JP2019038198A - Foamed resin laminate - Google Patents

Abstract

To provide a foamed resin laminate which has a phenol resin foamed layer and a metal layer, and has good handleability and workability.SOLUTION: A foamed resin laminate has a phenol resin foam layer 1, a flexible surface material 2 provided on at least one surface of the phenol resin foam layer 1, and a metal layer 3 provided on the flexible surface material 2, where a skid resistance of the surface 3a of the metal layer 3 which is measured by a slipperiness test according to JIS A 1454 is 0.5 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a foamed resin laminate.

Laminates having a phenolic resin foam layer are used in various fields as heat insulating materials because they are excellent in flame retardancy, heat resistance, chemical resistance, corrosion resistance, and the like. An aluminum foil layer may be used as a face material that improves flame retardancy and heat resistance at low cost.
In Patent Document 1, a phenolic resin foam plate is provided as a heat insulating plate on the outdoor side of the structural face material, an aluminum foil layer is provided on the outdoor side surface, and a nonflammable copper-clad material and lightweight concrete are provided on the outdoor side. A heat insulating fireproof outer wall structure provided with a panel is described. In an Example, the aluminum foil layer is affixed on the phenol resin foam board with the tape.
Patent Document 2 describes a nonflammable heat insulating panel in which an aluminum foil coated with a resin coating for corrosion prevention is laminated on one side or both sides of a phenolic resin foam plate via a nonwoven fabric or a woven fabric sheet.

Japanese Patent Laid-Open No. 2006-113823 JP 2003-239417 A

However, in a laminated plate in which a metal layer such as an aluminum foil is laminated on a phenolic resin foam plate as described in Patent Documents 1 and 2, the surface on the metal layer side is slippery. There is a problem that the nature is not good.
An object of the present invention is to provide a foamed resin laminate having a phenolic 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 face material, the surface layer being covered with a metal layer or a protective film A metal layer,
A foamed resin laminate having a slip resistance coefficient on the surface of the surface layer measured by a slidability test of JIS A 1454 of 0.5 or more.
[2] The foamed resin laminate according to [1], wherein two or more protrusions or recesses are formed on the surface of the surface layer at intervals.
[3] The foamed resin laminate according to [1] or [2], wherein two or more through holes are formed in the metal layer at intervals.

  ADVANTAGE OF THE INVENTION According to this invention, it has a phenol resin foam layer and a metal layer, and a foamed resin laminated board with favorable handleability and workability | operativity is obtained.

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

The foamed resin laminate of the present invention (hereinafter also simply referred to as a laminate) is a flexible face material (hereinafter also simply referred to as a face material) on at least one surface of the phenol resin foam layer and the phenol resin foam layer. ) Through the surface layer. The surface layer is a metal layer or a metal layer covered with a protective film.
The slip resistance coefficient measured by the JIS A 1454 slip test 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 slip property test, when there is a difference in the slip resistance coefficient depending on the direction in which the slide piece slides on the test piece, at least the TD direction (Transverse Direction) and the MD direction (Machine Direction) are measured, and 0.5 or more in both directions. It means that.
When the slip resistance coefficient is 0.5 or more, it becomes difficult to slip, and handling and workability are improved. The slip resistance coefficient is preferably 0.8 or more, and more preferably 1.0 or more. Even if the surface of the surface layer is processed in order to increase the slip resistance coefficient, the surface layer itself does not follow, and problems such as tearing occur on 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, and more preferably 0 to 0.4.

  The slip resistance coefficient on the surface of the surface layer can be increased by forming convex portions or concave portions at intervals on the surface of the surface layer. The interval between the convex portions or the concave portions may not be constant, but the interval between the convex portions or the concave portions 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. It is preferable. Moreover, it is preferable that the shape and size of a convex part or a recessed part 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 so that the protective film follows the through-holes. May be formed. Although the interval between the through holes may not be constant, it is preferable that the interval 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. The shape and size of the through hole are preferably uniform.

<First aspect>
FIG. 1 is a cross-sectional view schematically showing a laminate according to the first embodiment.
In the laminated plate of this embodiment, a metal layer 3 is provided on one surface of a plate-like phenolic resin foam layer 1 via a flexible face material 2. A flexible face material 2 ′ is provided on the other surface of the phenol resin foam layer 1, and no metal layer is 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 using an adhesive layer. Specifically, the phenol resin foam layer 1 and the face material 2 are bonded together by an adhesive force when thermosetting in the state where the face material 2 is laminated on the phenol resin foam layer 1. The face material 2 and the metal layer 3 are bonded together via an adhesive layer (not shown).
Reference numeral 1 a is a joint surface 1 a with the face material 2 of the phenol resin foam layer 1. In this specification, the “joining surface of the phenolic resin foam layer with the flexible face material” refers to the surface that becomes the surface of the phenol resin foam layer when the flexible face 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 respectively have the convex portions 2b and 3b that follow the joint surface 1a. Have. The surface 3a of the metal layer 3 is the outermost surface of the laminate.

In this aspect, the convex part 2b is discontinuous, and the concave part 2d exists between the adjacent convex parts 2b. The rising portion 2c of the convex portion 2b refers to 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. When such a point is cut in the thickness direction with a cross section including a straight line passing through the apexes of the three adjacent convex portions 2b, the ridge line of the central convex portion 2b (the line formed by the surface 2a of the face material 2) and This is the point where the bottom surface of the concave portion 2d existing on the left and right of the central convex portion 2b comes into contact.
In this embodiment, fine irregularities due to the fibers of the face material 2 or embossing may exist on the bottom surface of the recess 2d, but the height is lower than the thickness T of the face material 2, or the depth is thick. Recesses smaller than the length T are ignored.
In this aspect, the planar view shape of the convex portion 2b is a shape of a region surrounded by the rising portion (outer edge) 2c of the convex portion 2b.
In this specification, the shape in plan view means a shape when the line of sight is viewed perpendicular to the surface 2a of the face material 2.
The planar view shape of the convex part 2b can be made into circular shapes, such as polygonal shapes, such as a rectangle and a hexagon, perfect circle shape, an ellipse shape, and an ellipse shape.

