JPH0418331A - Manufacture of phenol form composite body - Google Patents

Abstract

PURPOSE:To obtain a composite body, in which an expandable phenol layer containing aggregate particles and a face material are unified, by covering the upper section of the face material with an expandable phenol resin composition and using the face material. CONSTITUTION:Two expandable resin-coated tabular bodies covered with expandable phenol resin compositions are manufactured, one tabular body is laid to a lower section, and a mold 4 is located on the tabular body while being conformed to the phen 1 expandable resin composition 1. The inside of a cavity 5 formed by a mold 4 is filled with perlite 6 in an approximately full manner, the other expandable resin-coated tabular body is positioned while downward directing a coated surface, the upper section of the tabular body is covered with a cover 8, and the mold 4 is located between press materials 7 and press- heated. Perlite particles 6 are dispersed uniformly to the whole phenol form in a phenol form composite body 9, and all of air gaps among particles are filled with the phenol form.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a method for producing a phenol foam composite. More specifically, the present invention relates to a method for producing a composite phenolic resin foam molding (phenol foam) useful for various cushioning materials, heat insulating materials, exterior panels, partition boats, etc.

(b) Conventional technology As a conventional method for manufacturing phenol foam, a face material is placed at the bottom of the mold, a powdered foamable phenol resin composition is sprinkled and filled on the surface of this face material, and then the face material is placed at intervals. A known method is to place the material and heat it to foam and harden it.

On the other hand, a method is known in which a lightweight aggregate such as plastic foam particles or perlite is mixed with a powdered foamable phenolic resin composition, and then the mixture is filled into a predetermined mold and heated to foam. There is.

(c) Problems to be Solved by the Invention However, in such a manufacturing method, vibrations, shocks, etc. during work may cause the powder of the foamable phenolic resin composition to be dispersed unevenly, causing the powder to be dispersed into aggregates such as Nili, pearlite, etc. The resulting laminate of phenolic foam and face material caused by sedimentation may have inconsistent quality due to variations in the density of the phenol foam, and problems with the adhesion between the face material and the phenol foam. In particular, if aggregates such as perlite are added to the foam layer, there will be areas where the aggregates come into contact with the facing material, which may cause problems with adhesion.

The inventors of this invention conducted intensive studies to solve the above technical problem, and as a result, they came up with the idea of using a foamable phenolic resin composition by coating it on a surface material, and in order to complete this invention. It's arrived.

(d) Means for Solving the Problems Thus, according to the present invention, there is provided a foamable phenolic resin composition in which one or both surfaces of the face material are comprised of a phenolic resin initial condensate, a decomposable foaming agent, and a curing agent added as necessary. A foamable resin-coated plate is prepared, and at least one pair of the foamable resin-coated plate is covered with the foamable phenolic resin composition coating layer facing each other with an aggregate particle filled layer interposed therebetween. The foamed phenolic resin composition is placed in a mold and then subjected to conditions for foaming and hardening, thereby obtaining a composite in which the foamed phenol layer containing aggregate particles and the face material are integrated. A method of making a phenol foam composite is provided.

In this invention, the molten material of the foamable phenolic resin composition for the face material is coated in advance with a solution, and when foam molding is performed using this, the molded product meets the industrial requirements as described below. It may be an advantage.

The phenolic resin initial condensate used in this invention includes:
Examples include novolac type and resol type phenolic resin initial condensates. Here, the novolak-type phenolic resin initial condensate is a so-called novolak-type phenolic resin, which is obtained by reacting phenols and aldehydes in the presence of an acidic catalyst. This means that polymerization can proceed further below. This resin is generally solid at room temperature. On the other hand, the resol-type phenolic resin initial condensate is a so-called resol-type phenolic resin known in the art, which is obtained by reacting phenols and excess aldehydes in the presence of a basic catalyst, and is acid-cured. This means that polymerization can proceed with a chemical agent and heating.

Such resol-type phenolic resin itself is a liquid containing about 20% of reaction water, but it is further dehydrated (evaporated of water) to form a solid (containing about 1% of water), and then This solid material is pulverized to obtain a powdered resol type phenol resin used in the present invention. Of course, a commercially available powdered resol type phenol resin may also be used.

