ARTICLE WITH A FILM ADHERED AND LAMINATE

Abstract

An article with a film adhered includes a film layer, a glass particle-containing layer, and an adherend in this order to facilitate high flame retardance. A laminate used to produce such article.

Claims

1. An article with a film adhered comprising a film layer, a glass particle-containing layer, and an adherend in this order.

2. The article according to claim 1, wherein the article further comprises an adhesive layer between the glass particle-containing layer and the adherend; the glass particle-containing layer is a buffer layer that is in contact with the film layer and the adhesive layer; and, the buffer layer comprises a binder and glass particles dispersed in the binder.

3. The article according to claim 2, wherein the binder is an acrylic resin.

4. The article according to claim 1, wherein the article further comprises an adhesive layer between the film layer and the glass particle-containing layer; the glass particle-containing layer is a primer layer that is in contact with the adherend and the adhesive layer; and the primer layer comprises a binder and glass particles dispersed in the binder.

5. The article according to claim 4, wherein the binder is an inorganic binder.

6. The article according to claim 1, wherein the glass particle-containing layer is an adhesive layer that is in contact with the adherend.

7. The article according to claim 2, wherein the adhesive layer comprises an acrylic adhesive.

8. The article according to claim 1, wherein the glass particles are glass frits.

9. The article according to claim 1, wherein a softening point of the glass particles is from 300? C. to 900? C.

10. The article according to claim 1, wherein the film layer comprises polyvinyl chloride.

11. The article according to claim 1, wherein the adherend comprises at least one selected from the group consisting of plasterboard, calcium silicate board, flame-retardant plywood, and mortar.

12. The article according to claim 1, wherein a thickness of the glass particle-containing layer is from 10 ?m to 220 ?m.

13. A laminate comprising a film layer and a glass particle-containing layer disposed on the film layer.

14. The laminate according to claim 13, wherein the glass particle-containing layer comprises glass particles and an adhesive for adhering the laminate to an adherend.

15. The laminate according to claim 13, wherein the glass particles are glass frits.

16. The laminate according to claim 13, wherein a softening point of the glass particles is from 300? C. to 900? C.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0013] FIG. 1 is a schematic cross-sectional view of an article of the first embodiment and a laminate of an embodiment.

[0014] FIG. 2 is a schematic cross-sectional view of an article of the second embodiment.

[0015] FIG. 3 is a schematic cross-sectional view of an article of the third embodiment and a laminate of another embodiment.

[0016] FIG. 4 is a graph illustrating the relationship between heat release rate and time in Example 12 and a control.

[0017] FIG. 5 is a graph illustrating the relationship between heat release rate and time in Example 13, Example 14, and the control.

DESCRIPTION OF EMBODIMENTS

[0018] Hereinafter, the present invention will be described in more detail with reference to the drawings for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0019] In the present disclosure, the term film encompasses articles referred to as sheets.

[0020] In the present disclosure, pressure-sensitive adhesive refers to the characteristic of a material or composition that the material or composition adheres to various surfaces with just light pressure for a short time in the temperature range of usage, such as from 0? C. to 50? C., and does not exhibit a phase change (from liquid to solid).

[0021] In the present disclosure, adhesive(ness) is used interchangeably with pressure-sensitive adhesive.

[0022] In the present disclosure, disposed on refers to not only the case of being directly disposed on, but also the case of being indirectly disposed on, that is, disposed on via another material or layer.

[0023] An article with a film adhered according to an embodiment includes a film layer, a glass particle-containing layer, and an adherend in this order. The glass particle-containing layer located between the film layer and the adherend softens or melts at an elevated temperature to form a thin glass film between the adherend and the film layer. The formed thin glass film acts as a barrier layer to block or suppress the flow of oxygen, flammable gas, and the like between the adherend and the film layer, making it possible to render the article with the film adhered flame-retardant as a whole. By providing the glass particle-containing layer separately from the film layer, flame retardance can be imparted to the article without adversely affecting the appearance of the film layer, such as surface glossiness or transparency, and mechanical properties of the film layer, such as tensile strength or flexural strength.

[0024] The material and shape of the adherend is not limited as long as the adherend is an article to which a film can be adhered. Examples of the adherend include plasterboard, mortar, cement, concrete, wood, stone, paper, cloth, glass, plastic, porous ceramics, brick, rock wool acoustic board, and calcium silicate board. The plasterboard may have one side or both sides coated with paper. The adherend is not limited to a plate-like shape such as a wall material and may have a rod-like shape, a film-like shape, a spherical shape, an irregular shape, or another three-dimensional shape.

