Laminate and partitioning wall member

Abstract

To provide a laminate which has such extensibility as to substantially prevent cracking and peeling from a paper base material, even if a stress is applied thereto during use or transportation, and even if a corrugated cardboard is waved by heating, generates a residual layer due to heat in the fire, and has such excellent fire resistance as to inhibit the heated paper base material from reaching its ignition point and from being combusted.SOLUTION: A laminate includes: a paper base material; and at least one fire-resistant layer which is integrally laminated on at least one surface of the paper base material, and contains 100 pts.mass of a resin binder and 20 to 250 pts.mass of a glass frit.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate and a partition wall member. [Background technology]

[0002] BACKGROUND ART Corrugated cardboard has been used as a building material in the past because of its light weight and ease of processing.

[0003] Patent Document 1 proposes a mounting structure for mounting an interior board to a construction surface, in which the interior board is mounted to the construction surface via corrugated cardboard. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-194832 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the corrugated cardboard used in the mounting structure of the inner layer board in Patent Document 1 is not fireproofed, and there is a problem in that the corrugated cardboard may burn in the event of a fire, causing the fire to spread.

[0006] One approach to preventing or mitigating the spread of fire caused by burning cardboard is to laminate metal foil onto the surface of the cardboard. However, this creates another problem: the heat from the fire will heat the metal foil, which will then heat the cardboard, causing it to reach its ignition point and begin to burn.

[0007] It is also possible to form a non-combustible or flame-retardant layer containing a synthetic resin on the surface of the cardboard, but this may cause problems such as stress applied during use or transportation causing the non-combustible or flame-retardant layer to deform, causing cracks in the non-combustible or flame-retardant layer, which may then allow flames to reach the cardboard through the cracks and cause it to start burning.

[0008] When corrugated cardboard is heated, it becomes wavy. When heated by the heat of a fire, the cardboard becomes wavy, and the metal foil, non-combustible layer, and flame-retardant layer cannot follow the wavy shape of the cardboard and peel off from the cardboard. This can allow flames to reach the cardboard through the peeled-off parts, causing the cardboard to start burning.

[0009] In order to prevent cracks from occurring in the non-combustible layer or the flame-retardant layer and thereby reduce fire resistance, it is conceivable to increase its thickness, but this would exacerbate the problem that when the cardboard corrugates due to the heat of a fire, the non-combustible layer or the flame-retardant layer cannot adapt to this corrugation phenomenon.

[0010] Conversely, it is possible to reduce the thickness of the non-combustible or flame-retardant layer, but reducing the thickness of the non-combustible or flame-retardant layer will result in a problem of reduced fire resistance of the non-combustible or flame-retardant layer.

[0011] As described above, the ability of the non-combustible or flame-retardant layer to conform to deformation of the corrugated board and fire resistance are contradictory and difficult to achieve at the same time, and a technology that can achieve both of these properties is desired.

[0012] The present invention provides a laminate that has extensibility (hereinafter sometimes simply referred to as "extensibility") that generally prevents cracking or peeling from the paper substrate, even when stress is applied during use or transportation or when the cardboard becomes wavy due to heating, and that has excellent fire resistance (hereinafter sometimes simply referred to as "fire resistance") that can prevent the heat of a fire from producing a residue layer, heating the paper substrate to its ignition point, and causing combustion. [Means for solving the problem]

[0013] The laminate of the present invention is A paper substrate; The paper substrate is characterized by having a fire-resistant layer laminated integrally on at least one surface of the paper substrate and containing 100 parts by mass of a resin binder and 6 to 200 parts by mass of glass frit.

[0014] The partition wall member of the present invention includes the above laminate. [Effects of the Invention]

[0015] The laminate of the present invention has a fire-resistant layer containing a resin binder and glass frit in a predetermined ratio on at least one surface of a paper substrate, and therefore has excellent elongation and fire resistance. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a cross-sectional view showing a laminate of the present invention. [Figure 2] FIG. 3 is a cross-sectional view showing another example of the laminate of the present invention. [Figure 3] FIG. 3 is a cross-sectional view showing another example of the laminate of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] The laminate of the present invention comprises a paper substrate and a fire-resistant layer laminated on at least one surface of the paper substrate and containing glass frit and a resin binder.

[0018] [Paper substrate] The laminate contains a paper substrate. In the present invention, the "paper substrate" contains 60% by mass or more of a pulp component. The paper substrate preferably contains 70% by mass or more of a pulp component, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 99% by mass or more.