When the laminated plate is placed on a horizontal support and the height is measured by a laser displacement meter, the highest portion of the convex portion 2b can be the highest portion. Alternatively, the depth can be analyzed after observing the surface with an optical microscope, and the highest portion of the observed portion can be the apex.
The width W of the convex portion 2b refers to the longest portion of the distance between two points on a straight line that intersects the planar shape of the convex portion 2b at two points. For example, when the shape of the projection 2b in plan view is a perfect circle, the diameter is the width, and when it is a regular square, the length of the diagonal line is the width.

As for the size of the convex portion 2b on the surface 2a of the face material 2, the height H of the convex portion 2b is preferably 0.01 to 3 mm, and the width W of the convex portion 2b is preferably 1 to 20 mm. The height H of the convex portion 2 b is preferably larger than the thickness T of the face material 2.
When the height H of the convex portion 2b is not less than the lower limit of the above range, the effect of making the surface of the metal layer difficult to slip is excellent. It is easy to make a metal layer follow the shape of convex part 2b as it is below an upper limit.
When the width W of the convex portion 2b is within the above range, the effect of making the surface of the metal layer difficult to slide is excellent.

The distance D between 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 difficult to slide is excellent.
Further, by reducing the distance D between the adjacent convex portions 2b, the biting of the face material 2 on the joint surface 1a of the phenol resin foam layer 1 and the biting of the metal layer 3 on the surface 2a of the face material 2 are increased. The adhesiveness of the resin foam layer 1, the face material 2, and the metal layer 3 can be further improved.

As for the convex part area ratio in the surface of the face material 2, 15% or more and 80% or less are preferable. Here, the convex portion area ratio is a ratio of the total area of the convex portions 2b to the total area of the face material 2 in the laminated plate, and is expressed by the following equation.
In addition, the area of the convex part 2b means the area of the planar view shape of the convex part 2b. Note that the unit area in the formula is 25 cm ^{2 of the} test piece obtained by cutting the metal layer 3 from an arbitrary position of the laminated plate to a length of 5 cm × width of 5 cm, and this convex area ratio per unit area is laminated. Let it be the convex part area ratio of the face material 2 in the whole board.
Protrusion area ratio (%) = {(area of a plurality of protrusions per unit area) / (unit area)} × 100 [%]

In order to reduce the distance D between the adjacent convex portions 2b and improve the adhesion 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%.
It is excellent in the effect which makes the surface of a metal layer hard to slip as it is more than the lower limit of the said range. Moreover, it is excellent in the effect which improves the adhesiveness of the phenol resin foam layer 1, the face material 2, and the metal layer 3 as it is in the said range.

When the planar view shape of the convex part 2b is a perfect circle, 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 part 2b is a part of a spherical surface, the height H of the convex part 2b is 0.05 mm to 1 mm, and the planar view shape of the convex part 2b is a perfect hemisphere having a diameter of 1 to 10 mm. It can be.

In this embodiment, when a fine uneven pattern (not shown) by embossing is formed on the surface 2e of the face material 2 on the phenol resin foam layer 1 side, the adhesion between the face material 2 and the phenol resin foam layer 1 Is preferable in that it is further improved.
The uneven pattern (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 a large effect of improving adhesiveness.
As a method for embossing the synthetic fiber nonwoven fabric, for example, a known spunbond method, a method in which a crimped continuous fiber web developed under cooling conditions directly under the spinning nozzle is partially thermocompression bonded with a hot embossing roll, or Examples thereof include a method in which the shortened fiber web is crimped by heat treatment and partially thermocompression bonded with a hot 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. It is excellent in the suppression of the seepage of the phenol resin in the thermocompression bonding portion when it is at least the lower limit of the above range. 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.
It is preferable that the minimum space | interval of a thermocompression bonding part is 0.05-5 mm, and it is more preferable that it is 0.08-2 mm. Within the above range, the texture is not too hard and the effect of improving the adhesiveness of the phenolic resin foam layer is excellent. It is preferable that the thermocompression bonding portions are evenly distributed over the entire surface of the nonwoven fabric surface.
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 represented by the following formula.
Thermocompression bonding part density (pieces / cm ² ) = number of thermocompression bonding parts (pieces) / surface area of face material (cm ² )
Adhesiveness with a phenol resin foaming layer can be improved, suppressing the seepage of a phenol resin by a thermocompression bonding part because a thermocompression bonding part density is the said range.
The depth of the concave portion of the thermocompression bonding portion (that is, the depression formed by thermocompression bonding by hot embossing roll processing or the like) is preferably 0.01 to 1.0 mm. When the depth is less than 0.01 mm, there is a tendency that the bonding of the thermocompression bonding portion is small, and when it exceeds 1.0 mm, processing by an embossing roll or the like tends to be difficult.

[Manufacturing method of laminate]
The laminated board of this embodiment foams and cures the foamable phenolic resin composition on the face material 2, and before the foamable phenolic resin composition is completely cured, the phenolic resin foamed layer 1 is formed by embossing. The surface of the foam with a face material obtained by manufacturing a foam with a face material by simultaneously forming convex portions on the joint surface 1a of the face material 2 and the surface 2a on the metal layer 3 side of the face material 2 It can be manufactured by a method of providing a metal layer on the material.
The foamable phenol resin composition is prepared, for example, by supplying a phenol resin, a foaming agent, an acid catalyst, and, if necessary, optional components to a mixer or the like and mixing them.
Although the mixing order of each component is not specifically limited, For example, an arbitrary component is added and mixed with a phenol resin as needed, and a foaming agent and an acid catalyst are added to the obtained mixture.

