JP5430875B2 - Method for producing phenolic resin foam laminate - Google Patents

Description

  The present invention relates to a method for producing a phenolic resin foam laminate using a woven fabric or a nonwoven fabric as a face material.

  A phenol resin foam laminate is produced by mixing a resol type phenol resin obtained by adding and condensing phenol and formalin with an alkaline catalyst, mixing a surfactant, a foaming agent and a curing catalyst, and heating at room temperature or heating. As a surface material of the phenol resin foam laminate, a flexible face material is preferable. In particular, from the viewpoint of easy handling as a foam laminate, it is preferable to use a synthetic fiber nonwoven fabric or a woven fabric, and more economical. From the point of view, synthetic fiber nonwoven fabric is preferably used, but even if synthetic fiber nonwoven fabric is used, the raw material cost ratio of the face material occupying the phenolic resin foam laminate is large. It has been demanded to reduce the cost of the phenolic resin foam laminate by using.

  However, if a face material with a low basis weight is used, the resin composition tends to ooze out from the face material during production, and a discoloration (red) mark remains on the product surface of the phenolic resin foam laminate, resulting in improved product quality. In addition to causing poor appearance, the adhering resin contaminates the manufacturing equipment.

  In patent document 1, the manufacturing method of the phenol resin foam laminated board using a glass nonwoven fabric is proposed, and a phenol resin foams by arranging a nonflammable paper on the surface side of a glass nonwoven fabric through an adhesive material layer. Although it is prevented from oozing out to the body surface, in order to produce a high-performance phenolic resin foam laminate, it is necessary to quickly release moisture generated by the curing reaction to the surface. Providing a resin oozing prevention layer on the side will cause performance degradation. Moreover, since the result of the cost increase of a face material is brought about by laminating face materials, it is contrary to the objective.

  Therefore, Patent Document 2 discloses a technique of using a face material with a lower basis weight by using a woven or non-woven fabric with a limited fiber diameter as the face material of the phenol resin foam laminate.

Japanese Patent Publication No. 6-049297 Japanese Patent No. 3523196

  An object of the present invention is to provide a method capable of producing a phenolic resin foam laminate having a good appearance without causing the resin composition to ooze out to the surface of the face material, at a lower cost.

  In the present invention, a resin composition comprising at least a phenol resin, a surfactant, a hydrocarbon-containing foaming agent, and a curing agent is mixed in a mixing unit, and continuously discharged onto a traveling lower surface material. A method for producing a phenolic resin foam laminate in which an upper surface is coated with an upper surface material, and the resin composition is foam-cured, wherein at least the lower surface material is a woven fabric or a non-woven fabric, and at least the resin composition is a lower surface material. The average surface temperature of the lower surface material is adjusted in a range of 35 ° C. or more and 100 ° C. or less at a position where the ink is discharged upward.

In the present invention, the fiber diameter of the bottom surface member is not less 1μm or 20μm or less, and comprises a preferred embodiment the basis weight is 5 g / m ² or more 60 g / m ² or less.

  According to the present invention, a phenol resin foam laminate having a good appearance without causing the resin composition to exude from the face material without staining the production equipment with the resin composition is used. Can be provided while reducing costs.

  The phenolic resin foam laminate produced according to the present invention is a laminate in which a phenolic resin foam is sandwiched between and integrated with an upper surface material and a lower surface material. Is a foam that exists in a state of being uniformly dispersed in a phenol resin molded by a curing reaction.

  The closed cell ratio of the phenol resin foam in the present invention is 90% or more, preferably 95% or more. When the closed cell ratio is less than 90%, there is a concern that the foaming agent in the phenolic resin foam tends to be replaced with air and the heat insulation performance tends to be lowered.

