JP6944934B2 - Cosmetic material - Google Patents

Description

The present invention relates to a decorative material.

Conventionally, wood materials are used as decorative materials used for windows (bay window stands), toilets, washbasins (floor materials), etc. (see, for example, Patent Document 1 and the like). However, places such as windows, toilets, and washbasins have a lot of condensation and water (humidity, urine, etc.), and the temperature difference is large, such as hot in summer and cold in winter, so they are used in these places. If the veneer is made of wood, the water resistance is inferior, so that mold and warpage are likely to occur, and the veneer cannot be used stably.
In order to satisfy the water resistance of such a decorative material, it is conceivable to compose the decorative material with a resin material which is a non-wood material, and in particular, use a decorative material having a resin foam layer having excellent water resistance and heat insulating properties. Is also being studied (for example, Patent Document 2 and the like).

Japanese Unexamined Patent Publication No. 2001-123647 Japanese Unexamined Patent Publication No. 2008-238728

Since the decorative material having a resin foam layer is a non-wood material, it has excellent water resistance and can be said to be a decorative material that can solve the above-mentioned conventional problems.
However, in the case of a decorative material made of a resin material which is a non-wood material, warpage may occur due to a dimensional change due to the temperature of the resin material, while when a foamed resin material is used, there is a problem that the impact resistance is inferior. ..
In addition, when the decorative material having a resin foam layer is used as a window frame including a window stand, a figurine or a vase having a certain weight may be placed, while when it is used as a floor material, a toilet bowl or a washstand. Since building materials such as, washing machines, and electric appliances such as refrigerators may be placed, the load bearing capacity against dents on the surface of the decorative material due to a long-term load may become a problem.

An object of the present invention is to provide a decorative material which is excellent in water resistance and heat insulating property, can suppress the occurrence of warpage, and is excellent in load resistance under such a situation.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have configured the decorative material to have a non-foamed resin layer and a foamed resin layer having a small shrinkage stress due to heat, and serve as a decorative layer with respect to the thickness of the foamed resin layer. By defining the ratio of the total thickness of the non-foamed resin layer, the compressive elastic modulus of the foamed resin layer, and the linear expansion coefficient of the non-foamed resin layer and the foamed resin layer, load resistance is required while mitigating the influence of shrinkage due to heat. We have found that it can be used for various purposes, and have completed the present invention.

The present invention is a decorative material having a decorative layer, a non-foamed resin layer and a foamed resin layer, and the total thickness of the decorative layer and the non-foamed resin layer is 50% with respect to the thickness of the foamed resin layer. The compressive elasticity of the foamed resin layer is 15 MPa or more, the linear expansion coefficient of both the non-foamed resin layer and the foamed resin layer is 8 × 10 ⁻⁵ / ° C. or less, and the non-foamed resin is The decorative material is characterized in that the difference in linear expansion coefficient between the layer and the foamed resin layer ^{is within 3 × 10 −5 / ° C.}

In the decorative material of the present invention, the tensile elastic modulus of the non-foamed resin layer is preferably 180 MPa or more.
Further, the non-foamed resin layer preferably contains an inorganic compound.
Further, the thickness of the decorative material of the present invention is preferably 5 mm or more.

The decorative material of the present invention has a decorative layer, a non-foamed resin layer and a foamed resin layer, and the ratio of the total thickness of the decorative layer and the non-foamed resin layer to the thickness of the foamed resin layer and the compressive elastic modulus of the foamed resin layer. However, since each of them is defined to a predetermined value, it is possible to provide a decorative material which is excellent in water resistance, heat insulating property, and load resistance, and which can suppress the occurrence of warpage.

It is a schematic diagram which shows the cross section of a preferable example of the decorative material of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative material of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative material of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative material of this invention. This is an example of an elastic modulus chart showing the relationship between the load (N) and the elongation (%) on the test piece. (A) is a cross-sectional view in the thickness direction of the decorative material for window frame, which is a preferable example of the decorative material of the present invention, and (b) shows an example of a perspective view of the decorative material for window frame, (c). 1 is a cross-sectional view in the thickness direction of the raw material laminate used when assembling the decorative material for the window frame shown in (a) and (b), and (d) is a preferable example of the decorative material of the present invention. It is sectional drawing which shows the other example of the decorative material for a window frame, and (e) is the sectional view which shows still another example of the decorative material of this invention. (A) is an example of a decorative material for a window frame in which an edge tape is attached to the side surface of a bent portion, and (b) and (c) are decorative materials for a window frame having a notch on the side surface. It is a perspective view which shows each example. (A) is a cross-sectional view in the thickness direction of a raw material laminate used when assembling a decorative material for a window frame, which is a preferable example of the decorative material of the present invention, and (b) is a preferable example of the decorative material of the present invention. It is sectional drawing which shows the other example of the decorative material for a window frame which is an example. (A) is a cross-sectional view showing an example in which a decorative material for a window frame, which is a preferable example of the decorative material of the present invention, is applied to a window of a building, and (b) is a preferable example of the decorative material of the present invention. It is a top view which shows an example in which a decorative material for a window frame was applied to a window of a building, and (c) is a decorative material for a window frame which is a preferable example of the decorative material of the present invention, was applied to a window of a building. It is a perspective view which shows an example. (A) to (d) are cross-sectional views in the thickness direction of the raw material laminate and the window frame decorative material used when assembling the window frame decorative material which is a preferable example of the decorative material of the present invention. It is a top view which shows an example of the decorative material for a window frame which is a preferable example of the decorative material of the present invention, and an example of the decorative material for a window frame which is a preferable example of the decorative material of the present invention applied to a window of a building. .. (A) is a diagram for explaining a method of evaluating warpage when the decorative material according to Examples and Comparative Examples is used for a window frame, and (b) is a diagram for using the decorative material according to Examples and Comparative Examples as a floor material. It is a figure explaining the evaluation method of the warp when it is used for (floor). It is a figure explaining the test of the load bearing capacity of the decorative material which concerns on Example and comparative example. (A) is a diagram for explaining a method for evaluating the warp of a decorative material for a window frame according to the present invention, and (b) is a diagram for explaining a method for evaluating the warp of a decorative material for a window frame according to the present invention. (A) is a cross-sectional view showing a method of measuring the amount of warp in a mountain state (convex shape), and (b) is a cross-sectional view showing a method of measuring the amount of warp in a valley state (concave shape).

The decorative material of the present invention has a decorative layer, a non-foamed resin layer, and a foamed resin layer, and the total thickness of the decorative layer and the non-foamed resin layer is 50% or less of the thickness of the foamed resin layer. Is.
If the total thickness of the decorative layer and the non-foamed resin layer exceeds 50% of the thickness of the foamed resin layer, the decorative material of the present invention will be greatly warped. The total thickness of the decorative layer and the non-foamed resin layer with respect to the thickness of the foamed resin layer has a preferable lower limit of 3%, a preferable upper limit of 45%, a more preferable lower limit of 10%, and a more preferable upper limit of 30%. be.

Further, in the decorative material of the present invention, the compressive elastic modulus of the foamed resin layer is 15 MPa or more. If the compressive elastic modulus is less than 15 MPa, excellent load bearing resistance cannot be obtained, and impact resistance is also inferior. From the viewpoint of obtaining excellent load resistance and impact resistance, the compressive elastic modulus of the foamed resin layer is more preferably more than 15 MPa and not more than 150 MPa, and further preferably 20 MPa or more and 120 MPa or less. Here, the compressive elastic modulus is a value measured by preparing a test piece using the method described in JIS A9511: 2009 "Foam plastic heat insulating material" using a foamed resin layer. Specifically, a rectangular parallelepiped-shaped test piece having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm is cut out from the foamed resin layer, and the test piece is cut in the thickness direction at a compression rate of 10 mm / min using a tensile / compression tester. The compressive elastic modulus is measured perpendicularly to. Five test pieces are prepared, the compressive elastic modulus is measured for each test piece in the above manner, and the value obtained by arithmetically averaging them is taken as the compressive elastic modulus. The thickness of the rectangular parallelepiped test piece is changed to 3 mm instead of the thickness described in JIS.