A method of foaming and curing the foamable phenol resin composition on the face material 2 can be performed 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 material (foamable phenol resin composition). Is provided.
The foam molding apparatus includes a frame portion and heating means. A frame part is provided with the conveyor (a lower conveyor, an upper conveyor, a left conveyor, a right conveyor) arrange | positioned up and down, right and left so that the space corresponding to the shape of a foam with a face material may be formed. Foaming in the vertical direction is regulated by the lower conveyor and the upper conveyor, and foaming in the horizontal direction is regulated by the left conveyor and the right conveyor. The foamable phenol resin composition passing through the frame portion is heated by the heating means, and is foamed and cured. Examples of the foam molding apparatus include those described in JP 2000-218635 A.

  In this manufacturing system, first, the first face material 2 ′ is continuously supplied between the discharge device and the foam molding device. The foaming phenol resin composition is discharged onto the first face material 2 ′ from a plurality of nozzles by a discharge device. The second face material 2 is placed thereon and introduced into the frame part 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 to form a foam with face material. 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 cut to an arbitrary length with a cutting device. Thereby, a laminated board is obtained.

When producing a foam with a face material, before the foamable phenolic resin composition is completely cured, as a method of forming a convex portion by embossing, for example, as a foam molding apparatus, Japanese Patent No. 3837226, JP, The method of providing the recessed part corresponding to the convex part to be formed in the conveyance surface of an upper conveyor using the apparatus provided with the slat type double conveyor of 2000-218635 gazette is mentioned. When the foamable phenol resin composition is foamed 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 conveying surface of the lower conveyor. The second face material 2 is pressed against the conveying surface of the upper conveyor. At this time, the second face material 2 is formed with a convex part 2b embossed on the conveying surface having a concave part, and the convex surface that follows the joint surface 1a with the face material 2 of the phenol resin foam layer 1 is also formed. Part 1b is formed.
Alternatively, a method of pressing a plate (press die) having a concave portion 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 ( For example, there is a method in which a concave portion is provided on the transport surface of the second double conveyor described in Japanese Patent No. 3837226 and a convex portion is formed by embossing using the transport surface.
Further, for example, in a production method including a foam curing step and a post-curing step described in JP-A-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 You may form a convex part in the surface (surface 2a of the 2nd face material 2) of the foam with a face material by embossing.

The face materials 2 and 2 ′ are used by being drawn out from a state of being wound in a roll shape with respect to a cylindrical core called a winding core, and are wound with a winding tension when winding.
If the pulling tension applied to the face material when pulled out is too large, the fibers may be torn off. In addition, when the surface of the face material is provided with a concavo-convex pattern by embossing, if the pulling tension is too large, the concavo-convex pattern may be damaged or the thermocompression bonding part 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 is sandwiched between the slats to cause wrinkles, or the face material snakes and creases.
Therefore, the 20 drawing tension of the face material 2 is preferably 0.5 to 80 N / m, and more preferably 1 to 60 N / m.
The tension of the face material can be adjusted by pulling the face material from the nonwoven fabric roll via the tension adjusting roller and moving the position of the tension adjusting roller, or by using a motor or powder type clutch to the tension adjusting roller. Can be adjusted to the desired value by controlling the roller rotation with a tension controller, and the torque generated during these adjustments and the voltage required for motor and clutch control are converted to torque. The pulling tension can be measured.

The method of providing the metal layer on the face material 2 of the foam with face material can be implemented 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, a metal layer 3 is laminated thereon, and the metal layer 3 is applied to the face material 2 from above the metal layer 3 using a heat laminating roll or the like. Glue by applying pressure in the pressing direction. Alternatively, a sheet in which a metal layer and an adhesive sheet such as a polyethylene film are laminated in advance is used, and this sheet and the face material 2 are pressed against the face material 2 from above the metal layer 3 through the adhesive sheet. You may adhere | attach by applying the pressure of a direction. 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 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 such a viewpoint, the pressure applied to the metal layer 3 is preferably 0.01 to 8 MPa, and more preferably 0.05 to 5 MPa.
As an adhesive for integrating the face material 2 and the metal layer 3, a known adhesive can be used. Examples thereof include urethane adhesives, modified silicone resin adhesives, epoxy resin adhesives, acrylic resin adhesives, vinyl acetate resin adhesives, chloroprene resin adhesives, polyethylene films, and polypropylene films.

  The ratio of the area covered by the metal layer 3 (the 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 more than the said lower limit, the further improvement of the flame retardance of a laminated board can be aimed at.

Since the metal layer 3 which is the outermost surface has the convex part 3b, the laminated board of this aspect has a high slip resistance coefficient, is hard to slip, and is excellent in handling property and workability | operativity.
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 the convex portion 2b of the surface 2a of the face material 2. It can be adjusted according to the height (height H, width W) and density. The height H and width W of the convex portion 2b of the face material 2 and the distance D between the adjacent convex portions 2b can be measured by peeling the metal layer 3 from the laminated plate.
The metal layer 3 is in close contact with the surface 2 a of the face material 2, and the convex portion 3 b of the metal layer 3 follows the convex portion 2 b of the surface 2 a of the face material 2. Therefore, the metal layer 3 bites in the concave portions 2d between the adjacent convex portions 2b of the face material 2, and the adhesion between the face material 2 and the metal layer 3 is improved.
Moreover, in this aspect, the convex part 2 b of the face material 2 follows the convex part 1 b of the joint surface 1 a of the phenol resin foam layer 1. Therefore, biting of the face material 2 occurs in the concave portions between the adjacent convex portions 1b of the phenol resin foam layer 1, and the adhesion 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 laminate of the second embodiment.
In the laminated plate of this embodiment, a metal layer 13 is provided on one surface of a plate-like phenolic 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 no metal layer is 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 an adhesive layer. The face material 12 and the metal layer 13 are bonded together 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 laminate. Reference numeral 11 a is a joint surface of the phenolic 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 nonwoven fabric is a thermocompression bonding portion by embossing. The method of embossing the synthetic fiber nonwoven fabric is, for example, a known spunbond method, a method in which a crimped continuous fiber web developed under cooling conditions directly under the spinning nozzle is partially thermocompression bonded with a hot embossing roll, or latent crimping. Examples thereof include a method in which a long fiber web is crimped by heat treatment and partially thermocompression bonded with a hot 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. It is excellent in the effect which makes the surface of a metal layer hard to slip that it is more than the lower limit of the said range. Moreover, it is excellent in the suppression of the seepage 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 shape of the recess 12b in plan view is not particularly limited, but may be a polygonal shape such as a quadrangle or a hexagon, a circular shape such as a perfect circle shape, an ellipse shape, or an oval shape. Here, the shape of the recess 12b in plan view refers to a case where the line of sight is viewed perpendicular to the surface 12a of the face member 12.
In this embodiment, the concave portion 12b is discontinuous, and a convex portion 12d exists between the adjacent concave portions 12b.
The depth of the recess 12b (that is, the depth of the recess formed by thermocompression bonding by hot embossing roll processing) is preferably 0.01 to 1.0 mm. When the depth is less than 0.01 mm, there is a tendency that the bonding of the thermocompression bonding portion is small, and when it exceeds 1.0 mm, processing by an 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 represented by the following formula.
Thermocompression bonding part density (pieces / cm ² ) = number of thermocompression bonding parts (pieces) / surface area of face material (cm ² )
When the thermocompression partial density is not less than the lower limit of the above range, the foamable phenolic resin composition is less likely to ooze from the face material 12, and the effect of improving the adhesion between the face material 12 and the metal layer 13 is excellent. It is excellent in the effect which makes the surface of the metal layer 13 hard to slip as it is below the upper limit of the said range.