In addition to phenol, the above phenols include 3.5-xylenol, m-cresol, 2.5-xylenol,
Includes 3.4-xylenol, 2.4-xylenol, 0-cresol, p-cresol, and the like.

Aldehydes include formaldehyde, paraformaldehyde, hexamethylenetetramine, furfural,
Includes acetaldehyde, acetals, etc. A preferred precondensate for use in this invention is a condensate of phenol and formaldehyde.

The decomposable blowing agent in the present invention refers to inorganic and organic blowing agents that can decompose and generate gas during heat curing in a composition mixed with a phenolic resin initial condensate. Typical examples of these include organic decomposable blowing agents such as N,N dinitrosopentamethylenetetramine, benzenesulfonylhydrazide, azobisisobutyronitrile, azodicarbonamide, and paratoluenesulfonylhydrazide, as well as sodium bicarbonate, ammonium carbonate, Ammonium bicarbonate, ammonium nitrite, azide compounds (e.g. CaN5)? ,,: Which inorganic decomposition type blowing agent can be mentioned. All of these are in powder form.

The amount of the blowing agent to be added is the required amount mainly taking into account the desired final density of the blowing agent, or is suitably 1 to 50 parts by weight per 100 parts by weight of the phenolic resin initial condensate.
2 to 25 parts by weight is preferred.

Hardeners are used in particular when novolak-type phenolic resin precondensates are used. This curing agent means a compound that can be decomposed by heating and can undergo a crosslinking reaction with the novolac type phenol resin initial condensate.

Such a compound is, like formaldehyde, a compound used in phenol resin molding by reaction with phenols, and is usually in powder form.

Specific examples include hexamethylenetetramine, paraformaldehyde, methylal, dioxolane, trioxane, tetraoxane, trimethylolphosphine,
Examples include s-triazine.

The amount of curing agent added is generally 1 to 30 parts by weight per 100 parts by weight of novolac type phenolic resin, and 4 parts by weight.
~15 parts by weight is preferred.

In addition, it can be mixed with a cell regulator to further make cells finer and more uniform. Surfactants are used as the bubble control agent, and they are nonionic such as sorbitan fatty acid ester, silicon glycol copolymer, polyoxyethylene-based polyoxypropylene copolymer, and cationic such as alkylamine salt.

The foamable phenolic resin composition of the present invention may contain flame retardants and other various additives, such as fillers such as clay calcium carbonate, talc, and glass powder. The amount of these additives is preferably 100 parts by weight or less per 100 parts by weight of the phenolic resin initial condensate.

The solid resin composition of the present invention is usually prepared by kneading the above-mentioned phenolic resin initial condensate, a decomposable blowing agent, and, if necessary, a curing agent, using a heated roll or the like to uniformly mix the mixture, and then pulverizing the mixture. It is used in powder form with an outer diameter of 1xz or less. Of course, granules may also be used.

The material of the face material in the present invention is appropriately selected depending on the application, and examples thereof include metal, inorganic, wood, plastic, fiber, or a laminate thereof.

Metals include aluminum, iron, steel, copper, etc.
Inorganic materials include glass, asbestos, gypsum, calcium silicate, cement, etc. Wood materials include veneer, paper, etc., and plastic materials include polycarbonate, polyester, polyethylene, polyvinyl chloride, polypropylene, melamine resin, etc. However, fibrous materials include woven fabrics and non-woven fabrics.

The shape of the face material may be planar or curved. It may also be in the form of a hole.

Planar objects include those that are flat and those that have unevenness due to multiple surfaces (irregular shapes). Examples of the curved surface include corrugated and cylindrical shapes.

The covering surface of the facing material should preferably have a rough surface or an uneven surface because it is in a state where it is easy to adhere to the facing material or the foam. As one example, it is preferable to use metal foil laminated with nonwoven fabric or the like.

The thickness of the face material used in this invention is not particularly limited as long as it maintains its shape, and is appropriately selected depending on the application.

