Adhesive layer-forming coating material, and decorative sheet

Abstract

To provide: a coating for forming an adhesive layer which can form an adhesive layer having excellent transparency, flame retardancy, and adhesivity; and a decorative sheet in which the gap problem is solved and which can be used suitably as an interior material of an architectural structure.SOLUTION: A coating for forming an adhesive layer comprises: (A) 100 pts.mass of an acrylic polymer; (B) 3 to 120 pts.mass of at least one selected from the group consisting of a bromide of a compound having a bisphenol A structure, a bromide of a compound having an isocyanate ring structure, and a bromide of a phosphoric acid alkyl ester; and (C) 1 to 40 pts.mass of antimony pentoxide. Preferably, the coating further comprises (D) 0.01 to 10 pts.mass of a compound having two or more isocyanate groups in a molecule.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a paint for forming an adhesive layer. More specifically, the present invention relates to a paint for forming an adhesive layer capable of forming an adhesive layer excellent in transparency and flame retardancy, and a decorative sheet (adhesive film) including the adhesive layer formed using the paint for forming an adhesive layer.

Background Art

[0002] Conventionally, a decorative sheet (adhesive film) that is decorated has been pasted on the interior of a building, for example, on the surface of a wall or ceiling for decoration. When constructing a decorative sheet on a wall or the like, it is required to construct it without causing appearance defects such as swelling or wrinkles by biting air or foreign matter between the surface of the wall or the like and the surface of the adhesive layer of the decorative sheet. Therefore, from the viewpoint of workability, it is preferable to divide the decorative sheet into a size that is easy to work with and then construct it. In addition, since the product width of the decorative sheet is usually narrower than the width of the wall or ceiling of a building, it is normal to join the decorative sheets together in a butted state and paste them. However, the joint between the decorative sheets in a butted state is not perfectly constructed; the base film of the decorative sheet has shrunk; etc. Due to some reason, immediately after construction or over time after construction, a state where a slight gap is opened at the joint between the decorative sheets (hereinafter, this phenomenon may be referred to as "meski"). This is conspicuous and there is a problem of impairing the design of the wall or the like (hereinafter, sometimes referred to as the "meski problem"). In addition, among decorative sheets used for the interior of a building, decorative sheets such as a dark brown wood grain pattern are preferred. When white adhesive can be seen from the joint between dark brown decorative sheets, the meski becomes particularly conspicuous. Therefore, as a countermeasure against the meski problem, a highly transparent adhesive is desired.

[0003] Furthermore, regarding the materials used for building interiors, the Building Standards Act obliges the use of fireproof materials. These fireproof materials are classified into "non-combustible materials", "semi-non-combustible materials", and "flame-retardant materials", etc., and those that have passed the tests specified by the Ministry of Land, Infrastructure, Transport and Tourism are used after receiving review and certification. Therefore, the decorative sheet used for building interiors, as a decorative finishing material, needs to receive at least one of the review certifications.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problems of the present invention are to provide a paint for forming an adhesive layer that can form an adhesive layer excellent in transparency and flame retardancy, and a decorative sheet including the adhesive layer formed using the paint for forming an adhesive layer. A further problem of the present invention is to provide a paint for forming an adhesive layer that can form an adhesive layer excellent in transparency, flame retardancy, and adhesive strength, and a decorative sheet that solves the problem of bleeding and can be suitably used as an interior material for buildings.

Means for Solving the Problems

[0006] As a result of intensive research, the present inventor has found that the above problems can be achieved by a specific paint for forming an adhesive layer.

[0007] That is, aspects of the present invention are as follows. [1]. (A) 100 parts by mass of an acrylic polymer; (B) 3 to 120 parts by mass of at least one selected from the group consisting of brominated compounds having a bisphenol A structure, brominated compounds having an isocyanate ring structure, and brominated alkyl phosphates; and, (C) 1 to 40 parts by mass of antimony pentoxide; A paint for forming an adhesive layer containing the same. [2]. The paint for forming an adhesive layer according to [1], which does not contain antimony trioxide. [3]. Furthermore, (D) 0.01 to 10 parts by mass of a compound having two or more isocyanate groups in one molecule; The paint for forming an adhesive layer according to [1] or [2], which contains the same. [4]. The paint for forming an adhesive layer according to any one of [1] to [3], wherein the content of bromine atoms in at least one selected from the group consisting of brominated compounds having a bisphenol A structure, brominated compounds having an isocyanate ring structure, and brominated alkyl phosphates as the above component (B) is 40 to 80% by mass. [5]. The paint for forming an adhesive layer according to any one of [1] to [4], wherein the sum of the blending amount of at least one selected from the group consisting of brominated compounds having a bisphenol A structure, brominated compounds having an isocyanate ring structure, and brominated alkyl phosphates as the above component (B) and the blending amount of the above component (C) antimony pentoxide is 12 to 105 parts by mass. [6]. The paint for forming an adhesive layer according to any one of [1] to [5], wherein the mass ratio of the blending amount of at least one selected from the group consisting of brominated compounds having a bisphenol A structure, brominated compounds having an isocyanate ring structure, and brominated alkyl phosphates as the above component (B) to the blending amount of the above component (C) antimony pentoxide is 1 / 1 to 9 / 1. [7]. A decorative sheet including an adhesive layer formed using the paint for forming an adhesive layer according to any one of [1] to [6]. [8]. The decorative sheet according to item [7], wherein the visible light transmittance of the adhesive layer is 80% or more. [9]. The decorative sheet according to item [7] or [8], wherein the 180° peel adhesion to a stainless steel test plate measured under standard conditions is 10 to 50 N / 25 mm in accordance with the 10 adhesion of JIS Z0237:2009 of the decorative sheet.

[10] . Including an adhesive layer formed using the coating material for forming an adhesive layer according to any one of items [1] to [6]; Meeting the criteria of the heat generation test method (b) of 4.10.2 of the Fire and Heat Resistance Performance Test and Evaluation Business Method Manual of the General Incorporated Foundation Building Materials Testing Center; Materials used for interior decoration of buildings.

[11] . Including the decorative sheet according to any one of items [7] to [9]; Meeting the criteria of the heat generation test method (b) of 4.10.2 of the Fire and Heat Resistance Performance Test and Evaluation Business Method Manual of the General Incorporated Foundation Building Materials Testing Center; Materials used for interior decoration of buildings.

