JP6882933B2 - Decorative sheet and manufacturing method of decorative sheet - Google Patents

Description

The present invention relates to a decorative sheet and a method for producing the decorative sheet.

Decorative sheets are widely used as sheet-like interior building materials installed on the surfaces of walls, floors, ceilings, and the like. Some decorative sheets are decorated with wood grain or stone grain, and are also used for interior decoration.
On the other hand, the Building Standards Law stipulates the use of non-combustible and flame-retardant fireproof materials for interior building materials. Therefore, it is required that the decorative sheet also exhibits a predetermined fire protection performance.
Further, the adhesive used for the decorative sheet is required to exhibit adhesive performance even at low temperature and room temperature from the viewpoint of workability.

Patent Document 1 discloses a nonflammable decorative sheet containing a (meth) acrylic acid ester copolymer, a bromine-based flame retardant, antimony trioxide, a tack fire, and a polyisocyanate-based curing agent in the pressure-sensitive adhesive layer. ..

Japanese Unexamined Patent Publication No. 2010-229327

However, Patent Document 1 does not study the adhesive performance at low temperature and the constant load property, and is required to provide a decorative sheet having excellent fire resistance and workability and also excellent constant load property.
In view of the above circumstances, an object of the present invention is to provide a decorative sheet having excellent fire resistance, workability and constant load property, and a method for producing the decorative sheet.

The inventors have made the base material layer contain antimony trioxide, and the pressure-sensitive adhesive layer contains a pressure-sensitive adhesive and a brominated flame retardant so as not to contain antimony trioxide, without impairing the adhesive performance. Moreover, the antimony trioxide contained in the base material layer and the brominated flame retardant contained in the adhesive are mixed at the time of combustion of the decorative sheet, and the calorific value derived from the adhesive can be suppressed, resulting in fire resistance and workability. We have found that an excellent decorative sheet can be obtained, and completed the present invention.

That is, the present invention provides a decorative sheet having the following characteristics and a method for producing the decorative sheet.
(1) A decorative sheet comprising a base film and an adhesive layer provided on at least one side of the base film, wherein the base film contains antimony trioxide.
The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive and a brominated flame retardant, and does not contain antimony trioxide.
In the heat generation test below, 20 of the test piece when a laminate having a gypsum board having base paper on both surfaces and the decorative sheet laminated on the side to which the radiant heat of the gypsum board is given is used as the test piece. The total calorific value in the test time per minute is 7.2 MJ / m ² or less.
In the following initial adhesive strength test, the initial adhesive strength is 5 N / 25 mm or more in a 5 ° C environment, 15 N / 25 mm or more in a 23 ° C, 50% RH environment, and
A decorative sheet having a peeling distance of 5 mm or less in the constant load property test below.
Pyrogenic test: ISO 5660-1: conforms to 2002 Cone Calorimeter method, pyrogenic test initial adhesion radiation heat condition at the surface of the test piece is measured at 50kW / ^{m 2:} JIS Z0237: conforms to 2009, cosmetic A test in which the test piece of the sheet is attached to a stainless steel test plate (test plate) while being roller-bonded, and the test piece is peeled off at 180 ° with respect to the test plate within 30 seconds after the application under the condition of a peeling speed of 300 mm / min. Initial adhesive strength test measured by the method Constant load test: A test piece with a width of 25 mm and a length of 100 mm is cut out from a decorative sheet, and a 50 mm pressure-sensitive adhesive layer surface is roller-bonded to the test plate from one end of the test piece. After affixing the test plate while leaving it in a standard environment of 23 ° C. and 50% RH for 24 hours immediately after the affixing, the test plate was placed horizontally with the side to which the test piece was affixed facing downward, and the test piece was placed. A weight having a mass of 50 g is attached to the other end so that the test piece can be peeled off in the vertical direction, and after maintaining the state for 24 hours, the distance at which the test piece is peeled off from the surface of the test plate (peeling distance, mm). (2) The constant load property test measured in (2), wherein the pressure-sensitive adhesive layer contains 5 to 30 parts by mass of a bromine-based flame retardant as a dry mass with respect to 100 parts by mass of the dry pressure of the pressure-sensitive adhesive. Cosmetic sheet.
(3) The decorative sheet according to (1) or (2) above, wherein the bromine-based flame retardant is brominated isocyanurate.
(4) The cosmetic sheet according to (3) above, wherein the brominated isocyanurate is tris (2,3-dibromopropyl) isocyanurate.
(5) The decorative sheet according to any one of (1) to (4) above, wherein the pressure-sensitive adhesive layer further contains a phosphorus-based flame retardant.
(6) The decorative sheet according to (5) above, wherein the phosphorus-based flame retardant is a phosphoric acid ester-based flame retardant.
(7) The decorative sheet according to (6) above, wherein the phosphoric acid ester-based flame retardant is a condensed phosphoric acid ester.
(8) The decorative sheet according to any one of (1) to (7) above, wherein the pressure-sensitive adhesive contains an acrylic resin.
(9) The decorative sheet according to any one of (1) to (8) above, wherein the base film contains a vinyl chloride resin.
(10) The method for producing a decorative sheet according to any one of (1) to (9) above, wherein the pressure-sensitive adhesive layer is provided on the base film.

According to the present invention, it is possible to provide a decorative sheet having excellent fire resistance and workability, and a method for producing the decorative sheet.

It is sectional drawing which shows the structure of the decorative sheet of embodiment.