The density of the phenol resin foam in the present invention can be selected as desired depending on the ratio of the foaming agent, the oven temperature at the time of curing, etc., but is 10 kg / m ³ or more and 100 kg / m ³ or less, preferably 20 kg / m ³ or more and 60 kg / m ³ or less. When the density is less than 10 kg / m ³ , the mechanical strength such as compressive strength becomes small, the foam tends to be broken during the handling of the foam, and the surface brittleness also increases. On the other hand, if the density exceeds 100 kg / m ³ , the heat transfer of the resin part increases and the heat insulation performance may be lowered.

  The thermal conductivity of the phenol resin foam in the present invention is 0.015 W / m · K or more and 0.040 W / m · K or less.

  The phenol resin foam in the present invention is a resin composition obtained by adding a surfactant, a hydrocarbon-containing foaming agent, and an acid curing catalyst (curing agent) to at least a phenol resin, and uniformly dispersing them. It is obtained by curing using an oven or the like.

  Examples of the phenol resin used in the present invention include a resol type phenol resin synthesized with an alkali metal hydroxide or an alkaline earth metal hydroxide, a novolac type phenol resin synthesized with an acid catalyst, and an ammonia resol type synthesized with ammonia. Examples thereof include a benzyl ether type phenol resin synthesized with a phenol resin or lead naphthenate, etc. Among them, a resol type phenol resin is preferable. The resol-type phenol resin is polymerized by heating phenol and formalin as raw materials at a temperature range of 40 to 100 ° C. with an alkali catalyst. Moreover, you may add additives, such as urea, at the time of resole resin polymerization as needed. In the case of adding urea, it is more preferable to mix urea methylolated with an alkali catalyst in advance into the resole resin. Since the resole resin after synthesis usually contains excess water, the amount of water suitable for foaming is adjusted during foaming. In addition, aliphatic hydrocarbons or alicyclic hydrocarbons having a high boiling point or mixtures thereof, diluents for viscosity adjustment such as ethylene glycol and diethylene glycol, and other additives may be added to the phenol resin as necessary. it can.

  As the face material used in the present invention, in addition to the adhesive strength with the resin composition (face material peel strength), product strength, and ease of handling (flexibility), moisture generated by the curing reaction is included. In view of these, it is appropriate that at least the lower surface material, preferably the upper and lower surface materials are woven or non-woven fabrics. Moreover, the cross-sectional shape of the fiber is not limited, and when a woven or non-woven fabric made of flat yarn is used, the effect of suppressing the seepage of the resin composition from the face material can be further enhanced. Furthermore, the material of the face material is not limited.

  The fiber diameter of the woven or non-woven fabric used as the face material in the present invention is preferably 1 μm or more and 20 μm or less. When the fiber diameter is larger than 20 μm, the seepage rate of the resin composition from the face material increases, and the peel strength of the resin composition from the face material decreases, and the face material easily peels from the product. In order to increase the peel strength, it is preferable to increase the basis weight, but this is not preferable because the cost increases. In addition, it is not preferable to make the fiber diameter smaller than 1 μm because the economical efficiency at the time of manufacturing the face material is lowered.

In the present invention, the preferred basis weight of the face material is in the range of 5 g / m ^{2 to} 60 g / m ² . If the basis weight is less than 5 g / m ^{2, the} rate of seeping of the resin composition from the face material increases, which is not preferable. On the other hand, if the basis weight exceeds 60 g / m ² , it becomes expensive, which is not preferable from the viewpoint of economy, and the peel strength also decreases.

  In the present invention, the preferred basis weight of the face material is in a range lower than before. This is because when the resin composition comes into contact with the face material, the surface temperature of the face material is adjusted to a predetermined range. Even so, the resin composition in contact with the face material is cured before being heated by the face material and exuding to the surface side.

  The face material peel strength of the phenolic resin foam laminate obtained by the present invention is preferably 400 g or more and 1000 g or less in a predetermined measurement method described later.