[0019] The pulp component contained in the paper substrate is not particularly limited, and examples thereof include chemical pulp, mechanical pulp, and recycled paper pulp. Examples of chemical pulp include unbleached softwood kraft pulp (NUKP), unbleached hardwood kraft pulp (LUKP), bleached softwood kraft pulp (NBKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), semi-bleached softwood kraft pulp (NSBKP), sulfite hardwood pulp, and sulfite softwood pulp. Examples of mechanical pulp include thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP), chemi-ground pulp (CGP), refiner ground pulp (RGP), ground pulp (GP), pressurized stone ground pulp (PGW), and stone ground pulp (SGP). Examples of waste paper pulp include pulp derived from waste paper such as newspapers, magazines, office paper, communication paper, cardboard, and paper containers. The pulp components may be used alone or in combination of two or more. Chemical pulp is preferred as the pulp component.

[0020] The paper substrate may contain an internal additive selected appropriately as needed. Examples of the internal additive include internal sizing agents, retention aids, freeness improvers, paper strength improvers, various starches, basic aluminum compounds, water-soluble aluminum compounds, silica sol, antifoaming agents, coloring dyes, coloring pigments, fluorescent whitening agents, pH adjusters, pitch control agents, and slime control agents. The internal additives may be used alone or in combination of two or more.

[0021] The paper substrate has a basis weight of 100 g / m 2 More than 110g / m 2 More preferably, 120 g / m 2 More preferably, 130 g / m 2 More preferably, 150 g / m 2 More preferably, 200 g / m 2 More preferably, 2500g / m 2 More preferably, the weight of the paper substrate is 5000 g / m 2 Preferably less than 4000 g / m2 Preferably less than 3500 g / m 2 Preferably less than 3000 g / m 2 Less than 2800 g / m is more preferable. 2 Less than 2500g / m is more preferable. 2 Less than 2000g / m is more preferable. 2 Less than 1500g / m is more preferable. 2 Less than 1000g / m is more preferable. 2 Less than 800g / m is more preferable. 2 Less than 600 g / m is more preferable. 2 Less than 500g / m is more preferable. 2 Less than 450 g / m is more preferable. 2 Less than 400 g / m is more preferable. 2 More preferably, the paper substrate has a basis weight of 100 g / m or less. 2 When the weight per unit area of ​​the paper substrate is 500 g / m or more, delamination between the fire-resistant layer and the paper substrate is prevented, and flames in the event of a fire are prevented from unexpectedly reaching the paper substrate, thereby improving the fire resistance of the laminate. 2 When the weight per unit area of ​​the paper substrate is less than 100%, the lightness and processability of the laminate can be improved. The weight per unit area of ​​the paper substrate is a value measured in accordance with JIS P8124 "Paper and paperboard - Method for measuring basis weight".

[0022] The density of the paper substrate is 0.5 g / m 3 More than 0.55g / m 3 More preferably, 0.6 g / m or more 3 More preferably, 0.8 g / m or more 3 The density of the paper substrate is preferably 1.2 g / m or more. 3 Less than 1.0 g / m is preferred 3 More preferably, the density of the paper substrate is 0.5 g / m or less. 3 When the density of the paper substrate is 1.2 g / m or more, delamination between the fire-resistant layer and the paper substrate is prevented, and flames in the event of a fire are prevented from unexpectedly reaching the paper substrate, thereby improving the fire resistance of the laminate. 3When the density is less than 1 / 2, the lightweight and processability of the laminate can be improved. The density of the paper substrate is a value calculated from the thickness and basis weight of the paper substrate. The thickness of the paper substrate is a value measured in accordance with JIS P8118:2014 Paper and paperboard - Test methods for thickness, density and specific volume.

[0023] The bending strength of the paper substrate is 0.0001N / mm 2 More than 0.0002N / mm is preferable. 2 More preferably, 0.0003N / mm 2 The bending strength of the paper substrate is more preferably 0.1000 N / mm 2 Preferably less than 0.0500N / mm 2 The following is more preferable. When the bending strength of the paper substrate is within the above range, stress applied to the laminate A during use or transportation of the laminate A before a fire occurs can be smoothly absorbed, and the laminated state between the fireresistant layer and the paper substrate can be stably maintained without causing cracks in the fireresistant layer. Furthermore, in the event of a fire, stress applied to the laminate by heating can also be smoothly absorbed, and the laminated state between the fireresistant layer and the paper substrate can be stably maintained, which can generally prevent flames from penetrating between the fireresistant layer and the paper substrate, causing the paper substrate to burn and spread the fire. The bending strength of the paper substrate refers to a value measured in accordance with JIS K7171.

