JP2016047613A - Phenol resin foam laminated sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a phenol resin foam laminated sheet that uses a flexible surface material containing paper and sufficiently ensures peel strength of the surface material.SOLUTION: The phenol resin foam laminated sheet has surface materials disposed on at least the upper and lower faces of a phenol resin foam having a density in a range of not less than 15 kg/mto not more than 50 kg/m, a closed-cell rate in a range of 70% or more and an average cell diameter in a range of not less than 20 μm to not more than 180 μm. The surface material is a flexible surface material containing paper and has a peel strength of the surface material of 250 g or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a phenol resin foam laminate and a method for producing the same, and more particularly, a phenol resin foam laminate provided with a flexible face material containing paper, in which peeling of the face material occurs from the base material. The present invention relates to a difficult phenolic resin foam laminate and a method for producing the same.

  The acid-curing phenol resin foam made from resol-type phenolic resin is less flammable, generates less smoke, and has good heat insulation properties. For example, outer wall materials such as metal siding, partition panels, etc. It is used for building materials such as ceiling materials, fire doors, shutters, etc. In addition, the acid curable phenolic resin foam is widely used as a cold insulating material for building materials and industrial plants.

  Here, the phenol resin foam is filled with a composition (foamable phenol resin composition) containing, for example, a phenol resin, a foaming agent, between the upper and lower face members, and foamed and cured. It is manufactured as a phenolic resin foam laminate having face materials provided on the upper and lower surfaces of the phenolic resin foam. And as a face material used for a phenol resin foam laminate, a flexible face material containing paper can be selected because it is excellent in handleability or inexpensive. However, when a flexible face material made of paper is used, it is difficult for the phenol resin to sufficiently penetrate into the face material such as kraft paper when the phenol resin foam laminate is manufactured. Therefore, the adhesive strength between the face material and the phenol resin foam (base material) (peeling strength of the face material from the base material, hereinafter referred to as “face material peel strength”) becomes insufficient, and a slight external force However, there was a problem that the face material was easily peeled off.

In order to solve this problem, for example, in Patent Document 1, as a face material, by using a special glass paper whose air permeability is limited to a specific range, an adhesive strength between the phenol resin foam and the face material is used. There are proposals to improve this. And according to the said technique, although it has been reported that the adhesive strength between a phenol resin foam and a face material can be improved compared with the past, it is practically sufficient for a face material peel strength. It was not possible.
On the other hand, in patent document 2, the proposal which covers the surface defect of foams, such as a wrinkle and peeling, is made | formed by embossing the surface material containing a cellulose component. However, this technique only covers the surface defects, and in the phenolic resin foam laminate in which the flexible face material containing paper is arranged, the problem of improving the face material peeling strength is fundamentally It has not been solved.
Japanese Patent No. 3097003 JP 2012-240238 A

  Therefore, even in the case of using a flexible face material containing paper, it has been difficult to impart practically sufficient face material peel strength to the phenolic resin foam laminate by the above-described conventional technique. Therefore, peeling of the face material from the phenol resin foam can be sufficiently suppressed for the conventional phenol resin foam laminate even when a flexible face material containing paper is used as the face material. It has been required to ensure the face material peel strength.

  Therefore, the present inventor has intensively studied to solve the above problems, and in the production of a phenolic resin foam laminate in which flexible face materials containing paper are arranged on the upper and lower surfaces, the amount of foam nucleating agent, and foaming By optimizing the surface temperature of the face material when in contact with the conductive phenol resin composition, the adhesion with the face material of the phenol resin foam is ensured, and the face material has a sufficient peel strength compared to the past. It has been found that a phenolic resin foam laminate can be obtained.

  That is, the present invention provides the following [1] to [3].