  Further, the resin seepage rate from the face material in the phenolic resin foam laminate obtained by the present invention means that the resin composition is discharged onto the lower surface material, so that the lower surface material side per surface area to the surface layer side. It is defined as the area ratio where the resin composition exudes. The resin seepage rate from the face material is most preferably 0%, and if it exceeds 30%, the surface appearance defect of the product and the equipment will be contaminated as a whole, so it is preferable to suppress it to 30% or less.

  In this invention, it adjusts so that the average surface temperature of this lower surface material may become 35 to 100 degreeC in the position which discharges a resin composition on a lower surface material. More preferably, it is 45 degreeC or more and 80 degrees C or less. Heating and controlling the surface temperature of the lower surface material in this way can complete curing before the resin composition oozes out in the thickness direction of the lower surface material and the surface layer side. The exudation of the composition can be suppressed. If it is less than 35 ° C., it becomes difficult to complete the curing of the resin composition in the face material before the resin composition exudes from the face material, and if it exceeds 100 ° C., the foaming / curing reaction of the resin composition is difficult. Since it is promoted too much, the resin composition in the face material is cured before the resin composition sufficiently penetrates into the face material, and the face material peel strength is lowered. In the present invention, the average surface temperature is adjusted as described above for the lower surface material from which the resin composition is discharged. Preferably, when the upper surface material of the resin composition is covered with the upper surface material, By adjusting the average surface temperature to a range of 35 ° C. or more and 100 ° C. or less as in the case of the lower surface material, the same effect, that is, sufficient peel strength can be achieved and prevention of bleeding can be achieved. In this case, the average surface temperature can be individually adjusted for each of the upper and lower surface materials, and the temperature difference between the upper and lower surface materials may be set within this range.

  The method for heating the surface of the face material according to the present invention is not particularly limited as long as it is a heating device, and examples thereof include a hot air blower and a far infrared heater. The face material heating method is not particularly limited, and is a method of irradiating a far-infrared heater with respect to the width direction of the face material to travel, a method of blowing hot air with a slit nozzle, or a greenhouse to provide a resin. Examples include a method of adjusting the heating temperature immediately after discharging the composition.

  The starting molar ratio of phenols to aldehydes in the phenolic resin used in the present invention is preferably from 1: 1 to 1: 4.5, more preferably from 1: 1.5 to 1: 2.5. Phenols that are preferably used in the synthesis of the phenol resin in the present invention are phenol and other phenols. Examples of other phenols include resorcinol, catechol, o-, m- and p-cresol, Examples include xylenols, ethylphenols, and p-tertbutylphenol. Dinuclear phenols can also be used.

  The aldehydes preferably used in the present invention are formaldehyde and other aldehydes, and examples of the other aldehydes include glyoxal, acetaldehyde, chloral, furfural, benzaldehyde and the like. Urea, dicyandiamide, melamine, etc. may be added as additives. In the present invention, when these additives are added, the phenol resin refers to the one after the additives are added.

  When the resol type phenol resin is used, the viscosity at 40 ° C. is preferably 3,000 mPa · s or more and 100,000 mPa · s or less, more preferably 5,000 mPa · s or more and 50,000 mPa · s or less. The water content is preferably 3% by weight or more and 30% by weight or less.

  The surfactant and the foaming agent may be added in advance to the phenol resin, or may be added simultaneously with the acid curing catalyst.

  As the surfactant used in the present invention, those generally used for the production of phenol resin foams can be used, and among them, nonionic surfactants are effective, for example, the co-polymerization of ethylene oxide and propylene oxide. Alkylene oxide, a condensation product of alkylene oxide and castor oil, condensation products of alkylene oxide and alkylphenols such as nonylphenol and dodecylphenol, fatty acid esters such as polyoxyethylene fatty acid ester, polydimethylsiloxane, etc. Of these, silicone compounds and polyalcohols are preferred. One type of surfactant may be used, or two or more types may be used in combination. Moreover, although there is no restriction | limiting in particular about the usage-amount, It uses preferably in the range of 0.3-10 weight part per 100 weight part of phenol resin compositions.

