JPH0233301B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field This invention relates to a phenolic resin composite foam laminate. More specifically, the present invention relates to a composite foam laminate in which a specific phenolic resin foam and a film material are integrated, and which is useful for building materials, supporting materials, panels, etc.

(B) Prior Art Conventionally, a foamable resin composition prepared by mixing a novolac-type or resol-type phenolic resin initial condensate with a required amount of a decomposition-type blowing agent and a curing agent is usually
It is used in powder form, and the amount of powder is usually 100 mesh or more and the bulk specific gravity is 1 or less.

However, in order to obtain a phenolic resin molded product by mixing the above composition with other particles, it is difficult to obtain a uniform mixture unless the particle size is 1 mm or less and the bulk specific gravity is about the same as that of the above composition. Even if this was heated and foamed, it was extremely difficult to obtain a molded article of phenolic resin having a uniform mixed foam layer.

In this regard, the present inventors previously coated aggregate particles that were not reactive with the foamable resin composition to be coated, and filled the mold with the foamable resin-coated particles. We have previously proposed a synthetic resin foam molded product containing aggregate particles in which aggregate particles are substantially uniformly dispersed by heating, etc. It was also discovered that the two can be fused and integrated.

(C) Problems to be Solved by the Invention However, when a film material such as a metal film or a plastic film is used as the above-mentioned surface material, heated air introduced between the film material and the foam during molding However, air pockets tend to form and depressions are likely to occur in the laminated film after molding due to air contraction, making it difficult to obtain a composite foam laminate with good surface smoothness and excellent adhesion to the foam.

The present invention has been made to solve these problems, and aims to provide a film material-phenol resin composite foam laminate that has excellent surface smoothness and fusion properties.

(d) Means and effects for solving the problems Thus, according to the present invention, a foamable resin containing a novolac type or resol type phenolic resin initial condensate, a decomposition type blowing agent, and a curing agent added as necessary. After coating the aggregate particles with the composition to obtain foamable resin-coated particles, a film material having perforations is attached to a molding die, the coated particles are filled into the mold, and the mold is closed. Then, the foamable resin composition is heat-treated at a temperature at which it foams and hardens, thereby producing a composite foam in which the phenolic resin foam in which aggregate particles are substantially uniformly dispersed and the film material are fused and integrated. A method for producing a phenolic resin composite foam laminate is provided, the method comprising obtaining a laminate.

The most characteristic feature of this invention is that a film material having many perforations is used as the film material, which allows the film material to have smoothness and fusion properties at the same time during foam molding of the above-mentioned specific expandable resin-coated particles. The point is that the layers are well integrated. That is,
A large number of perforations formed in the film material act as pores during heat molding, and act as vent holes for heated air and the like brought in between the film material and the foam to be molded. Therefore, in the resulting laminate, substantially no air pockets are formed between the film material and the foam, so that they are uniformly fused, and a laminate with excellent film surface smoothness can be obtained.

Examples of the phenolic resin initial condensate used in this invention 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 known in the art that is obtained by reacting phenols and aldehydes in the presence of an acidic catalyst, and in the presence of a curing agent. means that polymerization can proceed further. This resin is generally in powder form 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. It means a substance that can undergo polymerization by using an agent and heating. Such resol type phenolic resin itself is a liquid containing about 20% reaction water, but
This is further dehydrated (water is evaporated) to form a solid material (containing approximately 1% water), and then this solid material is pulverized to obtain the powdered resol type phenolic resin used in the present invention. Of course, a commercially available powdered resol type phenolic resin may also be used.

The above phenols include, in addition to phenol,
3,5-xylenol, m-cresol, 2,5
-xylenol, 3,4-xylenol, 2,4
-xylenol, o-cresol, p-cresol, etc. Albuhydes include formaldehyde, paraformaldehyde, hexamethylenetetramine, furfural, acetalzehyde, acetals, and the like. A preferred precondensate for use in this invention is a condensate of phenol and formaldehyde.

The decomposable blowing agent in this invention means an inorganic or organic blowing agent that can decompose and generate gas during heat curing in a composition mixed with a phenolic resin initial condensate. Representative examples of these include N,N'-dinitrosopentamethylenetetramine,
Organic decomposition type blowing agents such as benzenesulfonyl hydrazide, azobisisobutyronitrile, azodicarbonamide, paratoluenesulfonyl hydrazide, as well as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite,
Examples include inorganic decomposition type blowing agents such as azide compounds (eg CaN ₆ ). All of these are in powder form.

