JP2018069672A - Incombustible decorative sheet, incombustible decorative member and method for producing incombustible decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an incombustible decorative sheet which has sufficient weatherability even in an exposure to the outdoor over a long period and improves the cracking phenomenon and solvent resistance of a pattern layer in a folded part and to provide an incombustible decorative member using the same.SOLUTION: There is provided an incombustible decorative sheet which comprises a pattern layer 7 composed of an ink layer on one surface of an olefin raw fabric layer 2 as a support comprising an olefinic resin, an urethane-based adhesive layer 3, an urethane-based anchor layer 6 for improving adhesiveness, an acrylic resin layer 4 and a fluorine-based resin layer 5 in this order, wherein a primer layer 10 for improving the adhesiveness with a metal substrate 8 is provided on the other surface and no crack is caused in the pattern layer even when a decorative member prepared by sticking the decorative sheet to the metal substrate is folded.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet for use in interior and exterior materials of buildings such as houses, building materials such as construction materials and fittings, furniture fixtures, vehicle interiors, housing equipment, furniture for furniture, etc. In particular, the present invention relates to a non-combustible decorative sheet and a non-combustible decorative steel plate suitable for surface decoration of building members that require weather resistance and heat resistance such as entrance sliding doors.

  Conventionally, a decorative sheet made of a polyvinyl chloride resin, which is inexpensive and excellent in processability, has been most commonly used as a decorative sheet for use in various applications as described above.

However, in recent years, it has been pointed out that polyvinyl chloride resin becomes a direct or indirect factor in the generation of toxic substance dioxin during combustion, and a material that replaces polyvinyl chloride resin was used from the viewpoint of environmental protection. The development of decorative sheets has come to be requested.
In response to such a demand, for example, a decorative sheet using a thermoplastic resin other than a polyvinyl chloride resin such as a polyolefin resin, an acrylic resin, or a polyester resin has already been put into practical use. Substitution is progressing gradually.

  However, all of these alternative resins are inferior in thermal adhesiveness compared to polyvinyl chloride resin, and as in the case of a decorative sheet using conventional polyvinyl chloride resin, cosmetics are applied by thermal lamination. When trying to manufacture a sheet, there is a problem that it is difficult to obtain a necessary adhesive strength.

  Therefore, for example, Patent Document 1 discloses a thermoadhesive resin layer made of vinyl chloride-vinyl acetate copolymer resin (hereinafter referred to as vinyl acetate) -acrylic resin between a thermoplastic resin substrate and a surface resin layer. A method of providing a device has also been proposed. According to this method, heat lamination is performed by interposing a heat-adhesive resin layer that is sufficiently thermally activated in a low-temperature region where no breakage, elongation, deformation, deterioration, or the like of the sheet occurs, and exhibits good adhesion. Sufficient laminate strength can be achieved. However, since the said heat bondable resin layer consists of resin inferior to heat resistance, there exists a problem in which the obtained decorative sheet is inferior in heat resistance. Patent Document 2 discloses a method in which a heat sealant layer is provided using a thermoplastic resin-thermoplastic resin-heat sealant-acrylic resin, but an adhesive is applied to an aluminum substrate or the like. When the base material is folded after using it to wrap the sheet, there is a problem in workability such as the pattern layer of the decorative sheet is broken at the folded portion.

  There are proposals for melt extrusion laminating as an alternative to thermal laminating, but these require large-scale and expensive manufacturing equipment, and are difficult to use for high-mix low-volume production and short delivery times. Since there is a problem that the kind of the resin is limited, the heat laminating method cannot be completely replaced.

  There is also a proposal to use an acrylic resin with excellent weather resistance for the surface transparent resin layer by the dry laminating method, but there is no good adhesive layer when the thermoplastic resin substrate is an olefin substrate, and it is suitable for exterior use Usable adhesiveness was not obtained.

  On the other hand, with the recent increase in awareness of the safety of living spaces, non-flammability is required for decorative sheets for decorating window frames and entrances, which are exterior materials for houses, etc. There is more to need that.

JP 2000-326451 A Japanese Patent No. 5630161

  A decorative sheet in which an acrylic resin layer and an olefin resin layer are laminated by a heat laminating method via a heat sealant is wrapped with an adhesive on an aluminum substrate, and then bent to form a bent portion called roll forming. There is a problem that the printed pattern breaks. This is because when the bending process is performed, the surface of the lower layer resin is locally stretched and the pattern layer cannot follow. This also has a problem with the thickness of the lower layer resin, but also comes from the fact that the heat laminated upper layer resin is stretched more than the lower layer resin, thereby stretching the ink layer. In addition to the printing layer, acrylic resin also has a problem that its solvent resistance is low, and there is an urgent need for coexistence with countermeasures against cracking of the pattern layer due to bending.