  The hydrocarbon content contained in the blowing agent used in the present invention is desirably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. If the hydrocarbon content is less than 50% by weight, the global warming potential of the foaming agent is undesirably high. As the hydrocarbon contained in the foaming agent used in the production of the phenolic resin foam laminate of the present invention, a cyclic or chain alkane, alkene or alkyne having 3 to 7 carbon atoms is preferable, and foaming performance, chemical stability From the viewpoint of the property (does not have a double bond) and the thermal conductivity of the compound itself, an alkane or cycloalkane having 4 to 6 carbon atoms is more preferred. Specific examples include normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, and the like. Among them, normal pentane, isopentane, cyclopentane, neopentane pentane, and normal butane, isobutane, cyclobutane butane have good foaming characteristics in the production of the phenolic resin foam laminate of the present invention, and heat conduction. The rate is particularly preferred because of its relatively low rate.

  In the present invention, two or more of these hydrocarbons can be mixed and used. Specifically, a mixture of 5 to 95% by weight of pentanes and 95 to 5% by weight of butanes is preferable because it exhibits good heat insulation characteristics in a wide temperature range. Among them, normal pentane or a combination of isopentane and isobutane has high heat insulation performance in a wide range from a low temperature range to a high temperature range, and it can be said that these compounds are advantageous in use because they are inexpensive. Moreover, when hydrocarbons and HFCs such as 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, and pentafluoroethane having a low boiling point are used in combination as a blowing agent, the low temperature characteristics of the phenol resin foam are improved. However, since the global warming potential as a mixed foaming agent is increased, it is not preferable to use HFCs in combination. Further, a low boiling point substance such as nitrogen, helium, argon, air may be added to the foaming agent as the foam nucleating agent.

  The acid curing catalyst used in the present invention is not particularly limited, but when an acid containing water is used, there is a possibility that the foam cell wall may be destroyed. Therefore, phosphoric anhydride and aryl sulfonic anhydride are considered preferable. Examples of the aryl sulfonic anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecyl benzene sulfonic acid, benzene sulfonic acid, and naphthalene sulfonic acid. May be used alone or in combination of two or more. Further, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like may be added as a curing aid. In addition, these curing catalysts may be diluted with a solvent such as ethylene glycol or diethylene glycol.

  After the acid curing catalyst is added to the phenol resin, the acid curing catalyst is uniformly dispersed as quickly as possible using a pin mixer or the like. The amount of foaming agent used varies depending on the type. For example, when a mixture of 50% by weight of isopentane and 50% by weight of isobutane is used as the foaming agent, it is preferably 2 parts by weight or more and 20 parts by weight or less, more preferably 4 parts by weight or more and 17 parts by weight or less with respect to 100 parts by weight of the phenol resin. Used in less than part.

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

  If necessary, a foam nucleating agent such as nitrogen, a bulking agent such as a phenol resin foam powder or aluminum hydroxide powder, a solid foam nucleating agent, a plasticizer, and the like may be added. In particular, the phenol resin composition is further improved in suppressing the exudation from the face material when it is in contact with the face material in a more foamed (fluffed) state than in contact with the face material in the liquid (wet) state. be able to.

  The foam curing temperature of the resin composition after being sandwiched between the upper and lower surface materials is preferably 40 ° C. or higher and 130 ° C. or lower, more preferably 60 ° C. or higher and 110 ° C. or lower. Curing may be performed in one stage, or may be cured in several stages by changing the curing temperature according to the degree of curing.

  First, a method for evaluating the composition, structure, and characteristics of the phenolic resin and phenolic resin foam laminate in the present invention will be described.

[Viscosity of phenolic resin]
A rotational viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part 3 ° × R-14) was used, and the measured value was obtained after stabilization at 40 ° C. for 3 minutes.