[0025] In an embodiment, the adherend contains at least one selected from the group consisting of plasterboard, calcium silicate board, flame-retardant plywood, and mortar. In this embodiment, the article can be used as a fireproof wall covering material.

[0026] Examples of the material of the film layer include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polystyrene, polyvinyl chloride, polyvinyl acetate, polyurethane, vinyl chloride-vinyl acetate copolymers, acrylic resins, acrylic urethane resins, polycarbonates, cellulose, and fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride, as well as blends thereof.

[0027] In an embodiment, the film layer contains polyvinyl chloride. Polyvinyl chloride, which has outstanding flame retardance, is possible to further enhance the fireproof performance of the article.

[0028] The film layer may contain other optional components, such as fillers, colorants such as pigments and dyes, heat stabilizers, UV absorbing agents, and antioxidants.

[0029] The film layer may be a single layer, or may be a laminate of a plurality of layers. The film layer may have undergone surface treatment such as embossing treatment, primer treatment, corona treatment, and plasma treatment, and may further contain a decorative layer such as a printed layer, a plated layer, and a vapor deposited layer, or a surface-protecting layer such as a hard coat layer.

[0030] The thickness of the film layer may be, for example, greater than or equal to approximately 10 ?m, greater than or equal to approximately 30 ?m, or greater than or equal to approximately 50 ?m, or may be less than or equal 15 to 400 ?m, less than or equal to 300 ?m, or than or equal to 200 ?m. By setting the thickness of the film layer to be within the range described above, an article having excellent flame retardance can be obtained.

[0031] The glass particles contained in the glass particle-containing layer are not particularly limited, and examples thereof include glass frits, glass balloons, and glass beads. It is advantageous that the glass particles are glass frits from the perspective that materials with various softening points can be selected.

[0032] Examples of the glass particles include the ones that use silicon oxide (SiO.sub.2), phosphorus oxide (P.sub.2O.sub.5), or boron oxide (B.sub.2O.sub.3) as the first component. The glass particles may further optionally contain at least one element selected from the group consisting of Li, Na, K, Be, Mg, Ca, Sr, Zn, B, Al, Pb, and P which is different from the elements contained in the first component. Specific examples of the material of the glass particle include soda lime glass, borate glass, borosilicate glass, phosphate glass, and aluminophosphate glass. The glass particles are preferably free of lead.

[0033] The softening point of the glass particles may be, for example, higher than or equal to approximately 300? C., higher than or equal to approximately 320? C., or higher than or equal to approximately 340? C., or may be lower than or equal to approximately 900? C., lower than or equal to approximately 850? C., or lower than or equal to approximately 800? C. By setting the softening point of the glass particles to be higher than or equal to approximately 300? C., it is possible to secure the stability of the shape of the article in a relatively high temperature range in which flame does not occur. By setting the softening point of the glass particles to be lower than or equal to approximately 900? C., the thin glass film can be quickly formed at a high temperature such as in an environment that is exposed to flame.

[0034] The average particle size of the glass particles may be, for example, greater than or equal to approximately 1 ?m, greater than or equal to approximately 3 ?m, or greater than or equal to approximately 5 ?m, or may be less than or equal to approximately 60 ?m, less than or equal to approximately 50 ?m, or less than or equal to approximately 40 ?m. By setting the average particle size of the glass particles to be greater than or equal to approximately 1 ?m, resin dispersibility can be improved. By setting the average particle size of the glass particles to be approximately less than or equal to 60 ?m, surface smoothness of the article can be secured. The average particle size of the glass particles is the particle diameter at 50% of the cumulative volume (D.sub.50) measured using a laser diffraction/scattering-type particle size distribution measuring device.

[0035] The content of glass particles in the glass particle-containing layer may be, for example, greater than or equal to approximately 4 mass %, greater than or equal to approximately 6 mass %, or greater than or equal to approximately 8 mass %, or may be less than or equal to approximately 85 mass %, less than or equal to approximately 70 mass %, or less than or equal to approximately 50 mass %. By setting the content of glass particles in the glass particle-containing layer to be greater than or equal to approximately 4 mass %, flame retardance performance can be imparted to the article. By setting the content of glass particles in the glass particle-containing layer to be less than or equal to approximately 85 mass %, interlayer adhesion of the article can be secured.