Effects of the Invention

[0008] The adhesive layer formed using the coating material for forming an adhesive layer of the present invention is excellent in transparency and flame retardancy. The adhesive layer formed using the preferred coating material for forming an adhesive layer of the present invention is excellent in transparency, flame retardancy, and adhesive strength. Therefore, the decorative sheet (adhesive film) of the present invention has solved the problem of meshing (even if meshing occurs, it is not noticeable at a practically satisfactory level). Therefore, the decorative sheet (adhesive film) of the present invention can be suitably used as an interior material for buildings.

Modes for Carrying Out the Invention

[0009] In this specification, the term "resin" is used as a term that includes resin mixtures containing two or more resins and resin compositions containing components other than resins. In this specification, the term "film" is used interchangeably or replaceably with "sheet". In this specification, the terms "film" and "sheet" are used for those that can be industrially wound into a roll. The term "plate" is used for those that cannot be industrially wound into a roll. Also, in this specification, laminating one layer on top of another layer in order includes both directly laminating those layers and laminating with one or more other layers such as an anchor coat intervening between those layers.

[0010] In this specification, the term "or more" related to a numerical range is used to mean a certain numerical value or more than a certain numerical value. For example, 20% or more means 20% or more than 20%. The term "or less" related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Also, the symbol "~" related to a numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value. Here, the other certain numerical value is a numerical value larger than a certain numerical value. For example, 10~90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper limit and the lower limit of a numerical range can be arbitrarily combined, and arbitrarily combined embodiments should be construed as being read. For example, from the description "usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less." or "usually 10~40%, preferably 20~30%" related to the numerical range of a certain property, it should be construed that the numerical range of that certain property is 10~40%, 20~30%, 10~30%, or 20~40% in one embodiment.

[0011] Unless otherwise specified or except in the case of examples, all numerical values used in this specification and the claims should be understood as being modified by the term "about". Without intending to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of the significant figures and by applying ordinary rounding techniques.

[0012] 1. Coating for forming an adhesive layer: The coating for forming an adhesive layer of the present invention contains: (A) an acrylic polymer; (B) at least one selected from the group consisting of brominated compounds having a bisphenol A structure, brominated compounds having an isocyanate ring structure, and brominated alkyl phosphates; and (C) antimony pentoxide. The coating for forming an adhesive layer of the present invention preferably further contains (D) a compound having two or more isocyanate groups in one molecule. Hereinafter, each component will be described.

[0013] (A) Acrylic polymer The above component (A) is an acrylic polymer, and typically is a copolymer having (meth)acrylate as a main component (usually 50 parts by mass or more, typically 80 parts by mass or more). Here, (meth)acrylate means acrylate or methacrylate. The above component (A) acrylic polymer serves as a main ingredient of the adhesive to exhibit adhesiveness and to incorporate other optional components such as the above components (B), (C), and (D).

[0014] Examples of the above component (A) include copolymers of (meth)acrylate and one or two or more of carboxyl group-containing monomers, epoxy group-containing monomers, hydroxyl group-containing (meth)acrylates, and other monomers copolymerizable therewith.

[0015] Examples of the above (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate.

[0016] Examples of the above carboxyl group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, and 2-carboxyethyl (meth)acrylate. Examples of the above epoxy group-containing monomer include glycidyl (meth)acrylate and 4-hydroxybutyl glycidyl ether (meth)acrylate. Examples of the above hydroxyl group-containing (meth)acrylic acid ester include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. The above other monomers are usually compounds having a carbon-carbon double bond, typically compounds having an ethylenic double bond. Examples of the above other monomers include ethylene, propylene, and styrene. Note that (meth)acrylic acid means acrylic acid or methacrylic acid.

[0017] The acid value of the above component (A) is preferably 90 mgKOH / g or less, more preferably 78 mgKOH / g or less, still more preferably 72 mgKOH / g or less, and most preferably 67 mgKOH / g or less, from the viewpoint of improving the workability during the cold winter season. On the other hand, from the viewpoints of initial adhesiveness, prevention of peeling, prevention of curling, and prevention of the occurrence of fraying, it is preferably 20 mg / KOH or more, more preferably 33 mgKOH / g or more, still more preferably 39 mgKOH / g or more, and most preferably 44 mgKOH / g or more.

[0018] In this specification, the acid value is the number of milligrams of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the sample, and is a value measured according to the neutralization titration method of 3.1 in JIS K0070-1992.

[0019] The mass average molecular weight of the above component (A) is preferably 300,000 or more, more preferably 500,000 or more, still more preferably 550,000 or more, and most preferably 650,000 or more, from the viewpoint of imparting appropriate hardness to the adhesive and preventing peeling, curling, and the occurrence of fraying. On the other hand, from the viewpoint of coatability, it is preferably 1,200,000 or less, more preferably 1,000,000 or less, and still more preferably 850,000 or less.

[0020] In this specification, the mass average molecular weight is determined using gel permeation chromatography (GPC). The GPC measurement is performed using the high-performance liquid chromatography system "SHODEX GPC-101 (trade name)" of Showa Denko K.K., and polystyrene columns (exclusion limit is 4×10 8 of the column and 1×10 4A column of each type is connected and used. ) is used, and the conditions are a measurement temperature of 40°C, a flow rate of 1mL / min, a mobile phase of tetrahydrofuran (THF) for high performance liquid chromatography, and a sample concentration of 1mg / mL. A molecular weight calibration curve is created using standard polystyrene. For the theory of GPC and the actual measurement, reference books such as "Size Exclusion Chromatography: High Performance Liquid Chromatography of Polymers, Author: Mori Sadao, First Edition, 10th December 1991" by Kyoritsu Shuppan Co., Ltd. and "Synthetic Polymer Chromatography, Editors: Otani Hajime, Takarazaki Tatsuya (the character "崎" is written with the character "立" at the top), First Edition, 25th July 2013" by Ohmsha Co., Ltd. can be referred to.