The manufacturing method of the laminated board of this aspect uses the face material 12 in which the recessed part 12b was previously formed in one side as either a 1st face material or a 2nd face material, and the 1st face material or the 2nd face material. 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 face material. At this time, the phenol resin composition is foamed and cured on the surface of the face material 12 on which the concave portion 12b is not formed. Next, a laminate is obtained by providing the metal layer 13 on the surface of the foam with face material on the side where the concave portion 12b of the face material 12 is formed.
A method of foaming and curing the foamable phenol resin composition between the first face material and the second face material can be performed 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 in the first aspect.

In the laminated plate of this aspect, since the metal layer 13 which is the outermost surface has the recess 13b, the slip resistance coefficient is high, the slip is difficult, and the handling property 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. ) And the existing density (thermocompression partial density). The area or the like of the recess 12b of the face material 12 can be measured by peeling the metal layer 13 from the laminated plate.
The metal layer 13 is in close contact with the surface 12 a of the face material 12, and the recess 13 b of the metal layer 13 follows the recess 12 b of the surface 12 a of the face material 12. Therefore, the metal layer 13 bites in the recess 12b of the face material 12, and the adhesion 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 on the metal layer 13 side of the face material 12, but the surface 12e on the phenolic resin foam layer 11 side of the face material 12 is the same as in the first mode. A fine uneven pattern may be provided by embossing.
In the example of FIG. 2, the recess 12 b on the surface 12 a of the face material 12 is a thermocompression bonding portion by embossing, but the recess 12 b 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 setting the space portion where the fibers surrounded by the warp and weft of the face material 12 do not exist as the recess 12b.

<Third Aspect>
FIG. 3 is a cross-sectional view schematically showing the laminated plate of the third aspect.
In the laminated plate of this embodiment, a metal layer 23 is provided on one surface of a plate-like phenolic resin foam layer 21 via a flexible face material 22. A flexible face material 22 ′ is provided on the other surface of the phenol resin foam layer 21, and no metal layer is 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 an adhesive layer. The face material 22 and the metal layer 23 are bonded together via an adhesive layer (not shown).
Reference numeral 22 a is a surface of the face material 22 on the metal layer 23 side, and reference numeral 21 a is a joint surface of the phenolic resin foam layer 21 with the face material 22.

In this embodiment, a plurality of through holes 24 are formed in the metal layer 23. By providing the through hole 24, the slip resistance coefficient of the surface 23a of the metal layer 23 can be increased.
The shape of the through hole 24 in plan view is, for example, a circle such as a perfect circle or an ellipse; a triangle such as an isosceles triangle or a regular triangle; a rectangle such as a rectangle, a square, or a rhombus; a pentagon; a polygon such as a hexagon; Is 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 shapes of the through holes 24 in plan view, a circle without a corner or a polygon without an acute angle is preferable, and a circle is more preferable because it is easy to prevent breakage due to expansion of the metal layer 23.
When the shape in plan view is a slit, the length of the slit in the short direction is set to 0.05 mm for convenience, and the opening area per one is adjusted by adjusting the length in the slit longitudinal direction. Further, when the plan view shape is a triangle, a quadrangle, or a polygon, each side may not 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 MD direction, and 0.00008 to 3.2 mm ² in area. 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 shape of each through hole 24 in plan view is equal to or greater 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. It is excellent in the radiant heat reflective effect and the flame-retardant improvement effect as it is below the upper limit of the said range.

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 another through hole 24 closest to the center is equal (that is, a plurality of through holes 24 are regularly arranged). ) Here, “equal” to the distance p means that it 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 lower limit, the effect of increasing the slip resistance coefficient of the surface 23a of the metal layer 23 is excellent. If distance p is below the said upper limit, it will be excellent in the radiant heat reflection effect and the improvement effect of a flame retardance.

The aperture ratio in the metal layer 23 is 0.001% to 0.5%, preferably 0.008% to 0.35%, and more preferably 0.011% to 0.2%. If the aperture ratio is equal to or higher than the lower limit, the effect of increasing the slip resistance coefficient of the surface 23a of the metal layer 23 is excellent. If the aperture ratio is less than or equal to the above upper limit value, the effect of improving the radiant heat reflection effect and flame retardancy is excellent.
The aperture 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 measurement region) / (area of metal layer in measurement region) × 100 (1)
For example, an arbitrary area of a 10 cm × 10 cm square is set as a measurement area. This measurement region is observed with a microscope (× 10 to 100 times), and the opening area of the through hole 24 is measured. By dividing the total area of the measurement regions of all the opening area of the through-hole 24 of the measurement region ^{(cm 2) (100cm 2)} , the aperture ratio is obtained.