  There is also a proposal for laminating an acrylic resin layer and a base material layer via an adhesive by a dry laminating method, but when the base material layer is an olefin base material, there is no adhesive layer that can adhere well to both, and the exterior Adhesiveness that can be used for applications could not be obtained.

  The present invention has been made in order to solve such problems, and the problem is that it has sufficient weather resistance even in outdoor exposure over a long period of time, and the cracking phenomenon of the pattern layer in the bent portion. Another object of the present invention is to provide a nonflammable decorative sheet having improved solvent resistance and a nonflammable decorative member using the same.

As means for solving the above-mentioned problems, the invention according to claim 1 of the present invention is characterized in that a pattern layer composed of an ink layer on one surface of an olefin raw fabric layer which is a support composed of an olefin resin, and a urethane-based adhesive. Layer, urethane anchor layer that improves adhesion, acrylic resin layer, and fluorine resin layer are provided in this order,
On the other side, in the nonflammable decorative sheet provided with a primer layer that improves the adhesion with the metal substrate,
A decorative member made by bonding the primer layer side of a non-combustible decorative sheet to a metal substrate is JIS K.
When the bendability is evaluated by a bending test based on 6744, it is a nonflammable decorative sheet characterized in that no cracks are generated in the pattern layer.

Moreover, the invention according to claim 2 consists of a urethane adhesive in which the urethane adhesive layer has a polyester resin as a main chain,
The non-flammable decorative sheet according to claim 1, wherein the urethane anchor layer is made of a urethane anchor agent having an acrylic resin as a main chain.

  Moreover, invention of Claim 3 is a nonflammable decorative sheet of Claim 1 or 2 which contains a ultraviolet absorber in the said urethane type anchor layer.

  The invention according to claim 4 is the nonflammable decorative sheet according to claim 3, wherein the ultraviolet absorbent is a triazine ultraviolet absorbent.

The invention described in Claim 5 is made from the olefinic raw layers of polypropylene resin, claim 1, wherein the organic solid content weight is 44 g / m ² or more 67 g / m ² or less The nonflammable decorative sheet according to any one of the above.

  The invention according to claim 6 is the nonflammable decorative sheet according to any one of claims 1 to 5, wherein the fluorine-based resin layer is made of polyvinylidene fluoride resin.

  The invention according to claim 7 comprises the decorative sheet according to any one of claims 1 to 6 on the metal substrate facing the primer layer side, and a nonflammable makeup. It is a member.

  The invention according to claim 8 is the nonflammable decorative member according to claim 7, wherein the metal substrate is made of aluminum, iron, stainless steel, or copper.

In the invention according to claim 9, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less by the corn calorie combustion test according to ISO 5660-1, and the maximum heat generation rate for 20 minutes after the start of heating is The nonflammable decorative member according to claim 8, wherein a crack or a hole penetrating to the back surface is not formed for 20 minutes after the start of heating without exceeding 200 kW / m ² continuously for 10 seconds or more.

Moreover, invention of Claim 10 is a manufacturing method of the nonflammable decorative sheet in any one of Claims 1-6,
Hydrophilizing the surface of the olefin raw fabric layer;
A step of printing a urethane printing ink on one surface of the hydrophilic olefin raw material layer to form a pattern layer;
Forming a urethane-based primer layer that improves the adhesion to the metal substrate on the surface of the other olefin raw fabric layer that has been hydrophilized;
Producing a laminate comprising the fluororesin layer and the acrylic resin layer, and forming the urethane anchor layer on the acrylic resin layer side of the laminate to produce a laminate A;
Forming the urethane-based adhesive layer on the pattern layer;
And a step of dry laminating the urethane-based adhesive layer facing the urethane-based anchor layer side of the laminate A, and a method for producing a nonflammable decorative sheet.

  The invention according to claim 11 is the method for producing a nonflammable decorative sheet according to claim 10, wherein the hydrophilization treatment is a corona discharge treatment.

  The invention according to claim 12 is the method according to claim 10 or 11, characterized in that the method for producing a laminate comprising the fluorine resin layer and the acrylic resin layer is a T-die method. It is a manufacturing method of a nonflammable decorative sheet.