[0021] The glass transition temperature of the component (A) may be, from the viewpoint of improving workability during application at low temperatures, preferably −30° C. or lower, more preferably −40° C. or lower, even more preferably −50° C. or lower, and most preferably −55° C. or lower. On the other hand, from the viewpoint of maintaining adhesive strength at high temperatures and preventing peeling, curling, and mesic marks, the glass transition temperature may be preferably −80° C. or higher, more preferably −70° C. or higher, and even more preferably −60° C. or higher.

[0022] In this specification, the glass transition temperature of the above component (A) is a calculated value obtained by a conventional method, that is, a value obtained from the following formula (Fox's formula). 1 / (Tg+273)=W1 / (Tg1+273)+W2 / (Tg2+273)+W3 / (Tg3+273)+···+W n / (Tg n +273) In the formula, Tg is the glass transition temperature (°C) of a polymer consisting of n kinds of monomers, and W1, W2, W3...W n is the mass% of each monomer in the monomer composition, and Tg1, Tg2, Tg3...Tg n is the glass transition temperature (° C.) of the homopolymer of each monomer. For the glass transition temperature of each homopolymer, values listed in, for example, the Polymer Handbook can be used.

[0023] As the above component (A), one or a mixture of two or more of these can be used.

[0024] (B) Bromide of a compound having a bisphenol A structure, etc. The above component (B) is one or more selected from the group consisting of brominated compounds having a bisphenol A structure, brominated compounds having an isocyanate ring structure, and brominated alkyl phosphates. The above component (B) functions to exhibit flame retardancy.

[0025] The brominated compound having a bisphenol A structure is a brominated compound of bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a compound having a structure in which one or two phenolic hydroxyl groups of bisphenol A are substituted, or an oligomer having these as main constituent monomers (usually 50% by mass or more, preferably 75% by mass or more). In one embodiment, the brominated compound having a bisphenol A structure may be a compound in which one or more hydrogen atoms in the aromatic ring of bisphenol A are substituted with bromine atoms, a compound having a structure in which one or two phenolic hydroxyl groups of the compound are substituted, or an oligomer having these as main constituent monomers (usually 50% by mass or more, preferably 75% by mass or more). In one typical embodiment, the brominated compound having a bisphenol A structure may be 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as "TBBA"), a compound having a structure in which one or two phenolic hydroxyl groups of TBBA are substituted, or an oligomer having these as main constituent monomers (usually 50% by mass or more, preferably 75% by mass or more).

[0026] Examples of brominated compounds having the bisphenol A structure include 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-methoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(2,3-dibromopropoxy)phenyl)propane, 2,2-bis(4-allyloxy-3,5-dibromophenyl)propane, 2,2-bis(3,5-dibromo-4-(2-hydroxyethyl)phenyl)propane, and oligomers, epoxy oligomers, and carbonate oligomers of one or more of these compounds.

[0027] The brominated compound having the isocyanate ring structure is a compound represented by the general formula (1).

[0028]

Chemical formula

[0029] In the general formula (1), R1, R2, and R3 are aliphatic hydrocarbon groups that may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group, and at least one of these is an aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with bromine atoms. R1, R2, and R3 may be different from each other or the same.

[0030] In one typical embodiment, the brominated compound having the isocyanate ring structure may be a brominated trisalkyl isocyanurate compound. The alkyl group of the brominated trisalkyl isocyanurate compound is usually an aliphatic hydrocarbon group that may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group, and one or more hydrogen atoms are substituted with bromine atoms.

[0031] Examples of the brominated compound having the isocyanate ring structure include tris(2,3-dibromopropyl) isocyanurate.

[0032] The brominated product of the above alkyl phosphate ester is a compound represented by the general formula (2).

[0033] [Chemical formula]

[0034] In the general formula (2), R'1, R'2, and R'3 are an aromatic ring, an aliphatic cyclic group, an ether group, or an aliphatic hydrocarbon group which may contain an ester group, or hydrogen, and at least one of these is an aliphatic hydrocarbon group which may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group, and at least one of these has one or more hydrogen atoms substituted by bromine atoms. R'1, R'2, and R'3 may be different from each other or the same.

[0035] In one of the typical embodiments, the brominated product of the above alkyl phosphate ester may be a brominated product of trisalkyl phosphate ester. The alkyl group of the brominated product of the trisalkyl phosphate compound is usually an aliphatic hydrocarbon group which may contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group, and one or more hydrogen atoms are substituted by bromine atoms.

[0036] Examples of the brominated product of the above alkyl phosphate ester include tris(tribromoneopentyl) phosphate.

[0037] Among these, as the above component (B), from the viewpoints of the adhesive strength at high temperatures (in summer) and reworkability (the difficulty of adhesive residue when re-sticking during construction), the brominated product of the compound having the above bisphenol A structure and the brominated product of the compound having the above isocyanate ring structure are preferable.

[0038] From the viewpoint of flame retardancy, the bromine atom content in the above component (B) is usually 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more. On the other hand, from the viewpoint of transparency, it may usually be 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less.

[0039] As the above component (B), one or a mixture of two or more of these can be used.

[0040] From the viewpoint of flame retardancy, the blending amount of the above component (B) is usually 3 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, based on 100 parts by mass of the above component (A). On the other hand, from the viewpoints of transparency and adhesiveness, it may usually be 120 parts by mass or less, preferably 90 parts by mass or less, more preferably 75 parts by mass or less, still more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, and most preferably 30 parts by mass or less.

[0041] (C) Antimony pentoxide The above component (C) is antimony pentoxide. The above component (C) functions to enhance flame retardancy due to its synergistic effect with the above component (B).

[0042] Antimony pentoxide and antimony trioxide among the above component (C) are often collectively referred to as antimony oxide. And antimony trioxide is also used as a white pigment (antimony white). Nevertheless, it is surprising that the adhesive containing the above component (C) antimony pentoxide exhibits transparency.

[0043] The average particle diameter of the above component (C) is not particularly limited. From the viewpoints of dispersibility in the adhesive and coatability of the paint for forming the adhesive layer, the average particle diameter of the above component (C) may usually be 50 μm or less, preferably 40 μm or less, more preferably 25 μm or less. On the other hand, from the viewpoint of handleability, it may usually be 0.001 μm or more, preferably 0.01 μm or more, more preferably 0.1 μm or more.

