JP6993165B2 - Phenol resin foam laminated board - Google Patents

Description

The present invention relates to a phenolic resin foam laminated board.

The phenolic resin foam laminated board has excellent heat insulating performance, and is used in various fields such as buildings, transport aircraft, containers, etc., which require heat insulating performance.
By the way, as a method for manufacturing a thermosetting resin foam laminated board, for example, an uncured foamable thermosetting resin composition is continuously discharged onto a face material running on a conveyor, and further, another method is used. A method of coating a similar face material of the above, foaming and thermosetting is known.
In particular, in the production of a phenol resin foam laminated board, the water vapor generated from the foamable phenol resin composition during foam curing is quickly and efficiently dissipated to promote the curing of the resin and have excellent physical properties. Getting the product is important.
For the rapid release of this moisture, a flexible surface material having breathability as shown in Patent Document 1, for example, a synthetic fiber non-woven fabric is used, and a double slat type conveyor having a predetermined aperture ratio is used. , A technique for manufacturing a phenolic resin foam laminated board is used.
By the way, according to this method, a bulge having the same shape of the opening formed in the slat conveyor and the shape in a plan view is formed on the surface of the foam laminated plate. As an example of such a phenol resin foam laminated board having a bulge on the surface, Patent Document 2 discloses a laminated board containing a halogenated unsaturated hydrocarbon as a foaming agent.

Japanese Patent No. 5551155 Japanese Patent No. 6139769

However, the phenolic resin foam laminated board described in Patent Document 2 has a problem that sufficient adhesive strength cannot be obtained when it is applied to the wall surface of a building by using an adhesive or the like because of its surface shape.

An object of the present invention is to develop a necessary and sufficient adhesive strength when a phenol resin foam laminated board is applied to a wall surface using an adhesive or the like, and further suppress the exudation of the phenol resin foam from the face material. However, it is an object of the present invention to provide a laminated board having excellent adhesive strength with a face material and having a beautiful appearance.

As a result of diligent research to achieve the above object, the present inventor has found that it is effective to provide a predetermined ratio of flat portions on the surface of the laminated body, to use a specific face material, and the like. The invention was completed. That is, the present invention is as follows.

[1]
The foaming agent contains at least one compound selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene, as described above. Phenol formaldehyde foam in which the total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is 30% by mass or more. A phenolic resin foam laminated board in which a face material is laminated on at least one side of the body.
The face material is a synthetic fiber non-woven fabric, the grain size is 20 g / m ² or more and 300 g / m ² or less, and the convex portion is 3% or more on the surface of the face material laminated portion at an area ratio of 15% or more and 80% or less. The length in the MD direction is 5 to 64 mm in an area ratio of 40% or less, the length in the MD direction is the same over the entire length in the TD direction, and a flat portion extending continuously between both ends in the TD direction is formed. A phenolic resin foam laminated board which is formed and has an area ratio of a flat portion of 3 to 50% .
[2]
The foaming agent contains at least one compound selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene, as described above. Phenol formaldehyde foam in which the total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is 30% by mass or more. A phenolic resin foam laminated board in which a face material is laminated on at least one side of the body.
The face material is a synthetic fiber non-woven fabric, the grain size is 20 g / m ² or more and 300 g / m ² or less, and the convex portion is 2% or more on the surface of the face material laminated portion at an area ratio of 15% or more and 80% or less. Flat parts are formed with an area ratio of 50% or less.
The flat portion has a length of 5 to 64 mm in the MD direction, the length in the MD direction is the same over the entire length in the TD direction, and the phenol resin foam laminated plate extends continuously between both ends in the TD direction. ..
[3]
The foaming agent contains at least one compound selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene, as described above. Phenol formaldehyde foam in which the total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is 30% by mass or more. A phenolic resin foam laminated board in which a face material is laminated on at least one side of the body.
The face material is a synthetic fiber non-woven fabric, the grain size is 20 g / m ² or more and 300 g / m ² or less, and the convex portion is 2% or more on the surface of the face material laminated portion at an area ratio of 15% or more and 80% or less. A flat portion having an area ratio of 50% or less and a length in the MD direction extending in the TD direction of 3 to 150 mm is formed.
A phenolic resin foam laminated board in which the face material has a crimping portion and the density of the crimping portion is 2 pieces / cm ² or more and 29 pieces / cm ² or less.
[4]
The phenolic resin foam laminate according to [1] or [2] , wherein the face material has a crimping portion and the density of the crimping portion is 2 pieces / cm ² or more and 29 pieces / cm ² or less.
[5]
The phenolic resin foam laminate according to any one of [1] to [4], wherein the foaming agent contains a hydrocarbon and / or a halogenated saturated hydrocarbon.
[6]
The process of pulling out the first face material from the face material roll with a force of 0.5 to 80 N / m,
A step of discharging a foamable phenol resin composition containing a phenol resin, a foaming agent, a surfactant, and a curing agent onto the first face material,
A second face material made of the same material as the first face material is pulled out from the face material roll with a force of 0.5 to 80 N / m so that the drawing speed becomes the same as that of the first face material. The step of superimposing on the effervescent phenol resin composition discharged on the face material of
A process of sandwiching a foaming phenol resin composition sandwiched between face materials by a slat type double conveyor provided with a plurality of holes in a slat plate forming a transport surface, and a process of sandwiching the foamable phenol resin composition.
The step according to any one of [1] to [5] , which comprises a step of foaming and curing the effervescent phenol resin composition by setting the pressure applied to the slat plate of the slat type double conveyor to 2 kN / m ² to 20 kN / m ² . The method for producing a phenol resin foam laminated board according to the above method.

The phenolic resin foam laminated board of the present invention exhibits necessary and sufficient adhesive strength when applied to the wall surface using an adhesive or the like, and further suppresses the exudation of the phenolic resin foam from the face material, thereby suppressing the surface material. It provides a laminated board with excellent adhesive strength to the material and a beautiful appearance.

Hereinafter, embodiments for carrying out the present invention (hereinafter, may be referred to as “the present embodiment”) will be described in detail.

As a method for producing the phenol resin foam laminated board of the present embodiment, for example, a step of pulling out the first face material from the face material roll with a force of 0.5 to 80 N / m, a phenol resin, a foaming agent, and surface activity. The step of discharging the effervescent phenol resin composition containing the agent and the curing agent onto the first face material and the second face material of the same material as the first face material are 0.5 to 80 N / A step of pulling out from the face material roll so that the drawing speed becomes the same as that of the first face material with a force of m and superimposing it on the foamable phenol resin composition discharged onto the first face material, and a transport surface. In a slat type double conveyor provided with a plurality of holes in the slat plate forming the above, the step of sandwiching the foamable phenol resin composition sandwiched between the face materials and the pressure applied to the slat plate of the slat type double conveyor are 2 kN / A method including a step of foaming and curing the effervescent phenol resin composition at m ² to 20 kN / m ² is used.

In addition, in this specification, the "face material laminated part surface" of the phenol resin foam laminated board means the surface of the phenol resin foam laminated board on the side where the face material is laminated. When the face material is laminated on both sides of the phenol resin foam, the surface of the face material laminated portion may be one surface or both surfaces.

Generally, in the production of a phenol resin foam laminated board, the water vapor generated from the foamable phenol resin composition during foam curing is quickly and efficiently dissipated to promote the curing of the phenol resin, resulting in excellent physical properties. It is important to get the product you have.
For the rapid release of this water, a flexible surface material having breathability as shown in Patent Document 1, for example, a synthetic fiber non-woven fabric is used, and a plurality of openings are obtained so as to have a predetermined aperture ratio. A technique for manufacturing a phenolic resin foam laminated board using a slat type double conveyor whose portion is provided on the slat board is used.
The opening is preferably formed by forming a through hole in the slat plate.