≪Cosmetic sheet≫
The decorative sheet of the present invention is a decorative sheet including a base film and an adhesive layer provided on at least one side of the base film.
The base film contains antimony trioxide,
The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive and a brominated flame retardant, and does not contain antimony trioxide.
In the heat generation test below, 20 of the test piece when a laminated body having a gypsum board having base paper on both surfaces and the decorative sheet laminated on the side to which radiant heat is given of the gypsum board is used as the test piece. The total calorific value in the test time per minute is 7.2 MJ / m ² or less.
In the following initial adhesive strength test, the initial adhesive strength is 5 N / 25 mm or more in a 5 ° C environment, 15 N / 25 mm in a 23 ° C, 50% RH environment, and
A decorative sheet having a peeling distance of 5 mm or less in the constant load property test below.
Pyrogenic test: ISO 5660-1: conforms to 2002 Cone Calorimeter method, pyrogenic test initial adhesion radiation heat condition at the surface of the test piece is measured at 50kW / ^{m 2:} JIS Z0237: conforms to 2009, cosmetic A test in which the test piece of the sheet is attached to a stainless steel test plate (test plate) while being roller-bonded, and the test piece is peeled off at 180 ° with respect to the test plate within 30 seconds after the application under the condition of a peeling speed of 300 mm / min. Initial adhesive strength test measured by the method Constant load test: A test piece with a width of 25 mm and a length of 100 mm is cut out from a decorative sheet, and an adhesive layer surface of 50 mm from one end of the test piece is roller-bonded to the test plate. After affixing the test plate while leaving it in a standard environment of 23 ° C. and 50% RH for 24 hours immediately after the affixing, the test plate was placed horizontally with the side to which the test piece was affixed facing downward, and the test piece was placed. A weight having a mass of 50 g is attached to the other end so that the test piece can be peeled off in the vertical direction, and after maintaining the state for 24 hours, the distance at which the test piece is peeled off from the surface of the test plate (peeling distance, mm). Constant load property test measured in 1. Hereinafter, a decorative sheet according to an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing the configuration of the decorative sheet of the present embodiment. The decorative sheet 1 of the present embodiment includes a base film 10 and an adhesive layer 20 provided on one side of the base film 10. The release liner 30 is not an essential configuration in the decorative sheet of the present invention.

(Fever test)
The decorative sheet 1 is excellent in fire resistance. The fire resistance means that in the exothermic test, the total calorific value of the test piece tested in the test time of 20 minutes is 7.2 MJ / m ² or less.

Hereinafter, the exothermic test will be described.
The exothermic test is known as one of the methods for evaluating non-combustible materials. The exothermic test in the present specification is an exothermic test in which the radiant heat condition on the surface of the test piece is measured at ^{50 kW / m 2 in accordance with the ISO 5660-1: 2002 cone calorimeter method.}
In the exothermic test, the furnace of the cone calorimeter is preheated before the exothermic test so that the radiant heat condition on the surface of the test piece ^{is measured at 50 kW / m 2.} The test time of 20 minutes is the time after the heating of the surface of the test piece is started by the furnace of the cone calorie meter.

In the exothermic test in the present specification, as a test piece, a laminate having a plaster board and the decorative sheet laminated on the side to which the radiant heat of the plaster board is given is used. The size of the test piece shall be 99 ± 1 mm square. The gypsum board is a non-combustible gypsum board, is not fireproofed, has a flat plate shape, has a smooth surface shape, a thickness of 12.5 (± 0.5) mm, and a specific gravity of 0.65 or more. The weight should be 8.1 kg / m ² or more, and the base paper should be attached to both surfaces. The base paper has a thickness of 0.45 mm or less and a weight of 250 g / m ² or less. Non-combustible certification means non-combustible material certified by the Building Standards Law (2000 Ministry of Construction Notification No. 1400).

The total calorific value of the test piece of the decorative sheet of the embodiment in the test time of 20 minutes is 7.2 MJ / m ² or less, ^{preferably 7.0 MJ / m 2} or less, and 6.5 MJ / m. more preferably ² or less, and more preferably 6.0 mJ / ^{m 2} or less. The decorative sheet used for the test piece that achieves the total calorific value has excellent fire resistance.

It is preferable that the decorative sheet of the embodiment satisfies the heat generation test standard specified by the Building Standards Act (Ministry of Construction Notification No. 1400, 2000) (passes the heat generation test). The criteria for the exothermic test have the following three items regarding the test piece. 1) The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, 2) There are no cracks or holes that penetrate to the back surface, which is harmful for fire prevention, for 20 minutes after the start of heating, 3) 20 after the start of heating. The maximum heat generation rate shall not exceed ^{200 kW / m 2} continuously for 10 seconds or more for a minute.

Hereinafter, the configuration of the decorative sheet of the present embodiment will be described in detail.

(Base film)
The material of the base film 10 is not particularly limited, and for example, polyester such as polyethylene terephthalate (PET), polyolefin such as polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyurethane (PU), and polymethyl. It was composed of resins such as methacrylate (PMMA), polyvinyl chloride, vinylidene polyvinylfluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer. Things can be mentioned.

The base film 10 contains antimony trioxide. By including antimony trioxide in the base film, the flame retardancy of the base film can be enhanced.
The base film 10 preferably contains a vinyl chloride resin. The vinyl chloride resin has the advantages of being hard to burn and having good elongation, so that it is easy to install.
The vinyl chloride resin is a polymer having a repeating unit derived from vinyl chloride.
The vinyl chloride-based resin may be a homopolymer of vinyl chloride, or may be a copolymer of vinyl chloride and a monomer copolymerizable with the vinyl chloride. Examples of the copolymer include vinyl chloride-based copolymers such as ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, and vinyl chloride-halogenated olefin copolymer. In the vinyl chloride-based copolymer, the amount of the repeating unit derived from vinyl chloride is preferably 50 mol% or more, more preferably 70 mol% or more, based on all the repeating units.