[Moisture content of phenolic resin]
Dissolve the phenol resin in dehydrated methanol (manufactured by Kanto Chemical Co., Inc.) in the range of 3 to 7% by weight, measure the water content of the solution, and determine the water content in the phenol resin. Asked. For the measurement, a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd., MKC-510) was used.

[Phenolic resin foam density]
A 20 cm square phenolic resin foam laminate was used as a sample, and the surface material and siding material of this sample were removed, and the weight and apparent volume were measured. The value was measured according to JIS-K-7222.

〔Thermal conductivity〕
It measured according to the flat plate heat flow meter method of JIS-A-1412 at the phenol resin foam laminated board sample 200 square mm, the low temperature board 5 degreeC, and the high temperature board 35 degreeC.

[Fiber diameter of face material]
Using a scanning electron microscope, a 500 times magnified photograph of the face material was taken, and evaluation was performed by obtaining an average diameter per 10 fibers from the shallower depth of focus, that is, from the surface side of the photograph. The measurement conditions of the scanning electron microscope were Hitachi Electron Microscope S-800, and the acceleration voltage was 20 kilovolts. The sample was pretreated by performing gold sputtering for 3 minutes under a current condition of 15 mA.

[Amount of surface material]
Measured according to “mass per unit area” of JIS-L-1906 “Testing method for general long-fiber nonwoven fabric”.

[Surface material peel strength]
The lower surface material peel strength was evaluated by the following measurement method (FIG. 1). First, in a foam laminate plate sample having a width of 50 mm and a length of 120 mm (product flow direction), an evaluation sample having a thickness of 25 mm is prepared from the lower surface material side after peeling the upper surface material. Next, after making a 20 mm incision in the thickness direction from the side where the upper surface material was arranged with a cutter at a position in the length direction of 20 mm, the evaluation sample is carefully divided by hand in the thickness direction at the incision position. (At this time, do not apply a force in the longitudinal direction so that the lower surface material does not peel off). The evaluation sample is held with the longitudinal cut side down and the opposite end with the clamp 1 at an angle of 45 ° with the horizontal plane. The end of the sample for evaluation on the side not held by the clamp 1 is clamped by the paper clip 4, and the container 6 connected to the tip of the clip 4 by the metal wire 5 is set. Next, using a pump, water is continuously poured into the empty container 6 at a charging rate of 100 g / min. The weight of water in the container when the face material 3 peels 50 mm or more from the cut position in the longitudinal direction is weighed, and the weight is defined as the face material peel strength value.

[Resin seepage rate from face material]
After marking the area where the resin composition exudes on the bottom material of the product with a pen, mark the area of 0.3 m × 0.3 m of the foam laminate with a digital camera, and after correcting the color tone, Using the pixel counter software, the number of pixels where the resin composition exudes and the number of pixels in the entire 0.3 m × 0.3 m area were counted, and the exudation area ratio was determined by the following formula.

  Resin oozing rate from the face material (%) = (number of pixels in the enclosed portion / 0.3 m × 0.3 m total number of pixels in the area) × 100

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.

<Synthesis of phenolic resin>
The reactor was charged with 3500 kg of 52 wt% formaldehyde and 2510 kg of 99 wt% phenol, stirred with a propeller rotary stirrer, and the temperature inside the reactor was adjusted to 40 ° C. with a temperature controller. Next, the reaction was carried out by increasing the temperature while adding a 50 wt% aqueous sodium hydroxide solution. When the Ostwald viscosity reached 60 centistokes (measured value at 25 ° C.), the reaction solution was cooled, and 570 kg of urea (corresponding to 15 mol% of the charged amount of formaldehyde) was added. Thereafter, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50 wt% aqueous solution of paratoluenesulfonic acid monohydrate.

  When this reaction solution was dehydrated at 60 ° C. and the viscosity and water content were measured, the viscosity at 40 ° C. was 5,800 mPa · s, and the water content was 5% by weight. This is designated as phenol resin A-U.