[0036] The thickness of the glass particle-containing layer may be, for example, greater than or equal to approximately 10 ?m, greater than or equal to approximately 15 ?m, or greater than or equal to approximately 20 ?m, or may be less than or equal to approximately 220 ?m, less than or equal to approximately 100 ?m, or less than or equal to approximately 50 ?m. By setting the thickness of the glass particle-containing layer to be greater than or equal to approximately 10 ?m, interlayer adhesion of the article can be secured. By setting the thickness of the glass particle-containing layer to be less than or equal to approximately 220 ?m, surface smoothness of the article can be secured.

[0037] It is advantageous that content of glass particles in the glass particle-containing layer per unit area is greater than or equal to approximately 30 g/m.sup.2, greater than or equal to approximately 45 g/m.sup.2, or greater than or equal to approximately 60 g/m.sup.2, or less than or equal to approximately 600 g/m.sup.2, less than or equal to approximately 300 g/m.sup.2, or less than or equal to approximately 150 g/m.sup.2. With this, it is possible to use a small amount of glass particles to efficiently form a thin glass film having the thickness necessary to impart the desired fireproof performance to the region of the article corresponding to the glass particle-containing layer.

[0038] The glass particle-containing layer may contain a binder or an adhesive.

[0039] Organic binders such as an acrylic resin, a polyurethane, a polyolefin, a polyester, a rubber-based resin, a silicone resin, a vinyl acetate resin, or blends thereof can be used as the binder. Inorganic binders such as ammonium polyphosphate, layered silicate mineral clay, an alkali metal silicate aqueous solution, or blends thereof can also be used as the binder.

[0040] An acrylic resin, a polyurethane, a polyolefin, a polyester, a rubber-based resin, a silicone-based resin, or a vinyl acetate resin, or blends thereof can be used as the adhesive. The adhesive may be also a pressure-sensitive adhesive containing a tacky adhesive polymer. It is advantageous that the adhesive contains an acrylic adhesive from the perspective of weather resistance and transparency.

[0041] The binder or adhesive may contain other optional components, such as fillers, colorants such as pigments and dyes, heat stabilizers, UV absorbing agents, and antioxidants. These optional components may be dissolved or dispersed in the binder or adhesive. In an embodiment, the binder or adhesive contains a white pigment such as titanium oxide. In this embodiment, the adherend surface can be concealed.

[0042] In a first embodiment, the article further includes an adhesive layer between the glass particle-containing layer and the adherend, in which: the glass particle-containing layer is a buffer layer that is in contact with the film layer and the adhesive layer; and the buffer layer contains a binder and glass particles dispersed in the binder.

[0043] FIG. 1 illustrates a schematic cross-sectional view of the article of the first embodiment. An article 10 includes a film layer 12, a glass particle-containing layer 14, and an adherend 16, and further includes an adhesive layer 18 between the glass particle-containing layer 14 and the adherend 16. The glass particle-containing layer 14 is a buffer layer 24 that is in contact with the film layer 12 and the adhesive layer 18. The buffer layer 24 contains a binder 144 and glass particles 142 dispersed in the binder.

[0044] The adhesive layer may contain, for example, an acrylic resin, a polyurethane, a polyolefin, a polyester, a rubber-based resin, a silicone-based resin, or a vinyl acetate resin, or blends thereof. The adhesive layer may be a pressure-sensitive adhesive layer containing a tacky adhesive polymer. It is advantageous that the adhesive layer contains an acrylic adhesive from the perspective of weather resistance and transparency. The adhesive layer may be free of, or may contain, glass particles such as those contained in the buffer layer.

[0045] The thickness of the adhesive layer may be, for example, greater than or equal to approximately 5 ?m, greater than or equal to approximately 10 ?m, or greater than or equal to approximately 20 ?m, or may be less than or equal to approximately 200 ?m, less than or equal to approximately 100 ?m, or less than or equal to approximately 50 ?m. By setting the thickness of the adhesive layer to be greater than or equal to approximately 5 ?m, adhesion to various substrates can be secured. By setting the thickness of the adhesive layer to be less than or equal to approximately 200 ?m, it is possible to form an adhesive layer economically and efficiently.

[0046] The glass particles and binder contained in the buffer layer (glass particle-containing layer) are the same as in the description above. The binder is preferably an organic binder such as an acrylic resin, a polyurethane, a polyolefin, a polyester, a rubber-based resin, a silicone resin, a vinyl acetate resin, a vinyl chloride resin, or blends thereof, more preferably an acrylic resin, due to their excellent adhesion to both the film layer and the adhesive layer. More preferably, the binder is an acrylic resin.