The amount of the blowing agent to be added is the required amount, mainly taking into consideration the density of the desired final foam, but 1 to 50 parts by weight is appropriate for 100 parts by weight of the phenolic resin initial condensate; ~15 parts by weight is preferred.

Hardeners are used in particular when novolak-type phenolic resin precondensates are used. This curing agent refers to a compound that is decomposed by heating and capable of crosslinking the novolak type phenolic resin initial condensate.
Such a compound is a compound used to form a phenolic resin by reacting with phenols, similar to formaldehyde, and is usually in powder form. Specific examples include hexamethylenetetramine, paraformaldehyde, methylal, dioxolane, traoxane, tetraoxane, tramethylolphosphine, S-triazine, and the like.

The amount of the curing agent added is generally 1 to 30 parts by weight, preferably 4 to 15 parts by weight, per 100 parts by weight of the novolak type phenolic resin.

The powdered resin composition of the present invention is usually prepared by kneading the above-mentioned phenolic resin initial condensate, a decomposable foaming agent, and, if necessary, a curing agent, using a heated roll or the like to uniformly mix the mixture, and then crushing it. Diameter 1mm
Used in powder form: Of course, granules may also be used.

The foamable resin composition of the present invention may also contain small amounts of other various additives, such as fillers such as clay and talc. These additives are
Novolac type or resol type phenolic resin 100
It is preferably 100 parts by weight or less.

On the other hand, the aggregate serving as the core of the expandable resin-coated particles includes organic or inorganic particles or a mixture thereof, but it is preferably one that does not react with the expandable resin composition.

Examples of inorganic materials include perlite, shirasu balloons, glass balloons, glass foam particles, glass cotton particles, rock wool particles, slag, clay foam particles, sand, plaster particles, and metallic particles.

Examples of organic substances include synthetic resin particles and foamed particles thereof, wood powder particles, paper particles, etc., but usually 100
Resins having heat resistance of ℃ or higher are preferable, and examples thereof include styrene-maleic anhydride copolymer resin foam beads, polypropylene foam beads, and the like.

There is no particular limitation on the shape of the aggregate particles, and they may be spherical, crushed fragments, or irregularly shaped.
The size of the particles ranges from microscopic particles with a shape of 1 mm to particle diameters of 40 to 50 mm.
Any size up to large grains is fine. The density of aggregate particles is not particularly limited; when considering the use of lightweight foam molded products, it is sufficient to select one with a density of 1 g/cm ² or less, even if the aggregate is of high density. good.

The method of coating the aggregate particles with the foamable resin composition is within the temperature range where the powdered foamable resin composition melts and adheres, that is, from the softening point of about 80°C to about 110 to 120°C, where it foams and hardens. A method of heating aggregate particles to a temperature in the range of There is a method of coating aggregate particles by heating and hardening.

Another method is to use a binder. Typical binders include water, methyl alcohol, toluene, and the like. Among these, water is most preferred. When such a binder is used, for example, the aggregate particles and the powdered foamable resin composition may be rolled together in a pan-type granulator while spraying the binder. When these binders are used, it is preferable to remove the binders through a drying process after coating and granulation. This is because, for example, if water remains, it may have an adverse effect on the expansion ratio and bubbles. Further, any binder may be used as long as it does not adversely affect the foaming process. For example, the binder may include a 3-5% aqueous solution of sticky polyvinyl alcohol, silicone oil,
Animal and vegetable oils may also be used. When these binders are used, they remain in the coated particles of the present invention, and such coated particles are also included in the present invention.

The amount of coating of the foamable resin composition on the aggregate particles varies depending on the foamability of the composition, the type and shape of the aggregate, etc., but it is usually necessary to coat the aggregate particles with a weight of 5 g or more per 1 liter volume of the aggregate particles. Good coverage is 15-500g. The coating condition at this time is good enough that the composition is evenly coated on the aggregate particles, but
When obtaining a molded article, there is no problem even if the coating is mottled.

Note that the coating resin composition of the expandable resin-coated particles of the present invention obtained may be a partially foamed and hardened composition having secondary foamability.

On the other hand, the film material used in this invention is
Examples include metal films and plastic films, and specific examples thereof include aluminum foil, copper foil, polyethylene film, polypropylene film, and vinyl chloride film. These film materials may be further laminated with a suitable paper material, and one preferred embodiment is to use a laminated film in which each of the above-mentioned films and foils are laminated with so-called flame-retardant paper. be. Further, the thickness of these film materials is not particularly limited, but a thickness of about 0.05 to 1.0 mm is usually suitable.