The vinyl chloride resin may be used alone or in combination of two or more. In addition, the vinyl chloride resin can be used in combination with other resins. As the other resin, a resin compatible with the vinyl chloride resin is preferable. When the vinyl chloride resin and the other resin are used in combination, the blending amount of the other resin is usually 1 to 50 parts by mass, preferably 5 to 30 parts by mass, based on 100 parts by mass of the vinyl chloride resin. It may be preferably 5 to 10 parts by mass.

The thickness of the base film 10 is preferably 100 μm or more and 300 μm or less, more preferably 130 to 250 μm, and further preferably 150 to 200 μm. When a plurality of layers of the base film are provided, the thickness of the base film is the sum of the thicknesses of each base film. The thickness of the base film 10 can be obtained as an average value obtained by measuring the thickness of 10 randomly selected places.
When the thickness of the base film 10 is 100 μm or more and 300 μm or less, the decorative sheet is excellent in workability and fire resistance.

(Colorant)
The base film 10 may contain various additives, if necessary. Examples of the additive include a colorant.
The colorant may be contained in, for example, the base film 10. The colored base film can be produced by blending a colorant with a resin composition that is a raw material of the base film and molding the resin composition.

Coloring may be applied to the inside of the base film by printing on the base film 10. Alternatively, coloring may be applied as a printing layer (not shown) formed on the base film 10. The printing layer is formed by, for example, printing the base film 10 with an ink containing a colorant. The ink may be impregnated in the base film 10 or may be deposited on the base film.

As the colorant, an organic pigment, an inorganic pigment, or a dye can be used. As the black pigment, for example, carbon black, copper oxide, iron tetraoxide, manganese dioxide, aniline black, activated charcoal and the like are used. Examples of yellow pigments include chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, nables ero, naphthol ero S, hanza ero, benzine ero G, benzine ero GR, quinoline ero lake, etc. Permanent yellow NCG, tartrazine lake, etc. are used. As the orange pigment, for example, red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indus lem brilliant orange RK, benzidine orange G, indus lem brilliant orange GKM and the like are used. Examples of red pigments include red iron oxide, cadmium red, lead tan, mercury sulfide, cadmium, permanent red 4R, resole red, pyrozolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, and rhodamine. Lake B, alizarin lake, brilliant carmine 3B and the like are used. As the purple pigment, for example, manganese purple, fast violet B, methyl violet lake and the like are used. As the blue pigment, for example, dark blue, cobalt blue, alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, induslen blue BC and the like are used. As the green pigment, for example, chromium green, chromium oxide, pigment green B, malachite green lake, final yellow green G and the like are used. As the white pigment, for example, zinc white, titanium oxide, antimony white, zinc sulfide and the like are used. As the extender pigment, for example, barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like are used.

Further, as the dye, for example, a basic dye, an acid dye, a disperse dye, a direct dye and the like are used. Examples of such dyes include niglosin, methylene blue, rose bengal, quinoline yellow, ultramarine blue and the like.

The blending amount of the colorant may be, for example, 0 to 40% by mass or 10 to 30% by mass in 100% by mass of the base film.
The colorant may be used alone or in combination of two or more.

(Adhesive layer)
The pressure-sensitive adhesive layer 20 has a function of attaching the decorative sheet 1 (excluding the release liner 30) to the adherend. The pressure-sensitive adhesive layer 20 contains a brominated flame retardant and does not contain antimony trioxide. If the pressure-sensitive adhesive layer contains antimony trioxide, the sticky physical properties tend to decrease, which is not preferable.
The content of the brominated flame retardant in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 20 is 5 to 30 parts by mass, preferably 10 to 20 parts by mass as a dry mass with respect to 100 parts by mass of the dry mass of the pressure-sensitive adhesive. It is a mass part.

Examples of the brominated flame retardant include tetrabromobisphenol A, tetrabromobisphenol A diallyl ether, tetrabromobisphenol A dimetharyl ether, tetrabromobisphenol A diglycidyl ether, and tribromophenol adduct of tetrabromobisphenol A diglycidyl ether.
Tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol Brominated bisphenol compounds such as S-bis (2,3-dibromopropyl ether), tetrabromobisphenol S, or derivatives thereof,
Hexabromobenzene, pentabromotoluene, ethylenebispentabromodiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, pentabromobenzyl bromide, bis (2,4,6-tribromophenoxy) ethane, tetrabromophthalic anhydride, octabromotrimethylphenyl Brominated aromatic compounds such as indan, pentabromobenzyl acrylate, tribromophenylallyl ether, 2,3-dibromopropyl pentabromophenyl ether or derivatives thereof,
Mono (2,3-dibromopropyl) isocyanurate, di (2,3-dibromopropyl isocyanurate), tris (2,3-dibromopropyl) isocyanurate, mono (2,3,4-tribromobutyl) ) Isocyanurate, brominated isocyanurate such as di (2,3,4-tribromobutyl) isocyanurate, tris (2,3,4-tribromobutyl) isocyanurate or ethylenebistetrabromophthalimide, Bromine and nitrogen atom-containing compounds such as ethylenebisdibromonorbornandicarboxyimide, 2,4,6-tris (2,4,6-tribromophenoxy) 1,3,5-triazine,
Tetrabromobisphenol A Polycarbonate Oligomer, Tetrabromobisphenol A Diglycidyl Ether and Brominated Bisphenol Additives Epoxy oligomers and other brominated bisphenol derivative oligomers,
Brominated acrylic resin, such as pentabromobenzyl acrylate polymer,
Bromine and phosphorus atom-containing compounds such as tris (tribromoneopentyl) phosphate, tris (bromophenyl) phosphate,
Examples include brominated inorganic compounds such as ammonium bromide. Among these, brominated isocyanurate is preferable, and tris (2,3-dibromopropyl) isocyanurate is more preferable from the viewpoint of excellent solubility in a solvent.