[0044] In this specification, the average particle diameter of the particles is the particle diameter at which the cumulative percentage from the smaller particles is 50% by mass in the particle diameter distribution curve measured by the laser diffraction / scattering method. The above particle diameter distribution curve can be measured, for example, using the laser diffraction / scattering particle size analyzer "MT3200II (trade name)" of Nikkiso Co., Ltd.

[0045] The blending amount of the above component (C) is usually 1 part by mass or more, preferably 3 parts by mass or more, more preferably 4 parts by mass or more, still more preferably 5 parts by mass or more, and most preferably 6 parts by mass or more, from the viewpoint of flame retardancy, based on 100 parts by mass of the above component (A). On the other hand, from the viewpoints of transparency and adhesiveness, it may usually be 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and most preferably 10 parts by mass or less.

[0046] The mass ratio of the blending amount of the above component (B) to the blending amount of the above component (C) (blending amount of the above component (B) / blending amount of the above component (C)) may usually be 1 / 1 to 9 / 1, preferably 1.5 / 1 to 6 / 1, more preferably 2 / 1 to 4.5 / 1, and still more preferably 2.5 / 1 to 3.6 / 1, from the viewpoint of the synergistic effect of flame retardancy.

[0047] The sum of the blending amount of the above component (B) and the blending amount of the above component (C) is usually 4 parts by mass or more, preferably 12 parts by mass or more, more preferably 18 parts by mass or more, and still more preferably 25 parts by mass or more, from the viewpoint of flame retardancy, based on 100 parts by mass of the above component (A). On the other hand, from the viewpoints of transparency and adhesiveness, it may usually be 160 parts by mass or less, preferably 105 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, and most preferably 50 parts by mass or less.

[0048] (D) Compound having two or more isocyanate groups in one molecule The above-mentioned component (D) is a compound having two or more isocyanate groups (-N=C=O) in one molecule. The above-mentioned component (D) reacts with the hydroxyl groups in the upper component (A) to form a urethane bond, etc., thereby imparting appropriate hardness to the adhesive layer and functioning to prevent peeling, curling, and meshing.

[0049] Examples of the above-mentioned component (D) include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adducts of tolylene diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate, trimethylolpropane adducts of isophorone diisocyanate, isocyanurate bodies of tolylene diisocyanate, isocyanurate bodies of hexamethylene diisocyanate, isocyanurate bodies of isophorone diisocyanate, polyisocyanates such as biuret bodies of hexamethylene diisocyanate; and urethane crosslinking agents such as blocked isocyanates of the above polyisocyanates, etc.

[0050] As the above-mentioned component (D), one or a mixture of two or more of these can be used. Also, within the limit not contrary to the object of the present invention, if desired, catalysts such as dibutyltin dilaurate and dibutyltin diethylhexoate may be added.

[0051] The blending amount of the above-mentioned component (D) is not particularly limited because it is an optional component. From the viewpoint of surely obtaining the use effect of the above-mentioned component (D), the blending amount of the above-mentioned component (D) is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, still more preferably 0.2 part by mass or more, and most preferably 0.3 part by mass or more, based on 100 parts by mass of the above-mentioned component (A). On the other hand, from the viewpoint of maintaining the adhesive strength at low temperatures (in winter), it may usually be 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, and most preferably 1.6 parts by mass or less.

[0052] The coating material for forming the pressure-sensitive adhesive layer of the present invention may contain a solvent as desired in order to dilute it to a concentration that is easy to apply. The above solvent is not particularly limited as long as it does not react with the pressure-sensitive adhesive component or catalyze (accelerate) the self-reaction (including the degradation reaction) of these components. Examples of the above solvent include 1-methoxy-2-propanol, isopropanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the above solvent, one or a mixture of two or more of these can be used.

[0053] The coating material for forming the pressure-sensitive adhesive layer of the present invention can further contain optional components other than the above components (A) to (D) as desired, within the limit not contrary to the object of the present invention. Examples of the above optional components include flame retardants other than the above components (B) and (C), photopolymerization initiators, antistatic agents, surfactants, leveling agents, thixotropic agents, anti-fouling agents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, pigments, and fillers other than the above component (C). The blending amount of the above optional components is not particularly limited, but when the above component (A) is 100 parts by mass, it may usually be 10 parts by mass or less, or about 0.01 to 10 parts by mass.

[0054] The coating material for forming the pressure-sensitive adhesive layer of the present invention preferably does not contain antimony trioxide from the viewpoint of transparency. Here, "not containing" means that it is not intentionally blended. When antimony trioxide is intentionally blended, an amount of usually 1 part by mass or more is blended with respect to 100 parts by mass of the above component (A). Therefore, "not containing antimony trioxide" can be rephrased as having a content of antimony trioxide of usually less than 1 part by mass, preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less, still more preferably 0.01 part by mass or less, and most preferably 0.001 part by mass or less with respect to 100 parts by mass of the above component (A).

[0055] The coating material for forming the pressure-sensitive adhesive layer of the present invention can be obtained by mixing and stirring these components.

[0056] 2. Decorative sheet (adhesive film): The cosmetic sheet (adhesive film) of the present invention includes an adhesive layer formed using the coating composition for forming an adhesive layer of the present invention. The cosmetic sheet (adhesive film) of the present invention usually has an adhesive layer formed using the coating composition for forming an adhesive layer of the present invention on one side of a film substrate.

[0057] 2-1. Adhesive layer The adhesive layer included in the cosmetic sheet (adhesive film) of the present invention is formed using the coating composition for forming an adhesive layer of the present invention.

[0058] The method for forming an adhesive layer using the coating composition for forming an adhesive layer of the present invention is not particularly limited, and known web coating methods can be used. As the above web coating method, from the viewpoint of applying the coating composition with good productivity by a roll-to-roll method, for example, methods such as rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferable.

[0059] The thickness of the adhesive layer of the cosmetic sheet (adhesive film) of the present invention is appropriately determined in consideration of the use of the adhesive film and its important properties. From the viewpoint of ensuring sufficient adhesive strength, the thickness of the adhesive layer of the adhesive film (cosmetic sheet) of the present invention may usually be 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, and most preferably 30 μm or more. On the other hand, from the viewpoint of enabling easy application, it may usually be 100 μm or less, preferably 80 μm or less, more preferably 60 μm or less, still more preferably 50 μm or less.