[1] A face material is arranged on at least the upper and lower surfaces of the phenol resin foam having a density of 15 kg / m ³ or more and 50 kg / m ³ or less, a closed cell ratio of 70% or more, and an average cell diameter of 20 μm or more and 180 μm or less. A phenolic resin foam laminate, wherein the face material is a flexible face material containing paper, and the face material peel strength is 250 g or more.
[2] The phenol resin foam laminate according to [1], wherein the face material contains glass fiber.
[3] A step of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, and an acidic curing agent using a mixer, and the mixed foamable phenol resin composition on a face material A step of discharging, and a step of foaming and curing the foamable phenolic resin composition discharged on the face material to obtain a phenol resin foam laminate in which the face material is arranged on at least the upper and lower surfaces of the phenol resin foam; and The foamable phenolic resin composition includes a foam nucleating agent in a proportion of 0.1% by mass to 0.6% by mass with respect to the foaming agent, and contains paper as the face material. Use of a face material, wherein the average temperature of the face material surface when the face material and the foamable phenol resin composition are in contact is 5 ° C. or more and 40 ° C. or less, and manufacturing a phenol resin foam laminate Method.

  ADVANTAGE OF THE INVENTION According to this invention, it is a phenol resin foam laminated board using the flexible face material containing paper, Comprising: A phenol resin foam laminated board with which face material peeling strength was fully ensured can be obtained.

It is explanatory drawing of the measuring method of face material peeling strength.

  Hereinafter, the present invention will be described in detail according to preferred embodiments thereof. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

(Phenolic resin foam laminate)
The phenolic resin foam laminate in this embodiment (hereinafter sometimes referred to as “foam laminate”) is a phenolic resin in which a large number of bubbles are dispersed in a phenolic resin formed by a curing reaction. It is a laminate comprising a foam and a face material provided on at least the upper and lower surfaces of the phenol resin foam.
The foam laminate of this embodiment is characterized in that the peel strength between the upper and lower surface materials and the phenol resin foam is strong, and the face material is difficult to peel off, so that it can be easily handled as a foam laminate.

<Phenolic resin foam>
The density of the phenol resin foam of the phenol resin foam laminate of the present embodiment is 15 kg / m ³ or more and 50 kg / m ³ or less, preferably 20 kg / m ³ or more and 40 kg / m ³ or less. When the density is 15 kg / m ³ or more, mechanical strength such as compressive strength can be ensured, and breakage during handling of the foam can be avoided. On the other hand, if the density is 50 kg / m ³ or less, the heat transfer of the resin portion is difficult to increase, so that the heat insulation performance can be maintained. The density of the phenol resin foam can be adjusted to a desired value mainly by changing the ratio of the foaming agent and the curing conditions.

  The closed cell ratio of the phenol resin foam of the phenol resin foam laminate is 70% or more, preferably 80% or more. If the closed cell ratio is less than 70%, there is a concern that the foaming agent in the phenolic resin foam laminate has a tendency to deteriorate the heat insulation performance by replacing air. The closed cell ratio of the phenol resin foam is, for example, the addition amount of the foam nucleating agent, the temperature of the foamable phenol resin composition when the face material and the foamable phenol resin composition are in contact, and the average temperature of the face material surface, It can be adjusted to a desired value by changing the curing conditions.

  The average cell diameter of the phenol resin foam of the phenol resin foam laminate is 20 μm or more and 180 μm or less, preferably 40 μm or more and 150 μm or less. It can suppress that the density of a foam becomes high as an average bubble diameter is 20 micrometers or more. As a result, since the heat transfer rate of the resin part in the foam can be reduced, the heat insulation performance of the phenol resin foam can be ensured. On the other hand, when the average cell diameter is 180 μm or less, an increase in thermal conductivity due to radiation is suppressed, and a decrease in the heat insulating performance of the foam can be avoided. The average cell diameter of the phenol resin foam is, for example, the amount of foam nucleating agent added, the temperature of the foamable phenol resin composition when the foamable phenol resin composition contacts the face material, and the average temperature of the face material surface. It can be adjusted to a desired value by changing the curing conditions.

  And the phenol resin foam of a phenol resin foam laminated board is manufactured from the foamable phenol resin composition containing a phenol resin, surfactant, a foaming agent, a foaming nucleus agent, and an acidic hardening | curing agent, for example. The foamable phenol resin composition may optionally contain components other than those described above.