During the production of the phenolic resin foam laminated board of the present embodiment, the water vapor generated from the foamable phenol resin composition is uniformly and promptly dissipated from the surface of the laminated board, and the foamable phenol from a face material such as a synthetic fiber non-woven fabric. In order to suppress the exudation of the resin composition, the shape and arrangement of the opening of the slat plate, the adjustment of the opening ratio, and the slat plate when the foamable phenol resin composition is formed into a plate shape by the slat type double conveyor. It is effective to adjust the applied pressure and the pulling force of the upper and lower face materials drawn from the face material roll.
At this time, the pressure applied to the slat plate is 2 kN / m ² to 20 kN / m ² , preferably 4 kN / m ² to 16 kN / m ² , and the pulling force of the upper surface material and the lower surface material drawn from the face material roll is 0.5 to. By setting the temperature to 80 N / m, preferably 1 to 60 N / m, various forms of protrusions are formed on the surface of the phenol resin foam laminated plate. The pressure applied to the slat plate may be 1 kN / m ² to 30 kN / m ² , and the pulling force of the upper surface material and the lower surface material drawn from the face material roll is 0.2 to 100 N / m. May be good.
The upper and lower face materials drawn from the face material roll are pulled out by a nip roller capable of controlling rotation and further towed by a slat type double conveyor. "Pulling force" refers to the tension of the face material applied between the nip roller and the slat type double conveyor. The pulling force of the upper surface material and the pulling force of the lower surface material may be the same or different.
The pull-out force of the face material can be adjusted to a desired value by adjusting the rotation of the nip roller or by separately providing a roller for tension adjustment and moving the position of the tension adjusting roller.
The pressure applied to the slat plate is measured by a load cell attached to the back surface side of the foam contact surface of the slat plate, and the pressure can be adjusted to a desired value by changing the slat plate spacing or the like.

By satisfying the above conditions, as a result, a convex portion having a height to the apex of the convex portion, that is, a convex portion having a height of 0.01 to 3 mm and a width of the convex portion of 1 to 20 mm is formed. In many cases, the height of the convex portion is larger than the thickness of the face material.

When the pressure applied to the slat plate is 2 kN / m ² or more, the effervescent phenol resin composition can penetrate into the face material to the extent required, and the adhesive strength between the face material and the phenol resin foam can be obtained. Is likely to increase. If it is within 20 kN / m ² , it becomes easy to suppress the exudation of the effervescent phenol resin composition.
When the pulling force of the upper and lower face materials pulled out from the face material roll is 0.5 N / m or more, wrinkles are less likely to occur on the surface of the face material during molding, which is preferable in appearance. On the other hand, if the pulling force of the upper and lower face materials pulled out from the face material roll is within 80 N / m, it becomes easy to improve the adhesive strength of the face material.

The shape of the plan view of the region surrounded by the rising portion (outer edge) of the convex portion (the plan view shape of the convex portion) can be various, and for example, by changing the shape of the opening of the slat plate, for example. It can be a polygonal shape such as a quadrangle or a hexagon, a perfect circle shape, an elliptical shape, or a circular shape such as an oval shape.
Here, the shape of the convex portion in a plan view means a shape when the line of sight is perpendicular to the surface on which the face materials of the laminated plates are laminated. Further, the rising portion of the convex portion means a set of points where the ridge line from the bottom surface of the concave portion to the apex of the convex portion is substantially separated from the bottom surface of the concave portion. Such points are formed by the ridgeline of the central convex portion (the line formed by the surface of the laminated plate) and the central convex portion when cut in the thickness direction so as to pass through the vertices of the three adjacent convex portions. It is a point where the bottom surfaces of the recesses existing on the left and right (the surface formed by the interface between the face material and the phenolic resin foam plate) come into contact with each other. It should be noted that the bottom surface of the recess has irregularities derived from the fibers of the face material, the crimping portion such as the thermocompression bonding portion, and the fine wrinkles of the face material, but these are ignored.
The apex of the convex part is the highest point in each area surrounded by the rising point of the convex part when the laminated board is placed on a horizontal Tokiwa and the height is measured with a laser displacement meter. Can be. Alternatively, the surface of the laminated board can be observed with an optical microscope and then depth-analyzed, and the highest point in each region surrounded by the rising points of the convex portion in the observed portion can be set as the apex.
As the cutting tool, it is preferable to use a sharp object such as a razor or a heat insulating material cutter.
The width of the convex portion is the longest part of the distance between the two points of the straight line intersecting the shape of the convex portion in the plan view. For example, in the case of a perfect circle shape, it is the diameter and is a regular quadrangle. In the case of, it means a diagonal line. When the shape of the convex portion in a plan view is a perfect circle shape in a plan view, the diameter is preferably 1 mm or more and 10 mm or less, or 5 mm or more and 8 mm or less.
The convex portion is, for example, a concave portion, that is, a columnar column having a height of 0.05 mm to 1 mm and a diameter of 3 to 10 mm from the portion between the rising portion of the convex portion to the rising portion of the adjacent convex portion to the apex of the convex portion. You can also do things.
Further, the width of the concave portion formed between the adjacent convex portions, that is, the distance from the rising portion of the convex portion to the rising portion of the adjacent convex portion is preferably 0.01 to 10.00 mm, and is 0. .1 to 4 mm is more preferable. By arranging the openings in the slat plate so that the distance between the adjacent convex portions becomes small, water vapor can be uniformly dissipated from the laminated plate. On the other hand, since the recess corresponds to a portion other than the opening of the slat plate, the width must be the minimum distance necessary for maintaining the strength of the slat plate and the opening.

The opening of the slat plate may be set so that the opening ratio is 15% or more and 80% or less. The lower limit of the aperture ratio may be 15% or more, preferably 15% or more, as a range capable of accelerating the emission of water vapor from the obtained phenol resin foam laminated plate, promoting curing, and obtaining excellent adhesive strength of the face material. It is 20% or more, more preferably 25% or more, and particularly preferably 30% or more. The upper limit of the aperture ratio may be 80% or less from the viewpoint of maintaining the strength of the slat plate, preferably 75% or less, more preferably 70% or less, and particularly preferably 70% or less from the viewpoint of ease and economy when processing the slat plate. Is 65% or less.
The area ratio of the convex portion is almost determined by the opening ratio of the slat plate, and the area ratio of the convex portion is slightly smaller than the opening ratio.
Here, the aperture ratio of the opening is the ratio of the total area of the opening to the total area of the phenol resin foam laminated plate molded portion on the surface of the slat plate including the opening, and is represented by the formula (1). The total area of the phenolic resin foam laminated plate molded portion on the surface of the slat plate including the opening means the total area of the plan view shape of the surface of the slat plate including the opening.
Aperture ratio = {(total area of openings on the surface of the slat plate) / (total area of the molded portion of the phenolic resin foam laminated plate on the surface of the slat plate including the openings)} × 100 [%] ・ ・ ・ Equation (1)

In the phenolic resin foam laminated plate of the present embodiment, convex portions are formed on at least one surface at an area ratio of 15% or more and 80% or less, and convex portions are formed at an area ratio of 20% or more and 75% or less. It is more preferable that the convex portion is formed in an area ratio of 25% or more and 65% or less. Further, convex portions may be formed on the surfaces on both sides at an area ratio within the above range.
Here, the convex portion area ratio is the ratio of the total area of the convex portion to the total area of the surface having the face material in the plate-shaped laminated board in which the face material is laminated on at least one surface, and is the formula (2). ). The total area of the surface having the face material means the total area of the plan view shape.
The area of the convex portion means the area in a plan view of the region surrounded by the rising portion of the convex portion. The unit area in the formula is 25 cm ² in the plan view shape of the laminated board cut out from an arbitrary position of the laminated board to a length of 5 cm and a width of 5 cm, and the convex area area ratio per unit area is the entire laminated board. The convex area ratio of.
Convex area ratio (%) = {(total area of multiple convex parts existing per unit area) / (unit area)} x 100 [%] ... Equation (2)

Further, in order to maintain the strength of the slat plate, the aperture ratio of the opening is preferably 80% or less, and more preferably discontinuous, in which case the convex portion becomes discontinuous.