[0060] 2-2. Film substrate The above film substrate is a layer serving as the substrate of the cosmetic sheet (adhesive film) of the present invention.

[0061] Examples of the film base material include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellulose resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene-styrene copolymer, and styrene-ethylene-butadiene-styrene copolymer; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; and other resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, and polyether sulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. They also include laminated films formed by laminating two or more of these materials. Furthermore, these films may be transparent, opaque, have concealability, be colored, or have a unique color.

[0062] In one typical embodiment, the film base material may be colored and have concealability for the purpose of decorating and adorning an article by laminating a decorative sheet (adhesive film).

[0063] Among these, from the viewpoints of imparting good workability and flame retardancy in both the cold winter season and the hot summer season, polyvinyl chloride resin films are preferred as the film base material.

[0064] Examples of the polyvinyl chloride resin used as the material for the above polyvinyl chloride resin film include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylic acid copolymer, vinyl chloride-(meth)methyl acrylate copolymer, vinyl chloride-(meth)ethyl acrylate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and other vinyl chloride-based copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride; modified (such as chlorinated) polyvinyl chloride or vinyl chloride-based copolymers such as post-chlorinated vinyl copolymers; and the like. Furthermore, chlorinated polyolefins such as chlorinated polyethylene, whose chemical structure is similar to that of polyvinyl chloride, may be used. Among these, polyvinyl chloride (vinyl chloride homopolymer) is preferred. As the above polyvinyl chloride resin, one or a mixture of two or more of these can be used.

[0065] Other resins commonly used in polyvinyl chloride resin compositions can be further included in the above polyvinyl chloride resin. The blending ratio of the other resin is not particularly limited as long as it does not contravene the object of the present invention. The blending ratio of the other resin may be usually 0 to 40% by mass, preferably 0 to 30% by mass, more preferably 5 to 25% by mass, with the total of the above polyvinyl chloride resin and the other resin being 100% by mass.

[0066] Examples of the other resin include ethylene-vinyl acetate copolymer; ethylene-(meth)acrylic acid copolymer, ethylene-(meth)methyl acrylate copolymer; ethylene-(meth)ethyl acrylate copolymer; core-shell rubbers such as methacrylate-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / ethylene-propylene rubber graft copolymer, acrylonitrile-styrene / acrylic acid ester graft copolymer, methacrylate / acrylic acid ester rubber graft copolymer, methacrylate-acrylonitrile / acrylic acid ester rubber graft copolymer, etc.; and the like. As the other resin, one or a mixture of two or more of these can be used.

[0067] The above polyvinyl chloride resin can further contain a plasticizer usually used in a polyvinyl chloride resin composition. The blending amount of the above plasticizer is usually 100 parts by mass or less, preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the above polyvinyl chloride resin (in the embodiment using the above other resin, the total of the above polyvinyl chloride resin and the above other resin).

[0068] Examples of the above plasticizer include phthalate plasticizers, trimellitate plasticizers, pyromellitate plasticizers, adipate plasticizers, itaconate plasticizers, citrate plasticizers, cyclohexanedicarboxylate plasticizers, and epoxy plasticizers.

[0069] Examples of the above plasticizers include, as polyhydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and as polycarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Polyester plasticizers using monohydric alcohols and monocarboxylic acids as stoppers can be mentioned if necessary.

[0070] Examples of the above phthalate plasticizers include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate, etc.

[0071] Examples of the above trimellitate plasticizers include tri(2-ethylhexyl) trimellitate, tri(n-octyl) trimellitate, and tri(isononyl) trimellitate, etc.

[0072] Examples of the above adipate plasticizers include bis(2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate, etc.

[0073] Examples of the above epoxy plasticizers include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester, etc.

[0074] Examples of the above plasticizers include trimellitic acid-based plasticizers, tetrahydrophthalic acid diester-based plasticizers, glycerin ester-based plasticizers, epoxyhexahydrophthalic acid diester-based plasticizers, isosorbide diester-based plasticizers, phosphate-based plasticizers, azelaic acid-based plasticizers, sebacic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, pyromellitic acid-based plasticizers, biphenyltetracarboxylic acid ester-based plasticizers, and chlorine-based plasticizers.

[0075] As the above plasticizer, one or a mixture of two or more of these can be used.

[0076] In addition, the above polyvinyl chloride-based resin can further contain substances usually used in polyvinyl chloride-based resin compositions to the extent that it does not conflict with the object of the present invention. Optional components that can be included are pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, nucleating agents, mold release agents, antistatic agents, urea-formaldehyde waxes, and additives such as surfactants; and the like. The blending amount of these optional components is usually 50 parts by mass or less, or about 0.01 to 50 parts by mass when the total of the polyvinyl chloride-based resin and the above other resin is 100 parts by mass.

[0077] The method for obtaining the above polyvinyl chloride-based resin film using the above polyvinyl chloride-based resin is not particularly limited. Examples of the above method include a method using a device equipped with a calendar roll rolling machine and a winding machine, and a method using a device equipped with an extruder, a T-die, and a winding machine.

[0078] Examples of the above calendar roll rolling machine include vertical three-roll, vertical four-roll, L-type four-roll, reverse L-type four-roll, and Z-type rolls.

[0079] Examples of the above extruder include a single-screw extruder, a co-rotating twin-screw extruder, and a counter-rotating twin-screw extruder.

[0080] Examples of the T-die include a manifold die, a fishtail die, a coat hanger die, and the like.

[0081] The thickness of the polyvinyl chloride resin film is not particularly limited, but from the viewpoint of handleability, it may usually be 20 μm or more, preferably 50 μm or more, more preferably 80 μm or more. On the other hand, from the viewpoint of workability during construction, it may usually be 400 μm or less, preferably 300 μm or less, more preferably 250 μm or less.

[0082] On the surface that becomes the front surface in the actual use state of the film base material, a printing layer may be provided, if desired, to enhance the design feeling. The printing layer is provided to impart high designability and can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine. Here, the actual use state means a state in which the decorative sheet is used for decoration of the surfaces of various articles. Also, the surface that becomes the front surface in the actual use state means the surface that is usually visually recognized in the actual use state.