[0047] The thickness of the buffer layer (glass particle-containing layer) may be, for example, greater than or equal to approximately 10 ?m, greater than or equal to approximately 15 ?m, or greater than or equal to approximately 20 ?m, or may be less than or equal to approximately 100 ?m, less than or equal to approximately 70 ?m, or less than or equal to approximately 50 ?m. By setting the thickness of the buffer layer to be greater than or equal to approximately 10 ?m, interlayer adhesion of the article can be secured. By setting the thickness of the buffer layer to be less than or equal to approximately 100 ?m, surface smoothness of the article can be more effectively secured.

[0048] In a second embodiment, the article further includes an adhesive layer between the film layer and the glass particle-containing layer, in which: the glass particle-containing layer is a primer layer that is in contact with the adherend and the adhesive layer; and the primer layer contains a binder and glass particles dispersed in the binder.

[0049] FIG. 2 illustrates a schematic cross-sectional view of the article of the second embodiment. An article 10 includes a film layer 12, a glass particle-containing layer 14, and an adherend 16, and further includes an adhesive layer 18 between the film layer 12 and the glass particle-containing layer 14. The glass particle-containing layer 14 is a primer layer 34 that is in contact with the adherend 16 and the adhesive layer 18. The primer layer 34 contains a binder 144 and glass particles 142 dispersed in the binder.

[0050] The adhesive layer is the same as in the description in the first embodiment.

[0051] The glass particles and binder contained in the primer layer (glass particle-containing layer) are the same as in the description above. When the adherend includes an inorganic material such as plasterboard, the binder is preferably an inorganic binder such as ammonium polyphosphate, layered silicate mineral clay, an alkali metal silicate aqueous solution, or blends thereof.

[0052] The weight per unit area of the primer layer (glass particle-containing layer) may be, for example, greater than or equal to approximately 10 g/m.sup.2, greater than or equal to approximately 15 g/m.sup.2, or greater than or equal to approximately 20 g/m.sup.2, or may be less than or equal to approximately 70 g/m.sup.2, less than or equal to approximately 60 g/m.sup.2, or less than or equal to approximately 50 g/m.sup.2. By setting the weight per unit area of the primer layer to be greater than or equal to approximately 10 g/m.sup.2, stable combustion inhibition effect can be obtained. By setting the thickness of the primer layer to be less than or equal to approximately 70 g/m.sup.2, it is possible to form a primer layer economically and efficiently.

[0053] The thickness of the primer layer (glass particle-containing layer) may be, for example, greater than or equal to approximately 10 ?m, greater than or equal to approximately 15 ?m, or greater than or equal to approximately 20 ?m, or may be less than or equal to approximately 100 ?m, less than or equal to approximately 70 ?m, or less than or equal to approximately 50 ?m. By setting the thickness of the primer layer to be greater than or equal to approximately 10 ?m, interlayer adhesion of the article can be secured. By setting the thickness of the primer layer to be less than or equal to approximately 100 ?m, surface smoothness of the article can be more effectively secured.

[0054] In a third embodiment, the glass particle-containing layer is an adhesive layer that is in contact with the adherend.

[0055] FIG. 3 illustrates a schematic cross-sectional view of the article of the third embodiment. An article 10 includes a film layer 12, a glass particle-containing layer 14, and an adherend 16. The glass particle-containing layer 14 is an adhesive layer 18 that is in contact with the adherend 16.

[0056] The material of the adhesive layer (glass particle-containing layer) are the same as in the description in the first embodiment. It is desirable that the glass particles are evenly dispersed in the adhesive.

[0057] The thickness of the adhesive layer (glass particle-containing layer) may be, for example, greater than or equal to approximately 5 ?m, greater than or equal to approximately 10 ?m, or greater than or equal to approximately 20 ?m, or may be less than or equal to approximately 100 ?m, less than or equal to approximately 70 ?m, or less than or equal to approximately 50 ?m. By setting the thickness of the adhesive layer to be greater than or equal to approximately 5 ?m, adhesion to various substrates can be secured. By setting the thickness of the adhesive layer to be less than or equal to approximately 100 ?m, it is possible to form an adhesive layer economically and efficiently.

[0058] An embodiment provides a laminate including a film layer and a glass particle-containing layer disposed on the film layer. The laminate can be used to produce the article described above. The film layer and the glass particle-containing layer are the same as in the description regarding the article described above.