The size of the surface material used in this invention is not particularly limited, but one with a width of 3 cm to 3 m is suitable, and the length depends on the intended use. A piece cut as appropriate is used.

The amount of the foamable phenolic resin composition coated on the face material in this invention depends on the desired thickness and density of the foam molded product, but is generally 5 g/m to the face material.
”~l OKg/m2 is suitable, preferably 10
9/m'-5Kg/m'.

In addition, the coating amount of the above composition is 5 g/m' to 10 Kg/m'
The thickness of the final foam corresponding to m2 is determined by the aggregate used in this invention (for example, perlite, shirasu balloon, glass balloon, glass foam granules, viscous granules, viscous foam granules, cement granules, stone particles, synthetic resin particles, (synthetic resin foam particles, etc.)
2mM to 3002Z due to the presence of .

The foamable resin-coated plate-like body of the present invention is obtained by coating the foamable resin composition on the intended surface (one surface, both surfaces, or a portion thereof) of the surface material.

Methods for coating with a molten material include: 1) Spreading the composition powder on the surface material and melting it by heating, preferably by hot pressing, or heating and melting and pressing with a roll etc.; 2)
) The composition is first melted in a container, and the surface material is applied by contacting it without moving; 3) The powder is melted in the air using a thermal sprayer, etc. and simultaneously applied by spraying; 4) After the powder is kneaded in an extruder, it is subsequently made into a film or notebook-like melt and applied to the facing material, 5) The facing material is heated to a temperature at which the powder melts, and the powder is placed on the facing material, 6) ) The composition may be melted using an M-type grinder and transferred to the surface material while it is viscous.

Method 5) is suitable when the surface material has an irregular shape or a curved surface. Further, method 6) is a method suitable for continuous formation.

Further, as a coating method, there is also a method in which a foamable phenolic resin composition is dissolved in a solvent such as water, alcohol, toluene, etc. and applied to the surface of the facing material.

Furthermore, the surface of the facing material may be pre-moistened with a solvent such as water, alcohol, toluene, etc., and then the foamable phenolic resin composition may be sprayed and dissolved to coat the surface.

The above-mentioned coating method is appropriately selected depending on the material and shape of the face material.

The composition may be used in the form of pellets, tablets, flakes, etc., depending on the case.

The use of the above-mentioned solvent is also preferred in that when the composition is used in a small amount, it can be uniformly spread and applied to the surface material.

The melting temperature of the composition is a temperature sufficient for melting and at a temperature at which foaming does not proceed much (120° C. or lower). In order to adjust to this temperature, the temperature of the heating source must be 150~2
It is suitable for heating at 00°C for a short time.

In addition, when the foamable phenol resin composition is applied, it is desirable that the composition in the coating layer be in a foamed state of 50% or less.

In the present invention, the foamable phenolic resin composition does not necessarily need to cover the entire surface material, but may partially cover the surface material. For example, one in which only the periphery of the face material is covered is included.

The above method provides a foamable resin-coated plate for use in the present invention.

The manufacturing method of the present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereby.

(E) Examples Example 1 Novolac type phenol-formaldehyde resin powder 1
To 00 parts by weight, 10 parts by weight of dinitrosopentamethylenetetramine as a blowing agent and 10 parts by weight of xamethylenetetramine as a curing agent were added and kneaded using heated rolls. Thereafter, it was pulverized to obtain a powdered resin composition. This foamable phenolic resin composition is a powder with a 100% mottling content of 0.5%, a melting point of 810C, and a gelation time of 7% at 150°C.
It was 6 seconds.

Next, as shown in Fig. 1, this foamable phenolic resin composition (1) 16.09 mm was spread with a uniform thickness on the release paper (2) in a size of 250: J square x 2507 shoulders. As shown in FIG. 2, it is placed on a plate heater (3) heated to 150° C. for 1 minute to melt and coat.