  The invention according to claim 13 is the method for producing a nonflammable decorative sheet according to any one of claims 10 to 12, wherein the method for forming the urethane anchor layer is gravure printing.

  According to the nonflammable decorative sheet of the present invention, a pattern layer composed of an ink layer on one surface of an olefin raw fabric layer that is a support composed of an olefin resin, a urethane adhesive layer, and a urethane system that improves adhesion An anchor layer, an acrylic resin layer, and a fluorine resin layer are provided in this order, and a primer layer that improves adhesion to the metal substrate is provided on the other surface, so that it is nonflammable In addition, it is possible to provide a decorative sheet having sufficient weather resistance even in outdoor exposure over a long period of time.

  Moreover, according to the manufacturing method of the nonflammable decorative sheet of this invention, the nonflammable decorative sheet of this invention can be provided.

  In addition, according to the non-combustible decorative member of the present invention produced by bonding the primer layer side of the non-combustible decorative sheet of the present invention to a metal substrate, it has sufficient weather resistance even in outdoor exposure over a long period of time, It is possible to provide a decorative member having nonflammability by improving the cracking phenomenon and solvent resistance of the pattern layer in the bent portion.

It is a schematic sectional drawing explaining an example of the layer structure of the nonflammable decorative member using the nonflammable decorative sheet of this invention. It is the photograph which illustrated the condition of the printed pattern of the bending part at the time of performing the roll forming process of a nonflammable decorative member, (a) is the nonflammable decorative sheet of this invention shown in Example 1 of Table 1 In the non-combustible decorative member used, when the roll forming process is performed, the printed pattern of the bent portion is not cracked. (B) is the non-combustible shown in Comparative Example 1 of Table 1 When the nonflammable decorative member using the decorative decorative sheet is subjected to roll forming, the printed pattern at the bent portion is cracked.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to FIG.

<Incombustible decorative sheet>
The nonflammable decorative sheet 1 of the present invention improves the adhesiveness of the pattern layer 7 made of an ink layer, the urethane-type adhesive layer 3 on one surface of the olefin raw fabric layer 2 that is a support made of an olefin resin, and the adhesive layer. A urethane anchor layer 6, an acrylic resin layer 4, and a fluorine resin layer 5 are provided in this order, and a primer layer 10 that improves adhesion to the metal substrate 8 is provided on the other surface. It is a nonflammable decorative sheet.

  The non-combustible sheet of the present invention is such that the decorative layer formed by adhering the primer layer side to the metal substrate does not cause cracks in the pattern layer when the bending property is evaluated by a bending test according to JIS K 6744. Is a feature.

  For the urethane-based adhesive layer 3, for example, a urethane-based adhesive having a polyester-based resin as a main chain can be suitably used. For the urethane anchor layer 6, for example, a urethane anchor material having an acrylic resin as a main chain can be preferably used.

  The urethane anchor layer 6 may contain an ultraviolet absorber.

Further, the olefin raw layer 2, for example, a polypropylene resin, it is preferable organic solids is 44 g / ^{m 2} or more 67 g / ^{m 2} or less. When the organic solid content is less than 44 g / m ² , workability during production deteriorates, and when it exceeds 67 g / m ² , nonflammability cannot be imparted.

  In addition, for example, a polyvinylidene fluoride resin can be suitably used for the fluorine-based resin layer 5.

<Non-combustible decorative material>
As illustrated in FIG. 1, the non-combustible decorative member 9 can be obtained by integrating the non-combustible decorative sheet 1 of the present invention on the metal substrate 8 by connecting the primer layer 10 side.

<Method for producing non-combustible decorative sheet>
Next, the manufacturing method of the nonflammable decorative sheet of this invention is demonstrated.
The nonflammable decorative sheet of the present invention includes a step of hydrophilizing the surface of the olefin raw fabric layer, and a step of printing a urethane printing ink on one surface of the hydrophilic olefin raw fabric layer to form a pattern layer; A step of forming a urethane primer layer for improving adhesion to the metal substrate on the surface of the other olefin raw layer subjected to the hydrophilic treatment, and a laminate comprising a fluorine resin layer and an acrylic resin layer. Forming a urethane anchor layer on the acrylic resin layer side of the laminate, producing a laminate A, forming the urethane adhesive layer on the pattern layer, and the urethane And a process of dry laminating the adhesive layer so as to face the urethane anchor layer side of the laminate A.