Further, in the decorative material of the present invention, the linear expansion coefficients of the non-foamed resin layer and the foamed resin layer are both 8 × 10 ⁻⁵ / ° C. or less, and the lines of the non-foamed resin layer and the foamed resin layer. The difference in the linear expansion coefficient of the expansion coefficient ^{is within 3 × 10 -5} / ° C.
When the linear expansion coefficient of the non-foamed resin layer and / or the foamed resin layer ^{exceeds 8 × 10 -5} / ° C, the decorative material expands and contracts greatly with respect to a temperature change. When the decorative material of the present invention is fitted, a problem such as pushing up the fitting portion occurs, while when it shrinks, a gap between the fitting portions is formed when two or more decorative materials of the present invention are fitted. Problems such as opening occur.
Further, when the difference in the coefficient of linear expansion between the non-foamed resin layer and the foamed resin layer ^{exceeds 3 × 10 −5} / ° C., the difference in the degree of expansion and contraction of each layer becomes large with respect to the temperature change. Will cause a large warp.
The coefficient of linear expansion of the non-foamed resin layer and the foamed resin layer ^{is preferably 8 × 10 -5} / ° C. or lower, and more preferably 7 × 10 ^-5 / ° C. or lower. Further, the difference between the linear expansion coefficient of the non-foamed resin layer and the linear expansion coefficient of the foamed resin layer ^{is preferably within 3 × 10 −5} / ° C., and preferably within 2 × 10 ⁻⁵ / ° C. More preferable.

Here, the linear expansion coefficient of the non-foamed resin layer and the foamed resin layer is such that a rectangular parallelepiped test piece having a length of 145 mm and a width of 300 mm is cut out from each layer member, and the test piece temperature is set to 0 ° C. and 40 ° C. using a constant temperature bath. The lateral dimensional change when each is stabilized is measured, and the dimensional change amount per unit temperature obtained from the dimensional change amount is defined as the coefficient of linear expansion. In the present invention, the dimensional change in the thickness direction of each layer member is extremely small as compared with the vertical and horizontal dimensional changes, and thus can be ignored.

Next, a typical structure of the decorative material of the present invention will be described with reference to FIGS.
1 to 3 are schematic views showing a cross section of a preferable decorative material 10 of the present invention.
In the aspect shown in FIG. 1, the decorative material 10 of the present invention has a foamed resin layer 1, a non-foamed resin layer 2, and a decorative layer 3 in this order. Further, in the embodiment shown in FIG. 2, the decorative layer 3 has a base resin layer 4, and has an adhesive layer 7, a transparent resin layer 5, and a surface protective layer 6 on the pattern layer 33. It has a foamed resin layer 1, a non-foamed resin layer 2, and a decorative layer 3 in this order.
Further, the embodiment shown in FIG. 3 is the same as the embodiment shown in FIG. 2 except that the non-foaming resin layer 2 has a three-layer structure, and the non-foaming layer 2 shown in FIG. 3 is the first. The structure has a thermoplastic resin layer 21, a glass component layer 22, and a second thermoplastic resin layer 23 in this order.

(Effervescent resin layer 1)
The foamed resin layer is a layer that mainly imparts heat insulating property, load resistance, and impact resistance to the decorative material of the present invention, and is formed by foaming a foamed resin composition.
The foaming ratio of the foamed resin layer is preferably 5 times or more and 20 times or less. If it is out of this range, a decorative material having excellent heat insulating properties, load resistance, and impact resistance may not be obtained. From the viewpoint of obtaining better heat insulating properties and load bearing capacity, the foaming ratio of the foamed resin layer is more preferably 5 times or more and 15 times or less, and further preferably 5 times or more and 12 times or less.

Further, in the decorative material of the present invention, the compressive elastic modulus of the foamed resin layer is 15 MPa or more as described above, but the compressive elastic modulus is JIS A9511: 2009 "foamed plastic heat insulating material" using the foamed resin layer. ], A test piece was prepared using a part of the method described in the above, and the value was measured.
Specifically, a rectangular parallelepiped-shaped test piece having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm is cut out from the foamed resin layer, and the test piece is cut from a direction perpendicular to the thickness direction using a tensile / compression tester. The compressive elastic modulus is measured at a compression rate of 10 mm / min. Five test pieces are prepared, the compressive elastic modulus is measured for each test piece in the above manner, and the value obtained by arithmetically averaging them is taken as the compressive elastic modulus.

The method for foaming the foamed resin composition is not particularly limited, and any known method can be adopted, but foaming by the bead method is preferable from the viewpoint of obtaining a homogeneous foamed resin layer. In the bead method, foamed resin particles (pre-foamed particles) are used as a raw material, the foamed resin particles are filled in a cavity of a mold, and the filled pre-foamed particles are secondarily foamed with steam to be pre-foamed particles. This is a method of obtaining a foamed resin layer by integrating the particles with each other by heat fusion.

The resin used for the foamed resin particles is preferably a thermoplastic resin.
Examples of the thermoplastic resin include polyethylene (PE), polypropylene (PP), polystyrene (PS), styrene-modified polyolefin resin, ethylene-vinyl acetate copolymer resin (EVA), and ethylene- (meth) acrylic acid resin. Polyolefin resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer, polyvinyl chloride resin (PVC), polyvinyl acetate resin, polyvinyl resin such as polyvinyl alcohol resin, polyethylene terephthalate resin ( Polyester resins such as PET resin), simple and copolymers of thermoplastic resins such as nylon, polyacetal resin, acrylic resin, polycarbonate resin, and polyurethane resin, or mixed resins thereof are preferable.
Among these, a polyolefin resin is preferable, and a polystyrene resin is particularly preferable, in consideration of the strength of the resin itself.

The styrene monomer forming the polystyrene resin is not particularly limited, and any known styrene monomer can be used. For example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, bromostyrene and the like can be mentioned. These styrene-based monomers may be one kind or a mixture of a plurality of kinds. A preferred styrene monomer is styrene.

The foamed resin particles are usually made into resin particles by polymerizing a seed particle made of a resin forming the foamed resin particles by absorbing a monomer such as a styrene monomer together with a plasticizer as required, and polymerizing the particles at the same time as the polymerization. Alternatively, it can be obtained by impregnating the resin particles with a foaming agent after polymerization and then foaming the resin particles. Further, the foamed resin particles can be obtained by a method of impregnating particles obtained by suspend polymerization of a monomer such as a styrene monomer in an aqueous medium with a foaming agent, or by putting a polystyrene resin into an extruder and melt-kneading the particles together with the foaming agent. Then, it can also be obtained by extruding into pressurized circulating water through a die having small holes and foaming the particles obtained by cutting with a rotary cutter in contact with the die.

Examples of the foaming agent include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N. Nitroso compounds such as'-dinitrosopentamethylenetetramine; azo compounds such as azodicarboxylicamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene; sulfonylhydrazides such as benzenesulfonylhydrazide and toluenesulfonylhydrazide Compounds: Azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide, and p-toluenesulfonyl azide are preferably used.
In addition, as the foaming agent, in addition to aliphatic hydrocarbons such as propane, normal butane, isopentane, normal pentane, and neopentane as physical foaming agents, fluorinated hydrocarbons such as difluoroethane and tetrafluoroethane having an ozone destruction coefficient of zero. Volatile foaming agents such as the like are also preferably mentioned.
These foaming agents may be used alone or in combination of two or more.
The amount of the foaming agent added may be appropriately determined according to the desired foaming ratio and compressive elastic modulus, but is preferably 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin, and is preferably 1 part by mass or more. More preferably, it is 10 parts by mass or less.

Examples of the plasticizer include fatty acid ester compounds such as propylene glycol fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester; dibutylphthalate (DBP), dioctylphthalate (DOP), and diisononylphthalate (DINP). Phthalate ester compounds; Adipic acid ester compounds such as diisobutyl adipate and dioctyl adipate; Sebacic acid ester compounds such as dibutyl sebacate and di2-ethylhexyl sebacate; Glycerin fatty acid ester compounds such as glycerin tristearate and glycerin tricaprylate; Natural fats and oils such as liquid paraffin, coconut oil, palm oil and rapeseed oil are preferably mentioned.
The plasticizer may be added when the monomer is polymerized, or may be added when the foaming agent is impregnated.
The amount of the plasticizer added may be appropriately determined according to the desired expansion ratio and compressive elastic modulus, but is preferably 0.2 parts by mass or more and less than 3 parts by mass, preferably 0.4 parts by mass with respect to 100 parts by mass of the resin. More than parts and less than 1.6 parts by mass are more preferable. If the amount of the plasticizer added is 0.2 parts by mass or more, the secondary transition temperature becomes low, which is advantageous for pre-foaming and molding at a low temperature, and if it is less than 3 parts by mass, the foam is less likely to shrink. Good appearance is obtained.

