JP6936080B2 - Foam resin laminated board - Google Patents

Description

The present invention relates to a foamed resin laminated board.

Laminated plates provided with a phenol resin foam layer are excellent in flame retardancy, heat resistance, chemical resistance, corrosion resistance, etc., and are therefore used in various fields as heat insulating materials. The aluminum foil layer may be used as a face material for improving flame retardancy and heat resistance at low cost.
In Patent Document 1, a phenol resin foam plate is provided as a heat insulating plate on the outdoor side of the structural facing material, an aluminum foil layer is provided on the outdoor side surface thereof, and a nonflammable copper upholstery and lightweight concrete are provided on the outdoor side. A heat insulating and fireproof outer wall structure with panels is described. In the embodiment, the aluminum foil layer is attached to the phenolic resin foam plate by tape.
Patent Document 2 describes a nonflammable heat insulating panel in which an aluminum foil coated with a resin for corrosion protection is laminated on one side or both sides of a phenol resin foam plate via a non-woven fabric or a woven fabric sheet.

Japanese Unexamined Patent Publication No. 2016-113823 Japanese Unexamined Patent Publication No. 2003-239417

However, in the case of a laminated plate in which a metal layer such as aluminum foil is laminated on a phenol resin foam plate as described in Patent Documents 1 and 2, the surface on the metal layer side is slippery, so that it is easy to handle and work. There is a problem that the sex is not good.
An object of the present invention is a foamed resin laminated board having a phenol resin foam layer and a metal layer and having good handleability and workability.

The present invention has the following aspects.
[1] A phenol resin foam layer and a surface layer provided on at least one surface of the phenol resin foam layer via a flexible surface material are provided, and the surface layer is coated with a metal layer or a protective film. It is a metal layer
A foamed resin laminated board having a slip resistance coefficient of 0.5 or more on the surface of the surface layer, as measured by a slipperiness test of JIS A 1454.
[2] The foamed resin laminated plate of [1], wherein two or more convex portions or concave portions are formed on the surface of the surface layer at intervals.
[3] The foamed resin laminated plate of [1] or [2], wherein two or more through holes are formed in the metal layer at intervals.

According to the present invention, a foamed resin laminated board having a phenol resin foam layer and a metal layer and having good handleability and workability can be obtained.

It is sectional drawing which shows typically the 1st aspect of this invention. It is sectional drawing which shows typically the 2nd aspect of this invention. It is sectional drawing which shows typically the 3rd aspect of this invention.

The foamed resin laminated board of the present invention (hereinafter, also simply referred to as a laminated board) has a flexible face material (hereinafter, also simply referred to as a face material) on at least one surface of the phenol resin foamed layer and the phenol resin foamed layer. ) Is provided with a surface layer. The surface layer is a metal layer or a metal layer coated with a protective film.
The slip coefficient of slip resistance measured by the slipperiness test of JIS A 1454 on the surface of the surface layer is 0.5 or more. When there is no protective film, the surface of the metal layer is the surface of the surface layer, and when there is a protective film, the surface of the protective film is the surface of the surface layer.
In the slipperiness test, if there is a difference in the value of the slip resistance coefficient depending on the direction in which the slip piece is slid on the test piece, measure at least in the TD direction (Transverse Direction) and the MD direction (Machine Direction), and 0.5 or more in both directions. Means that
When the slip resistance coefficient is 0.5 or more, it becomes difficult to slip and the handleability and workability are improved. The slip resistance coefficient is preferably 0.8 or more, more preferably 1.0 or more. Even if the surface layer surface is processed to increase the slip resistance coefficient, the surface layer itself will not follow and problems such as tearing will occur in the surface layer. Therefore, the slip resistance coefficient is preferably 2.0 or less, preferably 1.5 or less. More preferred.
The absolute value of the difference between the slip resistance coefficient in the TD direction and the slip resistance coefficient in the MD direction is preferably 0 to 0.6, more preferably 0 to 0.4.

The slip coefficient of slip resistance on the surface of the surface layer can be increased by forming protrusions or recesses on the surface of the surface layer at intervals. The distance between the convex portion or the concave portion does not have to be constant, but the distance between the convex portion or the concave portion is constant in the TD direction and the MD direction in that the difference in the slip resistance coefficient between the TD direction and the MD direction tends to be small. Is preferable. Further, it is preferable that the shape and size of the convex portion or the concave portion are uniform.

Further, the slip resistance coefficient on the surface of the surface layer can be increased by forming through holes in the metal layer at intervals. When the metal layer is covered with a protective film, the protective film and the metal layer may be provided with through holes at once, and the through holes are provided only in the metal layer, and the protective film has irregularities that follow the through holes. May be formed. The spacing between the through holes does not have to be constant, but it is preferable that the spacing between the through holes is constant in the TD direction and the MD direction in that the difference in slip resistance coefficient between the TD direction and the MD direction tends to be small. Further, it is preferable that the shape and size of the through holes are uniform.

<First aspect>
FIG. 1 is a cross-sectional view schematically showing the laminated board of the first aspect.
In the laminated board of this embodiment, a metal layer 3 is provided on one surface of a plate-shaped phenol resin foam layer 1 via a flexible surface material 2. A flexible face material 2'is provided on the other surface of the phenol resin foam layer 1, and a metal layer is not laminated on the face material 2'. In this example, the face material 2'is the same as the face material 2 except that the convex portion 2b is not formed.

The face material 2 is integrated with the phenol resin foam layer 1 without interposing an adhesive layer. Specifically, the phenol resin foam layer 1 and the face material 2 are bonded to each other by the adhesive force when the face material 2 is thermally cured in the state of being laminated on the phenol resin foam layer 1. The face material 2 and the metal layer 3 are bonded to each other via an adhesive layer (not shown).
Reference numeral 1a is a joint surface 1a of the phenol resin foam layer 1 with the face material 2. In the present specification, the "bonding surface of the phenol resin foam layer with the flexible surface material" refers to the surface that becomes the surface of the phenol resin foam layer when the flexible surface material is peeled from the phenol resin foam layer. means.
In this embodiment, the joint surface 1a has a convex portion 1b, and the surface 2a on the metal layer 3 side of the face material 2 and the surface 3a of the metal layer 3 have convex portions 2b and 3b following the joint surface 1a, respectively. Have. The surface 3a of the metal layer 3 is the outermost surface of the laminated board.

In this embodiment, the convex portion 2b is discontinuous, and the concave portion 2d exists between the adjacent convex portions 2b. The rising portion 2c of the convex portion 2b means a set of points where the ridge line from the concave portion 2d between the adjacent convex portions 2b to the apex of the convex portion 2b is substantially separated from the bottom surface of the concave portion 2d. Such points are the ridgeline of the central convex portion 2b (the line formed by the surface 2a of the face member 2) when cut in the thickness direction in a cross section including a straight line passing through the vertices of the three adjacent convex portions 2b. This is a point where the bottom surfaces of the concave portions 2d existing on the left and right of the central convex portion 2b come into contact with each other.
In this embodiment, the bottom surface of the recess 2d may have fine irregularities due to the fibers of the face material 2 or embossing, but the height is lower than the thickness T of the face material 2, or the depth is thick. Recesses smaller than T shall be ignored.
In this embodiment, the plan view shape of the convex portion 2b is the shape of the region surrounded by the rising portion (outer edge) 2c of the convex portion 2b.
In the present specification, the plan view shape means a shape when the line of sight is perpendicular to the surface 2a of the face material 2.
The plan view shape of the convex portion 2b can be a polygonal shape such as a quadrangle or a hexagon, a circular shape such as a perfect circle shape, an elliptical shape, or an oval shape.