  As the phenol resin, a resol type phenol resin synthesized with an alkali metal hydroxide or an alkaline earth metal hydroxide is used. The resol type phenol resin is synthesized by heating phenols and aldehydes as raw materials in the temperature range of 40 to 100 ° C. with an alkali catalyst. Moreover, you may add additives, such as urea, at the time of the synthesis | combination of a resol type phenol resin as needed, or after a synthesis | combination. When adding urea, it is more preferable to mix urea methylolated with an alkali catalyst in advance into the resol type phenol resin. Since the resol type phenolic resin after synthesis usually contains excessive moisture, the amount of moisture suitable for foaming is adjusted at the time of foaming. Phenol resins include aliphatic hydrocarbons or high-boiling alicyclic hydrocarbons, or mixtures thereof, diluents for viscosity adjustment such as ethylene glycol and diethylene glycol, and other material recycling powders as required. It is also possible to add additives.

  The starting molar ratio of phenols to aldehydes during the synthesis of the phenolic resin is preferably in the range of 1: 1 to 1: 4.5, more preferably in the range of 1: 1.5 to 1: 2.5. .

Here, the phenols preferably used in the synthesis of the phenol resin in this embodiment are phenol itself and other phenols. Examples of other phenols include resorcinol, catechol, o-, m- And p-cresol, xylenols, ethylphenols, p-tertbutylphenol and the like. Dinuclear phenols can also be used.
The aldehyde may be a compound that can serve as an aldehyde source, and as the aldehyde, it is preferable to use formaldehyde itself, other aldehydes or derivatives thereof. Examples of other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like.
Note that urea, dicyandiamide, melamine, or the like may be added to the phenol resin as an additive. In the present specification, when these additives are added, the “phenol resin” refers to the one after the additives are added.

The viscosity at 40 ° C. of the phenol resin is preferably 5,000 mPa · s or more and 100,000 mPa · s or less, more preferably 7,000 mPa · s or more and 50,000 mPa · s or less, and further preferably 9,000 mPa · s. · S to 40,000 mPa · s.
The water content of the phenol resin is preferably 1.5% by mass or more and 30% by mass or less.

  The surfactant, foaming agent and foaming nucleating agent contained in the foamable phenol resin composition may be added in advance to the phenol resin, or may be added simultaneously with the acidic curing agent.

  As the surfactant, those generally used for the production of phenol resin foams can be used. Among them, nonionic surfactants are effective, for example, alkylene which is a copolymer of ethylene oxide and propylene oxide. Oxides, condensation products of alkylene oxide and castor oil, condensation products of alkylene oxide and alkylphenols such as nonylphenol and dodecylphenol, polyoxyethylene alkyl ethers having 14 to 22 carbon atoms in the alkyl ether portion, Preference is given to fatty acid esters such as polyoxyethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, and polyalcohols. These surfactants may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular about the usage-amount, It uses preferably in 0.3 to 10 mass parts with respect to 100 mass parts of phenol resins.

  Although it does not specifically limit as a structural component of a foaming agent, It is preferable to use the hydrocarbon (HCs) and hydrofluorocarbon (HFCs) which do not destroy an ozone layer. In particular, since the global warming potential is small, it is more preferable to use hydrocarbons.

  The hydrocarbon is preferably a cyclic or chain alkane, alkene or alkyne having 3 to 7 carbon atoms, specifically, normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, Examples include isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, and cyclohexane. Among them, normal pentane, isopentane, cyclopentane, neopentane pentane and normal butane, isobutane, cyclobutane butane are preferably used. These hydrocarbons may be used alone or in combination of two or more.

  Examples of hydrofluorocarbons include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, hydrofluoroethane, hydrochlorofluoroethane, hydrobromofluoroethane, etc. Can do. These hydrofluorocarbons may be used alone or in combination of two or more.

  Here, the hydrocarbon content in the foaming agent is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. The amount of the foaming agent relative to the phenolic resin varies depending on the type of foaming agent, compatibility with the phenolic resin, and loss in the foaming / curing process. The amount is preferably 5 parts by mass or less, and more preferably 4.0 parts by mass or more and 9.5 parts by mass or less. If the amount of the foaming agent relative to the phenol resin is less than 3.0 parts by mass, the density becomes too high, which is not preferable. Moreover, since the density will become low too much that the quantity of the foaming agent with respect to a phenol resin is more than 11.5 mass parts, it is unpreferable.