The pressure-sensitive adhesive layer 20 preferably contains a phosphorus-based flame retardant. By incorporating a phosphorus-based flame retardant together with a bromine-based flame retardant in the pressure-sensitive adhesive layer, the flame retardancy of the decorative sheet can be further enhanced and the workability can be further enhanced.
Examples of the phosphorus-based flame retardant include a phosphate ester-based flame retardant, a polyammonium phosphate-based flame retardant, a melamine phosphate-based flame retardant, a phosphoric acid amide-based flame retardant, and a phosphazene compound-based flame retardant. Acid ester flame retardants are preferred.

As a commercially available phosphoric acid ester flame retardant, for example,
Non-halogen phosphate ester manufactured by Daihachi Chemical Industry Co., Ltd. TMP (trimethyl phosphate), TEP (triethyl phosphate), TPP (triphenyl phosphate), TCP (tricresyl phosphate), TXP (tricylenyl phosphate), CDP ( Cresildiphenyl phosphate), NDPP (2-naphthyldiphenyl phosphate), PX-110 (cresildi2,6-xylenyl phosphate), non-halogen condensed phosphate esters CR-733S, CR-741, PX-200, DAIGUARD-580, DAIGUARD-610, DAIGUARD-880,
TMCPP (tris (chloropropyl) phosphate), CR-900 (tris (tribromoneopentyl) phosphate), which is a halogen-containing phosphate ester,
CR-504L, CR-570, DAIGUARD-540, which are halogen-containing condensed phosphoric acid esters,
Phosflex series such as Axonobel Japan's Phosflex 112, 112B, 179A, Fireroll flex RDP, BDP, 4800, Firequel 220, EHC, Phylrol DPN, 6, DMMP, etc.
Leofos 35, 50, 65, 95, 110, TPP, RDP, BAPP, CDP and other Leofos series, Chronitex CDP, TCP, TXP and other Chronitex series, Leomore TIBP, which are non-halogen phosphate esters manufactured by Ajinomoto Fine Techno. Leomore series such as TOP, Durad series such as Leorube HYD-110, Durad CDP, TCP, TXP;
ADEKA Stub series of condensed phosphate esters manufactured by ADEKA such as PFR, FP-500, FP-600, and FP-700;
NcendXP-30, a condensed phosphoric acid ester manufactured by Albemar Japan, AntiblazeTMCP, a halogen-containing phosphoric acid ester, 195, AntiblazeV-6, a halogen-containing condensed phosphoric acid ester;
Reofos series such as ReofosTPP, RDP, BAPP, which are non-halogen phosphates manufactured by Chemtura Japan;
However, a condensed phosphate ester having low volatility is preferable.

Examples of the ammonium polyphosphate flame retardant include ammonium polyphosphate alone, a compound containing the ammonium polyphosphate as a main component, and the like.
The ammonium polyphosphate is a compound that can be represented by the general formula (NH ₄ ) _{r + 2} PrO _{3r + 1} (where r is an integer of 20 to 1000), and when r is sufficiently large, the formula of metaphosphoric acid is used. (NH ₄ PO ₃ ) _r (where r is the same as above) is a compound that can be approximated.
On the other hand, as the compound containing ammonium polyphosphate as a main component, the surface of the ammonium polyphosphate is coated with a thermosetting resin or microencapsulated, a melamine monomer, another nitrogen-containing organic compound, or the like. Examples thereof include those coated, those treated with a surfactant or a silicone compound, and those that are hardly soluble by adding melamine or the like in the process of producing ammonium polyphosphate.
Examples of commercially available ammonium polyphosphate flame retardants include Exolit-422, 463, 700, AP-750 manufactured by Clariant, Phos-chek-P / 30, P / 40 manufactured by Monsanto, and Sumitomo. Examples thereof include Sumisafe-P and PM manufactured by Kagaku Kogyo Co., Ltd., TERRAJU-S10, S20, C60, C70 and C80 manufactured by Chisso, and Antiblaze MC and PI manufactured by Albemar Japan.

The content of the phosphorus-based flame retardant in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 20 is 10 to 50 parts by mass, preferably 20 to 40 parts by mass, as a dry mass with respect to 100 parts by mass of the dry mass of the pressure-sensitive adhesive. It is a mass part.