Further, the foamed resin particles include a flame retardant, a flame retardant aid, a lubricant, a bond inhibitor, a fusion accelerator, an antistatic agent, a spreading agent, a bubble adjusting agent, and a cross-linking agent within a range that does not impair the physical properties. , Filler, colorant, heat insulating property improver (radiation inhibitor, etc.) and other additives may be included.

In the bead method, for example, the foamed resin particles are filled in the cavity of the mold, and the filled pre-foamed particles are preferably steam of 100 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 120 ° C. or lower. A foamed resin layer can be obtained by integrating the pre-foamed particles with each other by heat fusion while performing secondary foaming with a heating time of 10 seconds or more and 40 seconds or less using a heat medium such as the above. In this case, the average particle size of the generally used foamed resin particles is preferably 0.2 mm or more and 4 mm or less, and more preferably 0.5 mm or more and 2 mm or less. The average particle size of the foamed resin particles is defined by using a plurality of types of sieves having different meshes specified in JIS Z8801-1 “Test Sieve-Part 1: Metal Net Sieve”. It is obtained by stacking small sieves into large sieves, putting 100 g of foamed resin particles into the uppermost sieve, and vibrating the sieve to classify the foamable particles.
Specifically, a value obtained by multiplying the average particle size of the foamed resin particles remaining on the sieve of each opening by the number ratio thereof is calculated, and the sum of these values is taken as the average particle size of the foamed resin particles.
Average particle size = Σ (number ratio on each sieve x average particle size of particles on each sieve)
Here, the number ratio is a value obtained from the weight ratio of the effervescent particles remaining on each sieve and the size of the opening of each sieve.
Further, in the present invention, the foamed resin layer is not limited to the above-mentioned bead method, and is a resin composition for forming a foamed resin layer containing a resin for the foamed resin layer, a foaming agent, a plasticizer, an inorganic filler, and other necessary additives. A product is obtained by forming an unfoamed resin layer by a film-forming method such as an extrusion film-forming method using a T-die or a calendar film-forming method, and then foaming the product at 220 ° C. or higher and 250 ° C. or lower using a heating foaming furnace. You can also do it.

Further, as the foamed resin layer, a commercially available heat insulating board, for example, a bead method polystyrene foam heat insulating plate, an extruded polystyrene foam heat insulating plate, or the like can be used as long as it is within a predetermined expansion ratio and compressive elastic modulus. can.

The thickness of the foamed resin layer varies depending on the expansion ratio and the like, but is preferably 3 mm or more and 15 mm or less, more preferably 5 mm or more and 15 mm or less, and further preferably 5 mm or more and 12 mm or less. When the thickness of the foamed resin layer is within the above range, excellent heat insulating properties, load bearing resistance, and impact resistance can be obtained.
Further, the thickness of the foamed resin layer is thicker than that of the non-foamed resin layer described later. By being thicker than the non-foamed resin layer, excellent heat insulation, load resistance, and impact resistance can be obtained, and stress warpage due to the difference in elongation due to temperature with other layers such as the non-foamed resin layer. Is less likely to occur.

(Non-foamed resin layer 2)
The non-foamed resin layer is a layer that mainly imparts shape stability, water resistance, impact resistance, and scratch resistance to the decorative material of the present invention, and is a layer having a tensile elastic modulus of 180 MPa or more. preferable. If the tensile elastic modulus is less than 180 MPa, scratch resistance cannot be obtained. From the viewpoint of obtaining scratch resistance, the tensile elastic modulus is preferably 180 MPa or more and 3000 MPa or less, more preferably 1000 MPa or more and 3000 MPa or less, and further preferably 2000 MPa or more and 2500 MPa or less.
Further, when the tensile elastic modulus is within the above range, stress warpage due to a difference in elongation due to temperature or the like with another layer such as a foamed resin layer is less likely to occur. Here, for the tensile elastic modulus (E), a non-foamed resin layer punched into a dumbbell type test piece described in JIS K6732 (1996) is prepared, and a tensile compression tester is used under a temperature condition of 20 ° C. It was calculated by the following formula from the first straight line portion of the tensile stress-strain curve obtained by measuring under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 80 mm.
E = Δp / ΔE
E: Tension elastic modulus Δp: Stress difference due to the original average cross-sectional area between two points on a straight line ΔE: Strain difference between the same two points

The non-foamed resin layer preferably contains a thermoplastic resin.
Examples of the thermoplastic resin include polyvinyl chloride resins, polyvinyl acetate resins, polyvinyl alcohol resins and other polyvinyl resins, polyethylene, polypropylene, polystyrene, styrene-modified polyolefin resins, ethylene-vinyl acetate copolymer resins (EVA), and the like. Polyethylene resin such as ethylene- (meth) acrylic acid resin, polyester resin such as polyethylene terephthalate resin (PET resin), acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile- A simple substance and a copolymer of a thermoplastic resin such as a styrene copolymer, or a mixed resin thereof is preferably mentioned. Of these, polyolefin resins, acrylonitrile-butadiene-styrene copolymers, and polyvinyl chloride resins are preferable.

In the present invention, the non-foamed resin layer preferably contains an inorganic compound. By containing the inorganic compound, the coefficient of linear expansion of the non-foamed resin layer can be reduced, and as a result, the warpage of the decorative material of the present invention can be suppressed.
Examples of the inorganic compound include talc, calcium carbonate, silica, mica and the like.
The content of the inorganic compound is preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the resin component in the non-foamed resin layer. If it is less than 10 parts by mass, the linear expansion coefficient of the non-foamed resin layer may not be sufficiently reduced, and if it exceeds 70 parts by mass, the tensile elastic modulus of the non-foamed resin layer may be insufficient. .. A more preferable range of the content of the inorganic compound is 15 parts by mass or more and 65 parts by mass or less.

Further, the non-foamed resin layer may be composed of one layer or a laminate composed of two or more layers, but is a laminate composed of two or more layers, and is at least. It is preferable that one layer contains a glass component. That is, it is preferable that the non-foaming resin layer is a laminate composed of two or more layers, at least one layer is a thermoplastic resin layer, and the other one layer is a glass component layer containing a glass component. .. With such a configuration, excellent impact resistance can be obtained and shape stability is improved.
As the glass component layer containing a glass component, for example, a layer composed of glass fibers and the like are preferably mentioned.

In the present invention, the non-foamed resin layer is preferably a laminated body in which the thermoplastic resin layer and the glass component layer are alternately laminated, and among them, the first thermoplastic resin layer as shown in FIG. , A laminated body having a glass component layer and a second thermoplastic resin layer in this order is preferable.
When the non-foamed resin layer has a plurality of thermoplastic resin layers, the types of resins forming the plurality of thermoplastic resin layers may be the same or different, and the thickness of the plurality of thermoplastic resin layers may be the same. May be the same or different.

The thickness of the non-foamed resin layer is preferably 0.3 mm or more and 10 mm or less, and more preferably 1 mm or more and 5 mm or less. When the thickness of the non-foamed resin layer is within the above range, excellent water resistance, impact resistance, and scratch resistance can be obtained. In addition, stress warpage due to a difference in elongation due to temperature or the like with another layer such as a foamed resin layer is less likely to occur.
Further, the thickness of the non-foamed resin layer is thinner than that of the foamed resin layer as described above. Stress warpage due to the difference in elongation due to temperature or the like with other layers such as the foamed resin layer is less likely to occur.

(Decorative layer 3)
The decorative layer is a layer that imparts decorativeness to the decorative material of the present invention. For example, a concealing layer (solid printing layer) that is uniformly colored may be used, or various patterns may be printed using ink and a printing machine. It may be a pattern layer formed by printing, or it may be a layer in which a concealing layer and a pattern layer are combined (hereinafter, a pattern layer 33). The decorative layer may be a pattern provided by a transfer method or the like, a veneer or a sawn board obtained by thinly slicing wood, or a decorative sheet having a pattern on a colored base resin layer or base resin layer. But it may be. And among them, the decorative sheet shown below is more preferable. As shown in FIG. 2, the above-mentioned "decorative sheet" includes a base resin layer 4 and a pattern layer 33, an arbitrary layer such as a transparent resin layer 5 and a surface protection layer 6 described later, and the pattern layer 33 and the pattern layer 33. A laminated structure including an adhesive layer 7 for adhering the transparent resin layer 5 is preferable.

By providing the concealing layer, the base on which the decorative material of the present invention is provided can be concealed, and when the foamed resin layer, the non-foamed resin layer, or the like is colored or has uneven color, the intended color can be obtained. It can be given to adjust the color of the surface.
In addition, by providing the above pattern layer, a stone pattern that imitates the surface of rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), a cloth pattern that imitates a cloth grain or a cloth-like pattern, a tiled pattern, or a brick It is possible to add a pattern such as a stacking pattern or a pattern such as a parquet or a patchwork in which these are combined to the decorative sheet. These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing plates of the individual colors that make up the pattern. Will be done.