The area per opening is preferably 0.5 mm ² or more and 80 mm ² or less, more preferably 10 mm ² or more and 65 mm ² or less, and 15 mm ² from the viewpoint of sufficient water vapor dissipation and maintaining the strength of the slat plate. More than 50 mm ² or less is particularly preferable.

The area per convex portion is substantially the same as the area per opening. The area per convex portion is almost determined by the area per opening, and the area per convex portion is slightly smaller than the area per opening.
The area per convex portion is preferably 0.5 mm ² or more and 80 mm ² or less, more preferably 10 mm ² or more and 65 mm ² or less, and particularly preferably 15 mm ² or more and 50 mm ² or less.

The surface of the phenolic resin foam laminate of the present embodiment has a length of 3 to 150 mm in the product flow direction (MD direction) at the time of manufacturing the phenol resin foam laminate on at least one surface, and is perpendicular to the MD direction. A flat portion extending in the TD direction, which is a normal direction, is formed in an area ratio of 2% or more and 50% or less. The length of the flat portion in the MD direction is preferably 4 to 100 mm, more preferably 5 to 65 mm. The area ratio of the flat portion is preferably 3 to 50%, more preferably 3 to 20%.
This flat portion is formed by providing a continuous portion without an opening on the slat plate.
When a phenolic resin foam laminated board is applied to the wall surface of a building using a high-viscosity organic or inorganic adhesive, the length of the flat portion extending in the TD direction in the MD direction is less than 3 mm, or When the area ratio of the flat portion is less than 2%, the area ratio of the convex portion becomes large, and most of the convex portion is point-bonded at the apex of the convex portion, so that sufficient adhesive strength cannot be obtained.
Further, when the length of the flat portion extending in the TD direction in the MD direction exceeds 150 mm, or when the area ratio of the flat portion exceeds 50%, the area of the slat plate opening becomes small, so that the phenol resin foam laminate is laminated. Since the water vapor is not sufficiently dissipated from the plate and a cavity is formed on the surface layer of the foam due to swelling, the tensile strength of the foam is lowered, and at the same time, the adhesive strength at the time of bonding to the wall surface of the building is lowered.
Here, the flat portion may be a continuous flat portion between both ends of the surface of the phenol resin foam laminated plate in the TD direction. The length of the flat portion in the MD direction may be the same or different over the entire length in the TD direction.
The length of the flat portion in the MD direction refers to the average value of the lengths of one flat portion provided on the surface of the phenolic resin foam laminated plate in the MD direction with respect to the total length in the TD direction.
One flat portion may be provided, or a plurality of the flat portions may be provided. When a plurality of flat portions are provided, the length of each flat portion in the MD direction and the length in the TD direction may be the same or different.

Face materials are provided on one side or both sides of the phenolic resin foam laminated plate of the present embodiment. When the face materials are provided on both sides, each face material may be the same or different.
As the face material, a synthetic fiber non-woven fabric is preferably used. The synthetic fiber nonwoven fabric used in this embodiment includes a synthetic fiber nonwoven fabric made of polyamide (nylon, etc.), polyester (PET, etc.), acrylic resin, polypropylene (PP), polyethylene (PE), etc. manufactured by the spunbond method or the like. It can be preferably used.

The lower limit of the basis weight of the face material used in this embodiment is 20 g / m ² . Since the effervescent phenol resin composition contains a halogenated unsaturated hydrocarbon, the viscosity is lowered and the polarity is high, so that the affinity with the synthetic fiber non-woven fabric used as the face material, particularly the polyester non-woven fabric, is enhanced. , It becomes easy to seep into the face material, and it becomes easy to seep into the surface of the phenol resin foam laminated board, and the surface appearance deteriorates. Further, if the amount of exudation from the face material is further increased, the surface of the slat plate is contaminated with the exuded effervescent phenol resin composition, and it is necessary to polish and clean the surface of the slat plate each time. The basis weight of the face material is preferably 25 g / m ² or more, more preferably 30 g / m ² or more.
In particular, when a halogenated unsaturated hydrocarbon and a halogenated saturated hydrocarbon such as 2-chloropropane are used in combination as a foaming agent, the viscosity of the foamable phenol resin composition tends to be lower. When the texture of the face material is at least the above lower limit value, even when a halogenated unsaturated hydrocarbon and a halogenated saturated hydrocarbon are used in combination as a foaming agent, the exudation to the surface of the laminated board is suppressed. It will be easier.
The upper limit of the basis weight of the face material is 300 g / m ² , preferably 120 g / m ² or less, and more preferably 50 g / m ² or less. When the basis weight of the face material is not more than the upper limit value, the adhesiveness between the face material and the phenol resin foam is enhanced. If the basis weight of the face material exceeds 300 g / m ² , the printing becomes unclear when the serial number or product logo is printed on the surface of the phenolic resin foam laminated board with an inkjet printer or the like.

The difference between the basis weight of the face material peeled from the foam and the basis weight of the face material used is preferably 2 g / m ² or more and 12 g / m ² or less, more preferably 4 g / m ² or more and 10 g / m ² or less, and 6 g. The most preferable is / m ² or more and 10 g / m ² or less.
The basis weight of the peeled face material shall be the basis weight of the face material peeled by the same method as the peeling method used in the measurement / evaluation of the adhesive strength of the face material.

The fiber diameter of the synthetic fiber of the synthetic fiber nonwoven fabric is preferably 0.5 to 4.0 denier, more preferably 1.5 to 3.0 denier. When the fiber diameter of the synthetic fiber is not more than the upper limit value, it becomes easy to suppress the exudation of the foamable phenol resin composition onto the surface of the phenol resin foam laminated board. When the fiber diameter of the synthetic fiber is at least the above lower limit value, the handleability of the synthetic fiber is improved and the non-woven fabric is easily manufactured.

The thickness of the face material is not particularly limited, but is preferably 0.05 to 2.00 mm, more preferably 0.10 to 1.00 mm. When the thickness of the face material is at least the above lower limit value, the exudation to the surface of the phenol resin foam laminated board is likely to be suppressed. When the thickness of the face material is not more than the upper limit value, the handleability of the face material is improved.

It is preferable that so-called embossing is formed on the face material. By using the embossed face material, the strength of the face material itself is further increased.
Examples of the embossed pattern, the so-called embossed pattern, include a minus pattern, a point pattern, and a textured pattern. These patterns can be confirmed by referring to the embossed patterns applied to the spunbonded non-woven fabric "Eltus" of Asahi Kasei Corporation. In particular, the negative pattern embossing maintains the strength of the synthetic fiber non-woven fabric even if the number per unit area is small, and if the number per unit area is small, the thickness of the non-woven fabric increases and the foaming phenol resin composition. It has the effect of suppressing the seepage of objects into the slat plate, and further widens the distance between the fibers that make up the synthetic fiber non-woven fabric, making it easier for high-viscosity organic adhesives and mortar (sometimes called base coats) to penetrate. Therefore, the adhesive strength to the wall surface of the building can be increased.

To emboss the synthetic fiber non-woven fabric, for example, by a known spunbond method, the crimped fiber web developed under the cooling conditions directly under the spun is partially heated by a thermal embossing roll on which a predetermined embossing pattern is formed. It is manufactured by crimping or by partially heat crimping a latent crimped fiber web with a thermal embossed roll formed by crimping the latent crimped fiber web by heat treatment to form a predetermined embossed pattern.