In the decorative sheet of the present invention, the adhesive strength of the pressure-sensitive adhesive layer was 5N / 25 mm or more in the following initial adhesive strength test under an environment of 5 ° C. and 50% RH at 23 ° C. , 15N / 25mm or more, and the peeling distance is 5mm or less in the following constant load property test. The initial adhesive strength is based on JIS Z0237: 2009, and the test piece of the decorative sheet is attached to the stainless steel test plate (test plate) while being roller-bonded, and within 30 seconds after the application, the peeling speed is 300 mm / min. , The value measured by the test method of peeling the test piece to the test plate at 180 °, which is 5 N / 25 mm or more and 5 to 100 N / 25 mm in an environment of 5 ° C ± 1 ° C. It is preferably 8 to 40 N / 25 mm, more preferably 15 N / 25 mm or more, preferably 18 to 100 N / mm under a 23 ° C. ± 1 ° C., 50% RH environment, and preferably 20 to 40 N / 25 mm. Is more preferable. When the initial adhesive strength is 5 N / 25 mm or more, the adhesion between the adherend and the decorative sheet is good, which is preferable. When the adhesive strength is 100 N / 25 mm or less, the workability of the decorative sheet is good, which is preferable.
For constant load property, a test piece having a width of 25 mm and a length of 100 mm is cut out from a decorative sheet, and a 50 mm pressure-sensitive adhesive layer surface is attached to the test plate by roller pressure bonding from one end of the test piece. After leaving the test plate in a standard environment of 23 ° C. and 50% RH for 24 hours, the test plate was placed horizontally with the side to which the test piece was attached facing downward, and the test was performed on the other end of the test piece. A weight with a mass of 50 g is attached so that the piece peels off in the vertical direction, and after maintaining that state for 24 hours, the value is measured at the distance (peeling distance, mm) from which the test piece is peeled off from the surface of the test plate. It is 5 mm or less, preferably 3 mm or less. When the constant load property is 5 mm or less, it is preferable that the decorative sheet is less likely to come off and peel off after a lapse of time.

(Adhesive)
The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive and is formed by reacting a cross-linking agent. Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resins, urethane-based resins, and silicone-based resins, and acrylic-based pressure-sensitive adhesives containing acrylic resins are preferable. The content of the acrylic resin with respect to 100% by mass of the pressure-sensitive adhesive layer may be 20 to 99.9% by mass, 40 to 90% by mass, or 65 to 85% by mass. Examples of the acrylic resin include a polymer of (meth) acrylic acid ester, and examples thereof include a polymer or a copolymer having a structural unit derived from (meth) acrylic acid ester. The content of the structural unit derived from the (meth) acrylic acid ester is preferably 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, still more preferably 85 to 99% by mass, based on all the structural units. More preferably, it is 88 to 95% by mass. As the (meth) acrylic acid ester-based copolymer, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms, a monomer containing a functional group having an active hydrogen, and the like are optionally used. Examples thereof include a copolymer with the monomer of. In addition, in this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid".

Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth). ) Pentyl acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Examples thereof include myristyl acrylate (meth), palmityl (meth) acrylate, and stearyl (meth) acrylate. One of these may be used alone, or two or more thereof may be mixed and used.

Examples of the monomer containing a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2 (meth) acrylate. Hydromer group-containing monomers such as (meth) acrylic acid hydroxyalkyl esters such as −hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; acrylamide, methacrylic acid, N-methylacrylamide, Amid group-containing monomers such as N-methylmethacrylate, N-methylolacrylamide, and N-methylolmethacrylate; monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate. , (Meta) monoethylaminopropyl acrylate and the like (meth) monoalkylaminoalkyl acrylate; carboxylic acids having an ethylenically unsaturated bond such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like. And so on. One of these may be used alone, or two or more thereof may be mixed and used.

The amount of the cross-linking agent used may be, for example, 0.01 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester-based copolymer, for example, 0.1. It may be 10 parts by mass.
Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, amine-based cross-linking agents, and amino resin-based cross-linking agents.
Examples of the isocyanate-based cross-linking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2 , 4'-Diphenylmethane diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 2,4'-methylenebis ( Cyclohexyl isocyanate), polyhydric isocyanate compounds such as lysine isocyanate can be mentioned.

The thickness of the pressure-sensitive adhesive layer 20 is preferably 10 μm or more and 100 μm or less, more preferably 20 to 80 μm, and even more preferably 30 to 70 μm. When the thickness of the pressure-sensitive adhesive layer 20 is 10 μm or more, it is effective in suppressing ^{the total calorific value of the test piece in the exothermic test to 7.2 MJ / m 2 or less.} When the thickness of the pressure-sensitive adhesive layer 20 is 10 μm or more, the adhesive strength of the decorative sheet to the adherend is also satisfactorily exhibited. Further, when the thickness of the pressure-sensitive adhesive layer 20 is 100 μm or less, the workability of the decorative sheet is excellent.

Further, the pressure-sensitive adhesive layer 20 may contain a flame retardant other than the brominated flame retardant for the purpose of enhancing the flame retardancy of the decorative sheet.
Examples of such a flame retardant include a heat-foaming flame retardant. The heat-foaming flame retardant can impart heat-foaming property to the pressure-sensitive adhesive layer 20. The material that imparts heat-foaming property to the pressure-sensitive adhesive layer 20 is not limited to the heat-foaming flame retardant.

The heat-foaming flame retardant may be one known as an intomescent flame retardant. Nitrogen-containing substances such as ammonium polyphosphate, melamine polyphosphate, melamine phosphate, and phosphate esteramide as substances that exhibit the characteristics of the intomescent flame retardant and may be contained in the intomesent flame retardant ( Poly) Phosphate compounds; Examples thereof include nitrogen-containing pyrophosphate compounds such as piperazine pyrophosphate and melamine pyrophosphate. The thermofoamable flame retardant preferably contains at least one compound selected from the group consisting of ammonium polyphosphate, melamine polyphosphate, piperazine pyrophosphate, melamine pyrophosphate and phosphate esteramide, and among them, piperazine pyrophosphate and pyrolin. More preferably, it contains melamine acid. The heat-foamable flame retardant may contain a foamable material such as expanded graphite.