The hydrophilic treatment may be surface modification by corona discharge treatment.
Moreover, the T-die method may be sufficient as the method of producing the laminated body which consists of a fluorine resin layer and an acrylic resin layer.
Further, the method for forming the urethane anchor layer may be gravure printing.

<Method for producing non-combustible decorative member>
The nonflammable decorative member 9 of the present invention can be produced by bonding the primer layer 10 side of the nonflammable decorative sheet 1 of the present invention, for example, facing the metal substrate 8. A method of bonding the decorative sheet 1 to the metal substrate 8 can be suitably applied to dry lamination, but is not limited thereto.

  Next, examples of the nonflammable decorative sheet of the present invention will be described.

<Example 1>
As a base material, an olefin raw fabric layer 2 (thickness: 60 μm) made of a colored polypropylene resin and having a total organic solid content weight of 49.6 g / m ² was prepared. After the corona discharge treatment was applied to the front and back surfaces of the olefin raw fabric layer 2, a wood grain pattern was formed by gravure printing on the surface using urethane printing ink to form a pattern layer 7 (thickness: 2 μm). . Next, a primer layer 10 (thickness: 1 μm) was formed on the back surface by gravure printing using a back surface primer layer coating solution having the following composition.

  Next, the polyvinylidene fluoride resin and the acrylic resin layer forming mixture were melted with a T-die and extruded, and a laminate comprising a fluororesin layer and an acrylic resin layer (fluorine resin layer thickness: 5 μm, acrylic resin layer thickness: 45 μm) ) And a urethane anchor layer 6 (thickness: 1.5 μm) having an acrylic resin containing a triazine UV absorber (5 parts by weight) on the acrylic resin side as a main chain was formed by gravure printing (hereinafter referred to as “gravure printing”). Referred to as “Laminate A”).

  A urethane-based adhesive layer 3 (thickness in a dry state: 6 μm) was formed on the pattern layer 7 by applying a coating liquid composed of a two-component curable urethane-based adhesive having a polyester resin as a main chain. On top of the laminate A, the urethane anchor layer 6 side of the laminate A was faced and laminated by a dry laminating method to obtain a nonflammable decorative sheet 1 of the present invention.

(Backside primer layer coating solution)
The following two-component curable polyester urethane and a diluent solvent were mixed and homogenized to prepare a back surface primer layer coating solution.
Two-component curable polyester urethane (mixed polyester polyol and polyisocyanate in a ratio of 100: 3 (mass ratio)): 100 parts by weight Diluting solvent (mixed in a ratio of 1: 1 (mass ratio) of ethyl acetate and methyl isobutyl ketone) Mixed solvent): 20 parts by mass

<Comparative Example 1>
In Example 1, instead of the urethane-based adhesive layer 3 and the urethane-based anchor layer 6, a heat sealant layer (acrylic / vinyl acetate / polyester = 1/1/1, containing an isocyanate-based curing agent) 1 μm is provided, A decorative sheet was prepared by thermal lamination.

<Comparative example 2>
A nonflammable decorative sheet was prepared in the same manner as in Example 1 except that an olefin raw fabric layer (thickness: 90 μm) having a total organic solid content weight of 77.6 g / m ^{2 made} of a colored polypropylene resin was used. Got.

(Evaluation judgment method)
(1) Bending test A bending test in accordance with roll forming process aptitude and JIS K 6744 was performed.
Evaluation of roll forming process suitability is performed by sticking the non-combustible decorative sheet to a 1.0 mm-thick aluminum base material using an adhesive and bending it to 90 ° by forming process. If the opposite layer could not be seen from the acrylic resin layer side, the roll forming processability was determined to be acceptable (◯). Moreover, the bending test based on JISK6744 was done. (2) Nonflammability evaluation Conforms to ISO5660-1; when the total calorific value (MJ / m ² ) for 20 minutes after the start of heating is 8 MJ / m ² or less, it is determined to be acceptable (◯), and more than that is rejected ( X).
Moreover, it was set as the pass if it did not exceed 200 KW / m < ² > continuously for 10 seconds or more as a maximum heat release rate for 20 minutes after a heating start.
Moreover, when a crack and a hole generate | occur | produced in the base material, it was set as the rejection (x).