Example 1
Phenolic resin AU: 100 parts by weight 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 weight.

  7 parts by weight of a mixture of 50% by weight of isopentane and 50% by weight of isobutane as a blowing agent and 11 parts by weight of a mixture of 80% by weight of xylene sulfonic acid and 20% by weight of diethylene glycol as an acid curing catalyst with respect to 100 parts by weight of a phenol resin. The composition was supplied to a mixing head whose temperature was adjusted to 25 ° C., and supplied to the moving lower surface material through a multiport distribution pipe.

As the face material, a polyester non-woven fabric (“Spunbond E05020” manufactured by Asahi Kasei Fibers Co., Ltd., basis weight 20 g / m ² , thickness 0.11 mm) was used. The average fiber diameter was 13 μm.

  The foamable phenolic resin composition supplied on the lower surface material is coated with the upper surface material, and at the same time, sandwiched between the upper and lower surface materials, sent to a 85 ° C. slat type double conveyor, and cured with a residence time of 15 minutes. And then cured in an oven at 110 ° C. for 2 hours to obtain a phenolic resin foam laminate. Each of the upper and lower surface materials is upstream of the position at which the resin composition is discharged, and is guided to the heating chamber and heated and heated by hot air, whereby the resin composition is discharged onto the lower surface material in the width direction 4. The surface temperature of the upper and lower surface materials measured by the non-contact infrared radiation thermometer measurement at the point position was adjusted to 50 to 55 ° C. (the measured value of the lower surface material was 52 ° C.). The slat type double conveyor is designed to release moisture generated during curing to the outside. The resin composition coated with the upper and lower surface materials was molded into a plate shape by applying moderate pressure through the surface material from above and below with a slat type double conveyor to obtain a phenol resin foam laminate.

( Reference Example 2)
Example 1 with the exception that the surface temperature of the upper and lower surface materials was adjusted to 35 to 40 ° C. by non-contact infrared radiation thermometer measurement at the position in the width direction of 4 points where the resin composition was discharged onto the lower surface material. Similarly, a phenol resin foam laminate was obtained. The actual measurement value of the average surface temperature of the bottom material was 36 ° C.

(Example 3)
Example 1 with the exception that the surface temperature of the upper and lower surface materials was adjusted to 95 to 100 ° C. by non-contact infrared radiation thermometer measurement at the position of 4 points in the width direction where the resin composition was discharged onto the lower surface material. Similarly, a phenol resin foam laminate was obtained. In addition, the measured value of the lower surface material average surface temperature was 98 ° C.

Example 4
Non-contact infrared at a position of 4 points in the width direction in which a polyester non-woven fabric (a prototype with a basis weight of 6 g / m ² , a thickness of 0.05 mm) is used as the face material and the resin composition is discharged onto the lower face material. A phenolic resin foam laminate was obtained in the same manner as in Example 1 except that the average surface temperature of the upper and lower surface materials measured by the radiation thermometer was adjusted to 95 to 100 ° C. The average fiber diameter of the face material was 8 μm, and the measured value of the average surface temperature of the lower face material was 97 ° C.

( Reference Example 5)
Non-contact infrared at a position of four points in the width direction in which a polyester nonwoven fabric (a prototype with a basis weight of 60 g / m ² , a thickness of 0.21 mm) is used as the face material and the resin composition is discharged onto the lower face material. A phenolic resin foam laminate was obtained in the same manner as in Example 1 except that the average surface temperature of the upper and lower surface materials measured by the radiation thermometer was adjusted to 35 to 40 ° C. The average fiber diameter of the face material was 18 μm, and the measured value of the average surface temperature of the lower face material was 36 ° C.