When the pressure-sensitive adhesive layer contains a heat-foaming flame retardant, the content of the heat-foaming flame retardant in the pressure-sensitive adhesive layer 20 is preferably 10 to 45% by mass with respect to 100% by mass of the pressure-sensitive adhesive layer. It is more preferably ~ 40% by mass, and even more preferably 20 to 30% by mass. When the pressure-sensitive adhesive layer contains the heat-foaming flame retardant in the above proportion, the heat insulating property of the foamed layer formed after the heat-foaming of the pressure-sensitive adhesive layer becomes excellent, and more effectively, the test in the heat-generating test. The total calorific value of the piece ^{can be suppressed to 7.2 MJ / m 2} or less, and the adhesion to the adherend can be improved. If the amount of the flame retardant added exceeds the above upper limit with respect to 100% by mass of the pressure-sensitive adhesive layer, the adhesive strength of the pressure-sensitive adhesive layer may decrease and the state of adhesion to the adherend may deteriorate.

(Peeling liner)
Any known release liner 30 may be used. Examples of the base material of the release liner 30 include a resin film made of paper, polyethylene, polypropylene, polyester and the like. Then, a material in which the joint surface of the base material with the pressure-sensitive adhesive layer 20 is treated with a release agent (for example, a silicone-based release agent) is preferably used.

The thickness of the release liner 30 is not particularly limited, and is preferably about 20 to 200 μm, for example.

A fluororesin film containing a fluororesin as an outermost layer may be further laminated on the decorative sheet 1 on the side opposite to the side where the pressure-sensitive adhesive layer 20 of the base film 10 is provided.

The decorative sheet 1 may have irregularities formed on the surface of the base film 10 opposite to the side on which the pressure-sensitive adhesive layer 20 is provided. Examples of the unevenness include those formed by so-called grain processing and those having a wood grain shape.

The decorative sheet 1 of the present embodiment is preferably used by being attached to an interior such as a wall, floor, or ceiling in a building. It is preferable that the decorative sheet 1 of the present embodiment is attached to a gypsum board used for interiors such as walls, floors, and ceilings in a building to be used.

According to the decorative sheet 1 of the embodiment, the base film contains antimony trioxide, the pressure-sensitive adhesive layer contains the pressure-sensitive adhesive and the brominated flame retardant, and the base film does not contain antimony trioxide. It is possible to provide a decorative sheet having excellent properties. In the decorative sheet 1, the antimony trioxide contained in the base film and the brominated flame retardant contained in the adhesive layer are mixed in the event of a fire, and the heat generated during the combustion of the adhesive is suppressed, thereby reducing the total calorific value. It can be easily set to 7.2 MJ / m ² or less.

Further, the decorative sheet 1 has the initial adhesive strength of the pressure-sensitive adhesive layer of 5 N / 25 mm or more in a 5 ° C. environment and 15 N / 25 mm or more in a 23 ° C., 50% RH environment. Since the constant load is 5 mm or less, the adhesive physical properties are not deteriorated, and the workability at low temperature and normal temperature is excellent.

≪Manufacturing method of decorative sheet≫
The method for producing a decorative sheet of the present invention is the method for producing a decorative sheet of the present invention, in which the pressure-sensitive adhesive layer is provided on a base film containing the antimony trioxide.
In one embodiment, the decorative sheet can be manufactured, for example, as follows.

First, a pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is prepared. The pressure-sensitive adhesive composition is obtained by blending each component constituting the above-mentioned pressure-sensitive adhesive layer containing the pressure-sensitive adhesive and the brominated flame retardant in an appropriate ratio. At the time of blending, each component may be diluted in advance with a dispersion medium or solvent, or a dispersion medium or solvent may be added at the time of mixing.
Examples of the solvent include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, ethyl acetate, methyl ethyl ketone, acetone, tetrahydrofuran, isopropanol, dimethylformamide, N-methylpyrrolidone and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The pressure-sensitive adhesive composition obtained above is applied onto the base film to an appropriate thickness by a known coating device. Subsequently, the pressure-sensitive adhesive composition on the base film is heated and dried to remove the solvent in the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer is provided on the base film. The above-mentioned release liner may be attached to the pressure-sensitive adhesive layer.

Alternatively, the pressure-sensitive adhesive composition is applied to an appropriate thickness on a suitable release liner by a known coating device. Subsequently, the pressure-sensitive adhesive composition on the release liner is heated and dried to remove the solvent in the pressure-sensitive adhesive composition and form a pressure-sensitive adhesive layer on the release liner. After that, the pressure-sensitive adhesive layer may be transferred onto the base film, and the pressure-sensitive adhesive layer may be provided on the base film.

When a heat-foamable base film is used, the heat-foamable base film is manufactured by blending a heat-foamable flame retardant with a resin composition that is a raw material of the base film and molding the film. it can.

The heating temperature may be about 80 to 150 ° C.
Examples of the coating apparatus include a roll coater, a knife coater, a roll knife coater, a fountain die coater, a slot die coater, and a reverse coater.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
(Manufacturing of base film)
A base film was obtained by forming a composition for a base film obtained by melting the following base resin into a film having a thickness of 160 μm using a calendar.

Base resin:
Polyvinyl chloride (PVC): 100 parts by mass, dioctyl phthalate: 20 parts by mass, epoxy plasticizer: 5 parts by mass, barium zinc-based stabilizer: 2 parts by mass, titanium oxide (pigment): 10 parts by mass, trioxide Antimony (manufactured by Nihon Seiko Co., Ltd., trade name "PATOX-M"): 5 parts by mass

(Manufacturing of adhesive layer)
92 parts by mass of butyl acrylate and 8 parts by mass of acrylate as a monomer component, 200 parts by mass of ethyl acetate as a solvent, and 0.2 parts by mass of azobisisobutyronitrile as a polymerization initiator are placed in a reactor. Mixed. After degassing with nitrogen gas for 4 hours and gradually raising the temperature to 60 ° C., the polymerization reaction was carried out with stirring for 24 hours, and an ethyl acetate solution containing an acrylic copolymer having a weight average molecular weight of 650,000 (dry mass). A concentration of 33% by mass) was obtained.