[0024] The paper substrate may contain 60% by mass or more of a pulp component, and examples thereof include cardboard base paper (liner, corrugating medium (core) base paper), paperboard such as white cardboard, yellow cardboard, colored cardboard, and building paper, and corrugated cardboard. Corrugated cardboard is preferred as a paper substrate because of its light weight, ease of processing, and mechanical strength. Corrugated cardboard includes a core base paper bent into a corrugated cross section and a liner bonded to at least one surface of the core base paper to form an integrated unit.

[0025] As shown in FIG. 1, the corrugated board 1 may be a double-sided corrugated board formed by laminating liners 3, 3 on both sides of a corrugated core 2 bent in a cross-sectionally corrugated shape. As shown in FIG. 2, the corrugated board 1 may be a double-sided corrugated board formed by laminating multiple corrugated core 2, 2... and multiple liners 3, 3... alternately, with the liners 3, 3 forming the outermost layer. In the corrugated boards shown in FIGS. 1 and 2, the outermost layer may be formed by a corrugated core 2 bent in a cross-sectionally corrugated shape without laminating a liner on either side. While FIG. 2 shows a corrugated board 1 formed by alternating two corrugated core 2 and three liners 3, with the liners 3 forming the outermost layer, the corrugated board 1 may also be formed by alternating n corrugated core 2 and (n+1) liners 3, with the liners 3 forming the outermost layer. Note that n is a natural number.

[0026] The weight of the cardboard is 100g / m 2 More than 120g / m 2 More preferably, 140 g / m 2 More preferably, 160 g / m 2 More preferably, 200 g / m 2 More preferably, 250 g / m 2 More preferably, 300 g / m 2 More preferably, the weight of the corrugated board is 5000 g / m 2 Preferably less than 4000 g / m 2 Preferably less than 3500 g / m 2 Preferably less than 3000 g / m 2 Less than 2800 g / m is more preferable. 2 Less than 2500g / m is more preferable. 2 The weight of the cardboard is preferably 100 g / m or less. 2 When the weight of the corrugated board is 5000 g / m or more, delamination between the fire-resistant layer and the corrugated board is prevented, and flames in the event of a fire are prevented from unexpectedly reaching the paper substrate, thereby improving the fire resistance of the laminate. 2 When the thickness is not more than 100 μm, the lightweight property and processability of the laminate can be improved.

[0027] [Glass frit] A fire-resistant layer is integrally laminated on at least one surface (preferably both surfaces) of the paper substrate, and the fire-resistant layer contains glass frit and a resin binder.

[0028] Examples of glasses constituting the glass frit include phosphate glass, borate glass, bismuth oxide glass, silicate glass, and sodium oxide glass. Phosphate glass and borate glass are preferred, and phosphate glass is more preferred. These glass frits can be obtained by adjusting the composition ratios of B2O3, P2O5, ZnO, SiO2, Bi2O3, Al2O3, BaO, CaO, MgO, MnO2, ZrO2, TiO2, CeO2, SrO, VO5, SnO2, Li2O, Na2O, KO, CuO, and Fe2O3. The glass frits may be used alone or in combination.

[0029] The softening point of the glass constituting the glass frit is preferably 350 to 650° C., more preferably 360 to 560° C., particularly preferably 370 to 540° C., and most preferably 380 to 520° C. The softening point of the glass constituting the glass frit is the temperature at which the viscosity of the glass becomes 107.6 dPa s (log η=7.6).

[0030] The content of glass frit in the fire-resistant layer is 6 parts by mass or more, more preferably 7 parts by mass or more, and more preferably 8 parts by mass or more, relative to 100 parts by mass of the resin binder described below. The content of glass frit in the fire-resistant layer is 200 parts by mass or less, more preferably 190 parts by mass or less, more preferably 150 parts by mass or less, and more preferably 100 parts by mass or less, relative to 100 parts by mass of the resin binder described below. When the content of glass frit is 6 parts by mass or more, the fire resistance of the residue layer is improved, and it is possible to more effectively prevent the paper substrate from reaching its ignition point and ignition. When the content of glass frit is 200 parts by mass or less, the extensibility of the fire-resistant layer is improved, and even when the fire-resistant layer is deformed due to stress applied during use or transportation, or when the cardboard is wavy due to heating, it is possible to prevent the fire-resistant layer from cracking or peeling from the paper substrate, and it is possible to maintain excellent fire resistance.