A large number of perforations are formed in the film material.
The perforation may be a punched hole or a through hole punched with a needle or the like, as long as it functions as a gas mechanism at least during molding. Usually, the diameter of this perforation is 0.3 to 0.5 mm. If the pore diameter is less than 0.3 mm, the degassing effect will be insufficient and it will not be suitable, and if it exceeds 0.5 mm, the phenolic resin foam layer will bulge through the pores during molding, so it will not be suitable. The density of forming such perforations in the film material varies depending on the conditions, but it is set at 2 to 13 holes/cm ² in terms of the surface smoothness of the final foamed laminate and the adhesion of the film material. is preferable. Further, these perforations may be formed regularly or irregularly. In addition, when using a laminated film with the above-mentioned paper material, depending on the case, the perforation may be formed only in the metal film or plastic film, and it is not necessary to provide the perforation in the paper material. This is because paper material itself is porous and easily permeable to gas.

In the method of the present invention, the expandable resin-coated particles and the film having a large number of perforations are fusion-molded. Hereinafter, a specific example of this molding method will be explained with reference to the drawings.

First, as shown in FIG.
The foamed resin-coated particles 4 are filled 100%, preferably almost 100%, and the film material 3 having a large number of perforations is placed thereon. Next, press heating plate 1
The heater 5 built into the
Pressure 0.1~100 in the direction of the arrow while heating to 180℃)
It is pressed at Kg/cm ³ , especially 10 Kg/cm ³ , and then foamed and fusion molded.

The composite foam laminate thus obtained is
As shown in FIGS. 2 and 3, a large number of perforations made of aluminum foil 31 and noncombustible paper 32 are formed on both sides of a composite foam laminate in which aggregate particles 7 are uniformly dispersed in a phenolic resin foam layer 6. 8, the film material 3 is uniformly fused and integrated, and has excellent smoothness on both sides.

The laminate of this invention obtained in this way is
First, the phenolic resin foam layer is different from one in which a foamable resin composition and aggregate particles are simply mixed and foamed, and the aggregate is substantially uniformly dispersed in the foam. Here, a molded product in which aggregate particles are substantially uniformly dispersed means that aggregate particles are not present only in the surface layer or center of the molded product. Therefore, a molded body in which the aggregate particles are substantially uniformly dispersed is obtained, so that such a molded body has various quality characteristics such as high dimensional stability and uniform heat insulation effect. In addition, during foam molding, it has been recognized that the aggregate is substantially uniformly dispersed in the foam molded product even at a filling rate as low as 20% of the bulk volume capacity.

Further, due to the large number of perforations 8, during molding, gas does not interfere with the fusion of the film material to the foam layer, and no air pockets are formed. Therefore, it has superior fusion properties and smoothness compared to film materials without perforations.

Note that the laminate thus obtained is itself new. Therefore, the present invention provides foamable resin-coated particles in which aggregate particles are coated with a foamable resin composition containing a novolac type or resol type phenolic resin initial condensate, a decomposition type foaming agent, and a curing agent added as necessary. and a film material having a large number of perforations are fused and integrated by foaming, and aggregate particles are substantially uniformly dispersed in the phenolic resin foam. It is.

(E) Examples Next, the present invention will be explained with examples, but the invention is not limited thereby.

Example 1 10 parts by weight of a novolak type phenol-formaldehyde resin powder was mixed with 10 parts by weight of a foaming agent dinitrosopentamethylenetetramine and 10 parts by weight of a hardening agent hexamethylenetetramine, and kneaded with a heated roll. Thereafter, it was pulverized to obtain a powdered resin composition. This foamable resin composition is a powder with a 150 mesh residue of 2.4%, a melting point of about 80°C, and a 150
The gelation time at °C was 76 seconds.

Next, the above resin composition powder was granulated for 3 minutes using a pan-shaped granulator using pearlite (trade name: Fuyolite, manufactured by Fuyolite Industries) having an average particle size of 5.3 mm as an aggregate. Note that water was used as the binding material at that time, and was sprayed in a mist form from a nozzle. The ratio of raw materials during granulation is approximately 10 c.c. (bulk) of binder to 1000 c.c. (bulk) of aggregate, and 80 c.c. (bulk) of novolak type phenolic resin composition powder.