With respect to 100 parts by mass of the dry mass of the obtained acrylic copolymer, 2.25 parts by mass of an isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L") and a bromine-based flame retardant (Tris (2) , 3-Dibromopropyl) isocyanurate, manufactured by Manac, trade name "EB-70") in 15 parts by mass, phosphate ester flame retardant (manufactured by Daihachi Chemical Industry Co., Ltd., trade name "CR741", liquid at room temperature ) Was added as a dry mass in 30 parts by mass. The mixture was diluted with ethyl acetate to a dry mass concentration of 28% by weight to prepare a solution of the pressure-sensitive adhesive composition.
This solution was applied to a release liner so that the thickness of the pressure-sensitive adhesive layer after drying was 50 μm, dried at 100 ° C. for 1 minute, and then transferred to a base film to form a pressure-sensitive adhesive layer. The decorative sheet of Example 1 was prepared.

[Comparative Example 1]
A decorative sheet of Comparative Example 1 was produced in the same manner as the decorative sheet of Example 1 except that 5 parts by mass of antimony trioxide was added to the pressure-sensitive adhesive layer.

[Comparative Example 2]
A decorative sheet of Comparative Example 2 was produced in the same manner as the decorative sheet of Example 1 above, except that antimony trioxide was removed from the base film.

[Comparative Example 3]
In the same manner as the cosmetic sheet of Example 1, except that the brominated flame retardant (Tris (2,3-dibromopropyl) isocyanurate, manufactured by Manac Inc., trade name "EB-70") is removed from the flame retardant. A decorative sheet of Comparative Example 3 was produced.

[Comparative Example 4]
A decorative sheet of Comparative Example 4 was produced in the same manner as the decorative sheet of Example 1 except that 1 part by mass of antimony trioxide was added to the pressure-sensitive adhesive layer.

[Initial adhesive strength]
The decorative sheets of Examples 1 and Comparative Examples 1 to 4 cut into 25 mm × 300 mm were used as test pieces for measuring adhesive strength, and the test pieces were used as stainless steel test plates (test plates) in accordance with JIS Z0237: 2009. The test piece was affixed to the surface while crimping with a roller, and within 30 seconds after the affixing, the test piece was placed under the conditions of 23 ° C. ± 1 ° C., 50% RH environment, or 5 ° C. ± 1 ° C. The adhesive strength was measured by a test method of peeling off the test plate at 180 °. The results are shown in Table 1.

[Constant load property]
The constant load property of the obtained decorative sheet was evaluated. That is, a test piece having a width of 25 mm and a length of 100 mm is cut out from the obtained decorative sheet, and an adhesive layer surface of 50 mm from one end of the test piece is attached to the test plate while being roller-bonded to the test plate. It was left in a standard environment of 23 ° C. and 50% RH for 24 hours.
Next, the test plate is horizontally arranged with the surface to which the test piece is attached facing downward, and a weight having a mass of 50 g is attached to the other end of the test piece so that the test piece can be peeled off in the vertical direction. After maintaining the state for 24 hours, the distance at which the test piece was peeled from the surface of the test plate (peeling distance, mm) was measured, and the constant load property was evaluated according to the following criteria. The results obtained are shown in Table 1.

[Fever test]
Each decorative sheet (thickness 210 μm, 100 mm square) obtained in Examples and Comparative Examples was applied to a 12.5 mm thick non-combustible certified gypsum board (with base paper attached to both surfaces) cut into 100 mm squares. The cut pieces) were overlapped to form a laminated body, which was used as a test piece. The produced test piece was placed in an environment of 23 ° C. and 50% RH for 1 week or more, and then used in the following test.
For the test piece, a corn calorimeter (manufactured by Fire Testing Technology Ltd) is used, and the radiant heat condition on the surface of the test piece is measured at ^{50 kW / m 2 in accordance with the ISO 5660-1: 2002 corn calorimeter method.} A febrile test was performed. Here, the surface of the test piece (the side to which radiant heat is applied) is the surface of the decorative sheet of the test piece. In this way, the total calorific value of the test piece in the test time of 20 minutes was determined. The results are shown in Table 1.

The test piece of the decorative sheet of Example 1 had a low total calorific value and constant load value in a heat generation test time of 20 minutes, and also had a high initial adhesive strength in an environment of 5 ° C. and an environment of 23 ° C. On the other hand, the test piece of the decorative sheet of Comparative Example 1 had low values of total calorific value and constant load property (peeling distance) in the exothermic test time in 20 minutes, but under a 5 ° C environment and at 23. The initial adhesive strength value in the ℃ environment was low. The test piece of the decorative sheet of Comparative Example 2 had a high initial adhesive strength value under a 5 ° C. environment and a 23 ° C. environment, and a low constant load property (peeling distance) value, but generated heat for 20 minutes. The value of total calorific value at the sex test time was high. The test piece of the decorative sheet of Comparative Example 3 had a high initial adhesive strength value in a 5 ° C environment, but a low initial adhesive strength value in a 23 ° C environment, and had a constant load property (peeling distance). And the value of the total calorific value in the exothermic test time of 20 minutes was also high. The test piece of the decorative sheet of Test Example 4 had a low total calorific value and a low constant load property (peeling distance) value in the heat generation test time of 20 minutes, but under 5 ° C and 23 ° C environments. The value of the initial adhesive strength of was low.
From the above results, the decorative sheet of Example 1 has a lower total calorific value in the exothermic test time in 20 minutes, is excellent in fire resistance, and is 5 ° C., as compared with the decorative sheets of Comparative Examples 1 to 4. The initial adhesive strength under the environment and the environment of 23 ° C. was high, the value of constant load property (peeling distance) was low, and the workability was excellent.