  In addition, as blowing agent components other than hydrofluorocarbons and hydrocarbons, chlorinated hydrocarbons such as chlorinated aliphatic hydrocarbons can also be used. As the chlorinated aliphatic hydrocarbon, a linear or branched one having 2 to 5 carbon atoms is used. The number of bonded chlorine atoms is not limited, but is preferably 1 to 4, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferably used. These chlorinated aliphatic hydrocarbons may be used alone or in combination of two or more. Note that the chlorinated hydrocarbon does not include the above-described hydrofluorocarbon.

  In this embodiment, it is important to use a foam nucleating agent for the production of a phenol resin foam. As the foam nucleating agent, a low-boiling substance having a boiling point lower by 50 ° C. or more than that of the foaming agent, such as nitrogen, helium, argon, or air, can be added. Also, as solid foam nucleating agent, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, sand clay (kaolin), quartzite powder, quartz sand, mica, calcium silicate powder, wollastonite, glass powder, glass Inorganic powders such as beads, fly ash, silica fume, gypsum powder, borax, slag powder, alumina cement, and Portland cement, and organic powders such as phenol resin foam powder can also be added. These may be used alone or in combination of two or more.

  The addition amount of the foam nucleating agent to the foaming agent is preferably 0.1% by mass or more and 0.6% by mass or less, with the amount of the foaming agent being 100% by mass, and 0.2% by mass or more and 0.4% by mass or less. The following is more preferable. When the amount of the foam nucleating agent is less than 0.1% by mass, uneven foaming is likely to occur and the average cell diameter becomes too large, which is not preferable. Further, when the amount of the foam nucleating agent is more than 0.6% by mass, foaming of the foamable phenol resin composition is promoted, and the foamable phenol resin composition is difficult to permeate into the face material. It becomes difficult to obtain a phenolic resin foam laminate having peel strength.

  The acidic curing agent may be an acidic curing agent that can cure the phenol resin, and phosphoric acid, arylsulfonic acid, or an anhydride thereof is preferable. As arylsulfonic acid and its anhydride, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenolsulfonic acid, xylenolsulfonic acid, substituted xylenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, etc. And anhydrides thereof. These may be used alone or in combination of two or more. In this embodiment, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol or the like may be added as a curing aid. In addition, these curing agents may be diluted with a solvent such as ethylene glycol or diethylene glycol.

  The amount of the acidic curing agent used varies depending on the type, and when anhydrous phosphoric acid is used, it is preferably 5 to 30 parts by mass, more preferably 8 to 25 parts by mass with respect to 100 parts by mass of the phenol resin. Used in parts or less. When a mixture of 60% by mass of paratoluenesulfonic acid monohydrate and 40% by mass of diethylene glycol is used, it is preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 5 parts by mass with respect to 100 parts by mass of the phenol resin. Used in an amount of 20 parts by weight or more and 20 parts by weight or less.

<Face material>
As the face material disposed on at least the upper and lower surfaces of the phenol resin foam, a face material containing paper and having flexibility (flexible face material) is used. Examples of the flexible face material containing paper used include paper such as kraft paper, glass fiber mixed paper, calcium hydroxide paper, aluminum hydroxide paper, and magnesium silicate paper. These papers may be used by mixing (or laminating) with non-woven fabrics and woven fabrics composed mainly of polyester, polypropylene, nylon or the like, or non-woven fabrics of inorganic fibers such as glass fiber non-woven fabrics. And it is preferable that the flexible surface material containing the paper in this embodiment contains glass fiber from a viewpoint of improving the flame retardance and rigidity of a phenol resin foam laminated board. These face materials are usually provided in a roll form. Further, as the flexible face material, a material obtained by kneading an additive such as a flame retardant may be used.

<Peel material peel strength of phenolic resin foam laminate>
The face material peel strength is a value that correlates with the adhesive strength between the face material and the phenol resin foam in the phenol resin foam laminate. And the phenol resin foam laminate of this embodiment has a face material peel strength of 250 g or more, preferably 300 g or more, more preferably 350 g or more, and further preferably 400 g or more. Although an upper limit is not specifically limited, It is preferable that it is 1000 g or less. Here, as described later, the face material peel strength can be adjusted to a desired value by changing the average temperature of the face material surface when the face material and the foamable phenol resin composition are in contact with each other, and the amount of the foam nucleating agent.
In addition, the face material peeling strength of a phenol resin foam laminated board can be measured by the method as described in the Example of this specification.