The area of each crimping portion is preferably 0.05 to 5.0 mm ² , more preferably 0.07 to 3.0 mm ² . When the area is 0.05 mm ² or more, the strength of the face material is easily maintained, and when the area is 5.0 mm ² or less, it is easy to suppress the exudation of the effervescent phenol resin composition. The minimum spacing between the crimping portions is preferably 0.05 to 5 mm, more preferably 0.08 to 2 mm. If the minimum spacing is 0.05 mm or more, the adhesive strength between the foamable phenol resin composition and the face material tends to increase, and if it is 5 mm or less, the strength of the face material can be easily maintained. Further, it is preferable that the crimping portions are evenly distributed on the entire surface of the non-woven fabric surface.
The density of the crimping portion is preferably 2 pieces / cm ² or more and 250 pieces / cm ² or less, and more preferably 2 pieces / cm ² or more and 29 pieces / cm ² or less. The crimping portion density means the number of crimping portions per unit area, and is expressed by the following equation.
Crimping part density (pieces / cm ² ) = number of crimping parts (pieces) / surface area of face material (cm ² ) ・ ・ ・ Equation (3)
When the pressure-bonding portion density is 250 pieces / cm ² or less, it becomes easy to suppress the exudation of the effervescent phenol resin composition.
In addition, when using a high-viscosity organic adhesive or mortar on the wall surface of a building, the pressure-bonding portion density should be 29 pieces / cm ² or less so that the spacing between the fibers constituting the synthetic fiber non-woven fabric can be increased. Widespread and highly viscous organic adhesives and mortar easily penetrate into the non-woven fabric layer on the surface of the phenol resin foam laminated board, and it becomes easy to increase the adhesive strength to the wall surface. In addition, by setting the pressure-bonding portion density to 2 pieces / cm ² or more, it becomes easier to impart the tensile strength of the face material required for manufacturing the phenolic resin foam laminated board, and it becomes easier to prevent the face material from being torn during manufacturing. Can be done.
When the pressure-bonding portion density is 2 pieces / cm ² or more, when the serial number or product logo is printed on the surface of the phenolic resin foam laminated board with an inkjet printer or the like, the printed appearance is easily clarified and the laminated board printability is improved. Cheap.
Since the crimped portion is formed by crimping, it is slightly recessed as compared with other surfaces of the nonwoven fabric, but the depth of the recess is preferably 0.01 to 1.0 mm. When the depth is 0.01 mm or more, the strength of the nonwoven fabric is likely to be developed, and when the depth is 1.0 mm or less, the nonwoven fabric is likely to have an appropriate thickness, and the exudation of the effervescent phenol resin composition is easily suppressed.

The effervescent phenolic resin composition preferably contains a phenolic resin, a foaming agent, a surfactant, and a curing agent.

As the phenol resin, a resol type resin is preferable.
The resole-type phenol resin is a phenol resin obtained by reacting a phenol compound with an aldehyde in the presence of an alkaline catalyst.
Examples of the phenol compound include phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcinol and modified products thereof.
Examples of the aldehyde include formaldehyde, paraformaldehyde, furfural, acetaldehyde and the like.
Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, aliphatic amines (trimethylamine, triethylamine, etc.) and the like. However, the phenol compound, the aldehyde, and the alkaline catalyst are not limited to the above.
The ratio of the phenol compound to the aldehyde is not particularly limited. The molar ratio of phenolic compound: aldehyde is preferably 1: 1 to 1: 3, and more preferably 1: 1.3 to 1: 2.5.

The viscosity of the foamable phenol resin composition suitable for producing the foam laminated board of the present embodiment at 40 ° C. is preferably 1000 to 40,000 mPa · s, more preferably 2000 to 30,000 mPa · s. When the viscosity is set in this range, it becomes easy to adjust the closed cell ratio to 80% or more while optimizing the density of the foam plate. The viscosity can be in a preferable range by adjusting the water content contained in the phenol resin composition and the molecular weight of the phenol resin.
The viscosity at 40 ° C is the value after stabilizing at 40 ° C for 3 minutes using a rotary viscometer (manufactured by Toki Sangyo Co., Ltd., R-100 type, rotor part is 3 ° x R-14). The viscosity value was used. Can be measured by.

The foaming agent used in the production of the foam laminate of the present embodiment contains a halogenated unsaturated hydrocarbon. The halogenated unsaturated hydrocarbon has a lower thermal conductivity than the hydrocarbon, and a phenol resin foam laminated plate having excellent heat insulating performance can be obtained.
In addition, halogenated unsaturated hydrocarbons have a small ozone depletion potential (ODP) and global warming potential (GWP), and have a small impact on the environment. Further, since the halogenated unsaturated hydrocarbon is nonflammable, the flame retardancy of the phenol resin foam is enhanced.
Examples of the halogenated unsaturated hydrocarbon include 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers). ), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) (E and Z isomers), 1,2-dichloro-1,2-difluoroethene (E and Z isomers) Body), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) (E and Z isomer), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb) (E and Z isomers), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe) ( E and Z isomers), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 3-chloro-1 , 2,3-Trifluoropropene (HCFO-1233ye) (E and Z isomers), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 3,3-dichloro-3-fluoropropene , 1,2-Dichloro-3,3,3-trifluoropropene (HCFO-1223xd) (E and Z isomers), 2-chloro-1,1,1,4,4,4-hexafluoro-2- Butene (E and Z isomers), 2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene (E and Z variants) and the like can be mentioned.
These halogenated unsaturated hydrocarbons may be used alone or in combination of two or more.

The foaming agent used in the production of the phenol resin foam laminate of the present embodiment and the foaming agent contained in the phenol resin foam include at least 1,1,1,4,4,4-hexafluoro-2-butene. (HFO-1336mzz) and / or 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) are used. Examples of 1,1,1,4,4,4-hexafluoro-2-butene include product names: Opteon (registered trademark) 1100 and the like. Examples of 1-chloro-3,3,3-trifluoropropene include product names: Solstice (registered trademark) LBA and the like. The total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent may be 30% by mass or more. It is more preferably 50% by mass or more, and even more preferably 70% by mass or more.
If the content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is equal to or higher than the above lower limit, the phenolic resin The heat insulating property of the foam laminated board can be further improved.

As the hydrocarbon, cyclic or chain-shaped alkanes, alkanes, and alkynes having 3 to 7 carbon atoms are preferable, and specifically, normalbutane, isobutane, cyclobutane, normalpentane, isopentane, cyclopentane, neopentane, normal hexane, and the like. Examples thereof include isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane and the like. Among them, pentane such as normal pentane, isopentane, cyclopentane and neopentane and butane such as normal butane, isobutane and cyclobutane are preferably used. These hydrocarbons may be used alone or in combination of two or more.

Examples of the halogenated saturated hydrocarbon include linear or branched hydrocarbons having 2 to 5 carbon atoms. The number of bonded chlorine atoms is preferably 1 to 4, and examples thereof include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferable. The chlorinated hydrocarbon may be used alone or in combination of two or more.

In the present embodiment, it is preferable that the foaming agent further contains a hydrocarbon and / or a halogenated saturated hydrocarbon. That is, it is preferable that the phenolic resin foam contains a halogenated unsaturated hydrocarbon and / or a halogenated saturated hydrocarbon.

When the foaming agent contains a hydrocarbon, it is possible to suppress the viscosity of the effervescent phenol resin composition from becoming too low, and it becomes easy to suppress the exudation to the surface.
When the foaming agent contains a hydrocarbon, the mass ratio of the halogenated unsaturated hydrocarbon to the hydrocarbon is preferably 3: 9 to 9: 1 for the halogenated unsaturated hydrocarbon: hydrocarbon. It is more preferably ~ 7: 3, and even more preferably 4: 6 to 6: 4.
When the ratio of the halogenated unsaturated hydrocarbon is at least the above lower limit value, the heat insulating property of the phenol resin foam can be further enhanced. When the ratio of the halogenated unsaturated hydrocarbon is not more than the above upper limit value, the viscosity of the effervescent phenol resin composition does not become too low, and the ability to suppress exudation to the surface is likely to be enhanced. Further, the effervescent phenol resin composition has good foamability and can be sufficiently foamed even if the amount of the foaming agent is small.

When the foaming agent contains a halogenated saturated hydrocarbon, the mass ratio of the halogenated unsaturated hydrocarbon to the halogenated saturated hydrocarbon is as follows: halogenated unsaturated hydrocarbon: halogenated saturated hydrocarbon = 1: 9-9. It is preferably 1: 1, more preferably 3: 7 to 7: 3, and even more preferably 4: 6 to 6: 4.
The halogenated saturated hydrocarbon has high compatibility with the phenol resin composition, and the effervescent phenol resin composition containing the halogenated saturated hydrocarbon tends to have a lower viscosity. By adjusting it, it is possible to suppress the exudation to the surface.