[0031] [Resin binder] The fire-resistant layer of the laminate contains a resin binder in addition to the glass frit described above. The resin binder has adhesive properties that allow the fire-resistant layer to be laminated and integrated onto the paper substrate under normal conditions, and in the early stages of combustion of the fire-resistant layer, it acts to bond the glass frits together while maintaining the state in which the fire-resistant layer is laminated onto the paper substrate, thereby forming a residue layer having excellent fire resistance laminated onto the paper substrate.

[0032] The resin binder is not particularly limited, and examples thereof include synthetic resins such as thermoplastic resins and curable resins, elastomers, rubbers, etc. The resin binders may be used alone or in combination of two or more.

[0033] (thermoplastic resin) Examples of thermoplastic resins include polyolefin resins such as polypropylene resins and polyethylene resins, polyolefin resins such as ethylene-vinyl acetate copolymers, poly(1-butene), and polypentene, polystyrene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polycarbonate resins, polyphenylene ether resins, acrylic resins, polyamide resins, vinyl chloride resins, and polyisobutylene resins, with ethylene-vinyl acetate copolymers and polyvinyl chloride being preferred, and ethylene-vinyl acetate copolymers being more preferred. The thermoplastic resins may be used alone or in combination of two or more.

[0034] The vinyl chloride resin is not particularly limited, and examples thereof include vinyl chloride homopolymer (polyvinyl chloride); a copolymer of a vinyl chloride monomer and a monomer having an ethylenically unsaturated double bond copolymerizable with the vinyl chloride monomer; a graft copolymer in which vinyl chloride is graft-copolymerized onto a (co)polymer other than vinyl chloride, etc. The vinyl chloride resin may be used alone or in combination of two or more kinds.

[0035] Examples of monomers having an ethylenically unsaturated double bond copolymerizable with vinyl chloride monomer include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; aromatic vinyls such as styrene and α-methylstyrene; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. (Meth)acrylate means acrylate or methacrylate.

[0036] The (co)polymer to be graft-copolymerized with vinyl chloride is not particularly limited as long as it is capable of graft-copolymerizing vinyl chloride, and examples thereof include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, and chlorinated polypropylene.

[0037] (curable resin) The curable resin is a resin that hardens when a crosslinked structure is introduced by moisture, light irradiation, heat, or the like. Examples of the curable resin include thermosetting resins, moisture-curing resins, and photo-crosslinkable curable resins. The curable resin constituting the fire-resistant layer is usually a cured resin, but may be one that hardens over time during use. The curable resin may be used alone or in combination of two or more types.

[0038] Examples of the thermosetting resin include urethane resin, isocyanurate resin, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, alkyd resin, melamine resin, diallyl phthalate resin, etc., and epoxy resin is preferred. The thermosetting resin may be used alone or in combination of two or more kinds.

[0039] Examples of the moisture-curable resin include a polymer having a hydrolyzable silyl group and a polymer having a hydrolyzable isocyanate group, and it is preferable to use a polymer having a hydrolyzable silyl group. The moisture-curable resin may be used alone or in combination of two or more kinds.

[0040] In the presence of water, the hydrolyzable groups of the hydrolyzable silyl groups in the polymers are hydrolyzed to form silanol groups (≡SiOH). The silanol groups then undergo dehydration condensation to form crosslinked structures. In the presence of water, the hydrolyzable isocyanate groups in the polymers form urea bonds (-NHCONH-) while generating carbon dioxide, forming crosslinked structures.

[0041] The hydrolyzable silyl group is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom. The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, and an oxime group.

[0042] Among these, the hydrolyzable silyl group is preferably an alkoxysilyl group because of its mild hydrolysis reaction. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, and triphenoxysilyl; dialkoxysilyl groups such as propyldimethoxysilyl, methyldimethoxysilyl, and methyldiethoxysilyl; and monoalkoxysilyl groups such as dimethylmethoxysilyl and dimethylethoxysilyl.

[0043] The hydrolyzable isocyanate group refers to an isocyanate group that can form a urea bond (-NHCONH-) by hydrolysis.