[0059] The laminate may further include an adhesive layer disposed on the glass particle-containing layer on the opposite side of the film layer. The adhesive layer is the same as in the above description regarding the article.

[0060] FIG. 1 illustrates a laminate 100 adhered to an adherend 16. The laminate 100 includes a film layer 12, a glass particle-containing layer 14 disposed on the film layer 12, in which the glass particle-containing layer 14 is at the lower side of the film layer 12 in the drawing, and an adhesive layer 18.

[0061] The glass particle-containing layer may include glass particles and an adhesive for adhering the laminate to an adherend. In this embodiment, the surface of the glass particle-containing layer of the laminate may be protected by a release liner.

[0062] FIG. 3 illustrates a laminate 100 adhered to an adherend 16. The laminate 100 includes a film layer 12 and a glass particle-containing layer 14, in which the glass particle-containing layer 14 is an adhesive layer 18 containing glass particles 142 and an adhesive.

[0063] The article with a film adhered can be produced, for example, by a method including the following steps. A glass particle-containing composition containing glass particles, a binder or an adhesive, and, as needed, an additional component such as a solvent, a viscosity modifier, a defoamer, a leveling agent, a UV absorbing agent, an antioxidant, a pigment, or a dye, is applied onto a film layer and dried by heating as necessary to form a laminate including a film layer and a glass particle-containing layer disposed on the film layer. The preparation of the glass particle-containing composition can be performed by mixing components using a mixing device, such as a homo mixer or a planetary mixer.

[0064] When the glass particle-containing layer is a buffer layer containing a binder, an adhesive composition containing an adhesive and, as needed, an additional component such as a solvent, a viscosity modifier, a defoamer, a leveling agent, a UV absorbing agent, an antioxidant, a pigment, or a dye, is applied onto the glass particle-containing layer and dried by heating as necessary to form an adhesive layer disposed on the glass particle-containing layer at the opposite side of the film layer.

[0065] The application of the glass particle-containing composition and the adhesive composition can be performed by using, for example, a knife coater, a gravure coater, a roll coater, a die coater, or a bar coater. The heating and drying after the application can be performed, for example, at a temperature of from 60? C. to 120? C. for several tens of seconds to 10 minutes.

[0066] Prior to formation of the glass particle-containing layer, the film layer may be primed or subjected to surface treatment such as corona treatment or flame treatment as necessary.

[0067] Thereafter, the article with a film adhered can be produced by having the adhesive layer of the laminate face the adherend and adhere the laminate and the adherend together. When adhering the laminate and the adherend together, the laminate may be pressed against the adherend surface by a tool such as a roller, or may be by rubbing by hand.

[0068] The article with a film adhered can also be produced, for example, by a method including the following steps. A primer composition containing glass particles, a binder or a solvent or both, and, as needed, an additional component such as a viscosity modifier, an defoamer, a leveling agent, a UV absorbing agent, or an antioxidant, is applied onto an adherend and dried by heating as necessary to form a primer layer on the adherend.

[0069] The application of the primer composition can be performed by using, for example, a knife coater, a gravure coater, a roll coater, a die coater, or a bar coater. The heating and drying after the application can be performed, for example, at a temperature from 60? C. to 120? C. for several tens of seconds to 10 minutes.

[0070] Thereafter, the article with a film adhered can be produced by having the adhesive layer of the laminate having a film layer and an adhesive layer face the primer layer formed on the adherend and adhere the laminate and the adherend together. When adhering the laminate and the adherend together, the laminate may be pressed against the adherend surface by a tool such as a roller, or may be by rubbing by hand.

[0071] In the article according to an embodiment, the total calorific value measured in accordance with the ISO 5660-1:2015 cone calorimeter test in a total of 20 minutes is less than or equal to approximately 8 MJ/m.sup.2, or less than or equal to approximately 7.8 MJ/m.sup.2, or less than or equal to approximately 7.5 MJ/m.sup.2.

[0072] In the article according to an embodiment, the total time for which the heat release rate measured in accordance with the ISO 5660-1:2015 cone calorimeter test exceeds 200 kW/m.sup.2 is less than or equal to approximately 10 seconds, or less than or equal to approximately 8 seconds, or less than or equal to approximately 5 seconds.

[0073] The article with a film adhered and the laminate according to the present disclosure can be used in various fields where flame retardance is required, such as for buildings, automobiles, airplanes, ships, trains and electric/electronic devices.

EXAMPLES

[0074] In the following examples, specific embodiments of the present disclosure will be exemplified, but the present invention is not limited to those embodiments. All parts and percent are based on mass unless otherwise specified.