As the ink composition used for the decorative layer, a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is used. The binder resin is not particularly limited, and examples thereof include urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin, polyester resin, and nitrocellulose resin. Be done.
As the binder resin, any one of these can be used alone or in combination of two or more.
The colorants include carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petals, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, and isoindolinone. Organic pigments such as yellow and phthalocyanine blue, metal pigments consisting of scaly foil pieces such as dyes, aluminum and brass, titanium dioxide-coated mica, pearl gloss pigments consisting of scaly foil pieces such as basic lead carbonate, etc. Is preferably mentioned.

The thickness of the decorative layer is usually preferably about 5 μm or more and 3 mm or less.
When the decorative layer is a concealing layer (solid printing layer), a pattern layer, a pattern layer in which the concealing layer and the pattern layer are combined, or a pattern provided by a transfer method or the like, the thickness is preferably about 20 μm or less. When the decorative layer is a veneer or a sawn board, the thickness is preferably about 0.5 mm or more and 3 mm or less, and when the decorative layer is a decorative sheet, the thickness is preferably about 500 μm or less.
When the thickness of the decorative layer is within the above range, an excellent design can be imparted to the decorative material of the present invention, and concealment can be imparted.

(Base resin layer 4)
The base resin layer is a layer provided as desired, and is preferably a layer formed of a thermoplastic resin. As the thermoplastic resin, those exemplified as the thermoplastic resin provided in the foamed resin layer can be preferably mentioned. Of these, polyolefin resins are preferable, and polyethylene resins and polypropylene resins are more preferable.

The base resin layer may be transparent or colored, and is preferably colored from the viewpoint of concealing the base on which the decorative material is provided. As the colorant used, those exemplified as the colorant used in the decorative layer can be preferably mentioned.

The thickness of the base resin layer is preferably 10 μm or more and 150 μm or less, more preferably 30 μm or more and 100 μm or less, and further preferably 40 μm or more and 80 μm or less. When the thickness of the base resin layer is within the above range, it is easy to handle and the decorative material of the present invention does not become thicker than necessary.

Further, various additives such as a filler, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer may be added to the base resin layer, if necessary.

(Transparent resin layer 5)
The transparent resin layer is an arbitrary layer provided to protect the decorative layer, and is preferably a layer formed of a thermoplastic resin. As the thermoplastic resin, those exemplified as the thermoplastic resin provided in the foamed resin layer can be preferably mentioned. Of these, polyolefin resins are preferable, and polyethylene resins, polypropylene resins, and ionomer resins are more preferable.

The transparent resin layer is a transparent resin layer so that the decorative layer can be seen through. Here, transparent is a concept that includes not only colorless and transparent but also colored transparent and translucent.
Further, various additives such as a filler, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer are added to the transparent resin layer as necessary without impairing its transparency. May be good.

The thickness of the transparent resin layer is preferably 10 μm or more and 400 μm or less, more preferably 30 μm or more and 250 μm or less, and further preferably 50 μm or more and 100 μm or less. When the thickness of the transparent resin layer is within the above range, the decorative layer can be protected, the handling is easy, and the floor decorative material does not become thicker than necessary.

(Surface protection layer 6)
The surface protective layer is a layer provided as desired, which imparts surface characteristics such as impact resistance, load resistance, and scratch resistance to the decorative material of the present invention. The surface protective layer is provided on the outermost surface of the decorative material of the present invention.
The surface protective layer is preferably composed of a resin composition containing a curable resin coated on the decorative layer, or a transparent resin layer and an adhesive layer preferably provided, and cured. .. By containing the crosslink-cured curable resin, the surface characteristics of the decorative material of the present invention can be improved.

Examples of the curable resin used for forming the surface protective layer include an ionization radiation curable resin and a thermosetting resin, and a plurality of these are used, for example, an ionization radiation curable resin and a thermosetting resin. It may be a so-called hybrid type used together.
Of these, ionizing radiation curable resins are preferable from the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the surface characteristics, and some of them can be applied without a solvent and are easy to handle. From the viewpoint of ease, an electron beam curable resin is more preferable.

The ionizing radiation curable resin refers to a resin having an energy quantum capable of cross-linking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is cross-linked and cured by irradiating with ultraviolet rays or an electron beam. .. Specifically, it can be appropriately selected and used from the polymerizable monomer and the polymerizable oligomer or prepolymer conventionally used as an ionizing radiation curable resin.
As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate is particularly preferable. The polyfunctional (meth) acrylate may be any (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule, and is not particularly limited. One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

Next, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyester (meth) acrylate-based, or polyether (meth) Examples include acrylate type.
Further, as the above-mentioned polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer and a silicone (meth) acrylate-based oligomer having a polysiloxane bond in the main chain are also used. Oligomers, aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resins having many reactive groups in small molecules, or molecules such as novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. Among them are oligomers having a cationically polymerizable functional group.

In the present invention, monofunctional (meth) acrylate can be appropriately used in combination with the above-mentioned polyfunctional (meth) acrylate and the like for the purpose of lowering the viscosity thereof, as long as the object of the present invention is not impaired. .. One of these monofunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

Examples of the thermosetting resin include epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl group functional acrylic resin, carboxyl functional acrylic resin, and amide functional. Sexual copolymers, urethane resins and the like are preferably mentioned.

Further, as the thermosetting resin, a two-component curable resin is also preferably mentioned, and specifically, a two-component curable resin of a polyol and an isocyanate is preferable.
Here, as the above-mentioned polyol, for example, an acrylic polyol, a polyester polyol, an epoxy polyol and the like are preferably mentioned.
The isocyanate may be, for example, a polyvalent isocyanate having two or more isocyanate groups in the molecule, for example, 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, etc. Aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, aliphatic isocyanates such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Polyisocyanates such as (or alicyclic) isocyanates are used. Alternatively, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like are also used.

In addition, various additives can be contained in the resin composition constituting the surface protective layer as long as the performance is not impaired.
Examples of the above-mentioned various additives include an ultraviolet absorber (UVA), a light stabilizer (HALS, etc.), a polymerization inhibitor, a cross-linking agent, an antistatic agent, an adhesive improver, an antioxidant, a leveling agent, and a thixogenic property. Examples include agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents and the like.

The thickness of the surface protective layer is preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 20 μm or less. When the thickness of the surface protective layer is within the above range, excellent surface characteristics can be obtained.

(Adhesive layer 7)
The adhesive layer is a layer provided as necessary when laminating the resin layer when the base resin layer and the transparent resin layer are provided.
Examples of the adhesive used for the adhesive layer include urethane adhesive, acrylic adhesive, acrylic / urethane adhesive, polyester adhesive, polyester urethane adhesive, polyamide adhesive, polystyrene adhesive, cellulose adhesive and the like. Preferred. These adhesives can be used alone or as a mixture of two or more.

The thickness of the adhesive layer is preferably 1 μm or more and 30 μm or less, and more preferably 3 μm or more and 15 μm or less. When the thickness of the adhesive layer is within the above range, good adhesiveness can be obtained, and the decorative material of the present invention does not become thicker than necessary.

The decorative material of the present invention having each of the above layers has excellent impact resistance, heat insulation, water resistance, load resistance, scratch resistance, and ease of construction. It is suitable for window frames and flooring materials, especially for water-related applications such as toilets, washbasins, and kitchens.
The thickness of the decorative material of the present invention is preferably 5 mm or more, more preferably 6 mm or more and 30 mm or less, from the viewpoint of obtaining excellent impact resistance, heat insulating property, water resistance, load resistance, and scratch resistance. More preferably, it is 10 mm or more and 20 mm or less.
Further, in consideration of ease of construction, it is preferable that the thickness is the same as that of the wood flooring material provided in a place other than the water area such as a living room or a corridor.
The thickness of the wood flooring material is usually 8 mm, 12 mm, 15 mm, etc., and 12 mm is the standard thickness.
Depending on the characteristics of the final product, the decorative material of the present invention may be subjected to actual processing, V-shaped groove provision, chamfering on all four sides, etc. using a tenor, a router, or the like.
FIG. 4 shows a structure in which a male fruit 8a and a female fruit 8b are provided on the non-foamed resin layer 2 in the embodiment shown in FIG. 2 of the decorative material of the present invention.
Further, the decorative material of the present invention preferably has excellent weather resistance, and in particular, when used as a decorative material for a window frame as described later, the appearance change is slight even after a 4000-hour test in a sunshine weather test. It is preferable to have.