(Evaluation results)
FIG. 2 shows the state when an aluminum base material having a thickness of 0.1 mm is attached using an adhesive and is bent at 90 ° by forming, and Table 1 shows the evaluation results.

As shown in FIG. 2, the phenomenon in which the printed pattern at the bent portion does not break even when roll forming is performed in Example 1, whereas the printed pattern at the bent portion breaks in Comparative Example 1. Has occurred.
Table 2 shows the results of the roll forming process aptitude evaluation of the evaluation samples produced in Example 1 and Comparative Examples 1 and 2, the bending test based on JIS K 6744, and the nonflammability evaluation. In Example 1, all of these evaluations were good, whereas in Comparative Example 1, the nonflammability evaluation was good, but the roll forming processability and the results of the bending test based on JIS K 6744 were good. It wasn't. In Comparative Example 2, the suitability for roll forming and the results of the bending test based on JIS K 6744 were good, but the nonflammability evaluation was not good.

DESCRIPTION OF SYMBOLS 1 ... Nonflammable decorative sheet 2 ... Raw material of olefin layer 3 ... Urethane adhesive layer 4 ... Acrylic resin layer 5 ... Fluorine resin layer 6 ... Urethane anchor layer 7・ Picture layer (ink layer)
8 ... Metal substrate 9 ... Non-combustible decorative member 10 ... Primer layer

Claims (13)

On one surface of the olefin raw material layer, which is a support made of olefin resin, a picture layer made of an ink layer, a urethane adhesive layer, a urethane anchor layer for improving adhesion, an acrylic resin layer, fluorine System resin layer in this order,
On the other side, in the nonflammable decorative sheet provided with a primer layer that improves the adhesion with the metal substrate,
A decorative member formed by adhering the primer layer side of a non-combustible decorative sheet to a metal substrate is characterized in that the pattern layer does not crack when the bending property is evaluated by a bending test according to JIS K 6744. Nonflammable decorative sheet. The urethane adhesive layer is made of a urethane adhesive having a polyester resin as a main chain,
The non-flammable decorative sheet according to claim 1, wherein the urethane anchor layer is made of a urethane anchor agent having an acrylic resin as a main chain.   The nonflammable decorative sheet according to claim 1 or 2, wherein the urethane anchor layer contains an ultraviolet absorber.   The nonflammable decorative sheet according to claim 3, wherein the ultraviolet absorber is a triazine ultraviolet absorber. Wherein the olefin raw layer is made of a polypropylene resin, nonflammable decorative sheet according to any one of claims 1 to 4, characterized in that the organic solid content weight is 44 g / m ² or more 67 g / m ² or less.   The nonflammable decorative sheet according to any one of claims 1 to 5, wherein the fluorine resin layer is made of polyvinylidene fluoride resin.   A nonflammable decorative member comprising the decorative sheet according to claim 1 on a metal substrate facing the primer layer side.   The non-combustible decorative member according to claim 7, wherein the metal substrate is aluminum, iron, stainless steel, or copper. According to the ISO 5660-1 corn calorie combustion test, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and the maximum heat generation rate for 20 minutes after the start of heating is continued for 10 seconds or more to 200 kW / m ² . The nonflammable decorative member according to claim 8, wherein no cracks or holes penetrating to the back surface are formed for 20 minutes after starting heating. It is a manufacturing method of the nonflammable decorative sheet according to any one of claims 1 to 6,
Hydrophilizing the surface of the olefin raw fabric layer;
A step of printing a urethane printing ink on one surface of the hydrophilic olefin raw material layer to form a pattern layer;
Forming a urethane-based primer layer that improves the adhesion to the metal substrate on the surface of the other olefin raw fabric layer that has been hydrophilized;
Producing a laminate comprising the fluororesin layer and the acrylic resin layer, and forming the urethane anchor layer on the acrylic resin layer side of the laminate to produce a laminate A;
Forming the urethane-based adhesive layer on the pattern layer;
And a step of dry laminating the urethane adhesive layer facing the urethane anchor layer side of the laminate A, and a method for producing a nonflammable decorative sheet.   The method for producing a nonflammable decorative sheet according to claim 10, wherein the hydrophilization treatment is a corona discharge treatment.   The method for producing a nonflammable decorative sheet according to claim 10 or 11, wherein a method for producing a laminate comprising the fluorine resin layer and the acrylic resin layer is a T-die method.   The method for forming the urethane anchor layer is gravure printing, and the method for producing a nonflammable decorative sheet according to any one of claims 10 to 12.