[0075] The raw materials used in the production of the laminate and the article are shown in Table 1.

TABLE-US-00001 TABLE 1 Composition or description.sup.1) Supplier Tacky A 60 mass % EtOAc solution in which 2EHA-BA-AA is 62:32:6, adhesive Tg is ?57? C., and weight average molecular weight (Mw) is 290000 polymer 1 (ADH1) Tacky A 38 mass % EtOAc solution in which BA-AA is 94:6, Tg is ?48? C., adhesive and weight average molecular weight (Mw) is 650000 polymer 2 (ADH2) Dispersant 1 A 40 mass % EtOAc solution in which MMA-BMA-DMAEMA is (D1) 60:34:6, Tg is 63? C., and weight average molecular weight (Mw) is 68000 Crosslinking Epoxy crosslinking agent E-5XM (N,N,N,N-tetrakis(2,3- Soken Chemical agent 1 epoxypropyl)-m-xylene-?,?-diamine), 5 mass % MEK solution & Engineering (CL1) Co., Ltd. (Toshima-ku, Tokyo, Japan) Crosslinking Coronate (trade name) L-55E, Toluene diisocyanate type cross- Tosoh agent 2 linking agent, 55 mass % ethyl acetate solution Corporation (CL2) (Minato-ku, Tokyo, Japan) Glass frits 1 CH1538, SiO.sub.2 type, softening point is 800? C., D50 is 13 ?m Takara Standard (GL1) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 2 TH1368, SiO.sub.2B.sub.2O.sub.3 type, softening point is 820? C., D50 is 13 ?m Takara Standard (GL2) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 3 VY0144, P.sub.2O.sub.5Al.sub.2O.sub.3 type, softening point is 404? C., D50 is 17 ?m Takara Standard (GL3) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 4 CY0086, B.sub.2O.sub.3ZnO type, softening point is 569? C., D50 is 11 ?m Takara Standard (GL4) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 5 CY5600, B.sub.2O.sub.3 type, softening point is 630? C., D50 is 15 ?m Takara Standard (GL5) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 6 PANA84, P.sub.2O.sub.5 type, softening point is 400? C., D50 is 12 ?m Takara Standard (GL6) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 7 TH1368, SiO.sub.2B.sub.2O.sub.3 type, softening point is 820? C., D50 is 7 ?m Takara Standard (GL7) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 8 TH1368, SiO.sub.2B.sub.2O.sub.3 type, softening point is 820? C., D50 is 30 ?m Takara Standard (GL8) Co. Ltd. (Osaka- shi, Osaka, Japan) Glass frits 9 Ceradyne (trade name), lead-free low-melting-point glass powder 3M Japan Ltd. (GL9) V2211, SiO.sub.2Bi.sub.2O.sub.3ZnOB.sub.2O.sub.3SrOZrO.sub.2, softening point is 484? C. (Shinagawa-ku, Tokyo, Japan) Glass frits Ceradyne (trade name), low-melting-point glass powder 24936, 3M Japan Ltd. 10 (GL10) PbO.sub.2ZnOB.sub.2O.sub.3, softening point is 330? C. (Shinagawa-ku, Tokyo, Japan) Film 1 White PVC film having a thickness of 170 ?m formed by (FL1) calendering, polyvinyl chloride/ester plasticizer/organic stabilizer (acrylic resin, zinc stearate, and the like)/pigments (Titanium oxide, and the like) is 61.5/13.6/3.2/21.7 (mass ratio) Film 2 Pigmented PVC film having a thickness of 135 ?m formed by (FL2) calendering, polyvinyl chloride/ester plasticizer/organic stabilizer (acrylic resin, zinc stearate, and the like)/organic pigment is 66.5/19.5/12.7/1.3 (mass ratio) Cloisite 20A Montmorillonite clay BYK-Chemie GmbH (Wesel, Nordrhein- Westfalen, Germany) WP-2000 Chloroprene rubber based aqueous primer, approximately 48 3M Japan Ltd. mass % aqueous solution (Shinagawa-ku, Tokyo, Japan) AP420 Low molecular weight ammonium polyphosphate (APP), Clariant approximately 45 mass % aqueous solution International AG (Muttenz, Basel- Landschaft, Switzerland) .sup.1)BA: n-butyl acrylate; 2EHA: 2-ethylhexyl acrylate; AA: acrylic acid MMA: methyl methacrylate; BMA: butyl methacrylate; DMAEMA: dimethylaminoethyl methacrylate EtOAc: ethyl acetate; MEK: methyl ethyl ketone

Example 1

[0076] A slurry containing dispersant 1 (D1) and glass frits 5 (GL5) was prepared. The mass ratio of D1 to GL5 was 100:500 on the basis of non-volatile content. Film 1 (FL1) was coated with the slurry by using a knife coater. The slurry layer was dried at 65? C. for 3 minutes. After drying, a buffer layer having a thickness of 39 ?m was obtained.