The apex of the convex portion 2b can be the highest portion when the laminated plate is placed on a horizontal support and the height is measured by a laser displacement meter. Alternatively, the surface can be observed with an optical microscope and then depth-analyzed, and the highest portion in the observed portion can be set as the apex.
The width W of the convex portion 2b means the longest portion of the distance between the two points of the straight line intersecting the plan view shape of the convex portion 2b. For example, when the plan view shape of the convex portion 2b is a perfect circle, the diameter is the width, and when the convex portion 2b is a regular quadrangle, the diagonal length is the width.

The size of the convex portion 2b on the surface 2a of the face material 2 is preferably such that the height H of the convex portion 2b is 0.01 to 3 mm and the width W of the convex portion 2b is 1 to 20 mm. The height H of the convex portion 2b is preferably larger than the thickness T of the face material 2.
When the height H of the convex portion 2b is at least the lower limit of the above range, the effect of making the surface of the metal layer less slippery is excellent. When it is not more than the upper limit value, it is easy for the metal layer to follow the shape of the convex portion 2b.
When the width W of the convex portion 2b is within the above range, the effect of making the surface of the metal layer less slippery is excellent.

The distance D between the adjacent convex portions 2b (the distance from the rising portion 2c of the convex portion 2b to the rising portion 2c of the adjacent convex portion 2b) is preferably 0.01 to 4.00 mm.
When the distance D between the adjacent convex portions 2b is within the above range, the effect of making the surface of the metal layer less slippery is excellent.
Further, by reducing the distance D between the adjacent convex portions 2b, the bite of the face material 2 on the joint surface 1a of the phenol resin foam layer 1 and the bite of the metal layer 3 on the surface 2a of the face material 2 are increased, and the phenol is increased. The adhesiveness between the resin foam layer 1, the face material 2, and the metal layer 3 can be further improved.

The convex area ratio on the surface of the face material 2 is preferably 15% or more and 80% or less. Here, the convex portion area ratio is the ratio of the total area of the convex portion 2b to the total area of the face material 2 in the laminated board, and is expressed by the following equation.
The area of the convex portion 2b means the area of the convex portion 2b in a plan view shape. As the unit area in the formula, the area of the test piece cut out from an arbitrary position of the laminated plate to a length of 5 cm × width of 5 cm and the metal layer 3 was peeled off was set to 25 cm ^2, and the convex area ratio per unit area was laminated. It is the ratio of the convex portion area of the face material 2 to the entire plate.
Convex area ratio (%) = {(Area of multiple convex parts existing per unit area) / (Unit area)} x 100 [%]

In order to reduce the distance D between the adjacent convex portions 2b and improve the adhesiveness between the phenol resin foam layer 1, the face material 2 and the metal layer 3.
The convex area ratio is more preferably 20 to 75%, further preferably 25 to 70%, and particularly preferably 30 to 60%.
When it is at least the lower limit of the above range, the effect of making the surface of the metal layer less slippery is excellent. Further, when it is within the above range, the effect of improving the adhesiveness between the phenol resin foam layer 1, the face material 2 and the metal layer 3 is excellent.

When the convex portion 2b has a perfect circular shape in a plan view, the width W (diameter) is preferably 1 mm or more and 10 mm or less, and more preferably 5 mm or more and 8 mm or less.
For example, the surface shape of the convex portion 2b is a part of a spherical surface, the height H of the convex portion 2b is 0.05 mm to 1 mm, and the plan view shape of the convex portion 2b is a substantially hemispherical surface having a diameter of 1 to 10 mm. Can be.

In this embodiment, when a fine uneven pattern (not shown) is formed on the surface 2e of the face material 2 on the phenol resin foam layer 1 side by embossing, the adhesiveness between the face material 2 and the phenol resin foam layer 1 is formed. Is preferable in that
The pattern (pattern) of the uneven pattern by embossing is not particularly limited, and examples thereof include a minus pattern, a point pattern, and a crease pattern. A crease pattern is preferable because it has a large uneven pattern and has a large effect of improving adhesiveness.
As a method of embossing the synthetic fiber non-woven fabric, for example, a method of partially heat-bonding a crimped long fiber web developed under cooling conditions directly under the spun by a known spunbond method with a thermal embossing roll, or a latent winding method. Examples thereof include a method in which the expanded fiber web is crimped by heat treatment and partially heat-bonded by a thermal embossing roll.

Preferably area per one place of the thermocompression bonding part is 0.05~5.0mm ^2, more preferably 0.07~3.0mm ^2. When it is at least the lower limit of the above range, it is excellent in suppressing the exudation of the phenol resin in the thermocompression bonding portion. When it is not more than the upper limit of the above range, the texture is not too hard and the effect of improving the adhesiveness of the phenol resin foam layer is excellent.
The minimum distance between the thermocompression bonding portions is preferably 0.05 to 5 mm, more preferably 0.08 to 2 mm. Within the above range, the texture is not too hard, and the effect of improving the adhesiveness of the phenol resin foam layer is excellent. The thermocompression bonding portions are preferably evenly distributed over the entire surface of the non-woven fabric.
Thermocompression bonding part density is preferably from 5 to 200 pieces / cm ^2, more preferably 6 to 150 pieces / cm ^2. The thermocompression bonding part density means the number of thermocompression bonding parts per unit area, and is expressed by the following equation.
Thermocompression bonding part density (pieces / cm ² ) = number of thermocompression bonding parts (pieces) / surface area of face material (cm ² )
When the thermocompression bonding portion density is within the above range, it is possible to improve the adhesiveness with the phenol resin foam layer while suppressing the exudation of the phenol resin by the thermocompression bonding portion.
The depth of the recess (that is, the recess formed by thermocompression bonding by thermocompression bonding or the like) of the thermocompression bonding portion is preferably 0.01 to 1.0 mm. If the depth is less than 0.01 mm, the thermocompression bonding portion tends to be less bonded, and if it exceeds 1.0 mm, processing by embossing roll or the like tends to be difficult.

[Manufacturing method of laminated board]
In the laminated board of this embodiment, the foamable phenol resin composition is foamed and cured on the face material 2, and the phenol resin foam layer 1 is embossed before the foamable phenol resin composition is completely cured. A convex portion is simultaneously formed on the joint surface 1a between the face material 2 and the surface material 2 and the surface 2a on the metal layer 3 side of the face material 2 to produce a foam with a face material, and the surface of the obtained foam with a face material is produced. It can be manufactured by providing a metal layer on the material.
The effervescent phenol resin composition is prepared, for example, by supplying a phenol resin, a foaming agent, an acid catalyst and, if necessary, an arbitrary component to a mixer or the like and mixing them.
The mixing order of each component is not particularly limited, but for example, an arbitrary component is added to the phenol resin as needed and mixed, and a foaming agent and an acid catalyst are added to the obtained mixture.