In the manufacturing method of the laminated board of this aspect, the phenol resin composition is foamed and cured between the face material 22 and the face material 22 ′, and cured to form the phenol resin foam layer 21, thereby obtaining a foam with face material. . Subsequently, the laminated board is obtained by providing the metal layer 23 on the surface 22a of the face material 22 of the obtained foam with face material.
The foaming phenol resin composition can be foamed and cured between the face materials by using a known foam molding method.
In the metal layer forming step, for example, a metal foil in which the through holes 24 are 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 an adhesive to a position corresponding to the through hole 24 on the surface 22 a of the face material 22. By not having an adhesive at the position of the through hole 24, the moisture permeability of the laminate is further improved.
Or metal foil in which the through-hole 24 is not formed may be stuck on the face material 22, and the through-hole 24 may be formed after that.
Specifically, an adhesive is applied on the surface 22 a of the face material 22, a metal foil is laminated thereon, and the metal foil is bonded by applying pressure in a direction of pressing the metal foil against the face material 22. The pressure at this time is preferably 0.01 to 8 MPa, and more preferably 0.05 to 5 MPa.

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

In addition, it may replace with the metal layer 3 in a 1st aspect, and the metal layer 23 of this aspect may be used, and the slip resistance coefficient of the surface of a metal layer can be made higher.
Moreover, it may replace with the metal layer 13 in a 2nd aspect, and may use the metal layer 23 of this aspect, and can make the slip resistance coefficient of the surface of a metal layer higher.

The following description is common to the first to third aspects unless otherwise specified.
[Phenolic resin foam layer]
A plurality of bubbles are formed in the phenolic resin foam layer, the bubble wall is substantially free of pores, and at least some of the plurality of bubbles are closed cells that do not communicate with each other. . A bubble wall is comprised from the hardened | cured material of a phenol resin. The gas in the bubbles is a gas derived from the 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. The foamable phenol resin composition may further contain other components other than the phenol resin, the foaming agent, the acid catalyst, and the surfactant, as necessary, as long as the effects of the present invention are not impaired.

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

A foaming agent is not specifically limited, Well-known chemical foaming agents; Porous solid materials etc. can be used, such as hydrocarbons, such as isopentane and cyclopentane, and halogenated saturated hydrocarbons, such as HFC365mfc and 2-chloropropane. A foaming agent may be used individually by 1 type, and 2 or more types may be used in combination.
The blowing agent preferably contains a halogenated unsaturated hydrocarbon.
Halogenated unsaturated hydrocarbons have lower thermal conductivity than non-halogenated hydrocarbons such as isopentane. 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 insulation is improved.
Halogenated unsaturated hydrocarbons have a small ozone depletion potential (ODP) and global warming potential (GWP), and have a small impact on the environment. Moreover, since halogenated unsaturated hydrocarbon is nonflammable, the flame retardance of a phenol resin foam layer is improved.

The halogenated unsaturated hydrocarbon may be one in which all of the hydrogen atoms are substituted with halogen, or one in which some of the hydrogen atoms are substituted with halogen.
Chlorinated fluorinated unsaturated hydrocarbons include 1,2-dichloro-1,2-difluoroethene (E and Z isomers), 1-chloro-3,3,3-trifluoropropene (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-123) ye) (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 variants) and the like.

When the blowing agent contains a halogenated unsaturated hydrocarbon, it is more preferable that the blowing agent further contains a hydrocarbon.
When the foaming agent contains a hydrocarbon, it is possible to suppress the viscosity of the foamable phenol resin composition from becoming too low, and the oozing onto the surface of the face material is likely to be suppressed.
As a hydrocarbon, a well-known thing can be used as a foaming agent, and a thing with a boiling point of -20-50 degreeC is used suitably. Those having a cyclic molecular structure having 4 to 6 carbon atoms or a chain molecular structure having 4 to 6 carbon atoms are preferred, and examples thereof include isobutane, normal butane, cyclobutane, normal pentane, isopentane, cyclopentane, and neopentane.

When the blowing 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 3: 7 to 7 : 3 is more preferable, and 4: 6 to 6: 4 is more preferable.
When the proportion of the halogenated unsaturated hydrocarbon is not less than the above lower limit, the heat insulating property of the phenol resin foam layer can be further improved. If the ratio of the halogenated unsaturated hydrocarbon is not more than the above upper limit value, the viscosity of the foamable phenolic resin composition does not become too low, and the suppression of the exudation to the surface of the face material is likely to be enhanced. Moreover, the foamability of the foamable phenol resin composition is good, and foaming can be sufficiently achieved even if the amount of the foaming agent is small.

  The content of the foaming agent in the foamable phenol resin composition is preferably 1 to 25 parts by mass, more preferably 3 to 15 parts by mass, and further preferably 5 to 12 parts by mass per 100 parts by mass of the phenol resin. If it is less than the said lower limit, the foaming degree of a foamable phenol resin composition may become inadequate, and there exists a possibility that the heat insulation of a phenol resin foam board may fall. If the value exceeds the upper limit, the foamable phenol resin composition may be excessively foamed and the strength of the phenolic resin foam plate may be reduced.

  The thickness of the phenolic resin foam layer is determined in consideration of the heat insulating property required for the laminated plate, for example, preferably 10 to 200 mm, more preferably 20 to 100 mm, and still more preferably 40 to 60 mm. If it is more than the said lower limit, heat insulation can be improved more, and if it is below the said upper limit, a laminated board will not become thick too much and handling is easy.