[0044] (Polymer having hydrolyzable silyl groups) The polymer having a hydrolyzable silyl group is not particularly limited, and examples thereof include polyalkylene oxides having a hydrolyzable silyl group, acrylic polymers having a hydrolyzable silyl group, silicone resins having a hydrolyzable silyl group, urethane resins having a hydrolyzable silyl group, and polyolefin resins having a hydrolyzable silyl group.The polymer having a hydrolyzable silyl group preferably contains a polyalkylene oxide having a hydrolyzable silyl group or a silicone resin having a hydrolyzable silyl group.The polymer having a hydrolyzable silyl group may be used alone or in combination of two or more.

[0045] (Polyalkylene oxide having hydrolyzable silyl groups) In the polyalkylene oxide having a hydrolyzable silyl group, the hydrolyzable silyl group is preferably an alkoxysilyl group, more preferably a dialkoxysilyl group, more preferably a dimethoxysilyl group, and more preferably a propyldimethoxysilyl group.

[0046] The polyalkylene oxide having a hydrolyzable silyl group preferably has an average of 1 to 4 hydrolyzable silyl groups per molecule. When the number of hydrolyzable silyl groups in the polyalkylene oxide having a hydrolyzable silyl group is within the above range, the fire resistance of the fire-resistant layer is improved. The polyalkylene oxide having a hydrolyzable silyl group preferably has a hydrolyzable silyl group at at least one of both ends of its main chain.

[0047] The average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide having hydrolyzable silyl groups is 1 It can be calculated based on the concentration of hydrolyzable silyl groups in the polyalkylene oxide determined by H-NMR and the number average molecular weight of the polyalkylene oxide determined by GPC.

[0048] The polyalkylene oxide constituting the polyalkylene oxide having a hydrolyzable silyl group is a polyalkylene oxide having a main chain represented by the general formula: -(RO) m - (wherein R represents an alkylene group having 1 to 14 carbon atoms, and m represents the number of repeating units and is a positive integer.) The main chain skeleton of the polyalkylene oxide may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0049] In the present invention, an alkylene group is a divalent atomic group formed by removing two hydrogen atoms bonded to two different carbon atoms in an aliphatic saturated hydrocarbon, and includes both linear and branched atomic groups.

[0050] Examples of the alkylene group include an ethylene group, a propylene group [-CH(CH3)-CH2-], a trimethylene group [-CH2-CH2-CH2-], a butylene group, an amylene group [-(CH2)5-], and a hexylene group.

[0051] Examples of the main chain skeleton of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Among these, polypropylene oxide is preferred. Polypropylene oxide can improve the fire resistance of the fire-resistant layer.

[0052] The number average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group is preferably 3,000 or more, more preferably 10,000 or more. The number average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group is preferably 50,000 or less, more preferably 40,000 or less, and more preferably 30,000 or less. When the number average molecular weight of the polyalkylene oxide is 3,000 or more, the polyalkylene oxide does not easily thermally decompose into low molecular weight compounds, thereby improving the fire resistance of the fire-resistant layer. When the number average molecular weight of the polyalkylene oxide is 50,000 or less, the elongation of the fire-resistant layer is improved.

[0053] In the present invention, the number average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group means a value calculated in terms of polystyrene measured by GPC (gel permeation chromatography).

[0054] The number average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group can be measured, for example, using the following measuring device and under the following measuring conditions. Measuring device: TOSOH Corporation, product name "HLC-8121GPC / HT" Measurement conditions Column: TSKgelGMHHR-H(20)HT x 3 TSKguardcolumn-HHR(30)HT x 1 Mobile phase: o-DCB 1.0mL / min Sample concentration: 1 mg / mL Detector: Bryce type refractometer Standard material: Polystyrene (TOSOH Corporation, molecular weight: 500-8420000) Elution conditions: 145℃ SEC temperature: 145℃

[0055] Commercially available polyalkylene oxides having a hydrolyzable silyl group can be used. For example, examples of polyalkylene oxides having a hydrolyzable silyl group include those manufactured by Kaneka Corporation under the trade names "MS Polymer S-203," "MS Polymer S-303," "MS Polymer S-303H," "Silyl Polymer SAT-200," "Silyl Polymer SAT-350," and "Silyl Polymer SAT-400." Examples of polyalkylene oxides having a hydrolyzable silyl group include those manufactured by Asahi Glass Company Limited under the trade names "Excestar ESS-3620," "Excestar ESS-2420," "Excestar ESS2410," and "Excestar ESS3430."

[0056] A polyalkylene oxide having a polypropylene oxide main chain and a (methoxymethyl)dimethoxysilyl group at the end of the polypropylene oxide is commercially available from Kaneka Corporation under the trade name "HS-2."