The method of foaming and curing the effervescent phenol resin composition on the face material 2 can be performed by using a known foam molding method.
For example, a manufacturing system including a discharge device, a foam molding device arranged on the downstream side of the discharge device, and a cutting device arranged on the downstream side of the foam molding device is used.
The discharge device includes a mixing unit for mixing raw materials such as phenol resin, and a plurality of nozzles arranged along a direction orthogonal to the flow direction for discharging the mixed raw materials (foamable phenol resin composition). To be equipped with.
The foam molding apparatus includes a frame portion and heating means. The frame portion includes conveyors (lower conveyor, upper conveyor, left conveyor, right conveyor) arranged vertically and horizontally so as to form a space corresponding to the shape of the foam with face material. The lower and upper conveyors regulate vertical foaming, and the left and right conveyors regulate horizontal foaming. The effervescent phenolic resin composition that passes through the frame portion is heated, foamed, and cured by the heating means. Examples of such a foam molding apparatus include those described in JP-A-2000-218635.

In this manufacturing system, first, the first face material 2'is continuously supplied between the discharge device and the foam molding device. In the discharge device, the effervescent phenol resin composition is discharged from a plurality of nozzles onto the first face material 2'. The second face material 2 is placed on it, introduced into the frame portion of the foam molding apparatus, and heated at 30 to 95 ° C. As a result, the foamable phenol resin composition is foamed and cured between the first face material 2'and the second face material 2, and a foam with a face material is formed. The foam with the face material is taken out from the foam molding apparatus, the metal layer 3 is laminated on the surface of the second face material 2 via an adhesive layer (not shown), and the foam is cut to an arbitrary length by the cutting apparatus. As a result, a laminated board can be obtained.

When producing a foam with a face material, as a method of forming a convex portion by embossing before the foamable phenol resin composition is completely cured, for example, as a foam molding apparatus, Japanese Patent No. 3837226, Japanese Patent Application Laid-Open No. A method of providing a concave portion corresponding to a convex portion to be formed on the transport surface of the upper conveyor by using the device provided with the slat type double conveyor described in Japanese Patent Application Laid-Open No. 2000-218635 can be mentioned. When the foamable phenol resin composition foams between the first face material 2'and the second face material 2 in the frame portion of the foam molding apparatus, the first face material 2'is placed on the transport surface of the lower conveyor. It is pressed, and the second face material 2 is pressed against the transport surface of the upper conveyor. At this time, the second face material 2 is formed with a convex portion 2b embossed on the transport surface having a concave portion, and the convex portion 1a following the joint surface 1a of the phenol resin foam layer 1 with the face material 2 is also formed. Part 1b is formed.
Alternatively, a method of pressing a plate (pushing die) having a recess against the surface of the foam with a face material (the surface 2a of the second face material 2) immediately after being discharged from the foam molding apparatus and before being completely cured (a method). For example, a method of providing a concave portion on the transport surface of the second double conveyor described in Japanese Patent No. 3837226 and embossing with the transport surface to form a convex portion) can be mentioned.
Further, for example, in the manufacturing method including the foam curing step and the post-curing step described in Japanese Patent Application Laid-Open No. 2015-151484, a recess is provided on the surface of the spacer that separates the laminated plates in the post-curing step, and the surface of the spacer is used. A convex portion may be formed on the surface of the foam with a face material (the surface 2a of the second face material 2) by embossing.

The face materials 2 and 2'are used by being pulled out from a state in which they are wound in a roll shape with respect to a cylindrical core called a winding core, and are wound by applying a winding tension when winding.
If the pull-out tension applied to the face material when it is pulled out and used is too large, the fibers may be torn off. Further, when the surface of the face material is provided with an uneven pattern by embossing, if the pull-out tension is too large, the uneven pattern may be damaged or the thermocompression bonding portion may be peeled off. On the other hand, if the pull-out tension is too small, in the case of a slat type double conveyor, the face material may be caught between the slats and become wrinkled, or the face material may meander and crease.
Therefore, the 20 pull-out tension of the face material 2 is preferably 0.5 to 80 N / m, more preferably 1 to 60 N / m.
To adjust the pull-out tension of the face material, the face material is pulled out from the non-woven roll via the tension adjusting roller, and the position of the tension adjusting roller is moved, or a motor or powder clutch is used on the tension adjusting roller. The pull-out tension can be adjusted to a desired value by controlling the roller rotation with a tension controller, and the torque itself generated during these adjustments and the voltage required to control the motor and clutch are converted into torque. By doing so, the pull-out tension can be measured.

The method of providing the metal layer on the face material 2 of the foam with the face material can be carried out by a method of attaching the metal layer 3 on the surface 2a of the face material 2 using an adhesive. Specifically, an adhesive is applied on the surface 2a of the face material 2, the metal layer 3 is laminated on the surface material 2, and the metal layer 3 is applied to the face material 2 from above the metal layer 3 by using a thermal laminate roll or the like. Adhere by applying pressure in the pressing direction. Alternatively, using a sheet in which a metal layer and an adhesive sheet such as a polyethylene film are laminated in advance, the sheet and the face material 2 are pressed against the face material 2 from above the metal layer 3 via the adhesive sheet. Adhesion may be applied by applying directional pressure. If the pressure at this time is too small, the metal layer 3 cannot sufficiently follow the unevenness of the surface 2a of the face material 2, and if it is too large, the unevenness of the joint surface 1a and the surface 2a of the face material 2 is crushed and convex. The height of the part becomes insufficient. From this point of view, the pressure applied to the metal layer 3 is preferably 0.01 to 8 MPa, more preferably 0.05 to 5 MPa.
A known adhesive can be used as the adhesive for integrating the face material 2 and the metal layer 3. Examples thereof include urethane adhesives, modified silicone resin adhesives, epoxy resin adhesives, acrylic resin adhesives, vinyl acetate resin adhesives, chloroprene resin adhesives, polyethylene films, polypropylene films and the like.

The ratio of the area covered by the metal layer 3 (coverage of the metal layer) to the area (100%) of the surface 2a of the face material 2 is preferably 90% or more, more preferably 95% or more, and 98% or more. More preferably, 100% is particularly preferable. If it is at least the above lower limit value, the flame retardancy of the laminated board can be further improved.

In the laminated board of this embodiment, since the metal layer 3 on the outermost surface has the convex portion 3b, the slip resistance coefficient is high, the slip is hard, and the handleability and workability are excellent.
Since the convex portion 3b of the metal layer 3 follows the convex portion 2b of the surface 2a of the face material 2, the slip resistance coefficient of the surface 3a of the metal layer 3 is larger than that of the convex portion 2b of the surface 2a of the face material 2. It can be adjusted by the coefficient (height H, width W) and the abundance density. The height H, width W, distance D between adjacent convex portions 2b, and the like of the convex portion 2b of the face material 2 can be measured by peeling the metal layer 3 from the laminated plate.
Further, the metal layer 3 is in close contact with the surface 2a of the face material 2, and the convex portion 3b of the metal layer 3 follows the convex portion 2b of the surface 2a of the face material 2. Therefore, the metal layer 3 bites into the concave portion 2d between the adjacent convex portions 2b of the face material 2, and the adhesiveness between the face material 2 and the metal layer 3 is improved.
Further, in this embodiment, the convex portion 2b of the face material 2 follows the convex portion 1b of the joint surface 1a of the phenol resin foam layer 1. Therefore, the face material 2 bites into the concave portion between the adjacent convex portions 1b of the phenol resin foam layer 1, and the adhesiveness between the phenol resin foam layer 1 and the face material 2 is improved.