The content of the foaming agent in the effervescent phenol resin composition is preferably 1 to 25 parts by mass, more preferably 3 to 15 parts by mass, and even more preferably 5 to 12 parts by mass per 100 parts by mass of the phenol resin. When it is at least the above lower limit value, it is easy to lower the density of the phenol resin foam to the extent that good heat insulating performance is exhibited, and when it is within the above upper limit value, it is easy to moderately suppress the degree of foaming of the foamable phenol resin composition. , The strength required for building insulation can be obtained.

The effervescent phenolic resin composition may contain an effervescent nucleating agent. Examples of the foaming nucleating agent include low boiling point substances such as nitrogen, helium, argon, and air, which have a boiling point lower than that of the foaming agent by 50 ° C. or more. The foaming nucleating agent is, for example, aluminum hydroxide powder, aluminum oxide powder, calcium carbonate powder, talc, clay (kaolin), silica stone powder, silica sand, mica, calcium silicate powder, wallastnite, glass powder. , Glass beads, fly ash, silica fume, gypsum powder, porcelain sand, slag powder, alumina cement, inorganic powder such as Portland cement, and organic powder such as resin foam powder may be solid foam nucleating agents. The effervescent nucleating agent may be used alone or in combination of two or more.

The amount of the foaming nucleating agent added to the foaming agent is preferably 0.1% by mass or more and 1.0% by mass or less, and 0.2% by mass or more and 0.6, based on the total amount of the foaming agent (100% by mass). More preferably, it is by mass or less. If the amount of the foaming nucleating agent added is 0.1% by mass or more, uniform foaming is likely to occur, and if the amount of the foaming nucleating agent added is 1.0% by mass or less, the foaming of the effervescent phenol resin composition is likely to occur. Is easily promoted, the effervescent phenol resin composition is easily permeated into the face material, and it is easy to secure the adhesive strength between the face material and the phenol resin foam.

As the curing agent, an acidic curing agent capable of curing the phenol resin is used. Here, if an acid that does not contain water is used, the wall of the foam excluding bubbles and voids is less likely to be destroyed, so an anhydride-hardening agent is preferable. As the anhydrous acid curing agent, anhydrous phosphoric acid or anhydrous aryl sulfonic acid is preferable. Examples of the aryl sulfonic acid anhydride include toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, substituted phenol sulfonic acid, xylenol sulfonic acid, substituted xylenol sulfonic acid, dodecylbenzene sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid and the like. These 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. Further, these curing agents may be diluted with a solvent such as ethylene glycol and diethylene glycol.

The amount of the curing agent used is preferably 3 parts by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the phenol resin.

In the production of the foam laminated board of the present embodiment, a curing aid, a plasticizer, a flame retardant and the like can also be used.

Examples of the curing aid include resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol and the like. The curing aid may be used alone or in combination of two or more.

As the surfactant, those generally used for producing phenolic resin foams can be used, but among them, nonionic surfactants are effective, for example, a copolymer of ethylene oxide and propylene oxide. A alkylene oxide, a condensate of alkylene oxide and castor oil, a condensate of alkylene oxide and nonylphenol, a condensate of an alkylphenol such as dodecylphenol, a polyoxyethylene alkyl ether having 14 to 22 carbon atoms in the alkyl ether moiety, and further polyoxy. Fatal acid esters such as ethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, polyalcohols and the like are preferable. These surfactants may be used alone or in combination of two or more.

The amount of the surfactant used is not particularly limited, but is preferably used in the range of 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol resin.

Examples of the plasticizer include phthalates and glycols such as ethylene glycol and diethylene glycol, and among them, phthalates are preferably used. Further, aliphatic hydrocarbons, alicyclic hydrocarbons, or mixtures thereof may be used. The plasticizer may be used alone or in combination of two or more.

As flame-retardant agents, phosphoric acid esters such as red phosphorus, sodium phosphate, sodium dihydrogen phosphate, ammonium polyphosphate, chlorine-containing phosphoric acid ester, ammonium phosphates, melamine phosphates, aluminum phosphates, borophyllus Examples thereof include acid, sodium borate, zinc borate, ammonium carbonate, silicate stone (needle-shaped filler), expanded graphite, silicones and the like.

The phenolic resin foam laminated board of the present embodiment is used alone or in various applications by being bonded to an external member. Examples of the external member include one and a combination of a board-shaped material and a sheet-shaped / film-shaped material. Board-like materials include ordinary plywood, structural plywood, particle board, OSB, and other wood-based boards, as well as wood wool cement board, wood piece cement board, gypsum board, flexible board, medium density fiber board, and calcium silicate board. , Magnesium silicate plate, volcanic vitreous multi-layer plate and the like are suitable. The sheet-like and film-like materials include polyester non-woven fabric, polypropylene non-woven fabric, inorganic-filled glass fiber non-woven fabric, glass fiber non-woven fabric, paper, calcium carbonate paper, polyethylene-processed paper, polyethylene film, plastic moisture-proof film, asphalt waterproof paper, and aluminum. Foil (with or without holes) is suitable.

The appropriate range of the density of the phenolic resin foam in the present embodiment is preferably 15 kg / m ³ or more and 60 kg / m ³ or less, and more preferably 20 kg / m ³ or more and 50 kg / m ³ or less.
The thermal conductivity of the phenolic resin foam in the present embodiment is preferably 0.020 W / mK or less, more preferably 0.019 W / mK or less, and even more preferably 0.018 W / mK or less. If the thermal conductivity is within this range, good heat insulation performance can be obtained.
The appropriate range of the average cell diameter of the phenolic resin foam in the present embodiment is preferably 150 μm or less, a more preferable range is 40 to 120 μm, and a still more preferable range is 50 to 100 μm. When the average bubble diameter is within this range, the effect of suppressing radiation can be obtained, the convection in the bubbles can be suppressed, and good heat insulating performance can be obtained.
The appropriate range of the closed cell ratio of the phenolic resin foam in the present embodiment is preferably 80% or more, a more preferable range is 85% or more, and a further preferable range is 90% or more. If the closed cell ratio is within this range, good heat insulation performance can be maintained for a long period of time.

The limiting oxygen index of the phenolic resin foam in the present embodiment is preferably 28% by volume or more, more preferably 29% by volume or more, further preferably 32% by volume or more, and particularly preferably 34% by volume. The above is the most preferable, and it is 35% by volume or more. If the limiting oxygen index is 28% by volume or more, the heat insulating material tends to delay the spread of the fire.
The limiting oxygen index of the phenolic resin foam, that is, LOI, can be adjusted by the type and composition of the foaming agent, the type and composition of the surfactant, the type and composition of the flame retardant and the amount thereof.
For example, the lower the content of the flammable foaming agent in the foaming agent, that is, the higher the content of the highly flame-retardant halogenated hydrocarbon, the higher the LOI. Further, if the surfactant has a silicone-based surfactant, particularly a polyether chain having a −OH terminal, the LOI tends to be higher than when other surfactants are used. Further, the LOI can be increased by adding a phosphorus-based flame retardant or the like.

The brittleness of the phenolic resin foam of the present embodiment (JIS A 9511: 2006) is preferably 25% or less, more preferably 5 to 20%.

The evaluation method will be described below.