(Method for producing phenolic resin foam laminate)
Next, the manufacturing method of the phenol resin foam laminated board mentioned above is demonstrated.

  The manufacturing method of the phenol resin foam laminate includes a mixing step of mixing the above-described foamable phenol resin composition with a mixer, a discharge step of discharging the mixed foamable phenol resin composition onto the surface material, and a surface. A continuous production method comprising a foam laminate production process for producing a phenol resin foam laminate from a foamable phenolic resin composition discharged on a material is generally used. It is also possible to adopt the batch foam molding method used in the above.

  In the continuous production method, the foamable phenolic resin composition discharged on the face material is pre-molded so as to be leveled from the top and bottom while foaming and curing, and then molded into a plate shape while proceeding with foaming and curing. .

  In the continuous manufacturing method, as a method of preforming or forming, a method using a slat type double conveyor, a method using a metal roll or a steel plate, and a method using a combination of these for manufacturing purposes, etc. Various methods can be cited. Among these, for example, in the case of molding using a slat type double conveyor, the foamable phenol resin composition coated with the upper and lower face materials is continuously guided into the slat type double conveyor, and then heated. While adjusting the pressure to a predetermined thickness by applying pressure from above and below, it can be foamed and cured to be formed into a plate shape.

  Here, in order to achieve the phenol resin foam laminate of the present invention, it is important to suppress initial curing on the surface material surface as much as possible while controlling the foaming state of the foamable phenol resin composition. The details will be described below.

As described above, the face material containing paper is hard to penetrate the foamable phenol resin composition, and when the composition is cured to form a phenol resin foam laminate, the phenol resin foam laminate is formed. This face material has a problem that it is easily peeled off from the base material. When examined in more detail, it is considered that the following two factors can be cited as factors that do not provide a sufficient face material peel strength.
The first factor is that if foaming of the foamable phenolic resin composition progresses too much, the foamable phenolic resin composition and the facet will be cured when they come into contact with the facet and become a foam rather than a liquid. Adhesion proceeds in a contacted state, and the contact area may be reduced.
As a second factor, if the surface temperature of the face material in contact with the foamable phenol resin composition is high, the foamable phenol resin composition may be cured before penetrating the face material.

  And as a result of intensive studies after taking the above factors into consideration, even when a flexible face material containing paper is used, the amount of foam nucleating agent and the foamable phenol resin composition and flexibility It has been found that by optimizing the surface temperature of the face material at the time of contact with the adhesive face material, a phenol resin foam laminate having a practically sufficient face material peel strength as compared with the prior art can be obtained.

  Specifically, the foaming nucleating agent capable of adjusting foamability is used in an amount of 0.1% by mass to 0.6% by mass with the amount of the foaming agent being 100% by mass, and the foamable phenolic resin composition is The average temperature of the surface of the face material when discharged onto the flexible face material containing paper is set to 5 ° C. or more and 40 ° C. or less. Thus, the phenol resin foam laminated board provided with practically sufficient face material peeling strength can be manufactured by adjusting the quantity of a foam nucleating agent, and the average temperature of the face material surface.

  Here, in the manufacture of the phenolic resin foam laminate of the present embodiment, when the foamable phenolic resin composition contacts the face material, the average temperature of the face material surface is adjusted to 5 ° C. or more and 40 ° C. or less as described above. However, the temperature is preferably 5 ° C. or higher and 30 ° C. or lower, and more preferably 5 ° C. or higher and 20 ° C. or lower. If the temperature is less than 5 ° C., the curing of the surface and the inside of the foamable phenol resin composition is delayed, which is not preferable. On the other hand, if the temperature exceeds 40 ° C., the foamable phenolic resin composition is cured before it penetrates into the face material, and the face material peel strength decreases, which is not preferable. The “average temperature of the face material surface” means the surface temperature at the time of contact with the foamable phenolic resin composition at any 10 points (20 points in total) on the upper and lower face material surfaces, and averages them. The value obtained by doing.