<Second aspect>
FIG. 2 is a cross-sectional view schematically showing the laminated board of the second aspect.
In the laminated board of this embodiment, a metal layer 13 is provided on one surface of a plate-shaped phenol resin foam layer 11 via a flexible face material 12. A flexible face material 12'is provided on the other surface of the phenol resin foam layer 11, and a metal layer is not laminated on the face material 12'. The face material 12'is preferably the same as the face material 12 except that the recess 12b is not formed.
The face material 12 is integrated with the phenol resin foam layer 11 without interposing an adhesive layer. The face material 12 and the metal layer 13 are bonded to each other via an adhesive layer (not shown).
In this embodiment, the surface 12a of the face material 12 on the metal layer 13 side has a recess 12b, and the surface 13a of the metal layer 13 has a recess 13b that follows the recess 12b of the face material 12. The surface 13a of the metal layer 13 is the outermost surface of the laminated board. Reference numeral 11a is a joint surface of the phenol resin foam layer 11 with the face material 12.
In this embodiment, the recess 12b provided in the face material 12 which is a synthetic fiber non-woven fabric is a thermocompression bonding portion by embossing. The method of embossing the synthetic fiber non-woven fabric is, for example, a method of partially heat-bonding a crimped long fiber web developed under cooling conditions directly under the spun with a heat embossing roll by a known spunbond method, or latent crimping. Examples thereof include a method in which a long fiber web is crimped by heat treatment and partially heat-bonded by a thermal embossing roll.

Preferably the area of the recess 12b in the surface 12a of the face plate 12 (the area of one concave portion) is 0.05~5.0mm ^2, more preferably 0.07~3.0mm ^2. When it is at least the lower limit of the above range, the effect of making the surface of the metal layer less slippery is excellent. In addition, it is excellent in suppressing exudation of phenol resin in the thermocompression bonding portion. When it is not more than the upper limit of the above range, the texture is not too hard and the effect of improving the adhesiveness of the phenol resin foam layer is excellent.
The plan view shape of the recess 12b is not particularly limited, but may be a polygonal shape such as a quadrangle or a hexagon, or a circular shape such as a perfect circle, an ellipse, or an oval. Here, the plan view shape of the recess 12b means a case where the line of sight is perpendicular to the surface 12a of the face material 12.
In this embodiment, the recesses 12b are discontinuous, and the protrusions 12d exist between the adjacent recesses 12b.
The depth of the recess 12b (that is, the depth of the recess formed by thermocompression bonding by thermal embossing roll processing or the like) is preferably 0.01 to 1.0 mm. If the depth is less than 0.01 mm, the thermocompression bonding portion tends to be less bonded, and if it exceeds 1.0 mm, processing by embossing roll or the like tends to be difficult.

Preferably heat bonding portions density at the surface of the surface member 12 is 5 to 200 pieces / cm ^2, more preferably 6 to 150 pieces / cm ^2. The thermocompression bonding part density means the number of thermocompression bonding parts per unit area, and is expressed by the following equation.
Thermocompression bonding part density (pieces / cm ² ) = number of thermocompression bonding parts (pieces) / surface area of face material (cm ² )
When the thermocompression bonding partial density is at least the lower limit of the above range, the foamable phenol resin composition is less likely to seep out from the face material 12, and the effect of improving the adhesiveness between the face material 12 and the metal layer 13 is excellent. When it is not more than the upper limit of the above range, the effect of making the surface of the metal layer 13 less slippery is excellent.

In the method for producing a laminated board of this embodiment, a face material 12 having a recess 12b formed on one surface in advance is used as either the first face material or the second face material, and the first face material or the second face material is used. The phenol resin composition is foamed and cured between the face materials to form the phenol resin foam layer 11 to obtain a foam with a face material. At this time, the phenol resin composition is foamed and cured on the surface of the face material 12 on the side where the recess 12b is not formed. Next, a laminated plate is obtained by providing the metal layer 13 on the surface of the obtained foam with a face material on the side where the recess 12b of the face material 12 is formed.
The method of foaming and curing the effervescent phenol resin composition between the first face material and the second face material can be carried out by using a known foam molding method.
The method of providing the metal layer 13 on the face material of the foam with face material is the same as that of the first aspect.

In the laminated board of this embodiment, since the metal layer 13 on the outermost surface has the recess 13b, the slip resistance coefficient is high, the slip is hard to slip, and the handleability and workability are excellent.
Since the recess 13b of the metal layer 13 follows the recess 12b of the surface 12a of the face material 12, the slip resistance coefficient of the surface 13a of the metal layer 13 is the size (area) of the recess 12b of the surface 12a of the face material 12. ), It can be adjusted by the abundance density (thermocompression bonding partial density). The area of the recess 12b of the face material 12 can be measured by peeling the metal layer 13 from the laminated plate.
Further, the metal layer 13 is in close contact with the surface 12a of the face material 12, and the recess 13b of the metal layer 13 follows the recess 12b of the surface 12a of the face material 12. Therefore, the metal layer 13 bites into the recess 12b of the face material 12, and the adhesiveness between the face material 12 and the metal layer 13 is improved.

In the example of FIG. 2, the recess 12b is provided only on the surface 12a of the face material 12 on the metal layer 13 side, but the surface 12e of the face material 12 on the phenol resin foam layer 11 side is also the same as in the first aspect. May be provided with a fine uneven pattern by embossing.
Further, in the example of FIG. 2, the recess 12b on the surface 12a of the face material 12 is a thermocompression bonding portion by embossing, but the recess 12b may be formed by a method other than embossing.
For example, when a woven fabric is used as the face material 12, the same effect can be obtained by forming the space portion surrounded by the warp and weft of the face material 12 in which no fiber exists as the recess 12b.

<Third aspect>
FIG. 3 is a cross-sectional view schematically showing the laminated board of the third aspect.
In the laminated board of this embodiment, a metal layer 23 is provided on one surface of a plate-shaped phenol resin foam layer 21 via a flexible surface material 22. A flexible face material 22'is provided on the other surface of the phenol resin foam layer 21, and a metal layer is not laminated on the face material 22'. The face material 22'is preferably the same as the face material 22.
The face material 22 is integrated with the phenol resin foam layer 21 without interposing an adhesive layer. The face material 22 and the metal layer 23 are bonded to each other via an adhesive layer (not shown).
Reference numeral 22a is a surface of the face material 22 on the metal layer 23 side, and reference numeral 21a is a joint surface of the phenol resin foam layer 21 with the face material 22.

In this embodiment, the metal layer 23 is formed with a plurality of through holes 24. By providing the through hole 24, the slip resistance coefficient of the surface 23a of the metal layer 23 can be increased.
The plan view shape of the through hole 24 is, for example, a circle such as a perfect circle or an ellipse; a triangle such as an isosceles triangle or an equilateral triangle; a quadrangle such as a rectangle, a square or a diamond; a polygon such as a pentagon; a polygon such as a hexagon; a slit or the like. Can be mentioned.
The plan-view shapes of all the through holes 24 may be the same or different from each other. The opening areas of all the through holes 24 may be the same or different from each other.
Among the above-described plan shapes of the through holes 24, a circular shape having no corners or a polygonal shape having no acute corners is preferable, and a circular shape is more preferable, because it is easy to prevent the metal layer 23 from being torn due to expansion.
When the plan view shape is a slit, the length of the slit in the lateral direction is set to 0.05 mm for convenience, and the opening area per slit is adjusted by adjusting the length in the longitudinal direction of the slit. Further, when the plan view shape is a triangle, a quadrangle, or a polygon, each side does not have to be a straight line.
The size of each through hole 24 in plan view is 0.01 to ² mm in length in the TD direction, 0.01 to 2 mm in length in the MD direction, and 0.00008 to 3.2 mm 2 in area. Is preferable, and more preferably, the length in the TD direction is 0.5 to 1.5 mm, the length in the MD direction is 0.5 to 1.5 mm, and the area is 0.19 to 2.6 mm ² .
When the size of the plan view shape of each through hole 24 is equal to or larger than the lower limit of the above range, the effect of increasing the slip resistance coefficient of the surface 23a of the metal layer 23 is excellent. When it is not more than the upper limit of the above range, the radiant heat reflection effect and the flame retardancy improving effect are excellent.