1 ... Decorative sheet, 10 ... Base film, 20 ... Adhesive layer, 30 ... Release liner

Claims (10)

A decorative sheet comprising a base film and an adhesive layer provided on at least one side of the base film, wherein the base film contains antimony trioxide.
The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive, a bromine-based flame retardant, and a phosphorus-based flame retardant, and does not contain antimony trioxide.
In the heat generation test below, 20 of the test piece when a laminate having a gypsum board having base paper on both surfaces and the decorative sheet laminated on the side to which the radiant heat of the gypsum board is given is used as the test piece. The total calorific value in the test time per minute is 7.2 MJ / m ² or less.
In the following initial adhesive strength test, the initial adhesive strength is 5 N / 25 mm or more in a 5 ° C environment, 15 N / 25 mm or more in a 23 ° C, 50% RH environment, and
A decorative sheet having a peeling distance of 5 mm or less in the constant load property test below.
Pyrogenic test: ISO 5660-1: conforms to 2002 Cone Calorimeter method, pyrogenic test initial adhesion radiation heat condition at the surface of the test piece is measured at 50kW / ^{m 2:} JIS Z0237: conforms to 2009, cosmetic A test in which the test piece of the sheet is attached to a stainless steel test plate (test plate) while being roller-bonded, and the test piece is peeled off at 180 ° with respect to the test plate within 30 seconds after the application under the condition of a peeling speed of 300 mm / min. Initial adhesive strength test measured by the method Constant load test: A test piece with a width of 25 mm and a length of 100 mm is cut out from a decorative sheet, and a 50 mm pressure-sensitive adhesive layer surface is roller-bonded to the test plate from one end of the test piece. After affixing the test plate while leaving it in a standard environment of 23 ° C. and 50% RH for 24 hours immediately after the affixing, the test plate was placed horizontally with the side to which the test piece was affixed facing downward, and the test piece was placed. A weight having a mass of 50 g is attached to the other end so that the test piece can be peeled off in the vertical direction, and after maintaining the state for 24 hours, the distance at which the test piece is peeled off from the surface of the test plate (peeling distance, mm). Constant load property test measured by The decorative sheet according to claim 1, wherein the phosphorus-based flame retardant is a phosphoric acid ester-based flame retardant. The decorative sheet according to claim 2, wherein the phosphoric acid ester-based flame retardant is a condensed phosphoric acid ester. A decorative sheet comprising a base film containing a vinyl chloride resin and an adhesive layer provided on at least one side of the base film, wherein the base film contains antimony trioxide.
The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive and a brominated flame retardant, and does not contain antimony trioxide.
In the heat generation test below, 20 of the test piece when a laminated body having a gypsum board having base paper on both surfaces and the decorative sheet laminated on the side to which radiant heat is given of the gypsum board is used as the test piece. Total calorific value in the test time per minute is 7.2 MJ / m ² Is below
In the following initial adhesive strength test, the initial adhesive strength is 5 N / 25 mm or more in a 5 ° C environment, 15 N / 25 mm or more in a 23 ° C, 50% RH environment, and
A decorative sheet having a peeling distance of 5 mm or less in the constant load property test below.
Exothermic test: ISO 5660-1: 2002 Based on the cone calorimeter method, the radiant heat condition on the surface of the test piece is 50 kW / m. ² Fever test measured in
Initial adhesive strength: In accordance with JIS Z0237: 2009, a test piece of a decorative sheet is attached to a stainless steel test plate (test plate) while being roller-bonded, and the test is performed within 30 seconds after the application under the condition of a peeling speed of 300 mm / min. Initial adhesive strength test measured by a test method in which a piece is peeled off at 180 ° with respect to a test plate.
Constant load property test: A test piece having a width of 25 mm and a length of 100 mm is cut out from a decorative sheet, and a 50 mm pressure-sensitive adhesive layer surface is attached to the test plate by roller pressure bonding from one end of the test piece. After being left in a standard environment of 23 ° C. and 50% RH for an hour, the test plate is placed horizontally with the surface to which the test piece is attached facing downward, and the test piece is placed on the other end of the test piece. A constant load property test in which a weight with a mass of 50 g is attached so as to peel off in the vertical direction, and after maintaining that state for 24 hours, the test piece is peeled off from the surface of the test plate (peeling distance, mm). The decorative sheet according to claim 4, wherein the pressure-sensitive adhesive layer contains 5 to 30 parts by mass of a bromine-based flame retardant as a dry mass with respect to 100 parts by mass of the dry pressure-sensitive adhesive. The decorative sheet according to claim 4 or 5, wherein the brominated flame retardant is a brominated isocyanurate. The cosmetic sheet according to claim 6, wherein the brominated isocyanurate is tris (2,3-dibromopropyl) isocyanurate. The decorative sheet according to any one of claims 4 to 7, further comprising a phosphorus-based flame retardant in the pressure-sensitive adhesive layer. The decorative sheet according to claim 8, wherein the phosphorus-based flame retardant is a phosphoric acid ester-based flame retardant. The decorative sheet according to claim 9, wherein the phosphoric acid ester-based flame retardant is a condensed phosphoric acid ester.

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