[0077] Tacky adhesive polymer 1 (ADH1) and crosslinking agent 1 (CL1) were mixed to obtain an adhesive mixed solution. The mass ratio of ADH1 to CL1 was 100:0.25 on the basis of non-volatile content. A silicone-treated polyethylene-laminated paper liner was coated with the adhesive mixed solution by using a knife coater. The adhesive layer was dried at 95? C. for 5 minutes. After drying, an adhesive layer having a thickness of 38 ?m was obtained. The laminate of Example 1 was obtained by adhering the adhesive layer and the buffer layer on FL1 together.

Comparative Example 1

[0078] A laminate of Comparative Example 1 was obtained by the same procedure as in Example 1 with the exception that the adhesive layer and FL1 were directly adhered together without a buffer layer being formed on FL1.

Example 2

[0079] An adhesive mixed solution containing ADH1 and glass frits 1 (GL1) was prepared. The mass ratio of ADH1 to GL1 was 100:30 on the basis of non-volatile content. CL1 was added to the adhesive mixed solution and mixed. The mass ratio of ADH1 to CL1 was 100:0.18 on the basis of non-volatile content. A silicone-treated polyethylene-laminated paper liner was coated with the adhesive mixed solution by using a knife coater. The adhesive layer was dried at 95? C. for 5 minutes. After drying, an adhesive layer with a thickness of 45 ?m was obtained. The laminate of Example 2 was obtained by adhering the adhesive layer and FL1 together.

Example 3 to Example 11

[0080] Laminates of Examples 3 to 11 were obtained by the same procedure as in Example 2 with the exception that the type and compounded amount of glass frits were changed in accordance with the description in Table 3.

Comparative Example 2

[0081] A laminate of Comparative Example 2 was obtained by the same procedure as in Example 2 with the exception that GL1 was not used.

Fireproof Performance Test 1

[0082] A plasterboard (100 mm by 100 mm square with a thickness of 12.5 mm) was coated with the 3M (trade name) DI-NOC (trade name) primer DP900N3 (available from 3M Japan Ltd. based in Shinagawa-ku, Tokyo, Japan). The laminate was applied to the primer-coated surface of the plasterboard. The heat release rate (kW/m.sup.2) and total calorific value (MJ/m.sup.2) were measured using a cone calorimeter (available from Toyo Seiki Seisaku-sho, Ltd. based in Kita-ku, Tokyo, Japan) in accordance with ISO 5660-1:2015 under the condition of a radiant heat of 50 kW/m.sup.2. When the total time of heat release rate exceeding 200 kW/m.sup.2 was less than or equal to 10 seconds and the total calorific value in two minutes was less than or equal to 8 MJ/m.sup.2, the result was pass, otherwise fail.

[0083] The results of Example 1 and Comparative Example 1 are shown in Table 2.

TABLE-US-00002 TABLE 2 Adhesive layer Buffer layer ISO Tacky adhesive Thickness Glass thickness Film 5660-1 polymer [?m] frits [?m] layer test EXAMPLE 1 ADH1 38 GL5 39 FL1 PASS COMPARATIVE ADH1 38 FL1 FAIL EXAMPLE 1

Adhesive Force

[0084] A test piece was prepared by cutting a laminate into a rectangular shape having a width of 25 mm and a length of 150 mm. The test piece was adhered to an electrogalvanized steel sheet having a phosphoric acid coating (SECC-P, with a thickness of 1 mm, available from Paltek Corporation based in Hiratsuka-shi, Kanagawa, Japan) at 20? C. The adhering method was in accordance with JIS Z 0237:2009 10.2.4. The test piece was left at 20? C. for 24 hours. Using a tensile tester (Tensilon universal testing machine, model: RTC-1210A, available from A&D Company, Limited based in Toshima-ku, Tokyo, Japan), the adhesive force at the time of performing 90 degree peeling was measured at a peeling rate of 300 mm/min at 20? C.

