and a relatively large amount of an inorganic filler, Has a higher pH than that of the conventional product, and has good corrosion resistance against the contact member. The phenolic resin foam of the present invention is preferably used as fire-resistant insulating material in construction and other industrial fields.

Claims (10)

A foaming agent obtained by foam-curing a foamable phenolic resin molding material containing a phenol resin, a foaming agent, a foam stabilizer, a weathering agent, a plasticizer and an inorganic filler, wherein the foaming agent contains chloropropanes, , Carbonate, and zinc powder, and the molding material contains the acid curing agent in an amount of 5 to 25 parts by mass based on 100 parts by mass of the phenol resin, and the inorganic filler is contained in an amount of 70 to 220 mass parts And the plasticizer is a polyester polyol. The method according to claim 1, A phenolic foam having a pH of at least 3.0. delete 3. The method according to claim 1 or 2, A foamable phenolic resin molding material comprising 1 to 20 parts by mass of a foaming agent per 100 parts by mass of a phenol resin. delete 3. The method according to claim 1 or 2, Wherein the inorganic filler contains aluminum hydroxide. 3. The method according to claim 1 or 2, A phenolic resin foam having a thermal conductivity of 0.035 W / m · k or less. 3. The method according to claim 1 or 2, A phenolic resin foam having a density of 80 to 250 kg / m3. 3. The method according to claim 1 or 2, And a face material is formed on at least one surface of the phenolic resin foam. 10. The method of claim 9, Wherein the face material is at least one selected from a glass fiber nonwoven fabric, a spunbonded nonwoven fabric, an aluminum foil laminated nonwoven fabric, a metal plate, a metal foil, a plywood, a calcium silicate plate, a gypsum board and a woody cement board.