The arrangement pattern of the through holes 24 is not particularly limited. In this example, the distance p (pitch) between the center of any through hole 24 and the center of the other through hole 24 closest to the center is all equal (that is, a plurality of through holes 24 are regularly arranged. There is). Here, "equal to" the distance p means that the distance is within p ± 10%.
The distance p is, for example, preferably 1 mm or more and 50 mm or less, and more preferably 5 mm or more and 25 mm or less. When the distance p is equal to or greater than the above lower limit value, the effect of increasing the slip resistance coefficient of the surface 23a of the metal layer 23 is excellent. When the distance p is not more than the above upper limit value, the radiant heat reflection effect and the flame retardancy improving effect are excellent.

The opening ratio of the metal layer 23 is 0.001% or more and 0.5% or less, preferably 0.008% or more and 0.35% or less, and more preferably 0.011% or more and 0.2% or less. When the opening ratio is at least the above lower limit value, the effect of increasing the slip resistance coefficient of the surface 23a of the metal layer 23 is excellent. When the opening ratio is not more than the above upper limit value, the radiant heat reflection effect and the flame retardancy improving effect are excellent.
The opening ratio is a value obtained by the following equation (1). The "area of the metal layer" includes the opening area of the through hole 24.
Opening ratio (%) = (total area of through holes in the measurement area) ÷ (area of metal layer in the measurement area) x 100 ... (1)
For example, an arbitrary area of a square of 10 cm × 10 cm is used as a measurement area. This measurement area is observed with a microscope (× 10 to 100 times), and the opening area of the through hole 24 is measured. The opening ratio is obtained by dividing ^{the total of the opening areas (cm 2} ) of all the through holes 24 in the measurement area by the area of the measurement area (100 cm ^2).

In the method for producing a laminated board of this embodiment, the phenol resin composition is foamed, cured and cured between the face material 22 and the face material 22'to form a phenol resin foam layer 21 to obtain a foam with a face material. .. Next, a laminated plate is obtained by providing the metal layer 23 on the surface 22a of the face material 22 of the obtained foam with the face material.
The method of foaming and curing the effervescent phenol resin composition between the face materials can be performed by using a known foam molding method.
In the metal layer forming step, for example, a metal foil having a through hole 24 formed in advance is attached to the surface 22a of the face material 22 via an adhesive. At this time, it is preferable not to apply the adhesive to the position corresponding to the through hole 24 on the surface 22a of the face material 22. By not having an adhesive at the position of the through hole 24, the moisture permeability of the laminated board is further improved.
Alternatively, a metal foil in which the through hole 24 is not formed may be attached onto the face material 22, and then the through hole 24 may be formed.
Specifically, an adhesive is applied on the surface 22a of the face material 22, a metal foil is laminated on the surface material 22, and pressure is applied from above the metal foil in a direction of pressing the metal foil against the face material 22 to bond them. The pressure at this time is preferably 0.01 to 8 MPa, more preferably 0.05 to 5 MPa.

Since the metal layer 23 on the outermost surface of the laminated board of this embodiment has a through hole 24, the laminated board has a high slip resistance coefficient, is hard to slip, and is excellent in handleability and workability.

The metal layer 23 of the present embodiment may be used instead of the metal layer 3 of the first aspect, and the slip resistance coefficient of the surface of the metal layer can be further increased.
Further, the metal layer 23 of the present embodiment may be used instead of the metal layer 13 of the second aspect, and the slip resistance coefficient of the surface of the metal layer can be further increased.

The following description is common to the first to third aspects unless otherwise specified.
[Phenol resin foam layer]
A plurality of bubbles are formed in the phenol resin foam layer, and there are substantially no pores in the bubble wall, and at least a part of the plurality of bubbles is closed cells that do not communicate with each other. .. The bubble wall is composed of a cured product of phenol resin. The gas in the bubbles is a gas derived from a foaming agent.
The phenol resin foam layer is preferably formed by foaming and curing a foamable phenol resin composition containing, for example, a phenol resin, a foaming agent, an acid catalyst, and a surfactant. If necessary, the effervescent phenol resin composition may further contain other components other than the phenol resin, the effervescent agent, the acid catalyst and the surfactant, as long as the effects of the present invention are not impaired.

As the phenol resin, a resole type is preferable.
The resole-type phenol resin is a phenol resin obtained by reacting a phenol compound and an aldehyde in the presence of an alkaline catalyst.

The foaming agent is not particularly limited, and known chemical foaming agents such as hydrocarbons such as isopentane and cyclopentane and halogenated saturated hydrocarbons such as HFC365mfc and 2-chloropropane; porous solid materials and the like can be used. The foaming agent may be used alone or in combination of two or more.
The foaming agent preferably contains a halogenated unsaturated hydrocarbon.
Halogenated unsaturated hydrocarbons have a lower thermal conductivity than non-halogenated hydrocarbons such as isopentan. When the phenol resin foam layer contains a halogenated unsaturated hydrocarbon, the thermal conductivity of the phenol resin foam layer is lowered and the heat insulating property is enhanced.
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 layer is enhanced.

The halogenated unsaturated hydrocarbon may be one in which all hydrogen atoms are substituted with halogen, or one in which some hydrogen atoms are substituted with halogen.
Examples of chlorinated fluorinated unsaturated hydrocarbons include 1,2-dichloro-1,2-difluoroethane (E and Z isomers) and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (HCFO-1233zd). E and Z isomers), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) (E and Z isomers), 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 (HFO-1223xd) ( E and Z isomers), 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and Z isomers), and 2-chloro-1,1,1,3, 4,4,4-Heptafluoro-2-butene (E and Z isomers) and the like can be mentioned.

When the foaming agent contains a halogenated unsaturated hydrocarbon, it is more preferable to further contain a hydrocarbon.
When the foaming agent contains a hydrocarbon, it is possible to prevent the viscosity of the foamable phenol resin composition from becoming too low, and it is easy to suppress the exudation of the face material to the surface.
As the hydrocarbon, a known foaming agent can be used, and a hydrocarbon having a boiling point of -20 to 50 ° C. is preferably used. Those having a cyclic molecular structure having 4 to 6 carbon atoms or a chain molecular structure having 4 to 6 carbon atoms are preferable, and examples thereof include isobutane, normal butane, cyclobutane, normal pentane, isopentane, cyclopentane, and neopentane.

When the foaming agent contains a halogenated unsaturated hydrocarbon and a hydrocarbon, the mass ratio represented by the halogenated unsaturated hydrocarbon: hydrocarbon is preferably 1: 9 to 9: 1, and is preferably 3: 7 to 7. : 3 is more preferable, and 4: 6 to 6: 4 is even more preferable.
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 layer 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 of the face material 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.