The decorative material of the present invention is used for at least a part of a window frame of a building and is a decorative material for a window frame. The decorative material for a window frame is a foamed resin layer and at least a part of the surface of the foamed resin layer. The coating layer includes a decorative layer and a non-foamed resin layer on the foamed resin layer side of the decorative layer, and the coating layer is the upper side of the foamed resin layer. It can be suitably used as a decorative material for a window frame provided on the surface and the front surface.

In the decorative material for window frames, the coating layer covers at least a part of the surface of the foamed resin layer, and is provided on the upper surface and the front side surface of the foamed resin layer.
The upper surface of the foamed resin layer is the upper surface when the window frame decorative material is applied, and the front surface of the foamed resin layer is the window frame decorative material. This is the surface opposite to the outer wall surface of the building when it is constructed. By providing the coating layer on the upper surface and the front surface of the foamed resin layer in this way, a portion that can be seen by the user when the decorative material for the window frame is applied to the window. A mode in which a coating layer (decorative layer) is provided only on the surface can be used.
10 (a) to 10 (d) are cross-sectional views in the thickness direction of the raw material laminate and the window frame decorative material used when assembling the window frame decorative material, which is a preferable example of the decorative material of the present invention.
The decorative material for a window frame shown in FIG. 10A can be obtained, for example, by the following method.
First, the non-foamed resin layer 102 laminated on the decorative layer 103 is provided with a groove-shaped cut 106 having a triangular cross-sectional view, and the foamed resin layer 101 is laminated at a position adjacent to the cut 106. Then, the raw material laminate is bent at the cut 106 portion so that the foamed resin layer 101 is on the inside, and the non-foamed resin layer 102 is attached to the front end surface of the foamed resin layer 101 via pressure bonding or an adhesive. Can be obtained at.
Further, the decorative material for a window frame shown in FIG. 10B can be obtained, for example, by the following method.
First, a groove-shaped cut having a triangular cross-sectional view is provided on the non-foamed resin layer 102 laminated on the decorative layer 103, and the foamed resin layer 101 is laminated at a position adjacent to the cut to form the foamed resin layer 101. The vicinity of the side surface on the cut side is cut into a trapezoidal shape so as to be a continuous surface with the cut, and a groove-shaped cut 106'is provided with a triangular cross section. Next, another trapezoidal foamed resin layer 101 cut out by the foamed resin layer 101 is laminated on the non-foamed layer 102 via the cut 106'to prepare a raw material laminate. The trapezoidal foamed resin layer 101 is preferably laminated so as to have a continuous surface with the cutout 106'. Then, the foamed resin layer 101 is bent at the cut 106'so as to be inside, and the trapezoidal foamed resin layer 101 is attached to the end surface of the left foamed resin layer 101 on the cut 106' side by pressure bonding or an adhesive. You can get it by attaching it.
Further, the decorative board for the window frame shown in FIG. 10C can be obtained by, for example, the following method.
First, the non-foamed resin layer 102 laminated on the decorative layer 103 is provided with two groove-shaped cuts 106 having a triangular cross-sectional view, and the foamed resin layer 101 is laminated on the outside of the cuts 106 provided on the left side. Next, a cutout portion 107 having a shape into which the non-foamed layer 102 and the decorative layer 103 on the outside of the right cut 106 can be fitted is provided near the side surface of the foamed resin layer 101 on the side surface opposite to the non-foamed layer 102 side. A laminate is produced. Next, the foamed resin layer 101 is bent at the cut 106 portion so that the foamed resin layer 101 is on the inside, and the foamed resin layer 101 and the non-foamed layer 102 are attached by pressure bonding or via an adhesive.
Further, the decorative board for the window frame shown in FIG. 10D can be obtained by, for example, the following method.
First, the non-foamed resin layer 102 laminated on the decorative layer 103 is provided with two groove-shaped cuts 106 having a triangular cross-sectional view, and the foamed resin layer 101 is laminated on each of the outer sides of the cuts 106 provided on the left and right. do. Next, the foamed resin layer 101, the non-foamed layer 102, and the decorative layer 103 provided on the outside of the cut 106 on the right side are formed near the side surface opposite to the non-foamed layer 102 side of the cut 106 side surface of the foamed resin layer 101 provided on the left side. A raw material laminate is produced by providing a cutout portion 107'having a shape to be fitted. Next, the foamed resin layer 101 on the left side is bent at the cut 106 portion so as to be inside, and the foamed resin layer 101 on the left side, the non-foamed layer 102, and the foamed resin layer 101 on the right side are attached by pressure bonding or an adhesive. By doing so, you can get it.
In the window frame decorative materials shown in FIGS. 10 (c) and 10 (d), the lower surface of the foamed resin layer 101 and the coating layer (decorative layer 103 and the non-foamed resin layer 102) provided on the lower surface. May form the same surface, or one of them may form a protruding state.

Further, in the present invention, it is preferable that the foamed resin layer has a first region provided with a lower protruding portion that protrudes downward from the front end portion to the vicinity thereof.
FIG. 6 shows an example of a decorative material for a window frame, which is one of the uses of the decorative material of the present invention. FIG. 6A is a cross-sectional view in the thickness direction, FIG. 6B shows an example of a perspective view of the window frame decorative material (window frame) 60, and the window frame decorative material (window frame) 60 is In the vicinity of one end (the front end) of the decorative material of the present invention in which the non-foamed resin layer 62 and the decorative layer 63 are laminated in this order on the foamed resin layer 61, the foamed resin layer 61 is inside. A lower protruding portion (hereinafter, also referred to as a bent portion 65) in a folded state is formed. Further, the first region provided with the lower protruding portion (bending portion 65) is, for example, the region shown by A in FIG. 6 (b).
As shown in FIG. 6C, for example, such a decorative material 60 for a window frame is formed in a non-foamed resin layer 62 laminated on a decorative layer 63 with an M-shaped and groove-shaped cut in a cross-sectional view. 64 is provided at two places, a non-foamed resin layer 62 is laminated between the cuts 64 to prepare a raw material laminate, and another foamed resin layer 61 is laminated at a position separated by the thickness of the foamed resin layer 61. After that, the foamed resin layer 61 is bent at the cut 64 portion so as to be on the inside, and the foamed resin layers 61 are attached to each other by pressure bonding or via an adhesive. A decorative material for a window frame having a structure as shown can be obtained.
Further, as another configuration of the decorative material for the window frame, for example, the non-foamed resin layer 62 in a state of being laminated on the decorative layer 63 is provided with four groove-shaped cuts 66 having a triangular cross-sectional view, and the cuts 66 are provided. The foamed resin layer 61 is adhered onto the non-foamed resin layer 62 at a portion adjacent to the above, and a cutout portion 67 having a shape in which both ends of the foamed resin layer 61 in the middle can be fitted is provided near the side surfaces of the two foamed resin layers. Then, the foamed resin layer 61 is bent at the cut 66 portion so as to be inside, and the foamed resin layers 61 are bonded to each other via pressure bonding or an adhesive to form a window having a structure as shown in FIG. 6D. A decorative material for a frame can be obtained.
Further, as yet another configuration of the decorative material for the window frame, for example, the non-foamed resin layer 62 in a state of being laminated on the decorative layer 63 is provided with four groove-shaped cuts 66 having a triangular cross-sectional view inside. The foamed resin layer 61 (a) is laminated between the two cuts 66 provided in the above, and the foamed resin layers 61 (b) and 61 (c) are respectively non-foamed resin in the portions adjacent to the other cuts 66. A cutout portion 67'having a shape that adheres to the layer 62 and is fitted so that the side surfaces of the two foamed resin layers 61 (b) and 61 (c) do not come into contact with the foamed resin layer 61 (a) in the middle is provided. .. Then, the foamed resin layer 61 (a) is bent at the cut 66 portion so that the foamed resin layer 61 (a) is on the inside, and the foamed resin layers 61 (b) and 61 (c) are attached to each other by crimping or using an adhesive. Even if the processed dimensions of the foamed resin layers 61 (b) and 61 (c) as shown in (e) are rough, it is possible to obtain a decorative material for a window frame having a structure that can be folded without any problem. The cutout portion 67'provided of the foamed resin layers 61 (b) and 61 (c) before being bent at the cut 66 portion is a space 67 after the foamed resin layers 61 (b) and 61 (c) are attached to each other. '.
In the window frame decorative material, as shown in FIGS. 6A to 6E, the coating layer (non-foaming resin layer 62 and decorative layer 63) is further formed on the lower protruding portion of the foamed resin layer 61. It is preferable that the coating layer is provided on the lower surface, and the portion of the coating layer covering the upper surface of the foamed resin layer 61 and the portion of the coating layer covering the front surface of the foamed resin layer 61 are continuous. Is preferable.
Further, the decorative material for the window frame includes a portion of the foamed resin layer 61 of the coating layer that covers the front surface and a lower protruding portion (bent portion 65) of the foamed resin layer 61 of the coating layer. It is preferable that the portion covering the surface is continuous, the portion covering the upper surface of the foamed resin layer 61 of the coating layer, the portion covering the front side surface of the foamed resin layer of the coating layer, and the coating. It is preferable that the portion of the layer covering the lower surface of the lower protruding portion of the foamed resin layer is continuous.
Further, both side surfaces of the foamed resin layer in the first region and both side surfaces of the foamed resin layer excluding the first region (region B in FIG. 6B) are on the same surface. The decorative material for the window frame preferably has a rectangular shape in a plan view.
The foamed resin layers provided in FIGS. 6 (c) to 6 (e) and FIGS. 10 (a) to 10 (d) are provided by laminating with a coating layer in a flat state and then cutting into a desired shape. May be good.