[0083] Printing can be performed entirely or partially on the front surface of the above film substrate in its actual use state, either directly or through an anchor coat. Examples of patterns include metallic patterns such as hairline patterns, wood grain patterns, stone patterns imitating the surfaces of rocks such as marble, fabric patterns imitating fabric or cloth-like patterns, tile pasting patterns, brick stacking patterns, marquetry patterns, and patchwork. As printing ink, a mixture appropriately blended with pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, etc. in a binder can be used. As the above binder, for example, resins such as polyurethane-based resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene-based resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins, as well as resin compositions thereof, can be used. Also, metals such as aluminum, tin, titanium, and indium, and metal oxides thereof can be vapor-deposited entirely or partially on the front surface of the above film substrate in its actual use state by known methods. A metallic design is imparted by the formed thin film layer of metal or metal oxide.

[0084] A protective coating film layer may be further provided on the surface of the above printing layer to protect the printing layer.

[0085] Examples of the paint for forming the above protective coating film layer include paints based on urethane-based resins, polyester-based resins, acrylic resins, vinyl acetate resins, vinyl chloride resins, silicone resins, and fluorine-based resins as main agents. Among these, paints based on urethane-based resins, polyester-based resins, and acrylic resins as main agents are preferred. As the paint for forming the above protective coating film layer, those using one or a mixture of two or more of these as the main agent can be used.

[0086] For the paint for forming the above protective coating layer, organic solvents such as 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone can be used as desired.

[0087] For the paint for forming the above protective coating layer, additives such as antistatic agents, surfactants, leveling agents, thixotropy imparting agents, contamination preventing agents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, colorants, and fillers may be included in one or more than two kinds as desired.

[0088] The paint for forming the above protective coating layer is obtained by mixing and stirring these components.

[0089] The method for forming the above protective coating using the paint for forming the above protective coating layer is not particularly limited, and a known web coating method can be used. Examples of the above method include methods such as roll coating, gravure coating, reverse coating, roll brush, spray coating, air knife coating, and die coating.

[0090] The thickness of the above protective coating layer is not particularly limited. From the viewpoint of the protective function, the thickness of the above protective coating layer may preferably be 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more. On the other hand, from the viewpoints of the handleability of the web and the workability during film formation, the thickness of the above protective coating layer may preferably be 100 μm or less, more preferably 50 μm or less.

[0091] The adhesive layer formed using the paint for forming the adhesive layer of the present invention has a visible light transmittance measured according to the visible light transmittance of (a-3) in the following examples, and from the viewpoint of transparency, it may usually be 80% or more, preferably 82% or more, more preferably 84% or more, still more preferably 86% or more, even more preferably 88% or more, and most preferably 90% or more. The higher the visible light transmittance measured according to the visible light transmittance of (a-3) in the following examples, the better.

[0092] The adhesive layer formed using the coating composition for forming an adhesive layer of the present invention may preferably have an L* value measured according to the (b) whiteness of the following Examples of 43 or less, more preferably 38 or less, and still more preferably 34 or less, from the viewpoint of making the meski less noticeable. The lower the L* value measured according to the (b) whiteness of the following Examples, the better.

[0093] The cosmetic sheet (adhesive film) of the present invention has an adhesive strength (adhesive strength measured according to the (d) adhesive strength of the following Examples) of Method 1 (180° peel adhesive strength against a stainless steel test plate) measured in a standard state (temperature 23°C ± 1°C, humidity 50% ± 5%) according to the 10 adhesive strengths of JIS Z0237:2009, preferably 10 N / 25 mm or more, more preferably 14 N / 25 mm or more, still more preferably 17 N / 25 mm or more, and most preferably 20 N / 25 mm or more. On the other hand, from the viewpoint of reworkability, it may preferably be 50 N / 25 mm or less, more preferably 40 N / 25 mm or less.

Examples

[0094] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

[0095] Measurement method (a) Transparency: (a-1) Preparation of sample: Using a roll coater, a coating composition for forming an adhesive layer was applied onto the release surface of a biaxially stretched polyethylene terephthalate film “MRF38 (trade name)” with a thickness of 38 μm and one-sided release treatment by Mitsubishi Chemical Corporation (γ-1) so that the thickness after drying was 45 μm, and then dried in a drying oven to form an adhesive layer. Next, a new film (γ-1) was laminated and bonded onto the surface of the adhesive layer such that its release surface faced the adhesive layer side to obtain a measurement sample.

[0096] (a-2) Haze: In accordance with JIS K7136:2000, using the turbidimeter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd., with the sample prepared in the above (a-1), haze was measured under the condition that light was incident from the surface on the side of the above film (γ-1) laminated after the sample. Note that regardless of the provisions regarding the applicable range of the above JIS, measured values exceeding 40% were also described in the table as they were.

[0097] (a-3) Visible light transmittance: Except for measuring the sample prepared in the above (a-1) as it was (without laminating it to glass), in accordance with JIS A5759:2008, using the ultraviolet-visible-near-infrared spectrophotometer "V-570 (trade name)" of JASCO Corporation, visible light transmittance was measured under the condition that light was incident from the surface on the side of the above film (γ-1) laminated after the above sample.

[0098] (b) Whiteness: Using a roll coater, a coating material for forming an adhesive layer was applied on the easily peelable surface of the following release film (β-1) so that the thickness after drying would be 45 μm, and it was dried in a drying oven to form an adhesive layer. Next, the following base film (α-1) was laminated and bonded on the surface of the adhesive layer to obtain a measurement sample. Using the spectrophotometer "CM600d (trade name)" of Konica Minolta Japan, Inc. in accordance with JIS Z8722:2009, with the surface on the release film side of the measurement sample as the measurement surface, under geometric condition c and the condition including the component that becomes specular reflection, XYZ coordinates were measured, and L*a*b* coordinates were calculated by converting this. As an index of the visibility of mesh, the value of L* was described in the table.

[0099] Regarding L*a*b* coordinates, the homepage of Konica Minolta Japan, Inc. (the following address) etc. can be referred to. http: / / www.konicaminolta.jp / instruments / knowledge / color / part1 / 07.html

[0100] (c) Heat generation test: (c-1) Preparation of sample: On one square surface of a gypsum board with a side length of 99 mm and a thickness of 12.5 mm, 0.89 g (0.10 g in terms of solid content) of the synthetic rubber-based primer "Venridine RT (trade name)" of Aika Kogyo Co., Ltd. was uniformly applied, and then a decorative sheet (adhesive film) was overlapped and bonded thereon. At this time, the surface on the adhesive layer side of the decorative sheet (adhesive film) was made the bonding surface. Subsequently, the portion where the decorative sheet (adhesive film) protruded from the square surface of the gypsum board was cut to obtain a sample. The sample was cured at a temperature of 23°C ± 2°C and a relative humidity of 50% ± 5% to a constant mass before the exothermicity test was conducted.