Next, the coated particles obtained in this step were air-dried all day and night, and then dried at 70° C. for 6 hours in a hot air circulation constant temperature bath.

This obtained coated particle is aggregate (perlite)
The foamable resin composition powder was bonded to the surface of the coating, and after being melted and solidified, it did not peel off even when handled roughly.The coating was not yet completely foamed and had an average thickness of 80μ. Ta.

Next, mold release agent (product name: Toshiba Silicone)
A metal mold (inner diameter 917×
1823 x 15 mm) was made by laminating aluminum foil with a thickness of 7 μm and non-combustible paper with a basis weight of 140 g/cm ² , and furthermore, holes with a diameter of 0.3 mm and a vertical and horizontal spacing of 5 mm were formed (holes punched with a needle). A laminated film material was laid down, and then the coated particles were filled almost to the bulk capacity (100%). Then the first
As shown in the figure, place the same aluminum foil-noncombustible paper laminated film material as above, then place an aluminum plate (1000 x 2000 x 3 mm), close the lid, and apply pressure of 4 kg/cm ² from above and below using a press heating plate. Temperature 150℃×
Heated for 20 minutes.

After heating, the press heating plate was opened and the film material-composite foam laminate was taken out from the mold. The obtained laminate has film materials completely and uniformly fused on both sides, and the inside is a novolak type phenolic resin foam layer uniformly dispersed in aggregate particles, and the peel strength of the film material is 1.15 kg/ It was warm in ^cm2 . In addition,
To measure peel strength, test piece: original plate thickness x 40 (width) x
50 (length) mm; Test speed: 5 mm/min; A tensile jig (JISK-6767-B method) was used as the jig, and Esdyne 3000A and B were used for adhesion to the jig.

In such a laminate, the film material and the foam layer are firmly fused together, so even if an attempt is made to peel off the film material, the film material cannot be completely peeled off, and the fusion bond is so strong that the film material is destroyed. Ta.

Furthermore, there were no recesses caused by gas contraction between the film material and the foam layer, and the entire surface was smooth and uniformly fused to the foam layer.

(f) Effects of the invention The film material-composite foam laminate of this invention is
Aggregate particles are uniformly dispersed in the foam layer, and at least a portion or one surface of the foam layer is provided with a film material uniformly fused and integrated. If it is cylindrical, it can be used as a heat insulating board for buildings such as panels, and as a heat insulating pipe where the pipe itself is the facing material.

Furthermore, the laminate of this invention having metal foil has
Since it has the effect of dissipating static electricity, it is useful for various substrates in which generation and retention of static electricity is a problem, such as backboards of so-called electronic blackboards.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing an example of the manufacturing method of the present invention, and FIGS. 2 and 3 are a partial perspective view and a partial sectional view, respectively, showing an example of the phenolic resin composite foam laminate of the present invention. 1... Press heating plate, 2... Molding die, 3...
Film material, 31... Aluminum foil, 32...
Inothermal paper, 4: foamable resin-coated particles, 5: heater, 6: phenolic resin foam layer, 7: aggregate particles, 8: perforation.

Claims (1)

[Scope of Claims] 1. A foamable resin coating in which aggregate particles are coated with a foamable resin composition containing a novolak type or resol type phenolic resin initial condensate, a decomposition type foaming agent, and a curing agent added as necessary. A phenolic resin composite foam laminate, in which particles and a film material having a large number of perforations are fused and integrated by foaming, and aggregate particles are substantially uniformly dispersed in the phenolic resin foam. 2. The laminate according to claim 1, wherein the film material is a metal film, a plastic film, or a laminate film made of these and a paper material. 3. The laminate according to claim 2, wherein the metal film is aluminum foil. 4. The laminate according to claim 1, wherein the perforations are approximately 0.3 to 0.5 mm in diameter. 5 After coating the aggregate particles with a foamable resin composition containing a novolak type or resol type phenolic resin initial condensate, a decomposition type foaming agent, and a curing agent added as necessary, to form foamable resin-coated particles, A film material having a large number of perforations is mounted in a mold, the coated particles are filled into the mold, the mold is closed, and then the foamable resin composition is heated to a temperature at which it foams and hardens. By doing so, a phenolic resin composite foam laminate is obtained, in which a phenolic resin foam in which aggregate particles are substantially uniformly dispersed and a film material are fused and integrated. Manufacturing method.