As for such a decorative material for window frames, an edge tape 71, which is a wood end material, is attached to at least one side surface of the bent portion as in the decorative material for window frames (window frame) 701 shown in FIG. 7 (a). It is preferable that it is worn. Examples of the edge tape include a Panefuri band manufactured by Panefuri Kogyo Co., Ltd., Marblet S, and the like. In addition to this, the decorative layer 3 is attached to the side surface, or the non-foamed resin layer 2 is attached to the side surface, so that the decorative layer 3 (the coating layer) is provided on at least one side surface in the first region. You may. In this case, a group consisting of a coating layer covering at least a part of the surface of the foamed resin layer, and an edge tape, a decorative layer and a coating layer attached to at least one side surface of the foamed resin layer in the first region. It is preferable that at least one of the selected patterns has the same pattern.
Further, the window frame decorative material is provided with a notch 73 on one of the side surfaces to which the edge tape 71 is attached, as in the window frame decorative material (window frame) 701 shown in FIG. 7 (b), for example. Notches 73 may be provided on both sides to which the edge tape 71 is attached, as in the window frame decorative material (window frame) 702 shown in FIG. 7 (c).
The edge tape 71 on the side surface is preferably provided at a position where the notch 73 is not formed.
Further, when the notch 73 is provided on one of the side surfaces to which the edge tape 71 is attached, one of the both side surfaces in the first region A of the foamed resin layer 61 is the first region A in the foamed resin layer 61. It is preferable that the region B excluding the above-mentioned area B has an L-shape in a plan view protruding from one of the two side surfaces, and when notches 73 are provided on both sides to which the edge tape 71 is attached, the foamed resin is described above. It is preferable that both side surfaces in the first region A of the layer 61 project from both side surfaces in the region B excluding the first region A in the foamed resin layer 61 and have a T-shape in a plan view.
Further, in the present invention, the foamed resin layer may have a plan view trapezoidal shape as shown in FIG. The foamed resin layer 110 shown in FIG. 11 can be applied to a window provided at a corner, for example, by combining short sides.
In the window frame decorative material, the decorative material has a decorative layer, a non-foamed resin layer, and a foamed resin layer, and the ratio of the total thickness of the decorative layer and the non-foamed resin layer to the thickness of the foamed resin layer, and foaming. Since the compressive elastic modulus of the resin layer is specified to a predetermined value, it is excellent in water resistance and heat insulating property, and also in load resistance, and further, near one end of the decorative material. Since it has a bent portion, it is possible to suitably prevent the occurrence of warpage.
In such a decorative material for a window frame, it is preferable that the foamed resin layer is composed of a plurality of foamed resin members. Specifically, for example, in the case of the configurations shown in FIGS. 6 (a) to 6 (e), the foamed resin layer is composed of three members, and the configurations shown in FIGS. 8 (a) and 8 (b). In the case of, the foamed resin layer is composed of three members. Note that FIG. 8 shows an example of a decorative material for a window frame which is a preferable example of the decorative material of the present invention, and FIG. 8A shows an example of a decorative material for a window frame which is a preferable example of the decorative material of the present invention. It is a cross-sectional view in the thickness direction of the raw material laminate used in this case, and the decorative material (window frame) for a window frame is the present invention in which a non-foamed resin layer 82 and a decorative layer 83 are laminated in this order on a foamed resin layer 81. A lower protruding portion (hereinafter, also referred to as a bent portion) in a folded state so that the foamed resin layer 81 is inside is formed in the vicinity of one end portion (the end portion on the front side thereof) of the decorative material. There is.
In such a decorative material for a window frame, for example, as shown in FIG. 8A, a groove-shaped cut 86 having a triangular cross section is formed in a non-foamed resin layer 82 laminated on a decorative layer 83. A foamed resin layer 81 is laminated on the outside of the cut 86, and another foamed resin layer 81 is laminated at a position separated by the thickness of the foamed resin layer 81 to prepare a raw material laminate, and then foamed. The resin layer 81 is bent at the cut 86 portion so as to be on the inside, and the foamed resin layers 81 are bonded to each other via pressure bonding or an adhesive to form a window frame cosmetic having a structure as shown in FIG. 8 (a). The material can be obtained.
Further, as shown in FIG. 8B, a foamed resin having two groove-shaped cuts 66 having a triangular cross-sectional view and having the side surfaces tapered so that the edges of the cuts 66 are arranged at the cuts 66. After laminating the layers 81 (b) and 81 (c), the foamed resin layers 81 (b) and 81 (c) are bent at the cut 86 portion so that the foamed resin layers 81 (b) and 81 (c) are on the inside, and the foamed resin layers 81 (b) and 81 (c) are formed. c) By crimping or sticking each other via an adhesive, a decorative material for a window frame having a structure as shown in FIG. 8 (b) can be obtained.
Further, the decorative material of the present invention provided with the decorative layer 3 described above has excellent weather resistance, and particularly when the decorative material of the present invention is used for a window frame, the sunshine weather test 4000 with the decorative layer side as the surface. It is preferable that the change in appearance is slight even after a certain period of time (test conditions described later).

[Manufacturing method of decorative material]
The decorative material of the present invention can be produced, for example, through the following steps.

(Preparation process of foamed resin layer)
First, the foamed resin layer is prepared.
As described above, the foamed resin layer is preferably formed by a film forming method such as a bead method or a T-die extrusion film forming method or a calendar film forming method using a resin composition for forming a foamed resin layer, and the foaming magnification is preferably 5 times. It is foamed at a ratio of 20 times or more so that the compressive elastic modulus is 15 MPa or more.
The foaming ratio and compressive elastic modulus of the foamed resin layer can be appropriately adjusted depending on the foaming temperature at the time of foaming, the type of resin, the amount of the foaming agent and the plasticizer used, and the like.

(Preparation process for non-foamed resin layer)
Next, the foamed resin layer is prepared.
The non-foamed resin layer is formed by a film forming method such as an extrusion film forming method using a T die or a calendar film forming method, and is produced so that the tensile elastic modulus is 180 MPa or more.
The tensile elastic modulus of the non-foamed resin layer can be appropriately adjusted depending on the type of resin, the type of inorganic compound, the amount used, and the like.

(Formation process of decorative layer)
A decorative layer is formed on the non-foamed resin layer or a base resin layer provided as needed using the ink composition. The ink composition may be applied by, for example, gravure printing, offset printing, screen printing, flexographic printing, inkjet printing, or the like. When forming a concealing layer (solid printing layer), for example, it may be formed by various coating methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.

(Laminating process of transparent resin layer)
After forming the decorative layer, the transparent resin layer is preferably formed via an adhesive layer, if necessary. The adhesive layer may be formed by, for example, various coating methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating, and an extrusion film forming method using a T-die. The transparent resin is laminated at the same time as the film formation by the extrusion film formation method using the T die, and the transparent resin is preliminarily formed by the film formation method such as the extrusion film formation method using the T die or the calendar film formation method, and the dry lamination method or the like. It may be formed by a method of laminating by a thermal lamination method or the like.

(Process of forming surface protective layer)
The surface protective layer is a curable resin on the decorative layer or on the transparent resin layer after the step of forming the decorative layer or, in the case of laminating the transparent resin layer, after the step of laminating the resin layer. The composition is applied, and the uncured resin layer is applied by a known method such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, etc. so that the thickness after curing is about 3 μm or more and 40 μm or less. Then, the uncured resin layer can be formed by applying heat or irradiating the uncured resin layer with ionizing radiation such as an electron beam or ultraviolet rays to cure the uncured resin layer.