[0101] (C-2) Exothermicity test: Regarding the certification based on Article 2, No. 9 of the Building Standards Act and Article 108-2 of the Building Standards Enforcement Order, in accordance with the 4.10.2 Exothermicity Test Method (ii) of the Fire and Heat Resistance Test and Evaluation Business Method Manual of the General Incorporated Foundation Building Materials Testing Center, the exothermicity test was conducted on the sample prepared in the above (C-1) and evaluated according to the following criteria. A: Passed with a margin over the criteria of 4.10.2 Exothermicity Test Method (ii). That is, the total exothermic amount within 20 minutes after the start of heating is 7 MJ / m 2 or less; there are no cracks and holes penetrating to the fire-hazardous back surface within 20 minutes after the start of heating; and the exothermic rate within 20 minutes after the start of heating does not exceed 200 kW / m for 7 seconds or more continuously. 2 All of these conditions were satisfied. B: Passed the criteria of 4.10.2 Exothermicity Test Method (ii). That is, the total exothermic amount within 20 minutes after the start of heating is 8 MJ / m 2 or less; there are no cracks and holes penetrating to the fire-hazardous back surface within 20 minutes after the start of heating; and the exothermic rate within 20 minutes after the start of heating does not exceed 200 kW / m for 10 seconds or more continuously. 2 All of these conditions were satisfied. C: Satisfied the condition that there are no cracks and holes penetrating to the fire-hazardous back surface in the criteria of 4.10.2 Exothermicity Test Method (ii), but the total exothermic amount within 20 minutes after the start of heating is 8 MJ / m 2 or less; and the exothermic rate within 20 minutes after the start of heating does not exceed 200 kW / m for 10 seconds or more continuously.2 not exceeding; did not satisfy at least any one of them.

[0102] (ii) Adhesion: In accordance with the 10 adhesion of JIS Z0237:2009, the adhesion of Method 1 (180° peel adhesion to a stainless steel test plate) was measured under standard conditions (temperature 23°C ± 1°C, humidity 50% ± 5%).

[0103] Raw materials used (A) Acrylic polymer: (A-1) A solvent dilution of an acrylic polymer having an acid value of 51.8 mgKOH / g, a mass average molecular weight of 800,000, and a glass transition temperature of -58°C (including structural units derived from 2-ethylhexyl acrylate, acrylic acid, glycidyl methacrylate, and 2-hydroxyethyl methacrylate). Solids content (content of acrylic polymer) 45% by mass.

[0104] (B) Brominated compounds having a bisphenol A structure, etc.: (B-1) A brominated flame retardant (TBBA) of Toray Industries, Inc. "Frame Cut 120G (trade name)", average particle size 31 μm, bromine atom content 59% by mass. (B-2) A brominated flame retardant (2,2-bis(4-allyloxy-3,5-dibromophenyl)propane) of Teijin Limited "Firegard FG-3200 (trade name)", average particle size 281 μm, bromine atom content 51% by mass. (B-3) A brominated flame retardant (carbonate oligomer of TBBA) of Teijin Limited "Firegard FG-7000 (trade name)", average particle size 5 μm, bromine atom content 53% by mass. (B-4) A brominated flame retardant (carbonate oligomer of TBBA) of Teijin Limited "Firegard FG-7500 (trade name)", average particle size 23 μm, bromine atom content 52% by mass. (B-5) A brominated flame retardant (carbonate oligomer of TBBA) of Teijin Limited "Firegard FG-8500 (trade name)", average particle size 4 μm, bromine atom content 58% by mass. (B-6) Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., brominated flame retardant (2,2-bis(3,5-dibromo-4-(2,3-dibromopropoxy)phenyl)propane) "Pyrogard SR-720N (trade name)", average particle size 40 μm, bromine atom content 67% by mass. (B-7) Brominated flame retardant (tris(2,3-dibromopropyl) isocyanurate) "Pyrogard SR-750 (trade name)" of Daiichi Kogyo Seiyaku Co., Ltd., average particle size 9 μm, bromine atom content 65% by mass. (B-8) Brominated flame retardant (tris(tribromoneopentyl) phosphate) "CR-900 (trade name)" of Daihachi Chemical Industry Co., Ltd., average particle size 31 μm, bromine atom content 69% by mass.

[0105] (B') Brominated flame retardants other than brominated compounds having a bisphenol A structure, etc.: (B'-1) Brominated flame retardant (1,2-bis(pentabromophenyl)ethane) "SAYTEX 8010 (trade name)" of Albemarle Japan Co., Ltd., average particle size 6 μm, bromine atom content 82% by mass. (B'-2) Brominated flame retardant (N,N-ethylene-bis(tetrabromophthalimide)) "SAYTEX BT-93 (trade name)" of Albemarle Japan Co., Ltd., average particle size 3 μm, bromine atom content 67% by mass.

[0106] (C) Antimony pentoxide: (C-1) Antimony pentoxide "Antimony pentoxide (V) (trade name)" of Mitsuwa Chemical Co., Ltd., average particle size 16 μm. (C-2) Antimony pentoxide "Antimony pentoxide (trade name)" of High Purity Chemical Research Institute Co., Ltd., average particle size 19 μm.

[0107] (C') Antimony trioxide: (C'-1) Antimony trioxide "MSA-S (trade name)" of Yamanaka Sangyo Co., Ltd., average particle size 2 μm.

[0108] (D) Compounds having two or more isocyanate groups in one molecule: (D-1) A solvent-diluted solution of a compound having two or more isocyanate groups in one molecule from Tosoh Corporation (the main component is the tolylene diisocyanate 3-adduct of trimethylolpropane) "Coronate L-55E (trade name)", solid content (content of the compound having two or more isocyanate groups in one molecule) 55% by mass.