  Here, the temperature of the face material surface in contact with the foamable phenol resin composition can be measured by a non-contact infrared radiation thermometer. The means for adjusting the average temperature of the face material surface according to the present invention is not particularly limited. In order to cool the surface of the face material, cold air may be blown, but it is preferable to adjust to an appropriate range by lowering the ambient temperature. Moreover, the apparatus in the case of heating the surface of a face material is not specifically limited, A hot air blower, a far-infrared heater, etc. are mentioned. And the method of heating the surface of the face material is not particularly limited, and a method of irradiating a far-infrared heater to the traveling face material, a method of blowing hot air with a slit nozzle, and foaming by providing a heating chamber For example, a method of adjusting the heating temperature immediately after discharging the conductive phenol resin composition.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Synthesis of phenolic resin>
A reactor is charged with 3500 kg of a 52 wt% formaldehyde aqueous solution (52 wt% formalin) and 2510 kg of 99 wt% phenol (including water as an impurity), stirred with a propeller rotating stirrer, and the temperature inside the reactor is adjusted with a temperature controller. Adjusted to 40 ° C. Next, the reaction was carried out by raising the temperature while adding a 50 mass% aqueous sodium hydroxide solution. When the Ostwald viscosity reaches 60 centistokes (= 60 × 10 ⁻⁶ m ² / s, measured value at 25 ° C.), the reaction solution is cooled and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) Added. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.3 with a 50 mass% aqueous solution of paratoluenesulfonic acid monohydrate.

  The reaction solution was dehydrated at 60 ° C. and the viscosity and water content were measured by the following method. As a result, the viscosity at 40 ° C. was 6,100 mPa · s and the water content was 5.1% by mass. This is designated as phenol resin A-U.

<Moisture content>
The amount of water in the phenolic resin was measured using a Karl Fischer moisture meter MKA-510 (manufactured by Kyoto Electronics Industry Co., Ltd.).

<Viscosity>
Using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor portion 3 ° × R-14), the measured value after stabilizing at 40 ° C. for 3 minutes was taken as the viscosity of the phenol resin.

(Example 1)
Phenol resin AU: 100 parts by mass of ethylene oxide / propylene oxide block copolymer (manufactured by BASF, Pluronic F-127) as a surfactant was mixed at a ratio of 2.0 parts by mass. This is designated as phenol resin A-U1.

  The phenol resin A-U1: 100 parts by mass, 5.6 parts by mass of a mixture of 20% by mass of isopentane and 80% by mass of isopropyl chloride as a blowing agent, and 0.3 wt. %, And a foamable phenolic resin composition obtained by adding 13 parts by mass of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as an acidic curing agent is supplied to the mixing head of the mixer, and the multiport distribution pipe And fed onto the moving bottom material. In addition, the mixer (mixer) used what was disclosed by Unexamined-Japanese-Patent No. 10-225993. That is, there is an inlet for the foaming agent containing the phenol resin A-U1 and the foaming nucleating agent on the upper side surface of the mixer, and an inlet for the acidic curing agent is provided on the side surface near the center of the agitating portion where the rotor stirs. The equipped mixer was used. The part after the stirring part is connected to a nozzle for discharging the foam. That is, the mixer is composed of the mixing part (front stage) up to the acidic curing agent introduction port, the mixing part (rear stage) from the acidic curing agent introduction port to the stirring end part, and the dispensing end as the stirring end part to the nozzle. Yes. The distribution unit has a plurality of nozzles at the tip, and is designed so that the mixed foamable phenolic resin composition is uniformly distributed.

  The foamable phenolic resin composition supplied onto the lower surface material is covered with the upper surface material, and at the same time, sandwiched between the upper and lower surface materials, leading to an oven at 40 ° C. (first temperature adjustment section; residence time 4 minutes). After being preformed so as to be smoothed using a plurality of rolls, it was sent to an oven (second temperature control section) having a slat type double conveyor at 83 ° C. Then, the preformed foamable phenol resin composition was cured in a residence time of 15 minutes in a slat type double conveyor, and then cured in an oven at 110 ° C. for 2 hours to obtain a phenol resin foam laminate. In addition, in the slat type double conveyor, it was formed into a plate shape by applying moderate pressure from above and below through the face material. As the face material, a craft paper face material, which is a flexible face material containing paper on both the upper and lower sides, was used. And the average temperature of the upper-lower surface material surface at the time of contacting with a foamable phenol resin composition by non-contact type infrared radiation thermometer measurement was adjusted to 18 degreeC.