(1) Identification of the type of foaming agent component in the phenolic resin foam and calculation of the mass ratio of each foaming agent component Introduction Of the halogenated unsaturated hydrocarbons, hydrocarbons, and halogenated saturated hydrocarbons used as foaming agents Using a standard gas, the retention time under the following GC / MS measurement conditions was determined.
Next, the face material was peeled off from the phenol resin foam laminated plate, about 10 g of the phenol resin foam sample and the metal file were placed in a 10 L container (product name "Tedlar bag"), sealed, and 5 L of nitrogen was injected. The sample was scraped from the top of the tedler bag using a file and finely crushed. Subsequently, the sample was placed in a temperature controller whose temperature was adjusted to 81 ° C. for 10 minutes while still in the tedler bag. 100 μL of the gas generated in the tedler bag was sampled, and GC / MS analysis was performed under the measurement conditions shown below to identify the type of foaming agent component in the phenol resin foam.
The types of halogenated unsaturated hydrocarbons, hydrocarbons, and halogenated saturated hydrocarbons were identified from pre-determined retention times and mass spectra. Further, separately, the detection sensitivity of the generated gas component was measured by each standard gas, and the composition ratio was calculated from the detection area area and the detection sensitivity of each gas component obtained by GC / MS. The mass ratio of each gas component was calculated from the composition ratio and the molar mass of each identified gas component.
(GC / MS measurement conditions)
Gas Chromatography: Agilent Technologies "Agient 7890"
Column: "InertCap 5" manufactured by GL Sciences (inner diameter 0.25 mm, film thickness 5 μm, length 30 m)
Carrier gas: Helium flow rate: 1.1 ml / min Injection port temperature: 150 ° C
Injection method: Split method (1:50)
Sample injection volume: 100 μL
Column temperature: Hold at -60 ° C for 5 minutes, raise to 150 ° C at 50 ° C / min, hold for 2.8 minutes Mass spectrometry: "Q1000GC type" manufactured by JEOL Ltd.
Ionization method: Electron ionization method (70eV)
Scan range: m / Z = 10 to 500
Voltage: -1300V
Ion source temperature: 230 ° C
Interface temperature: 150 ° C

(2) Foam density A 20 cm square board was cut out from the phenol resin foam laminated board, the face material was removed, and the mass and apparent volume of the phenol resin foam were measured. The density (apparent density) was calculated according to JIS K 7222 using the obtained mass and apparent volume.

(3) Thermal Conductivity Measurement According to JIS A 1412-: 1999, the thermal conductivity of the phenolic resin foam in an environment of 23 ° C. was measured by the following method.
The phenolic resin foam laminated board was cut into 600 mm squares. The specimen obtained by cutting was placed in an atmosphere of 23 ± 1 ° C. and humidity of 50 ± 2%, and the change over time of the mass was measured every 24 hours, and the rate of change from the latest mass was 0.2% by mass or less. I kept that state until it became.
The heat conductivity of a 600 mm square phenolic resin foam laminate with a rate of change of 0.2% by mass or less from the latest mass was placed in the same environment after the face material was peeled off so as not to damage it. Introduced to the measuring device of.
The thermal conductivity was measured using a single test piece and a symmetrical configuration measuring device (Hideko Seiki Co., Ltd., trade name "HC-074 / 600"). The thermal conductivity in an environment of 23 ° C. was measured under the conditions of 13 ° C. for the low temperature plate and 33 ° C. for the high temperature plate.

(4) Average Bubble Diameter The average bubble diameter of the phenolic resin foam was measured by the following method with reference to the method described in JIS K 6402.
From the phenol resin foam laminate, the center of the phenol resin foam in the thickness direction was cut in parallel with the front and back surfaces of the phenol resin foam laminate, and a photograph was taken in which the cut cross section was magnified 50 times. Four straight lines with a length of 9 cm (corresponding to 1,800 μm in the actual foam cross section) were drawn at arbitrary positions in the obtained photographs, and the average value of the number of bubbles crossed by each straight line was calculated. The average bubble diameter is a value calculated by dividing 1,800 μm by the average value of the number of bubbles crossed.

(5) Closed cell ratio The measurement was carried out by the following method with reference to ASTM D 2856-94 (1998) A.
A cube piece of about 25 mm square was cut out from the central portion of the phenol resin foam in the phenol resin foam laminate in the thickness direction. When a thin piece having a uniform thickness of 25 mm could not be obtained, a piece having a uniform thickness was used by slicing the surface of a cube piece having a size of about 25 mm square by about 1 mm.
The length of each side was measured with a caliper, the apparent volume (V1: cm ³ ) was calculated, and the mass of the specimen (W: 4 significant digits, g) was measured. Subsequently, using an air pycnometer (Tokyo Science Co., Ltd., trade name "MODEL1000"), the closed space volume (V2: cm ³ ) of the specimen was measured according to the method described in Method A of ASTM D 2856.
In addition, the average bubble diameter (t: cm) was measured according to the above-mentioned average bubble diameter measuring method, and the surface area (A: cm ² ) of the sample was calculated from the length of each side of the sample.
From the obtained t and A, the opening volume (Va: cm ³ ) of the cut bubbles on the surface of the specimen was calculated from the following equation (4). The density of the solid phenol resin was 1.3 g / cm ³ , and the volume (Vs: cm ³ ) of the solid portion constituting the bubble wall contained in the sample was calculated from the following equation (5).
Va = (A × t) /1.14 ・ ・ ・ Equation (4)
Vs = W / 1.3 ・ ・ ・ Equation (5)
From the above results, the closed cell ratio was calculated by the following formula (6).
Closed cell ratio (%) = [(V2-Vs) / (V1-Va-Vs)] × 100 ・ ・ ・ Equation (6)
Foam samples under the same production conditions were measured 6 times, and the average value was used as a representative value.

(6) Limiting oxygen index (LOI)
The limiting oxygen index of the phenol resin foam was determined by the following method according to the measuring method C (JIS K 7201-2) of JIS A 9511-2017 6.13.3.
A test piece type II (10 mm × 10 mm × 150 mm) defined in JIS K7201-2 was cut out from the central portion in the thickness direction of the phenolic resin foam laminated plate. When the test piece contained a face material, the surface layer having a thickness of 1 mm including the face material was removed. The cut out test piece was cured in an atmosphere of 23 ° C. and a relative humidity of 50% for 88 hours or more until just before the test. The test was carried out using an AC type candle combustion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the limiting oxygen index was measured.

(7) Metsuke of face material The basis weight of the non-woven fabric used as a member of the phenolic resin foam laminated board is measured by the test method of "mass per unit area" specified in JIS L 1913: 2010 as it is. do.
When measuring the amount of texture of the non-woven fabric from the phenol resin foam laminated board, cut the non-woven fabric having the phenol resin foam from the phenol resin foam laminated board so that the number of places where only the phenol resin foam is reduced is as small as possible, and the non-woven fabric is used. Phenolic resin such as breaking the phenol resin foam entwined with the above by a physical method, immersing it in liquid nitrogen and freezing it, then breaking it by a physical method, immersing it in a solvent that dissolves and decomposes only the phenol resin foam, etc. The phenolic resin foam is removed by selecting an appropriate method according to the properties of the foam. If the adhesive etc. has penetrated into the non-woven fabric, break the adhesive etc. by a physical method, break it by a physical method after immersing it in liquid nitrogen and freezing it, dissolve / decompose only the adhesive etc. The adhesive or the like is removed by selecting an appropriate method according to the properties of the adhesive or the like, such as immersing it in a solvent. Then, the nonwoven fabric obtained from the phenol resin foam laminated board is measured by the test method of "mass per unit area" specified in JIS L 1913: 2010.
When the non-woven fabric of the phenol resin foam laminated board and the external member such as the wall surface are joined via an adhesive, and the adhesive has penetrated into the non-woven fabric, the phenol resin foam is formed. The non-woven fabric to which the adhesive is attached is cut from the composite so that the number of places where only the phenol resin foam is present is reduced and the number of places where only the adhesive is attached is reduced as much as possible. Phenol resin foaming, such as breaking the foam and adhesive by a physical method, immersing it in liquid nitrogen and freezing it and then breaking it by a physical method, or immersing it in a solvent that dissolves and decomposes only the phenol resin foam and / or the adhesive. The phenolic resin foam and the adhesive are removed by selecting an appropriate method according to the properties of the body and the adhesive, and then the non-woven fabric obtained from the composite is subjected to the "unit area" defined in JIS L 1913: 2010. The measurement is performed by the test method of "mass per hit".