(Example 6)
Non-contact infrared at a position of four points in the width direction in which a polyester non-woven fabric (a prototype with a basis weight of 20 g / m ² , a thickness of 0.15 mm) is used as the face material and the resin composition is discharged onto the lower face material. A phenolic resin foam laminate was obtained in the same manner as in Example 1 except that the average surface temperature of the upper and lower surface materials measured by the radiation thermometer was adjusted to 95 to 100 ° C. The average fiber diameter of the face material was 20 μm, and the measured value of the average surface temperature of the lower face material was 98 ° C.

( Reference Example 7)
Non-contact infrared at a position of four points in the width direction in which a polyester non-woven fabric (a prototype of 12 g / m ² and a thickness of 0.09 mm) is used as the face material and the resin composition is discharged onto the lower face material. A phenolic resin foam laminate was obtained in the same manner as in Example 1 except that the average surface temperature of the upper and lower surface materials measured by the radiation thermometer was adjusted to 35 to 40 ° C. The average fiber diameter of the face material was 10 μm, and the measured value of the average surface temperature of the lower face material was 36 ° C.

(Comparative Example 1)
Do not use hot air heating chamber (at this time, the average surface temperature of the bottom material measured by non-contact infrared radiation thermometer at 26 positions in the width direction where the resin composition is discharged onto the bottom material is 26 ° C. Except for the above, a phenol resin foam laminate was obtained in the same manner as in Reference Example 7. The average fiber diameter of the face material was 10 μm.

(Comparative Example 2)
Non-contact infrared is used at the position of four points in the width direction in which a polyester nonwoven fabric (a prototype with a basis weight of 60 g / m ² , a thickness of 0.21 mm) is used as the face material, and the resin composition is discharged onto the lower face material. A phenolic resin foam laminate was obtained in the same manner as in Example 1 except that the average surface temperature of the upper and lower surface materials measured by the radiation thermometer was adjusted to 100 to 105 ° C. The average fiber diameter of the face material was 20 μm, and the measured value of the average surface temperature of the lower face material was 105 ° C.

  The average surface temperature of the bottom material, the fiber diameter of the face material, the surface material weight, the face material peel strength, and the resin stain from the face material of the obtained phenolic resin foam laminate used in the above Examples and Comparative Examples Table 1 shows the delivery rate, product properties, and overall evaluation.

  The phenol resin foam laminate of the present invention is used as a wall heat insulating material, a roof heat insulating material, a room partition heat insulating material, a heat insulating material for a refrigerator and the like.

It is explanatory drawing of the measuring method of the face material peeling strength in the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Clamp 2 Foam part of sample for evaluation 3 Bottom material of sample for evaluation 4 Paper clip 5 Metal wire 6 Container

Claims (4)

At least a resin composition comprising a phenol resin, a surfactant, a hydrocarbon-containing foaming agent, and a curing agent is mixed in the mixing section, and continuously discharged onto the traveling lower surface material, and the upper surface is the upper surface material. Is a method for producing a phenolic resin foam laminate in which the resin composition is foam-cured after being coated with at least the lower surface material is a woven fabric or a nonwoven fabric, and at least the resin composition is discharged onto the lower surface material. In the position, the average surface temperature of the bottom material is adjusted in the range of 52 ° C. or more and 100 ° C. or less, a method for producing a phenolic resin foam laminate,
The method for producing a phenolic resin foam laminate, wherein the hydrocarbon is one or more selected from the group consisting of isopentane, neopentane, normal butane, isobutane, and cyclobutane. 2. The method for producing a phenolic resin foam laminate according to claim 1, wherein the fiber diameter of the lower surface material is 1 μm or more and 20 μm or less, and the basis weight is 5 g / m ² or more and 60 g / m ² or less. .   The method for producing a phenolic resin foam laminate according to claim 1 or 2, wherein the hydrocarbon is a mixture of isopentane and isobutane.   The manufacturing method of the phenol resin foam laminated board as described in any one of Claims 1-3 in which the said foaming agent contains the said hydrocarbon 50weight% or more.