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, still more preferably 0.019 W / m · K or less, and Most preferred is 018 W / m · K or less. If heat conductivity is the said upper limit, it is excellent in heat insulation.
The thermal conductivity of the phenolic resin foam layer can be adjusted by the type and composition of the foaming agent, the ratio of phenol and formaldehyde when synthesizing the resol type phenolic 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 whose terminal is —OH, the thermal conductivity tends to be lower than when other surfactant is 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 equal to or higher than the lower limit, the strength of the laminate is excellent, and when the density is equal to or lower than the upper limit, the heat insulation of the laminate is excellent.
Particularly in the first aspect, the density of the phenol resin foamed layer is preferably 25 to 55 kg / m ³ in that the convex portions 2b are easily formed on the surface 2a of the second face member 2 by embossing. 30-50 kg / m < ³ > is more preferable.
The density of the phenol resin foam layer is measured according to JIS A 9511: 2009.

The average cell diameter of the phenolic resin foam layer is preferably 50 to 200 μm, more preferably 50 to 150 μm, and further preferably 50 to 100 μm. When the average cell diameter is within the above range, the heat insulating properties of the laminate are excellent.
The average bubble diameter is measured, for example, by the following measurement method.
First, a test piece is cut out from approximately the center in the thickness direction of the phenol resin foam layer. Photograph the cut surface in the thickness direction of the specimen at 50 times magnification. Draw four straight lines with a length of 9 cm on the captured image. At this time, a straight line is drawn 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. 1800 μm is divided by the average value of the number of bubbles, and the obtained value is defined as the average bubble size.

[Flexible face material]
The face material is flexible and is preferably paper, woven fabric, or non-woven fabric. Examples of paper include craft paper, glass fiber mixed paper, and aluminum hydroxide paper. Examples of the woven fabric include a glass fiber woven fabric. Examples of the nonwoven fabric include needle punch nonwoven fabric, spunlace nonwoven fabric, thermal bond nonwoven fabric, and chemical bond nonwoven fabric.
Among them, spunbond nonwoven fabrics are easy to obtain due to their large industrial distribution, and it is possible to control the texture and fluffing of the nonwoven fabric surface layer by changing the pattern of heat-bonding points between the fibers using an embossed heating roll in production. It is preferable because it is easy to handle.

Examples of the material constituting the nonwoven fabric include synthetic fiber 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 these, synthetic resin fibers are preferable from the viewpoints of dimensional stability, economic efficiency, and handling properties at the time of humidification and water absorption.
When the face material is a synthetic fiber nonwoven fabric, it is possible to suppress the occurrence of wrinkles due to shrinkage of the face material due to moisture in the foamable phenol resin composition or water generated during the condensation of the phenol resin.

In the 1st mode or the 2nd mode, it is preferred that a face material does not contain a cellulose fiber. If the face material contains hygroscopic fibers such as cellulose fibers, the face material may shrink due to moisture in the phenol resin or condensed water during the curing reaction.
Since the laminated board of the third aspect is moisture permeable 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. The contraction of the is suppressed.
In the first aspect, a synthetic resin fiber or a glass fiber nonwoven fabric is preferable in that the convex portions 2b can be easily formed on the surface 2a of the face material 2 by embossing.
In the second aspect, a synthetic resin fiber or a glass fiber nonwoven fabric is preferable in that the surface material 12 on which the surface 12a is previously formed with unevenness is less likely to be stretched and contracted.

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, the foamable phenol resin composition can be prevented from oozing out on the surface of the face material.
In particular, when the foaming agent contains a halogenated unsaturated hydrocarbon, the viscosity of the foamable phenol resin composition is lowered by containing the foaming agent. When the viscosity of the composition is low, the composition is likely to ooze into the face material, and the composition is likely to ooze out to the surface of the face material. Thus, the composition can be prevented from oozing out.
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 adhesion between the face material and the phenol resin foam layer is enhanced.
In particular, in the first embodiment, the basis weight of the face material is preferably 15 to 100 g / m ² , in that it is easy to form the convex portion 2b on the surface 2a of the second face material 2 by embossing. 50 g / m ² is more preferable.
Moreover, in the 2nd aspect, it is preferable that the fabric weight of a face material is 20-100 g / m < ² > at the point which is easy to form the recessed part 12b in the surface 12a of the 2nd face material 12 by embossing. 70 g / m ² is more preferable.

Examples of the material of the synthetic fiber nonwoven 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.
Moreover, the fiber diameter of the synthetic fiber of the synthetic fiber nonwoven fabric is preferably 0.5 to 4.0 denier, and more preferably 1.5 to 3.0 denier.
When the fiber diameter of the synthetic fiber is equal to or less than the upper limit value, it is easy to suppress oozing to the surface of the face material.
When the fiber diameter of the synthetic fiber is equal to or greater than the lower limit, the handleability of the synthetic fiber is improved and it is easy to produce a nonwoven fabric.

Although the thickness of a face material is not specifically limited, 0.06-1.00 mm is preferable and 0.10-0.50 mm is more preferable. When the thickness of the face material is equal to or more than the lower limit value, it is easy to suppress the bleeding of the face material to the surface. When the thickness of the face material is not more than the above upper limit value, the handleability of the face material is more excellent.
In particular, in the first aspect, the thickness of the face material is preferably 0.06 to 0.8 mm, in that it is easy to form the convex portion 2b on the surface 2a of the second face material 2 by embossing. 0.10 to 0.40 mm is more preferable.
Further, in the second aspect, the thickness of the face material is preferably 0.10 to 1.0 mm in that it is easy to form the recess 12b on the surface 12a of the second face material 12 by embossing. 0.20 to 0.50 mm is more preferable.