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. If it is less than the above lower limit, the degree of foaming of the foamable phenol resin composition may be insufficient, and the heat insulating property of the phenol resin foam plate may be lowered. If it exceeds the above upper limit, the degree of foaming of the foamable phenol resin composition may be too high, and the strength of the phenol resin foam plate may decrease.

The thickness of the phenol resin foam layer is determined in consideration of the heat insulating property required for the laminated board and the like. For example, 10 to 200 mm is preferable, 20 to 100 mm is more preferable, and 40 to 60 mm is further preferable. If it is at least the above lower limit value, the heat insulating property can be further improved, and if it is at least the above upper limit value, the laminated plate is not too thick and easy to handle.

The thermal conductivity of the phenolic resin foam layer is preferably 0.022 W / m · K or less, more preferably 0.020 W / m · K or less, further preferably 0.019 W / m · K or less, and 0. Most preferably, it is 018 W / m · K or less. If the thermal conductivity is the above upper limit value, the heat insulating property is excellent.
The thermal conductivity of the phenol resin foam layer can be adjusted by the type and composition of the foaming agent, the ratio of phenol to formaldehyde when synthesizing the resol type phenol resin, the amount of acid catalyst, the type of surfactant, and the like.
For example, when the surfactant is a silicone-based surfactant, particularly one having a polyether chain having a −OH terminal, the thermal conductivity tends to be lower than when other surfactants are used.

The density of the phenol resin foam layer is preferably 10 to 100 kg / ^{m 3,} more preferably 15~70kg / ^{m 3,} more preferably ^{20~60kg / m 3, 25~55kg / m} 3 is especially preferred. When the density is at least the above lower limit value, the strength of the laminated board is excellent, and when it is at least the above upper limit value, the heat insulating property of the laminated board is excellent.
In particular, in the first aspect, the density of the phenol resin foam layer is preferably ^{25 to 55 kg / m 3} in that the convex portion 2b is easily formed on the surface 2a of the second face material 2 by embossing. More preferably, it is ³⁰ to 50 kg / m 3.
The density of the phenolic resin foam layer is measured according to JIS A 9511: 2009.

The average cell diameter of the phenol resin foam layer is preferably 50 to 200 μm, more preferably 50 to 150 μm, and even more preferably 50 to 100 μm. When the average cell diameter is within the above range, the heat insulating property of the laminated board is excellent.
The average cell diameter is measured by, for example, the following measuring method.
First, the test piece is cut out from approximately the center of the phenol resin foam layer in the thickness direction. The cut surface in the thickness direction of the test piece is photographed at a magnification of 50 times. Draw four straight lines with a length of 9 cm on the captured image. At this time, draw a straight line so as to avoid voids (voids of 2 mm ^{2 or more).} The number of bubbles crossed by each straight line (the number of cells measured according to JIS K6400-1: 2004) is counted for each straight line, and the average value per straight line is obtained. Divide 1800 μm by the average value of the number of bubbles, and use the obtained value as the average bubble diameter.

[Flexible surface material]
The face material has flexibility, and paper, woven fabric, and non-woven fabric are preferable. Examples of the paper include kraft paper, glass fiber mixed paper, and aluminum hydroxide paper. Examples of the woven fabric include glass fiber woven fabric. Examples of the non-woven fabric include needle-punched non-woven fabric, spunlace non-woven fabric, thermal-bonded non-woven fabric, and chemical-bonded non-woven fabric.
Among them, spunbonded non-woven fabric is easily available due to the large amount of industrial distribution, and it is also possible to control the texture and fluffing of the surface layer of the non-woven fabric by changing the heat fusion point pattern between fibers with an embossed heating roll in manufacturing. It is preferable because it is easy to handle.

Examples of the material constituting the non-woven fabric include synthetic resin fibers such as polypropylene fiber, polyethylene fiber, nylon fiber, polyester fiber, rayon fiber, acrylic fiber and aramid fiber, mineral fiber such as glass fiber, and natural fiber such as cotton and hemp. .. Among them, synthetic resin fibers are preferable from the viewpoints of dimensional stability, economy, and handleability during humidification and water absorption.
When the face material is a synthetic fiber non-woven fabric, it is possible to suppress the shrinkage of the face material and the occurrence of wrinkles due to the water content in the foamable phenol resin composition and the water generated during the condensation of the phenol resin.

In the first or second aspect, it is preferable that the face material does not contain cellulose fibers. If the face material contains hygroscopic fibers such as cellulose fibers, the face material may shrink due to the moisture in the phenol resin and the condensed water during the curing reaction.
Since the laminated board of the third aspect has moisture permeability obtained by the through holes 24 of the metal layer 23, even if the face material 22 contains cellulose fibers, the face material is made of water in the phenol resin or condensed water during the curing reaction. Shrinkage is suppressed.
In the first aspect, a synthetic resin fiber or a glass fiber non-woven fabric is preferable in that a convex portion 2b is easily formed on the surface 2a of the face material 2 by embossing.
In the second aspect, synthetic resin fibers or glass fiber non-woven fabrics are preferable in that the face material 12 having irregularities formed on the surface 12a in advance is unlikely to expand or contract.

The basis weight of the face material ^{is preferably 15 g / m 2} or more, and more preferably 20 g / m ² or more. When the basis weight of the face material is 15 g / m ² or more, it is possible to suppress the effervescent phenol resin composition from seeping out to the surface of the face material.
In particular, when the foaming agent contains a halogenated unsaturated hydrocarbon, the inclusion of the foaming agent lowers the viscosity of the foamable phenol resin composition. When the viscosity of the composition is low, the composition easily seeps into the face material, and the composition easily seeps out to the surface of the face material. Therefore, the basis weight of the face material should be at least the above lower limit value. It is possible to prevent the composition from exuding.
The upper limit of the basis weight of the surface material is preferably from 150 g / ^{m 2} or less, 100 g / ^{m 2} or less is more preferable. When the basis weight of the face material is not more than the above upper limit value, the adhesiveness between the face material and the phenol resin foam layer is enhanced.
In particular, in the first aspect, the basis weight of the face material is preferably ^{15 to 100 g / m 2 in} that a convex portion 2b is easily formed on the surface 2a of the second face material 2 by embossing. 50 g / m ² is more preferable.
Further, in the second aspect, the basis weight of the face material is preferably ²⁰ to 100 g / m 2 in that the recess 12b is easily formed on the surface 12a of the second face material 12 by embossing. 70 g / m ² is more preferable.

Examples of the material of the synthetic fiber non-woven fabric include synthetic resins such as polyester, polypropylene, nylon and polyethylene. Polyester, polypropylene and nylon are preferred.
One of these synthetic resins may be used alone, or two or more thereof may be used in combination.
The fiber diameter of the synthetic fiber of the synthetic fiber non-woven 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 is easy to suppress the exudation of the face material to the surface.
When the fiber diameter of the synthetic fiber is at least the above lower limit value, the handleability of the synthetic fiber is enhanced and the non-woven fabric can be easily manufactured.

The thickness of the face material is not particularly limited, but is preferably 0.06 to 1.00 mm, more preferably 0.10 to 0.50 mm. When the thickness of the face material is at least the above lower limit value, the exudation of the face material to the surface 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.
In particular, in the first aspect, the thickness of the face material is preferably 0.06 to 0.8 mm in that a convex portion 2b is easily formed on the surface 2a of the second face material 2 by embossing. More preferably 0.10 to 0.40 mm.
Further, in the second aspect, the thickness of the face material is preferably 0.10 to 1.0 mm in that the recess 12b is easily formed on the surface 12a of the second face material 12 by embossing. More preferably, it is 0.20 to 0.50 mm.