[0085] The results of Examples 2 to 11 and Comparative Example 2 are shown in Table 3.

TABLE-US-00003 TABLE 3 Adhesive layer Tacky Glass frits ISO Adhesive adhesive Thickness Part by Film 5660-1 force polymer [?m] Type mass layer Test [N/25 mm] Example 2 ADH1 45 GL1 30 FL1 PASS 14 Example 3 ADH1 41 GL2 30 FL1 PASS 12 Example 4 ADH1 41 GL3 30 FL1 PASS 15 Example 5 ADH1 40 GL4 30 FL1 PASS 16 Example 6 ADH1 41 GL5 30 FL1 PASS 14 Example 7 ADH1 40 GL6 30 FL1 PASS 14 Example 8 ADH1 41 GL7 30 FL1 PASS 14 Example 9 ADH1 41 GL8 30 FL1 PASS 13 Example 10 ADH1 42 GL6 10 FL1 PASS 16 Example 11 ADH1 39 GL6 50 FL1 PASS 11 Comparative ADH1 38 FL1 FAIL 18 Example 2

Example 12

[0086] Tacky adhesive polymer 2 (ADH2) and crosslinking agent 2 (CL2) were mixed to obtain an adhesive mixed solution. The mass ratio of ADH2 to CL2 was 97:3 on the basis of non-volatile content. An adhesive film with an adhesive layer having a thickness of 25 ?m formed was prepared by coating film 2 (FL2) with the adhesive mixed solution. A primer composition with a solid content of 74 mass % was prepared by mixing glass frits 9 (GL9) and WP-2000. Using a syringe and a spatula, a plasterboard (100 mm by 100 mm square having a thickness of 12.5 mm) was coated with the primer composition and dried for 24 hours at room temperature to produce a plasterboard with a primer layer having a mass of 0.48 g formed. The article of Example 12 was produced by applying the adhesive film onto the primer layer of the plasterboard.

Example 13

[0087] A primer composition was prepared by mixing glass frits 10 (GL10), Cloisite 20A, AP420, and water. The mass ratio of GL10 to Cloisite 20A, AP420, and water was 2:2:5:10. Using a syringe and a spatula, a plasterboard (100 mm by 100 mm square having a thickness of 12.5 mm) was coated with the primer composition and dried for 24 hours at room temperature to produce a plasterboard with a primer layer having a mass of 0.2 g formed. The article of Example 13 was prepared by applying the adhesive film produced in Example 12 onto the primer layer of the plasterboard.

Example 14

[0088] A plasterboard was coated with the primer composition of Example 13 to form a primer layer: then, the primer layer was coated with two more layers in the same procedure to produce a plasterboard with a primer layer formed that is approximately three times the mass of the primer layer of Example 13. The article of Example 14 was prepared by applying the adhesive film produced in Example 12 onto the primer layer of the plasterboard.

Fireproof Performance Test 2

[0089] The heat release rate (kW/m.sup.2) and total calorific value (MJ/m.sup.2) of the articles produced in Examples 12 to 14 were measured using a cone calorimeter (available from Fire Testing Technology Limited based in East Grinstead, West Sussex, UK) in accordance with ISO 5660-1:2015 under the condition of a radiant heat of 50 kW/m.sup.2. The fire growth rate (FIGRA) was calculated as the peak heat release rate divided by the time to the peak. An article in which the adhesive film of Example 12 was adhered to a plasterboard with no primer layer formed was used as a control: in the same manner as above, the heat release rate and the total calorific value of the article were measured, and the fire growth rate of the article was calculated. The results of Examples 12 to 14 and the control are shown in Table 4.

TABLE-US-00004 TABLE 4 Total calorific Peak heat value release rate Fire growth rate (MJ/m.sup.2) (kW/m.sup.2) [kW/(m.sup.2 .Math. s)] Control 9.5 200 13 Example 12 7.8 138 7.7 Example 13 7.3 217 11 Example 14 8.3 153 8.3

[0090] FIG. 4 is a graph illustrating the relationship between heat release rate and time in Example 12 and the control. FIG. 5 is a graph illustrating the relationship between heat release rate and time in Example 13, Example 14, and the control.

REFERENCE SIGNS LIST

[0091] 10 Article with a film adhered [0092] 12 Film layer [0093] 14 Glass particle-containing layer [0094] 142 Glass particles [0095] 144 Binder [0096] 16 Adherend [0097] 18 Adhesive layer [0098] 24 Buffer layer [0099] 34 Primer layer [0100] 100 Laminate