The heating temperature in the case of thermosetting is appropriately determined according to the resin used.
When an electron beam is used as ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but the uncured resin layer can usually be cured at an acceleration voltage of 70 kV or more and 300 kV or less. preferable. The irradiation dose is preferably an amount at which the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 kGy or more and 300 kGy or less (0.5 Mrad or more and 30 Mrad or less), preferably 10 kGy or more and 50 kGy or less (1 Mrad or more and 5 Mrad or less).
The electron beam source is not particularly limited, and for example, various electron beam accelerators such as cockloft Walton type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamistron type, and high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 nm or more and 380 nm or less are emitted.
The ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.

(Attachment process between non-foamed resin layer and decorative layer)
When the decorative layer is a decorative sheet, the non-foamed resin layer and the decorative layer can be attached to each other by using, for example, a heat-sensitive adhesive, a pressure-sensitive adhesive, or a hot melt adhesive. As the hot melt adhesive, for example, a reactive hot melt adhesive such as a urethane-based reactive hot melt (hereinafter, referred to as "PUR-based adhesive") is preferably used. This PUR-based adhesive contains a functional group (isocyanate group) that reacts with moisture in its components, and after cooling and curing, reacts with the moisture adhering to the substrate or the decorative sheet and the moisture given through them.
After the reaction, it does not melt even when heated and has a characteristic of having high adhesive strength.

(Attachment process of foamed resin layer and non-foamed resin layer)
The foamed resin layer obtained in the preparation step of the foamed resin layer and the non-foamed resin layer forming the decorative layer are attached by using the adhesive shown in the bonding step between the non-foamed resin layer and the decorative layer. Can be used.

In the window frame decorative material which is a preferable example of the decorative material of the present invention, the decorative material has a decorative layer, a non-foamed resin layer and a foamed resin layer, and the decorative layer and the non-foamed resin layer with respect to the thickness of the foamed resin layer Since the ratio of the total thickness and the compressive elasticity of the foamed resin layer are defined by predetermined values, the water resistance and the heat insulating property are excellent, and the load resistance is also excellent.
FIG. 9 (a) is a cross-sectional view showing an example in which a window frame decorative material, which is a preferable example of the decorative material of the present invention, is applied to a window of a building, and FIG. 9 (b) is a sectional view showing an example of the decorative material of the present invention. 9A is a plan view showing an example in which a decorative material for a window frame, which is a preferable example of the above, is applied to a window of a building, and FIG. 9C shows a decorative material for a window frame, which is a preferable example of the decorative material of the present invention, for a building. It is a perspective view which shows an example which was constructed in the window of.
That is, the window frame decorative material 90, which is a preferable example of the present invention, is usually installed on the indoor side of the lower part of the window 93 provided on the outer wall surface 91 of the building via an adhesive portion 92 such as mortar.
The window of the building to which the decorative material for the window frame, which is a preferable example of the present invention, is applied is not particularly limited, and for example, a window frame including a bay window stand can be preferably mentioned.
Further, the decorative material for a window frame, which is a preferable example of the present invention, is used for at least a part of the window frame. For example, in the case of a square window frame, the present invention covers any part or all of the four sides of the window frame. A decorative material for a window frame, which is a preferable example of the invention, is applied. Above all, it can be suitably installed on the lower side of the window frame.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

(Evaluation and measurement method)
The decorative materials obtained in Examples and Comparative Examples were evaluated and measured by the following methods.
(Evaluation of load bearing capacity)
As shown in FIG. 13, four metal jigs 52 having a square shape with a side of 2 cm square in contact with the sample surface of the decorative material 51 are placed so that the load is evenly applied to the four metal jigs 52. Place a weight under the following three conditions and leave it for one week. After that, a pass / fail judgment was made by visually observing the appearance state immediately after removing the weight.
If no significant dent marks could be discriminated, it was judged as "passed".
In addition, if the evaluation is ◎, it is judged that it can be used for flooring, if it is ○, it is judged that it can be used for window frames other than flooring, and if it is △, a slight dent mark is confirmed. However, it was judged that it could be used for window frames, and if it was x, it was judged that it could not be used for flooring or window frames.
Condition 1: 80 kg load (pressure: 5 kg / cm ² )
Condition 2: 48 kg load (pressure: 3 kg / cm ² )
Condition 3: 16 kg load (pressure: 1 kg / cm ² )
⊚: Passed under condition 1 ○: Passed under condition 2 △: Passed under condition 3 ×: Failed under condition 3

(Evaluation of tensile elastic modulus)
<Preparation of test piece>
The test piece of the non-foamed resin layer from the decorative materials according to Examples and Comparative Examples was cut out into a dumbbell type test piece described in JIS K6732 (1996) using an electric saw. After that, a factor (saw) that hinders the measurement of the stretching direction was removed with sandpaper to prepare a test piece.
<Measurement conditions>
The basic measurement conditions were set with reference to the items described in JIS K716-11994 (ISO 527-1: 1993).
That is, a digital caliper capable of reading up to 0.01 mm was used to measure the dimensions of the test piece, and the width and thickness were measured to determine the cross-sectional area Smm ² of the test piece.
The test piece was measured by fixing both ends in the length direction with a gripper.
The distance between the gripping tools is not changed during a series of tests, but as described above, the end of the test piece is gripped by the gripping tool, and the distance between the gripped gripping tools is measured with the above digital caliper. The initial length L0 = 80 mm ± 1%. When the device detection stress at that time exceeded the range of ± 1 MPa, the test piece was re-grasped.
The tensile stress follows the calculation method of the JIS standard, and the tensile force per unit area calculated based on the initial cross-sectional area is handled in MPa units.
The tensile elastic modulus is measured according to the JIS standard, and the stress (load) difference Δp (σ1-σ2) corresponding to the tensile strain value (elongation) ε1 = 0.10% to ε2 = 0.25% is strained. The tensile elastic modulus E was calculated by dividing by the difference ΔE (ε1-ε2). FIG. 5 shows an example of an elastic modulus chart showing the relationship between the load (N) and the elongation (%) on the test piece.
The tensile speed was measured using a measuring device conforming to the JIS standard, and this measurement was performed at a setting of 50 mm / min.
The initial load point was set to ≥ 0.3N, and the initial load point was used as the start point of the calculation instead of the test start point.
In the test, the measurement using Tencilon RTC-1310A manufactured by A & D Co., Ltd. was carried out 5 times, the maximum value and the minimum value of the tensile elastic modulus were excluded, and the average value of 3 points was recorded.

(Evaluation of coefficient of linear expansion)
A rectangular parallelepiped test piece with a length of 145 mm and a width of 300 mm is cut out from each layer of the decorative material, and a test is performed when the test piece temperature is stabilized at 0 ° C. and 40 ° C. using a constant temperature bath (built-in chamber TBL-6E20W0P2T manufactured by Espec). With respect to the width and length of the piece, the dimensions of a total of three points, which are 50 mm from the center and the end, are measured using a digital caliper that can read up to 0.01 mm.
The amount of dimensional change is calculated from the length dimensions obtained at each temperature and each location, and the value divided by the dimensional value at 0 ° C. is defined as the dimensional change rate: ΔL.
The coefficient of linear expansion at each measurement point is obtained by dividing ΔL obtained above by the amount of temperature change: ΔT, and the average value of the coefficient of linear expansion at three points of length is taken as the coefficient of linear expansion.