[Metal layer]
Examples of the metal layer include aluminum foil, aluminum alloy foil, copper foil, and stainless steel foil.
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. It is excellent in the heat insulation and the flame-resistant improvement effect by providing a metal layer as it is more than the said lower limit. When the amount is not more than the above upper limit value, the shape followability of the metal layer is excellent, irregularities are 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, and still more preferably 20 to 50 μm. It is excellent in the effect which increases the slip resistance coefficient of the surface by providing the metal layer which has a through-hole as it is more than the said lower limit. Moreover, it is excellent in the heat insulation and the flame-resistant improvement effect by providing a metal layer. When it is not more than the above upper limit value, the laminate can be made lightweight.
The surface of the metal layer may be covered with a protective film made of a resin such as an acrylic resin or an epoxy resin. By covering with a protective film, oxidation of the metal layer can be prevented. If the thickness of the protective film is too thin, the antioxidant effect is insufficient, and if it is too thick, the shape of the metal layer does not follow. 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, as in the first aspect, 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, the heat insulating property and the flame retardant property The thickness of the metal layer is 20 to 100 μm and the width W of the convex portion of the face material is 1 to 10 mm, and the height of the convex portion is high in terms of the excellent improvement effect and the effect of making the surface of the metal layer difficult to slip. It is preferable that the height 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, as in the second aspect, when a concave portion is provided on the surface of the face material on the metal layer side and a concave portion that follows the concave portion of the face material is provided on the surface of the metal layer, the effect of improving heat insulation and flame retardancy is achieved. The thickness of the metal layer is 20 to 100 μm, and the area of one concave portion on the surface of the face material is 0.05 to ⁵ mm ² , deep, because it is excellent and has an effect of making the surface of the metal layer difficult to slip. The thickness is preferably 0.01 to 1 mm, and the number of recesses per unit area (thermocompression partial density) is preferably 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 bonded portion Density) is 6 to 150 / cm ² .

Especially when the through hole is provided in the metal layer as in the third aspect, the thickness of the metal layer is excellent in the effect of improving the heat insulation and flame retardancy and the effect of making the surface of the metal layer difficult to slip. Of the through hole of the metal layer in a plan view, the length in the TD direction is 0.01-2 mm, the length in the MD direction is 0.01-2 mm, and the area is 0.00008-3. a 2 mm ^2, it is preferable aperture ratio of the metal layer is 0.5% or more 0.001%.
More preferably, the thickness of the metal layer is 20 to 50 μm, the length of the through hole in plan view, 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, The area is 0.19 to 2.6 mm ² , and the aperture ratio is 0.011% or more and 0.2%.

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

(Thermal conductivity)
In accordance with JIS A 9511: 2009, the thermal conductivity of the phenolic resin foam plate was measured. The same sample was measured twice and the average value was obtained.

(Slip resistance coefficient)
Based on the slidability test of JIS A 1454, the slip resistance coefficient of the surface of the surface layer was measured.
A portable slip tester (trade name: OH-101, manufactured by Tohoku Sokki Co., Ltd.) was used as the slip tester. 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. A test piece was prepared by wiping the surface of the laminate obtained in each example with a clean cloth. The direction of sliding the sliding piece on the test piece was measured as MD direction or TD direction, respectively. Sliding piece measurement was performed at room temperature (23 ± 2 ° C.).

(Weight per face)
Measured according to “mass per unit area” of JIS L 1906 “Testing method for general long-fiber nonwoven fabric”.

(Fiber diameter of face material)
Among the means for measuring the denier of elastic fibers and multifilament fibers, JIS-L-1013 is used for multifilament fibers. In addition, for elastic fibers, the elastic fibers are hung in an atmosphere of a standard state with no load, the yarn length (L: unit m) is measured, and the weight (W: unit g) is measured to measure denier (D ) Can be calculated from D = (W / L) × 9000, and this is performed 30 times, and the average value is taken as denier.
In 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 does not affect the elongation due to the self-weight effect of the elastic fiber is preferable, for example, 20 denier to The yarn length L of about 40 denier is preferably about 1 m.

[Example 1]
In this example, a laminate having the configuration shown in FIG. 1 was manufactured. As the first face material and the second face material (flexible face material), the material is polyester, the basis weight is 30 g / m ² , and the fiber diameter is 2.0 denier, and one surface is embossed. A synthetic resin nonwoven fabric on which a fine uneven pattern was formed was used. The area per embossed thermocompression bonding part (concave part) is 0.15 mm ² , the depth is 0.02 mm, the minimum distance between thermocompression bonding parts is 0.8 mm, and the thermocompression bonding part density is 100 pieces / cm ² . is there. The thickness (T) other than the thermocompression bonding portion is 0.15 mm.

100 parts by mass of liquid resol type phenolic resin (Asahi Organic Materials Co., Ltd., trade name: PF-339) and surfactant (silicone surfactant, “Part No. SH193” manufactured by Toray Dow Corning, polyether chain Terminal: -OH) 4 parts by mass and formaldehyde catcher agent (urea) 4 parts by mass were mixed and then allowed to stand at 20 ° C for 8 hours.
108 parts by mass of the obtained mixture, 15 parts by mass of a foaming agent (a mixture of HCFO-1233zd-E: cyclopentane = 40: 60 (mass ratio)), and an acid catalyst (a mixture of paratoluenesulfonic acid and xylenesulfonic acid) ) 15.0 parts by mass were mixed to prepare a foamable phenolic resin composition.
On the first face material, the foamable phenolic resin composition is continuously run from a discharge device provided with 16 nozzles (discharge port diameter: 10 mm length, 30 mm width) arranged in the TD direction. At 70 ° C. in a state where the thickness is 45 mm and the width is 1000 mm with a slat type double conveyor so as to be sandwiched between the first and second face materials. Foam molding was performed by heating for 300 seconds to form a phenolic resin foam layer. At this time, the first face material and the second face material were each pulled out from the face material roll so that the tension applied to the first face material and the second face material was 4 N / m, respectively.
The 1st face material and the 2nd face material were used in the direction where the surface in which the fine uneven | corrugated pattern (thermocompression-bonding part) was formed turns into the surface by the side of a phenol resin foam layer.
A hemispherical concave portion was formed by cutting on the conveying surface of the upper and lower conveyors of the slat type conveyor in contact with the second face material. When the foamable phenolic resin composition foams between the first face material and the second face material, the shape of the plan view is formed on the surface of the second face material by embossing on the conveying surface. Forming a raised circle having a perfect circle with a diameter (width W) of 5 mm and a center height (H) of 0.5 mm in a staggered arrangement, and at the same time, a second face material of the phenolic resin foam layer Convex portions following this were also formed on the joint surface of the film to obtain a foam with a face material. The distance D between adjacent convex portions was constant, and the distance D was adjusted so that the convex portion area ratio on the surface of the second face material was 40%.
30 g / m ^{2 of} adhesive (ethylene-vinyl acetate copolymer) was applied on the surface of the second face material of the obtained foam with face material, and the thickness pulled out from the roll was 30 μm. The 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 product thus obtained was cut to a length of 1820 mm to obtain a laminate.