In this way, two foamable resin-coated plate-like bodies coated with the foamable phenolic resin composition were made, and the - sheet was placed on the bottom as shown in Fig. 3, and a 250 mm + x 250 xx sheet was placed on top of it.
A mold (4) of X15+u is fitted with a square phenol foamable resin composition (1) of 250+u. Cavity (5) made with mold (4) as shown in Figure 4
Fill the inside with pearlite (average 5.3+u) (trade name Fuyolite, manufactured by Fuyolite Kogyo Co., Ltd.) (6) to almost a -cup (filling degree 100%), and add another sheet as shown in Figure 5. Place the foamed resin-coated plate-shaped body with the coated side facing down, cover it with a lid (8), and place it between the press materials (7) at 150°C and a press pressure of 40!?/cm2 at 1
Heat the press for 5 minutes. Take out the mold (4) from the press and place the phenol foam composite (9) in the mold (
4) Release from the mold.

The obtained phenol foam composite (9) was uniformly dispersed throughout the pearlite grains (6) or the phenol foam, and when cut, the voids between the grains (porosity 40%) were found.
were all filled with phenol foam. Moreover, no defects were observed in the pearlite grains.

Example 2 A foamable phenolic resin composition to be coated on release paper,
Twenty-five sheets of phenol foam composites were prepared using the same apparatus and under the same conditions as in Example 1, except that the amount was changed to 7 g. In all of the obtained phenol foam composites, pearlite grains are uniformly dispersed throughout the phenol foam, and when cut, all the voids between the grains are filled with phenol foam, which can be used as a product.

Put it to the test. The results are shown in Table I.

Comparative Example 1 10 h of the same foamable phenolic resin composition as in Example 1 was artificially mixed as uniformly as possible into 15 g of pearlite grains (trade name Fuyolite No. 7, manufactured by Fuyolite Kogyo Co., Ltd.). Using the same release paper and equipment as in Example 2, 25 sheets were manufactured under the same conditions.

Of these, 12 sheets have phenol foam between the pearlite grains and can be used as a product, but for the remaining 13 sheets, phenol foam does not fill some of the spaces between the pearlite grains, so Pearlite separated and could not be produced as a product.

Example 3 Example 1 except that the face material was changed to 50 μm thick aluminum foil
It was carried out using exactly the same equipment and method.

The obtained phenol foam composite was bonded with aluminum foil on both sides. Comparative Example 2 Peeling of face material The same equipment and method as Comparative Example 1 were used except that the face material was changed to the same 50 μm thick aluminum foil as in Example 3 and the foamable phenolic resin composition was changed to 1209. I went. The obtained phenol foam composite was glued on both sides with aluminum foil, and when it was cut, all the voids between the particles were filled with phenol foam. Regarding this, a peeling test of the face material was conducted. The results are shown in Table I.

Example 4 Example 3 except that the surface material was changed to non-combustible paper with a thickness of 150 μm
It was carried out using exactly the same equipment and method. A surface material peeling test was performed on the obtained phenol foam composite. The results are shown in Table I.

Comparative Example 3 A test was carried out using the same apparatus and under the same conditions as Comparative Example 2, except that the surface material was changed to the same non-combustible paper as in Example 4.

The obtained phenol foam composite was adhered on both sides with non-combustible paper, and when cut, it was found that all the voids between the particles were filled with phenol foam. Regarding this, a peeling test of the face material was conducted. The results are shown in Table 1.

Table E Measurement method According to JIS Z-1528, 90° peeling method.