(Evaluation of shape stability (evaluation of warpage))
As shown in FIGS. 12 (a) and 12 (b), the window frame decorative material 60 and the decorative materials 50a to 50a are applied on the mortar with the urethane adhesive 55 at a pitch of 300 mm and applied on the mortar ( Cured for 1 week). The following criteria are stipulated for the case of using it for a window frame (Fig. 12 (a)) and the case of using it for a floor (floor) (4 sheets of decorative materials 50a to d, Fig. 12 (b)). Each was evaluated. The warp is the amount of warp per 300 mm in the length direction, the value of + (plus) is the warp of the mountain state (convex), and the value of-(minus) is the warp of the valley (concave). Is. Then, as shown in FIGS. 14 (a) and 15 (a), a metal square columnar jig 65 having a length of 300 mm is placed on a test body (decorative material 60 for a window frame) to open the warp in a mountain state at both ends. The gap amounts r1 and r2 are measured and are average values thereof. As shown in FIGS. 14 (b) and 15 (b), the warp in the valley state is the same as the warp in the mountain state, with the amount of gap r3 formed between the jig 65 and the test piece (decorative material 50c). The maximum value. Note that FIG. 14A is a diagram illustrating a method for evaluating the warp of the decorative material for a window frame according to the present invention, and FIG. 14B is a diagram for explaining a method for evaluating the warp of the decorative material according to the present invention. FIG. 15A is a cross-sectional view showing a method for measuring the amount of warpage in a mountain state (convex shape), and FIG. 15B is a measurement of the amount of warpage in a valley state (concave shape). It is sectional drawing which shows the method.
<Window frame standard>
After being left in an environment of 5 ° C. for 3 days, it was left in an environment of 60 ° C. for 3 days, and the amount of width warp at the end of each condition was evaluated according to the following criteria. As the test body, the decorative material 60 for the window frame shown in FIGS. 6 (a) and 6 (b) was used. The dimensions of the window frame decorative material 60 when viewed in a plan view are 450 mm in width and 900 mm in length.
◯: ± 0.6 mm or less Δ: 0.6 mm or more, 1 mm or less, or less than -0.6 mm -1 mm or more ×: ± 1 mm or more <Floor standard>
After being left in an environment of 5 ° C. for 3 days, it was left in an environment of 40 ° C. for 3 days, and the amount of width warp at the end of each condition was evaluated according to the following criteria. The dimensions of the decorative material 50 when viewed in a plan view are 450 mm in width and 900 mm in length, and four of them are arranged side by side as shown in FIG. 12 (b), and the warp is as shown in FIG. 14 (b). One sheet was selected and measured.
◯: ± 0.6 mm or less Δ: 0.6 mm or more, 1 mm or less, or less than -0.6 mm, -1 mm or more ×: ± 1 mm or more <Comprehensive evaluation>
The overall evaluation was based on the following criteria.
◎: Window frame standard ○
○: Window frame standard △ and floor standard ○
△: Floor standard △
×: Floor standard ×

(Weather resistance test)
Sunshine weather meter: WEL-300 (manufactured by Suga Test Instruments Co., Ltd.) was used to irradiate sunshine carbon arc light from the side of the decorative layer under the following conditions, and the appearance state when the test was performed for 4000 hours was visually evaluated. .. As for the test conditions, one cycle in which step 2 is performed after step 1 below is set to 2 hours, and after one cycle, the test is repeated 2000 times in the manner of step 1 of the second cycle, and the evaluation is performed by defining the following criteria. bottom. The sunshine carbon arc light is irradiated through both steps 1 and 2.
◯: Level at which changes can hardly be recognized visually Δ: Level at which changes can be recognized but minor ×: Level at which changes can be clearly confirmed-: Not tested <Step 1>
Black panel temperature: 63 ° C, humidity: 50%
Operating time: 1 hour 42 minutes <Step 2>
Tank temperature: 40 ° C, humidity: 90%
Driving time: 18 minutes

(Example 1)
A stone pattern layer having a thickness of 2 μm was formed on a colored polypropylene resin film (thickness: 60 μm, color: white) using an ink composition (acrylic urethane) by gravure printing.
Next, an adhesive layer having a thickness of 2 μm was formed using a urethane-based dry laminating adhesive, and a transparent polypropylene resin film (thickness: 80 μm) was dry-laminated on the pattern layer.
A primer layer having a thickness of 1 μm was formed on the transparent polypropylene resin film using a two-component curable urethane resin. Then, an electron beam-curable resin composition (acrylate-based) is applied onto the primer layer at a coating amount of 15 g / m ² by gravure printing to form a coating film, and the coating film is cross-linked and cured by irradiating with an electron beam. A surface protective layer (thickness: 15 μm) was formed to prepare a decorative sheet (thickness: 160 μm), which was used as a decorative layer.
Next, an ABS resin sheet (tensile elasticity; 2400 MPa, thickness; 2 mm) containing 20% by mass of talc is prepared as the non-foamed resin layer, and faces the colored polypropylene resin film (base resin layer) of the decorative sheet. As described above, the non-foamed resin layer and the decorative sheet were attached by dry laminating via a urethane-based dry laminating adhesive.
Next, EPS resin (foaming agent; butane (7 parts by mass with respect to 100 parts by mass of polystyrene resin), plasticizer; liquid paraffin (0.15 parts by mass with respect to 100 parts by mass of polystyrene resin)) was used as the foamed resin layer. A foamed resin layer (foaming ratio; 10 times, polystyrene elastic coefficient; 43 MPa, thickness; 9 mm) prepared by the bead method was prepared, and the non-foamed resin layer and the foamed resin layer to which the above-mentioned decorative sheet was attached were attached. , PUR-based adhesive was used for sticking to prepare a decorative material.
Table 1 shows the results of evaluating the obtained decorative materials.

Examples 2 to 8 and Comparative Examples 1 to 3
A decorative material was produced in the same manner as in Example 1 except that the foamed resin layer and the non-foamed resin layer shown in Table 1 were replaced.
Table 1 shows the results of evaluating the obtained decorative materials.

In Table 1, the PVC according to Example 2 and Comparative Example 1 is a ^{vinyl chloride sheet obtained by adding a glass fiber resin to reduce the linear expansion coefficient to 5 × 10-5} / ° C. (Example 2 has a thickness of 4 mm). , Comparative Example 1 has a thickness of 5 mm), PP according to Examples 3 and 4 is a polypropylene resin sheet containing 45% by mass of talc, and PE according to Examples 5 and 6 and Comparative Example 2 contains 20% by mass of talc. The PE resin sheet containing the PP, and the PP according to Comparative Example 3, is a polypropylene resin sheet having an inorganic compound content such as talc of less than 10% by mass.
When the decorative material for the window frame having the structure shown in FIG. 6 (a) was manufactured using the decorative materials according to Examples and Comparative Examples, since all the decorative materials were made of non-wood material, the conventional one made of wood material was used. It was superior in water resistance and heat insulation to decorative materials. Further, the decorative materials according to Examples and Comparative Examples 1 and 2 were able to prevent the occurrence of warpage particularly preferably, but the decorative materials for window frames using the decorative materials according to Comparative Example 3 generated a large warp. ..
Further, the decorative material according to Example 1 was excellent in the weather resistance test.

According to the present invention, it is possible to obtain a decorative material which is excellent in water resistance and heat insulating property, can suppress the occurrence of warpage, and is also excellent in load resistance. The decorative material of the present invention is suitably used for flooring materials for houses, especially flooring materials for water-related applications such as toilets, washbasins, and kitchens, and window frames.

1, 61, 61 (a) to (c), 81, 81 (b), (c), 101, 110 Foamed resin layer 2, 62, 82, 102 Non-foamed resin layer 3, 63, 83, 103 Decorative layer 4 Base resin layer 5 Transparent resin layer
6 Surface protection layer 7 Adhesive layer 8a Male 8b Female 10, 50a to d, 51 Decorative material 21 First thermoplastic resin layer 22 Glass component layer 23 Second thermoplastic resin layer 33 Pattern layer 52 Metal jig 55 Urethane Adhesives 60, 701, 702, 90 Decorative materials for window frames 64, 66, 86, 106, 106'Cut 65 Bent 67, 107, 107' Cutout 71 Edge tape 73 Cutout 91 Outer wall surface 92 Adhesive 93 Glass window r1 to r3 Gap amount

Claims (4)

A decorative material having a decorative layer, a non-foamed resin layer, and a foamed resin layer.
The total thickness of the decorative layer and the non-foamed resin layer is 50% or less of the thickness of the foamed resin layer.
The compression elastic modulus of the foamed resin layer is 15 MPa or more, and the foamed resin layer has a compressive elastic modulus of 15 MPa or more.
The non-foaming resin layer contains an inorganic compound, and the inorganic compound is talc, calcium carbonate, silica or mica.
The content of the inorganic compound is 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the resin component of the non-foamed resin layer.
The linear expansion coefficients of the non-foamed resin layer and the foamed resin layer are both 8 × ^10-5 / ° C. or less, and the difference between the linear expansion coefficients of the non-foamed resin layer and the foamed resin layer is 3 × 10 ^−. A decorative material characterized by being within ^{5 / ° C.} The decorative material according to claim 1, wherein the non-foamed resin layer has a tensile elastic modulus of 180 MPa or more. The decorative material according to claim 1 or 2, wherein the non-foaming resin layer contains an inorganic compound. The decorative material according to claim 1, 2 or 3, wherein the thickness of the decorative material is 5 mm or more.

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