  And the characteristic (The density of a phenol resin foam, a closed cell rate, an average cell diameter, and face material peeling strength) of the obtained phenol resin foam laminated board was evaluated with the following method.

<Phenolic resin foam density>
A 20 cm square phenolic resin foam laminate was used as a sample, and after removing the face material from this sample, the mass and the apparent volume were measured according to JIS K7222.

<Closed cell ratio of phenol resin foam>
Measured according to ASTM-D-2856. Specifically, after removing the face material from the phenolic resin foam laminate, a cylindrical sample having a diameter of 35 mm to 36 mm is pierced with a cork borer and trimmed to a height of 30 mm to 40 mm, and then an air comparison specific gravity meter The sample volume was measured by the standard usage method (manufactured by Tokyo Science Co., Ltd., type 1,000). The value obtained by subtracting the volume of the wall (parts other than bubbles and voids) calculated from the sample mass and the density of the phenol resin from the sample volume, and dividing the value by the apparent volume calculated from the outer dimensions of the sample is the closed cell ratio It was. Here, the density of the phenol resin was 1.3 kg / L.

<Average cell diameter of phenol resin foam>
The average bubble diameter was measured by the following method with reference to the method described in JIS K6402.
Take a photograph of the cut surface of the test piece obtained by cutting almost the center in the thickness direction of the phenolic resin laminate in parallel to the front and back surfaces, and enlarge the cut surface by 50 times. 4 lines (corresponding to 1,800 μm in the actual foam cross section) are drawn, and the number of cells measured according to the number of bubbles crossed by each straight line is obtained by each straight line, and the average value thereof is obtained. A value obtained by dividing 1800 μm was defined as an average cell diameter.

<Surface peel strength>
The face material peel strength of the phenolic resin foam laminate was measured as follows (see FIG. 1).
First, a phenol resin foam laminate is cut into a width of 50 mm and a length of 120 mm (the length direction coincides with the product flow direction), and one of the face materials (a) and (b) located on the upper and lower surfaces. The face material (b) was peeled off. After that, the laminate 1 after peeling off the face material (b) was cut in a direction parallel to the upper and lower surfaces to prepare a sample 1 for evaluation having a face material (a), a width of 50 mm, a length of 120 mm, and a thickness of 25 mm.
Next, at a position 20 mm from one end in the length direction of the sample 1 for evaluation, a 20 mm deep cut was made in the thickness direction from the surface having no face material (a) using a cutter. At the cutting position, the base material 2 of the evaluation sample was carefully divided in the thickness direction. At this time, a force in the length direction was not applied so that the face material (a) (corresponding to the face material 3 in FIG. 1) was not peeled off from the base material 2.
Then, the part of the evaluation sample 1 in which the base material is divided is held at a 45 ° angle with the horizontal plane by the clamp 7 as shown in FIG. A container 6 connected by a metal wire 5 to the tip of the part having a shorter material length was set via a clamp 4.
Thereafter, water was continuously charged into the empty container 6 using a pump (not shown) at a charging rate of 100 g / min. The mass of water in the container 6 was measured when the face material 3 peeled 50 mm from the cut position in the length direction of the sample 1 for evaluation. The same operation was performed twice, and the average value of the total mass of the clamp 4, the metal wire 5, the container 6, and the obtained water was defined as the face material peel strength (a).
Separately, an evaluation sample having a face material (b), a width of 50 mm, a length of 120 mm, and a thickness of 25 mm was prepared, and the face material peel strength (b) was determined in the same manner as the face material peel strength (a). The lower value of the face material peel strength (a) and the face material peel strength (b) was taken as the face material peel strength (unit: g) of the phenol resin foam laminate.