[Metal layer]
Examples of the metal layer include aluminum foil, aluminum alloy foil, copper foil, stainless steel foil and the like.
In the first aspect or the second aspect, the thickness of the metal layer is preferably 5 to 200 μm, more preferably 20 to 100 μm, and particularly preferably 25 to 50 μm. When it is at least the above lower limit value, the effect of improving the heat insulating property and the flame retardancy by providing the metal layer is excellent. When it is not more than the above upper limit value, the shape followability of the metal layer is excellent, unevenness is easily formed on the surface of the metal layer, and the effect of increasing the slip resistance coefficient on the surface of the metal layer is excellent.
In the third aspect, the thickness of the metal layer is preferably 5 to 500 μm, more preferably 12 to 200 μm, still more preferably 20 to 50 μm. When it is at least the above lower limit value, the effect of increasing the slip resistance coefficient of the surface by providing the metal layer having through holes is excellent. In addition, the provision of the metal layer is excellent in improving heat insulation and flame retardancy. When it is not more than the above upper limit value, the laminated board can be made lightweight.
The surface of the metal layer may be coated with a protective film made of a resin such as an acrylic resin or an epoxy resin. Oxidation of the metal layer can be prevented by coating with a protective film. If the thickness of the protective film is too thin, the antioxidant effect is insufficient, and if it is too thick, it does not follow the shape of the metal layer. The coating amount of the protective film from this standpoint is preferably 0.1 to 0.6 g / ^{m 2,} more preferably 0.3 to 0.5 g / ^{m 2.} The thickness of the protective film is preferably uniform.

In particular, when a convex portion is provided on the surface of the face material on the metal layer side and a convex portion that follows the convex portion of the face material is provided on the surface of the metal layer as in the first aspect, heat insulation and flame retardancy are achieved. The thickness of the metal layer is 20 to 100 μm, the width W of the convex portion of the face material is 1 to 10 mm, and the height of the convex portion is excellent in that it is excellent in the effect of improving and making the surface of the metal layer less slippery. It is preferable that the H is 0.01 to 3 mm and the convex area ratio is 20 to 80%.
More preferably, the thickness of the metal layer is 25 to 50 μm, the width W of the convex portion of the face material is 5 to 8 mm, the height H is 0.05 to 1 mm, and the convex portion area ratio is 30 to 60%.

In particular, when a recess is provided on the surface of the face material on the metal layer side and a recess that follows the recess of the face material is provided on the surface of the metal layer as in the second aspect, the effect of improving heat insulation and flame retardancy is obtained. The thickness of the metal layer is 20 to 100 μm, and the area of one recess on the surface of the face material is 0.05 to ⁵ mm 2, and the depth is excellent in that it is excellent and has an excellent effect of making the surface of the metal layer less slippery. It is preferable that the thickness is 0.01 to 1 mm and the number of recesses per unit area (thermocompression bonding partial density) is 5 to 200 / cm ^2.
More preferably, the thickness of the metal layer is 25 to 50 μm, the area of one recess is 0.07 to ³ mm 2, the depth is 0.01 to 0.5 mm, and the number of recesses per unit area (thermocompression bonding portion). Density) is 6 to 150 pieces / cm ² .

In particular, when a through hole is provided in the metal layer as in the third aspect, the thickness of the metal layer is excellent in that it is excellent in the effect of improving heat insulation and flame retardancy and also in the effect of making the surface of the metal layer less slippery. Is 12 to 100 μm, and the plan-view shape of the through hole of the metal layer has a length of 0.01 to 2 mm in the TD direction, a length of 0.01 to 2 mm in the MD direction, and an area of 0.00008 to 3. It is preferably 2 mm ² and the opening ratio in the metal layer is 0.001% or more and 0.5%.
More preferably, the thickness of the metal layer is 20 to 50 μm, the plan-view shape of the through hole has a length of 0.5 to 1.5 mm in the TD direction, and a length of 0.5 to 1.5 mm in the MD direction. The area is 0.19 to 2.6 mm ² , and the opening ratio is 0.011% or more and 0.2%.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Measurement method>
The measurement methods used in Examples and Comparative Examples described later are shown below.

(Thermal conductivity)
The thermal conductivity of the phenolic resin foam plate was measured according to JIS A 9511: 2009. The same sample was measured twice, and the average value was calculated.

(Slip resistance coefficient)
The slip resistance coefficient of the surface of the surface layer was measured according to the slipperiness test of JIS A 1454.
As the slip tester, a portable slip tester (trade name: OH-101, manufactured by Tohoku Sokki Co., Ltd.) was used. As the sliding piece, a rubber sheet having a hardness of A80 (hardness according to a durometer hardness test specified in JIS K 6253-3) and a thickness of 5 mm was used. The surface of the surface layer of the laminated board obtained in each example was wiped with a clean cloth and used as a test piece. The direction in which the sliding piece was slid on the test piece was measured as the MD direction or the TD direction, respectively. The slip piece was measured at room temperature (23 ± 2 ° C.).

(Metsuke of face material)
The measurement was performed according to the "mass per unit area" of JIS L 1906 "general long fiber non-woven fabric test method".

(Fiber diameter of face material)
Among the means for measuring the denier of elastic fibers and multifilament fibers, 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 weight (W: unit g). ) Can be calculated from D = (W / L) × 9000, and this is performed 30 times, and the average value is taken as denier.
When measuring the denier of the elastic fiber, the length of the yarn length L is not particularly limited, but in order to obtain a numerical value with high accuracy, a length that is not affected by the elongation due to the own weight effect of the elastic fiber is preferable, 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.

[Example 1]
In this example, a laminated board having the structure shown in FIG. 1 was manufactured. The first face material and the second face material (flexible face material) are ^{non-woven fabrics having a polyester material, a grain size of 30 g / m 2} , and a fiber diameter of 2.0 denier, and are embossed on one side. A synthetic resin non-woven fabric having a fine uneven pattern was used. The area of each thermocompression bonding part (recess) by embossing is 0.15 mm ² , the depth is 0.02 mm, the minimum interval of the thermocompression bonding part is 0.8 mm, and the density of the thermocompression bonding part is 100 pieces / cm ² . be. The thickness (T) other than the thermocompression bonding portion is 0.15 mm.