Example 5 A cylindrical pellet with a diameter of about 2 shoulders and a length of about 4H made of the same foamable phenolic resin composition as in Example 1 of 305y/s2 was evenly spread on the upper surface of the release paper, and then 0.311/
Place u aluminum foil. Furthermore, 3059 is placed on the top surface of the aluminum foil.
/y'' of the above-mentioned beret is laid down, and a release paper is laid on the top surface.Heat it to 150°C and apply a pressure of 10 to 9/cm'' for 20 seconds with 1 nibble. When the upper and lower release papers were removed, both sides of the aluminum foil were coated with the foamable phenolic resin composition, resulting in an aluminum foil coated on both sides with the foamable phenolic resin composition. This phenolic resin composition is slightly foamed. A double-sided foamable phenolic resin composition-coated aluminum foil is cut to 250 zz x 250 x m. 250
Place aluminum foil on the underside of the mold of 1st x 250's shoulder x 20 + u, then spread perlite (Fuyolite No. 7, manufactured by Fuyolite Kogyo Co., Ltd.) to a depth of *Oxx, and on top of that, double-sided foaming phenol resin coated aluminum. Place the foil. Next, spread perlite to fill the inside of the mold, place aluminum foil on top, and close the mold. 150°C, 15 minutes, 50 to 9/
The obtained phenol foam composite has aluminum foil on the surface and center, and pearlite grains are uniformly dispersed throughout the phenol foam. All the voids between grains were filled with phenol foam.

Example 6 A surface material (trade name: Noyowa Cross, manufactured by Showa Aluminum Co., Ltd.) was sprayed with 5 cc/x'' of water to form a foamable phenolic resin composition 2569/ff11 similar to that of Example 1.
1 was evenly coated on the surface, and then left in a dryer at 65° C. for 3 hours. The resulting foamable phenolic resin composition-coated cloth has good adhesion between the cloth and the foamable phenolic resin. This was subjected to pressing acid form in the same manner as in Example 1.

Example 7 The same method as in Example 1 was carried out except that a paper honeycomb core material was used instead of perlite.

When the obtained 1-Niphenol foam composite was cut, it was found that all the voids were filled with phenol foam.

Example 8 Expandable phenolic resin composition 779 is applied only to the bottom surface material
/1 Use coated noncombustible paper, and use uncoated noncombustible paper for the top surface material. Nothing is allowed inside the cavity. The same apparatus and method as in Example 1 were used except for this.

The resulting phenol foam composite has a closed cell ratio of 65%.
It's a foam. The density was 55 ky/x3.

(f) Effects of the invention The foamable resin-coated plate-like body used in this invention can be produced in advance to an appropriate size and transported while coated.
It can be provided as a product for foaming when necessary.

The manufacturing method of the present invention using such a plate-like body is as follows:
It shows the following remarkable technical effects.

1) The adhesion between the face material and the foam in the final foam molded product is superior to that obtained by filling a foamable resin composition on the face material, heating and foaming and curing it as in the past. ing,
2) Even if the amount of phenol in the raw materials used is reduced to about half compared to conventional methods, a molded product that can withstand use can be obtained, so phenol can be saved. In other words, the amount required for the final foam volume was 809 to 1009/C, and it was rarely 15
M (!) 3) Since the face material is evenly coated, the foam becomes uniform. 4) When aggregate is added, there is no adhesion between the aggregate and the face material in simultaneous mixing and filling foaming. Also, if carried out according to this invention, there is always adhesion between the aggregate and the composition, so a stronger adhesive molded product can be obtained; 5) It is possible to perform foam molding on both sides of the facing material at the same time; 6) The facing material and the foam. It is difficult for cavities to form due to gas accumulation at the interface with the

[Brief explanation of drawings]

FIGS. 1 to 6 are configuration explanatory diagrams illustrating each step of the present invention, respectively. (1)...Expansible phenolic resin composition, (2)
...Release paper, (3) ...Plate heater, (4) ...Mold, (5) ...Cavity, (6) ...Pearlite, ( 7)...
Pressed material, (8)... Lid, (9)...
Phenol form complex.

Claims (1)

[Claims] 1. Fabricate a foamable resin-coated plate-like body in which one or both sides of the facing material are coated with a foamable phenolic resin composition consisting of a phenolic resin initial condensate, a decomposable foaming agent, and a curing agent added as necessary. Then, at least one pair of the foamable resin-coated plate bodies is placed in a mold such that the foamable phenolic resin composition coating layer faces each other with the aggregate particle filled layer interposed therebetween, and then the foamable phenolic resin composition is placed in a mold. 1. A method for producing a phenol foam composite, which comprises subjecting the composition to foaming and hardening conditions to obtain a composite in which a foamed phenol layer containing aggregate particles and a face material are integrated.