(8) Fiber diameter of face material Among the means for measuring the denier of elastic fibers and multifilament fibers, the multifilament fibers are in accordance with JIS L 1013. For elastic fibers, denier (D) is measured by hanging the elastic fibers in a standard atmosphere with no load, measuring the yarn length (L: unit m), and measuring the mass (W: unit g). ) Is calculated from the following equation (7), this is performed 30 times, and the average value is taken as the fiber diameter of the fiber itself.
D = (W / L) × 9000 ・ ・ ・ Equation (7)
When measuring the denier of the elastic fiber, the length of the yarn length L is not particularly limited, but in order to obtain an accurate value, the length is preferably such that the elongation due to the weight effect of the elastic fiber is not affected, for example, 20 denier or more. For a yarn having a yarn length of about 40 denier, the yarn length L is preferably about 1 m.

(9) Evaluation Method for Suppressing Exudation of Foamable Phenol Resin Composition on the Surface of Phenol Resin Foam Laminated Plate A phenol resin foam laminated board was manufactured by stacking two face materials shown in Table 1 in advance. When the effervescent phenol resin composition exudes, the two face materials adhere to each other due to the exuded effervescent phenol resin composition at that location. The bonded part can be visually confirmed, and the bonded part is marked, and the bonded part and the non-bonded part generated per 1 m × 1 m (1 m ² ) are binarized, manufactured by Adobe Systems Incorporated, and the product name is “Photoshop”. The area of the bonded portion was calculated by processing with the image processing software of "(Registered Trademark)", and used as "the ratio of the exuding area of the foamable phenol resin composition from the face material".
It was very difficult to visually detect the effervescent phenolic resin composition exuded from the face materials without omission, but according to this method, the parts where the face materials adhere to each other are not adhered to each other. Because there is a clear difference, it is possible to detect the exuded part without leaking.

(10) Measurement and evaluation of adhesive strength of face material The adhesive strength was measured by the following procedure. First, in the central portion of the end of the phenolic resin foam laminated plate having a width of 60 cm and a length of 120 cm, six strip-shaped cuts of 3 cm in the width direction and 30 cm in the longitudinal direction are provided, and the end of the strip is peeled off by about 3 cm. , Grip it with a paper clip, connect it to a force gauge, and peel it off at a speed of about 1 cm / sec while keeping the peeling angle between the face material and the core material (phenol resin foam plate) at 90 degrees. Record the maximum value at that time, and use the average value of the measured values of 10 points excluding the lowest value and the highest value among the measured values of 12 points on the front and back of the laminated board, and use the face material of the laminated board. The adhesive strength between the core material and the core material (g / 3 cm width). A force gauge with a maximum load of 50 kg was used, and the measured value was rounded off to the nearest whole number. As the value of the adhesive strength, the average of the measured values of the five laminated plates was calculated, and the one obtained by rounding off the ones digit was adopted and evaluated according to the following evaluation criteria.
≪Evaluation criteria≫
◯: Excellent adhesive strength (400 g / 3 cm width or more)
Δ: Medium adhesive strength (120/3 cm width or more and less than 400 g / 3 cm width)
X: Adhesive strength is inferior (less than 120 g / 3 cm width)

(11) Amount of texture of face material after peeling Using the face material peeled from the phenol resin foam in the measurement and evaluation of the above-mentioned face material adhesive strength, the same face material having a width of 3 cm was cut into 10 cm, and the measured weight was obtained. Was divided by the area of the face material to calculate the amount of grain per 1 m ² . The average of the calculated values of the five samples was calculated and used as the basis weight of the face material after peeling.

(12) Surface appearance Initial appearance: Evaluation of the initial surface appearance seen from the surface of the phenolic resin foam laminated board immediately after production was made for 20 laminated boards having a thickness of 45 mm, a width of 1000 mm, and a length of 910 mm. The surface of the above was visually observed and evaluated according to the following evaluation criteria.
≪Evaluation criteria≫
◯: About 20 out of 20 phenol resin foam laminated boards, there were no exudation stains, wrinkles, or creases.
Δ: Exuding stains, wrinkles, or creases were observed in 1 to 2 out of 20 phenol resin foam laminated boards.
X: Exuding stains, wrinkles, or creases were observed in 3 or more of the 20 phenol resin foam laminated boards.
Appearance over time: The sample used for the initial appearance observation was left in an oven at 110 ° C. for 14 days, the surface was visually observed, and the sample was evaluated according to the following evaluation criteria.
≪Evaluation criteria≫
○: No discoloration of the surface ×: Discoloration of the surface

(13) Surface layer state of the phenol resin foam laminated board For the manufactured 20 laminated boards having a thickness of 45 mm, a width of 1000 mm, and a length of 910 mm, swelling generated near the surface layer of the phenol resin foam laminated board was visually observed and said. A notch was made in the bulge from the top with a cutter, and the one in which the cavity could be visually confirmed on the surface layer was defined as "bulging".
≪Evaluation criteria≫
◯: No swelling was observed on the surface layer of 20 out of 20 phenol resin foam laminated boards.
X: For at least one phenol resin foam laminated board out of 20 sheets, swelling was observed on the surface layer of the laminated board.

(14) Printability on the surface of the phenolic resin foam laminated board The number 8 was printed on the board surface with black ink using an inkjet printer. After cutting out a sample of vertical 5 cm and horizontal 3 cm square including the figure 8 with a cutter, a black-and-white copy of the portion was taken and binarized with image software to calculate the proportion of the black part.
≪Evaluation criteria≫
◯: Percentage of black part 20% or more Δ: Percentage of black part 15% or more, less than 20% ×: Percentage of black part less than 15%

(15) Adhesive strength measurement method at the time of construction From the manufactured laminated board having a thickness of 45 mm, a width of 1000 mm and a length of 910 mm, a 50 mm square sample was cut out by making a cut in the thickness direction method.
AZ ONE's HIGH POWER MIXER TORNADE with a 50 mm diameter pitched turbine type stirring blade added to 500 g of base coat (PAREX 121 BASE Coat & Adhesive, International Priority Projects) with 500 g of ordinary cement and 75 g of water. The mixture was stirred with SM101 at 500 rpm for 3 minutes. This mixture was applied on the upper and lower face materials in a range of 20 ± 5 kg / m ² and cured at 23 ° C. and 50% Rh for 3 days. According to JIS K6849: 1994, a metal tensile test jig (adhesive surface is a square of 50 mm x 50 mm) was adhered to the above-mentioned mixture-coated surface of the cured sample with an epoxy resin, and the temperature was 23 ° C. and 50% RH. After curing for 24 hours under the conditions, a tensile test was conducted in the thickness direction of the sample at a tensile speed of 3 mm / MIN at AUTO GRAPH AG-X PLUS (manufactured by Shimadzu Corporation), and the strength at break was taken as the tensile strength. .. The average value of the 5 sample measurements was taken as the adhesive strength at the time of construction.
≪Evaluation criteria≫
◯: Excellent adhesive strength (150 kPa or more)
Δ: Adhesive strength is medium (100 kPa or more and less than 150 kPa)
X: Adhesive strength is inferior (less than 100 kPa)