[Example 2]
In this example, a laminate having the configuration shown in FIG. 2 was manufactured. The same synthetic resin nonwoven fabric as Example 1 was used for the 1st face material (flexible face material).
The second face material is a non-woven fabric having a polyester material, a basis weight of 30 g / m ² , and a fiber diameter of 2.0 denier, and has a concave portion (thermocompression-bonded portion) formed by embossing on one side. Synthetic resin nonwoven fabric having a rectangular shape in plan view, an area of one recess of 2 mm ² , a depth of 0.1 mm, a thermocompression bonding part density of 8 / cm ² , and a thickness other than the thermocompression bonding part of 0.15 mm Was used. The thermocompression bonding portions were arranged at equal intervals.
In the same manner as in Example 1, a foamable phenol resin composition was prepared. This foamable phenolic resin composition was discharged from the same discharge device as in Example 1 onto the first face material that was continuously running, and the second face material was stacked thereon, and Example 1 and It was heated and foamed under the same conditions to form a phenolic resin foam layer. In this example, no recess was provided on the conveying surface of the slat type conveyor.
In this example, the first face material was used in such a direction that the surface on which the fine concavo-convex pattern (thermocompression bonding portion) is formed becomes the surface on the phenolic resin foam layer side. The second face material was used such that the surface on which the concave portion (thermocompression bonding portion) was formed was the surface opposite to the phenol resin foam layer side.
30 g / m ^{2 of} adhesive (ethylene-vinyl acetate copolymer) was applied on the surface of the second face material of the obtained foam with face material, and the thickness pulled out from the roll was 30 μm. The 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 product thus obtained was cut to a length of 1820 mm to obtain a laminate.

[Example 3]
In this example, a laminate having the configuration shown in FIG. 3 was manufactured. The same synthetic resin nonwoven fabric as Example 1 was used for the first face material and the second face material (flexible face material).
In the same manner as in Example 1, a foamable phenol resin composition was prepared. This foamable phenolic resin composition was discharged from the same discharge device as in Example 1 onto the first face material that was continuously running, and the second face material was stacked thereon, and Example 1 and It was heated and foamed under the same conditions to form a phenolic resin foam layer. In this example, no recess was provided on the conveying surface of the slat type conveyor.
The 1st face material and the 2nd face material were used in the direction where the surface in which the fine uneven | corrugated pattern (thermocompression-bonding part) was formed turns into the surface by the side of a phenol resin foam layer.
30 g / m ^{2 of} adhesive (ethylene-vinyl acetate copolymer) was applied on the surface of the second face material of the obtained foam with face material, and the thickness pulled out from the roll was 30 μm. The aluminum alloy foil (JIS H 4160) having through holes 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 plan view, a diameter of 1 mm, an area of 0.8 mm ² , a pitch (distance p) of 20 mm, and are equally spaced, and an aperture ratio of 0.20%. .
The long product thus obtained was cut to a length of 1820 mm to obtain a laminate.

[Example 4]
In this example, Example 1 is the same as Example 1 except that the same through hole as in Example 3 was provided in the aluminum foil, and a protective film was provided by applying 0.4 g / m ² of epoxy resin on the surface of the aluminum foil. In the same manner, a laminate was produced.

[Comparative Example 1]
In this example, a laminated board was manufactured in the same manner as in Example 1 except that no concave portion was provided on the transport surface of the slat type conveyor.
This example corresponds to an example in which the through hole is not provided in the aluminum foil in the third embodiment.

<Evaluation>
The density of the phenolic resin foam layer of the laminated board of each example was 35 to 45 kg / m ³ in all examples, and the average cell diameter of the phenol resin foam layer was 80 to 120 μm in all examples.
About the laminated board of each example, when heat conductivity was measured by said method, all examples were 0.0180-0.0185W / m * K, and it was confirmed that it is excellent in heat insulation.
About the laminated board obtained in Examples 1-3, the slip resistance coefficient of the surface of a metal layer (aluminum foil) was measured by said method. The results are shown in Table 1.
About the laminated board obtained in Example 4, the slip resistance coefficient of the surface of a protective film was measured by said method. The results are shown in Table 1.

As shown in Table 1, the laminates obtained in Examples 1 to 4 have a slip resistance coefficient of 0.5 or more on the surface of the surface layer, which is higher than that of Comparative Example 1.
For example, when the installation work on the sloped roof was performed using the laminates obtained in each example, the laminate of Comparative Example 1 was slippery and the workability was liable to be reduced, whereas Example 1 The laminates (4) to (4) were not slippery and had good handleability and workability.

1, 11, 21 Phenolic resin foam layer 2, 2′12, 12 ′, 22, 22 ′ Flexible face material 3, 13, 23 Metal layer 1a, 11a, 21a Bonding surface 2a, 12a, 22a Flexible surface Metal layer side surface 3a, 13a, 23a Metal layer surface 1b, 2b, 3b Convex part 2c Rising part 2d Concave part 2e, 12e Surface of phenolic foam layer side of flexible face material 12b, 13b Concave part 12d Convex part Part 24 Through hole

Claims (3)

A phenol resin foam layer and a surface layer provided on at least one surface of the phenol resin foam layer via a flexible face material, the surface layer being a metal layer or a metal layer covered with a protective film Yes,
A foamed resin laminate having a slip resistance coefficient on the surface of the surface layer measured by a slidability test of JIS A 1454 of 0.5 or more.   The foamed resin laminate according to claim 1, wherein two or more convex portions or concave portions are formed on the surface of the surface layer at intervals.   The foamed resin laminate according to claim 1 or 2, wherein two or more through holes are formed in the metal layer at intervals.

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