(Example 2)
Example 1 except that nitrogen, which is a foam nucleating agent, is added in an amount of 0.6% by mass based on the foaming agent, glass fiber mixed paper is used for the upper and lower surface materials, and the average temperature of the upper and lower surface material surfaces is 23 ° C. In the same manner, a phenol resin foam laminate was obtained.

(Example 3)
A phenol resin foam laminate was prepared in the same manner as in Example 1, except that 0.1% by mass of nitrogen as a foam nucleating agent was added to the foaming agent, and the average temperature of the upper and lower surface materials was 19 ° C. Obtained.

(Comparative Example 1)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the foam nucleating agent was not added.

(Comparative Example 2)
A phenol resin foam laminate was prepared in the same manner as in Example 1 except that 0.7% by mass of nitrogen as a foam nucleating agent was added to the foaming agent, and the average temperature of the upper and lower surface materials was 20 ° C. Obtained.

(Comparative Example 3)
A phenol resin foam laminate was obtained in the same manner as in Example 1 except that the average temperature of the upper and lower surface materials was 42 ° C.

  The evaluation results of the characteristics of the phenol resin foam laminates obtained in Examples 1 to 3 and Comparative Examples 1 to 3 are summarized in Table 1.

  From Table 1, it turns out that the phenol resin foam laminated board obtained in Examples 1-3 has the performance superior to the phenol resin foam laminated board obtained in Comparative Examples 1-3. .

  ADVANTAGE OF THE INVENTION According to this invention, it is a phenol resin foam laminated board using the flexible face material containing paper, Comprising: A phenol resin foam laminated board with which face material peeling strength was fully ensured can be obtained.

1 Sample for evaluation 2 Base material (Phenolic resin foam)
3 Face material 4 Clamp 5 Metal wire 6 Container 7 Clamp

[1] A face material is arranged on at least the upper and lower surfaces of the phenol resin foam having a density of 15 kg / m ³ or more and 50 kg / m ³ or less, a closed cell ratio of 70% or more, and an average cell diameter of 20 μm or more and 180 μm or less. A phenol resin foam laminate, wherein the face material is a flexible face material containing paper, and the face material peel strength at an angle of 45 ° is 250 g or more. Foam laminate.
[2] The phenol resin foam laminate according to [1], wherein the face material contains glass fiber.
[3] A step of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, and an acidic curing agent using a mixer, and the mixed foamable phenol resin composition on a face material A step of discharging, and a step of foaming and curing the foamable phenolic resin composition discharged on the face material to obtain a phenol resin foam laminate in which the face material is arranged on at least the upper and lower surfaces of the phenol resin foam; and The foamable phenolic resin composition includes a foam nucleating agent in a proportion of 0.1% by mass to 0.6% by mass with respect to the foaming agent, and contains paper as the face material. Use of a face material, wherein the average temperature of the face material surface when the face material and the foamable phenolic resin composition are in contact is 5 ° C. or more and 19 ° C. or less. Method.

Claims (3)

A phenolic resin having face materials disposed on at least upper and lower surfaces of a phenolic resin foam having a density of 15 kg / m ³ or more and 50 kg / m ³ or less, a closed cell ratio of 70% or more, and an average cell diameter of 20 μm or more and 180 μm or less. A foam laminate,
The phenolic resin foam laminate, wherein the face material is a flexible face material containing paper, and the face material peel strength is 250 g or more.   The phenolic resin foam laminate according to claim 1, wherein the face material contains glass fiber. A step of mixing a foamable phenol resin composition containing a phenol resin, a surfactant, a foaming agent, and an acidic curing agent using a mixer;
Discharging the mixed foamable phenolic resin composition onto the face material;
Foaming and curing the foamable phenolic resin composition discharged on the face material to obtain a phenol resin foam laminate having face materials disposed on at least upper and lower surfaces of the phenol resin foam; and
Including
The foamable phenolic resin composition includes a foam nucleating agent at a ratio of 0.1% by mass to 0.6% by mass with respect to the foaming agent,
Using a flexible face material containing paper as the face material,
The method for producing a phenol resin foam laminate, wherein an average temperature of the surface of the face material when the face material and the foamable phenol resin composition are in contact is 5 ° C or higher and 40 ° C or lower.

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