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
(Example 1)
<Synthesis of phenolic resin>
3500 kg of 52 mass% formaldehyde aqueous solution and 2510 kg of 99 mass% phenol were charged in the reactor, stirred by a propeller rotary stirrer, and the temperature of the internal liquid in the reactor was adjusted to 40 ° C. by a temperature controller. Then, the temperature was raised while adding a 50 mass% sodium hydroxide aqueous solution to proceed the reaction. 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 amount of formaldehyde charged) was added. Then, the reaction solution was cooled to 30 ° C., and the pH was neutralized to 6.4 with a 50% by mass aqueous solution of p-toluenesulfonic acid monohydrate. When the viscosity of the obtained reaction solution (phenol resin composition) was measured by dehydration treatment at 60 ° C., the viscosity at 40 ° C. was 6,000 mPa · s and the water content was 5% by mass.
<Preparation of effervescent phenol resin composition>
A block copolymer of ethylene oxide-propylene oxide as a surfactant (manufactured by BASF, product name "Pluronic (registered trademark) F-127" with respect to 96.5 parts by mass of the reaction solution after dehydration containing a phenol resin as a main component. ”) Was mixed at a ratio of 3.5 parts by mass.
10 parts by mass of a mixture of 1-chloro-3,3,3-trifluoropropene and 60% by mass of cyclopentane as a foaming agent with respect to 100 parts by mass of the obtained phenol resin composition containing a surfactant. As a curing agent, 11 parts by mass of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol was supplied to a mixing head whose temperature was adjusted to 25 ° C. to obtain a foaming phenol resin composition.
<Manufacturing of phenolic resin foam laminated board>
Asahi Kasei Corporation's Eltus E01030 polyester, which has a grain size of 30 g / m ² , a crimping portion density of 12 pieces / cm ² , a fiber diameter of about 1.8 denier, and a crimping portion handle, that is, an embossed pattern, as the upper and lower surface materials. (PET) Non-woven fabric was used.
The above-mentioned effervescent phenolic resin composition was supplied onto the moving lower surface material through the multi-port piping. The foamable phenol resin composition supplied on the bottom surface material is coated with the top surface material and at the same time sandwiched between the upper and lower surface materials and sent to a slat type double conveyor at 85 ° C. and cured with a residence time of 20 minutes. Then, it was cured in an oven at 110 ° C. for 3 hours to obtain a phenol resin foam laminated board having a thickness of 45 mm. At this time, the upper and lower face materials were pulled out from the face material roll so that the pulling force applied to the upper and lower face materials was 4 N / m. Further, the pressure applied to the slat plate was set to 8 kN / m ² . The upper and lower slat plates of the slat type double conveyor used at this time are provided with a plurality of circular through openings having a diameter of 5 mm with an opening ratio of 47% so that the moisture generated during curing can be discharged to the outside. Further, a flat portion having a length of 8 mm in the MD direction and having no opening extending in the TD direction was provided at an area ratio of 5%.
The obtained phenol resin foam laminated board was cut into a width of 1000 mm and a length of 910 mm to prepare the laminated board of Example 1.

(Examples 2 to 24)
Except that the foaming agent, the aperture ratio of the slat plate, the length / area ratio of the flat part of the slat plate in the MD direction, the type of the face material, the pressure applied to the slat plate, and the pull-out force of the face material were changed under the conditions shown in Table 1. Laminated plates of Examples 2 to 24 were produced in the same manner as in Example 1.

(Comparative Example 1)
A laminated board was produced in the same manner as in Example 3 except that the aperture ratio of the slat plate was 30% and a flat portion having a length of 160 mm in the MD direction and no opening extending in the TD direction was provided at a ratio of 40%. did.

(Comparative Example 2)
A laminated board was produced in the same manner as in Example 3 except that the length of the flat portion in the MD direction was set to 2.3 mm.

(Comparative Example 3)
A laminated board was produced in the same manner as in Example 3 except that the aperture ratio of the slat board was 22% and the area ratio of the flat portion was 55%.

(Comparative Example 4)
The laminated board was provided in the same manner as in Example 3 except that the aperture ratio of the slat plate was 49% and a flat portion having a length of 3 mm in the MD direction and no opening extending in the TD direction was provided at a ratio of 1.5%. Made.

(Comparative Examples 5 to 6)
A laminated board was produced in the same manner as in Example 3 except that the type of the face material was changed under the conditions shown in Table 1.

(Comparative Example 7)
A laminated board was produced in the same manner as in Example 3 except that the aperture ratio of the slat board was 14% and the area ratio of the flat portion was 63%.

As shown in the above results, the phenolic resin foam laminates of Examples 1 to 24 to which the present invention is applied have a sufficiently low thermal conductivity, excellent heat insulating properties, and a foamable phenolic resin composition on the surface. Exuding and peeling of the face material were suppressed, the surface was excellent in beauty, the printability of the serial number and the like was good, and the adhesive strength when applied to the wall surface of the building was excellent.
On the other hand, in the laminated boards of Comparative Examples 1, 3 and 7, cavities were generated in the surface layer portion of the laminated boards, and the adhesive strength at the time of construction was low. The laminated boards of Comparative Examples 2 and 4 had low adhesive strength at the time of construction, and the laminated boards of Comparative Example 5 had a large amount of exudation of the foamable phenol resin composition on the surface, and the surface appearance was poor. The laminated board of Comparative Example 6 had poor printability on the surface of the laminated board.
From these results, it was confirmed that by applying the present invention, a laminated board having excellent heat insulating properties and excellent surface beauty can be obtained.

Claims (6)

The foaming agent comprises at least one compound selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene, as described above. Phenol formaldehyde foam in which the total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is 30% by mass or more. A phenolic resin foam laminated board in which a face material is laminated on at least one side of the body.
The face material is a synthetic fiber non-woven fabric, the grain size is 20 g / m ² or more and 300 g / m ² or less, and the convex portion is 3% or more on the surface of the face material laminated portion at an area ratio of 15% or more and 80% or less. The length in the MD direction is 5 to 64 mm in an area ratio of 40% or less, the length in the MD direction is the same over the entire length in the TD direction, and a flat portion extending continuously between both ends in the TD direction is formed. A phenolic resin foam laminated board which is formed and has an area ratio of a flat portion of 3 to 50% . The foaming agent contains at least one compound selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene, as described above. Phenol formaldehyde foam in which the total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is 30% by mass or more. A phenolic resin foam laminated board in which a face material is laminated on at least one side of the body.
The face material is a synthetic fiber non-woven fabric, and the basis weight is 20 g / m. ² More than 300g / m ² Below, a convex portion is formed on the surface of the face material laminated portion at an area ratio of 15% or more and 80% or less, and a flat portion is formed at an area ratio of 2% or more and 50% or less.
The flat portion has a length of 5 to 64 mm in the MD direction, the length in the MD direction is the same over the entire length in the TD direction, and the phenol resin foam laminated plate extends continuously between both ends in the TD direction. .. The foaming agent contains at least one compound selected from the group consisting of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene, as described above. Phenol formaldehyde foam in which the total content of 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene in the foaming agent is 30% by mass or more. A phenolic resin foam laminated board in which a face material is laminated on at least one side of the body.
The face material is a synthetic fiber non-woven fabric, and the basis weight is 20 g / m. ² More than 300g / m ² The following is a flat portion having a convex portion on the surface of the face material laminated portion having an area ratio of 15% or more and 80% or less, and a flat portion having a length in the MD direction of 3 to 150 mm extending in the TD direction in an area ratio of 2% or more and 50% or less. Is formed,
The face material has a crimping portion, and the density of the crimping portion is 2 pieces / cm. ² More than 29 pieces / cm ² The following is a phenol resin foam laminated board. The phenolic resin foam laminated board according to claim 1 or 2 , wherein the face material has a crimping portion, and the density of the crimping portion is 2 pieces / cm ² or more and 29 pieces / cm ² or less. The phenolic resin foam laminate according to any one of claims 1 to 4, wherein the foaming agent contains a hydrocarbon and / or a halogenated saturated hydrocarbon. The process of pulling out the first face material from the face material roll with a force of 0.5 to 80 N / m,
A step of discharging a foamable phenol resin composition containing a phenol resin, a foaming agent, a surfactant, and a curing agent onto the first face material,
A second face material made of the same material as the first face material is pulled out from the face material roll with a force of 0.5 to 80 N / m so that the drawing speed becomes the same as that of the first face material. The step of superimposing on the effervescent phenol resin composition discharged on the face material of
A process of sandwiching a foaming phenol resin composition sandwiched between face materials by a slat type double conveyor provided with a plurality of holes in a slat plate forming a transport surface, and a process of sandwiching the foamable phenol resin composition.
The invention according to any one of claims 1 to 5 , further comprising a step of foaming and curing the effervescent phenol resin composition by setting the pressure applied to the slat plate of the slat type double conveyor to 2 kN / m ² to 20 kN / m ² . The method for producing a phenolic resin foam laminated board according to the above method.