100 parts by mass of liquid resol type phenol resin (manufactured by Asahi Organic Materials Industry Co., Ltd., trade name: PF-339), surfactant (silicone-based surfactant, "Product No. SH193" manufactured by Toray Dow Corning Co., Ltd., polyether chain After mixing 4 parts by mass of −OH) and 4 parts by mass of a formaldehyde catcher (urea), the mixture was left at 20 ° C. for 8 hours.
108 parts by mass of the obtained mixture, 15 parts by mass of a foaming agent (HCFO-1233 zd-E: mixture of cyclopentane = 40: 60 (mass ratio)), and an acid catalyst (mixture of paratoluene sulfonic acid and xylene sulfonic acid). ) 15.0 parts by mass was mixed to prepare an effervescent phenolic resin composition.
This effervescent phenol resin composition is continuously run on the first face material from a discharge device provided with 16 nozzles (discharge port diameter: length 10 mm, width 30 mm) arranged in the TD direction. At 70 ° C., the second face material is layered on top of it, and the thickness is 45 mm and the width is 1000 mm with a slat type double conveyor so that it is sandwiched between the first and second face materials. It was heated for 300 seconds and foam-molded to form a phenol resin foam layer. At this time, the first face material and the second face material were pulled out from the face material rolls so that the tension applied to the first face material and the second face material was 4 N / m, respectively.
The first face material and the second face material were used so that the surface on which the fine uneven pattern (thermocompression bonding portion) was formed became the surface on the phenol resin foam layer side.
A hemispherical concave portion is provided by cutting on the transport surface of the upper and lower conveyors of the slat type conveyor in contact with the second face material. When the effervescent phenol resin composition foams between the first face material and the second face material, the surface of the second face material is formed into a plan view shape by embossing on the transport surface. It is a perfect circle, with a diameter (width W) of 5 mm and a height (H) of 0.5 mm at the center. A convex portion that follows this was also formed on the joint surface of the above, and a foam with a face material was obtained. The distance D between the adjacent convex portions was kept constant, and the distance D was adjusted so that the convex portion area ratio on the surface of the second face material was 40%.
^{An adhesive (ethylene-vinyl acetate copolymer) of 30 g / m 2 was} applied on the surface of the second face material of the obtained foam with face material, and the thickness of the foam was 30 μm drawn from the roll. Aluminum alloy foil (JIS H 4160) was laminated, and the aluminum alloy foil was bonded and integrated by applying a pressure of 0.2 MPa.
The long object thus obtained was cut to a length of 1820 mm to obtain a laminated board.

[Example 2]
This example is a reference example. In this example, a laminated board having the structure shown in FIG. 2 was manufactured. As the first face material (flexible face material), the same synthetic resin non-woven fabric as in Example 1 was used.
The second face material is a non-woven fabric made of polyester, having a grain ^{size of 30 g / m 2} , and having a fiber diameter of 2.0 denier. Synthetic resin non-woven fabric having a rectangular shape in plan view, an area of 1 recess is 2 mm ² , a depth of 0.1 mm, a thermocompression bonding part density of 8 pieces / cm ² , and a thickness other than the thermocompression bonding part is 0.15 mm. Was used. The thermocompression bonding portions were arranged at equal intervals.
An effervescent phenolic resin composition was prepared in the same manner as in Example 1. This effervescent phenol resin composition is discharged from the same discharge device as in Example 1 onto the first face material which is continuously running, and the second face material is superposed on the first face material, and the same as in Example 1. It was heated under the same conditions and foamed to form a phenol resin foam layer. In this example, no recess is provided on the transport surface of the slat type conveyor.
In this example, the first face material was used so that the surface on which the fine uneven pattern (thermocompression bonding portion) was formed was the surface on the phenol resin foam layer side. The second face material was used so that the surface on which the recess (thermocompression bonding portion) was formed was the surface opposite to the phenol resin foam layer side.
^{An adhesive (ethylene-vinyl acetate copolymer) of 30 g / m 2 was} applied on the surface of the second face material of the obtained foam with face material, and the thickness of the foam was 30 μm drawn from the roll. Aluminum alloy foil (JIS H 4160) was laminated, and the aluminum alloy foil was bonded and integrated by applying a pressure of 0.2 MPa.
The long object thus obtained was cut to a length of 1820 mm to obtain a laminated board.

[Example 3]
This example is a reference example. In this example, a laminated board having the structure shown in FIG. 3 was manufactured. As the first face material and the second face material (flexible face material), the same synthetic resin non-woven fabric as in Example 1 was used.
An effervescent phenolic resin composition was prepared in the same manner as in Example 1. This effervescent phenol resin composition is discharged from the same discharge device as in Example 1 onto the first face material which is continuously running, and the second face material is superposed on the first face material, and the same as in Example 1. It was heated under the same conditions and foamed to form a phenol resin foam layer. In this example, no recess is provided on the transport surface of the slat type conveyor.
The first face material and the second face material were used so that the surface on which the fine uneven pattern (thermocompression bonding portion) was formed became the surface on the phenol resin foam layer side.
^{An adhesive (ethylene-vinyl acetate copolymer) of 30 g / m 2 was} applied on the surface of the second face material of the obtained foam with face material, and the thickness of the foam was 30 μm drawn from the roll. The aluminum alloy foil (JIS H 4160) having through holes formed therein was laminated, and the aluminum alloy foil was bonded and integrated by applying a pressure of 0.2 MPa. The through holes of the aluminum foil have a circular shape in a plan view, a diameter of 1 mm, an area of 0.8 mm ² , a pitch (distance p) of 20 mm, and are arranged at equal intervals, and the opening ratio is 0.20%. ..
The long object thus obtained was cut to a length of 1820 mm to obtain a laminated board.

[Example 4]
In this example, in Example 1, the same through holes as in Example 3 are provided in the aluminum foil, and 0.4 g / m ² of epoxy resin is applied to the surface of the aluminum foil to provide a protective film. The laminated board was manufactured in the same manner as in the above.

[Comparative Example 1]
In this example, a laminated board was manufactured in the same manner as in Example 1 except that the transport surface of the slat type conveyor was not provided with a recess in Example 1.
This example corresponds to the example in which the aluminum foil is not provided with a through hole in the third embodiment.

<Evaluation>
The density of the phenol resin foam layer of the laminated board of each example was 35 to 45 kg / m ³ in each example, and the average cell diameter of the phenol resin foam layer was 80 to 120 μm in each example.
When the thermal conductivity of each of the laminated plates was measured by the above method, it was 0.0180 to 0.0185 W / m · K in each example, and it was confirmed that the heat insulating property was excellent.
With respect to the laminated plates obtained in Examples 1 to 3, the slip resistance coefficient on the surface of the metal layer (aluminum foil) was measured by the above method. The results are shown in Table 1.
With respect to the laminated board obtained in Example 4, the slip resistance coefficient on the surface of the protective film was measured by the above method. The results are shown in Table 1.

As shown in Table 1, the laminated boards obtained in Examples 1 to 4 have a slip resistance coefficient on the surface of the surface layer of 0.5 or more, which is higher than that of Comparative Example 1.
For example, when the work of installing on a sloped roof was performed using the laminated boards obtained in each example, the laminated boards of Comparative Example 1 were slippery and the workability was easily lowered, whereas in Example 1. The laminated boards of No. 4 were not slippery and had good handleability and workability.

1,11,21 Phenol resin foam layer 2,2'12,12', 22, 22'Flexible surface material 3,13,23 Metal layer 1a, 11a, 21a Joint surface 2a, 12a, 22a Flexible surface Surfaces on the metal layer side of the material 3a, 13a, 23a Surfaces on the metal layer 1b, 2b, 3b Convex parts 2c Rising parts 2d Recesses 2e, 12e Surfaces on the phenol resin foam layer side of flexible surface materials 12b, 13b Recesses 12d Convex Part 24 through hole

Claims (2)

A phenol resin foam layer and a surface layer provided on at least one surface of the phenol resin foam layer via a flexible surface material are provided, and the surface layer is a metal layer or a metal layer coated with a protective film. Yes, two or more convex portions are formed at intervals on the surface of the surface layer.
A foamed resin laminated board having a slip resistance coefficient of 0.5 or more on the surface of the surface layer, as measured by a slipperiness test of JIS A 1454. The foamed resin laminated plate according to claim 1 , wherein two or more through holes are formed in the metal layer at intervals.

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