[0109] (α) Substrate film: (α-1) A polyvinyl chloride resin film "S2340 FC2015 (trade name)" from Licentecnos Co., Ltd., thickness 160 μm, black with L*, a*, b* coordinates of L* = 25.2, a* = -0.1, b* = -1.1.

[0110] (β) Release film: (β-1) A biaxially oriented polyethylene terephthalate film "Cerapill WZ (trade name)" with one-sided easy-release treatment from Toray Film Processing Co., Ltd., thickness 38 μm.

[0111] Example 1 100 parts by mass of the above component (A-1), 25 parts by mass of the above component (B-1), 7.5 parts by mass of the above component (C-1), 1 part by mass of the above component (D-1) (0.55 parts by mass in terms of solid content. The values in terms of solid content are described in the table), 140 parts by mass of ethyl acetate, and 20 parts by mass of methyl ethyl ketone (described as "MEK" in the table) were mixed and stirred to obtain a paint for forming an adhesive layer. Next, using a roll coater, the paint for forming an adhesive layer obtained above was applied onto the easy-release surface of the above release film (β-1) so that the dried thickness would be 45 μm, and dried in a drying furnace to form an adhesive layer, thereby obtaining laminate 1. Subsequently, using the apparatus shown in the conceptual diagram in Figure 1, the laminate 1 obtained above and the substrate film 2 (the above substrate film (α-1)) were overlapped such that the adhesive layer of laminate 1 was on the side of substrate film 2, and fed and inserted between a rotating metal mirror roll 3 preheated to 30°C and a rotating pressure roll 4 with laminate 1 on the side of the metal mirror roll 3, and pressed to obtain a decorative sheet (adhesive film) 5. The above tests (i) to (iv) were conducted. The results are shown in Table 1.

[0112] Examples 2 to 20 Except for changing the formulation of the coating for forming the adhesive layer as shown in Table 1 or Table 2, the procedure was the same as in Example 1. The results are shown in Table 1 or Table 2.

[0113]

Table 1

[0114]

Table 2

[0115] The adhesive layer formed using the coating for forming the adhesive layer of the present invention was excellent in transparency and flame retardancy. The adhesive layer formed using the preferred coating for forming the adhesive layer of the present invention was excellent in transparency, flame retardancy, and adhesive strength. Further, since it was excellent in transparency and had a low whiteness, it was considered that the problem of meski was solved in the decorative sheet (adhesive film) in which the adhesive layer was formed using the preferred coating for forming the adhesive layer of the present invention. Furthermore, from the results of the heat generation test, it was considered that the member decorated with the decorative sheet (adhesive film) in which the adhesive layer was formed using the preferred coating for forming the adhesive layer of the present invention could receive the review and certification of "non-combustible material".

[0116] Since the coating for forming the adhesive layer of the present invention has the preferred characteristics as described above, it will be obvious to those skilled in the art that it is also useful for forming the adhesive layer of articles other than decorative sheets, for example, adhesive films other than decorative sheets.

Brief Description of the Drawings

[0117]

Figure 1

Explanation of Reference Numerals

[0118] 1: Laminate of release film and adhesive layer 2: Substrate film 3: Metal mirror roll 4: Pressure roll 5: Cosmetic sheet (adhesive film)

Claims

1. (A) 100 parts by mass of an acrylic polymer; (B) 3 to 120 parts by mass of at least one selected from the group consisting of brominated compounds having a bisphenol A structure and brominated compounds having an isocyanate ring structure; and (C) 1 to 40 parts by mass of antimony pentoxide; A paint for forming an adhesive layer, excluding those containing magnesium silicate hydrate clay minerals.

2. (A) 100 parts by mass of an acrylic polymer; (B) 3 to 120 parts by mass of at least one selected from the group consisting of brominated compounds having a bisphenol A structure and brominated compounds having an isocyanate ring structure; and (C) 1 to 40 parts by mass of antimony pentoxide; A paint for forming an adhesive layer, wherein the average particle diameter of the above component (C), antimony pentoxide, is 0.1 to 50 μm.

3. The paint for forming an adhesive layer according to claim 1 or 2, which does not contain antimony trioxide.

4. The paint for forming an adhesive layer according to any one of claims 1 to 3, further containing (D) 0.01 to 10 parts by mass of a compound having two or more isocyanate groups in one molecule.

5. The paint for forming an adhesive layer according to any one of claims 1 to 4, wherein the content of bromine atoms in at least one selected from the group consisting of brominated compounds having a bisphenol A structure and brominated compounds having an isocyanate ring structure as the above component (B) is 40 to 80% by mass.

6. The paint for forming an adhesive layer according to any one of claims 1 to 5, wherein the sum of the blending amount of at least one selected from the group consisting of brominated compounds having a bisphenol A structure and brominated compounds having an isocyanate ring structure as the above component (B) and the blending amount of the above component (C), antimony pentoxide, is 12 to 105 parts by mass.

7. The paint for forming an adhesive layer according to any one of claims 1 to 6, wherein the mass ratio of the blending amount of at least one selected from the group consisting of brominated compounds having a bisphenol A structure and brominated compounds having an isocyanate ring structure as the above component (B) to the blending amount of the above component (C), antimony pentoxide, is 1 / 1 to 9 / 1.

8. A decorative sheet including an adhesive layer formed using the paint for forming an adhesive layer according to any one of claims 1 to 7.

9. The decorative sheet according to claim 8, wherein the visible light transmittance of the above adhesive layer is 80% or more.

10. The decorative sheet according to claim 8 or 9, wherein the 180° peel adhesion to a stainless steel test plate measured under standard conditions is 10 to 50 N / 25 mm in accordance with the 10 adhesion of JIS Z0237:2009 of the above decorative sheet.

11. comprising an adhesive layer formed using the paint for forming an adhesive layer according to any one of claims 1 to 7; meeting the criteria of the heat generation test method (b) in 4.10.2 of the Fire and Heat Resistance Performance Test and Evaluation Business Method Manual of the Japan Building Research Institute; a material used for interior decoration of a building.

12. comprising the decorative sheet according to any one of claims 8 to 10; meeting the criteria of the heat generation test method (b) in 4.10.2 of the Fire and Heat Resistance Performance Test and Evaluation Business Method Manual of the Japan Building Research Institute; a material used for interior decoration of a building.

Images