[0057] A polyalkylene oxide having a polypropylene oxide main chain and an isopropyldimethoxymethylsilyl group at the end of the polypropylene oxide is commercially available from Kaneka Corporation under the trade name "SAX720."

[0058] [Acrylic polymer having hydrolyzable silyl groups] As the hydrolyzable silyl group contained in the acrylic polymer having a hydrolyzable silyl group, an alkoxysilyl group is preferred, a trialkoxysilyl group is more preferred, and a trimethoxysilyl group is particularly preferred, because the hydrolysis reaction is mild.

[0059] The method for introducing a hydrolyzable silyl group into an acrylic polymer is not particularly limited, and examples thereof include a method in which an unsaturated group is introduced into a copolymer of monomers constituting the main chain skeleton, and then a hydrosilane having a hydrolyzable silyl group is allowed to act on the copolymer to hydrosilylate the copolymer.

[0060] The main chain skeleton of the acrylic polymer having a hydrolyzable silyl group is preferably a copolymer of a monomer containing methyl (meth)acrylate and butyl (meth)acrylate, more preferably a copolymer of a monomer containing methyl methacrylate and butyl acrylate, and even more preferably a copolymer of a monomer containing methyl methacrylate and n-butyl acrylate. The acrylic polymer having a hydrolyzable silyl group, whose main chain skeleton is the copolymer, improves the fire resistance of the fire-resistant layer.

[0061] In the acrylic polymer having a hydrolyzable silyl group, the monomers used in the polymer constituting the main chain skeleton may further include other monomers in addition to methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate.Other monomers include, for example, styrene derivatives such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene; compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, and vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, methacrylonitrile, acrylonitrile, acrylamide, methacrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, trimethylsilyl vinyl ether, methyl ... Examples of vinyloxy group-containing compounds include ethylene glycol methyl vinyl ether, (4-vinyloxy)butyl benzoate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol divinyl ether, hexane-1,6-diol divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, di(4-vinyloxy)butyl isophthalate, di(4-vinyloxy)butyl glutarate, di(4-vinyloxy)butyl succinate, trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2-(N,N-diethylamino)ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether. These monomers may be used alone or in combination.

[0062] The polymerization method for the acrylic polymer having a hydrolyzable silyl group is not particularly limited, and known methods can be used. Examples of such polymerization methods include free radical polymerization, anionic polymerization, cationic polymerization, UV radical polymerization, living anionic polymerization, living cationic polymerization, and living radical polymerization.

[0063] [Silicone resin with hydrolyzable silyl groups] Silicone resin refers to a polymer having a main chain formed by repeating siloxane bonds (-Si-O-). Silicone resins having hydrolyzable silyl groups have a plurality of hydrolyzable silyl groups in the main chain of the silicone resin. Silicone resins having hydrolyzable silyl groups preferably have hydrolyzable silyl groups at both ends of the main chain of the silicone resin. The hydrolyzable silyl groups contained in silicone resins having hydrolyzable silyl groups are preferably dimethoxysilyl groups or trimethoxysilyl groups.

[0064] [Polymer having hydrolyzable isocyanate groups] Examples of polymers having a hydrolyzable isocyanate group include urethane resins having a hydrolyzable isocyanate group. Urethane resins refer to polymers having a main chain formed by repeating urethane bonds (-NHCOO-). Urethane resins having a hydrolyzable isocyanate group have a plurality of hydrolyzable isocyanate groups in the main chain of the urethane resin. Urethane resins having a hydrolyzable isocyanate group preferably have hydrolyzable isocyanate groups at both ends of the main chain of the urethane resin. Urethane resins include polyether-based urethane resins made from polyether polyol as a raw material and polyester-based urethane resins made from polyester polyol as a raw material, but any of these may be used.

[0065] [Photocrosslinkable curable resin] Photocrosslinkable curable resins have photocrosslinkable groups in their molecules, and when irradiated with light such as ultraviolet light, they form chemical bonds between the molecules, forming a crosslinked structure and curing.

[0066] The photocrosslinkable group may be any group capable of forming a chemical bond upon irradiation with light. The photocrosslinkable group is not particularly limited, and examples thereof include a thiol group, a glycidyl group, an oxetanyl group, a vinyl group, a (meth)acryloyl group, a benzophenone group, a benzoin group, and a thioxanthone group. Benzophenone group, benzoin group, and thioxanthone group are preferred, and a benzophenone group is more preferred. Note that (meth)acryloyl refers to methacryloyl or acryloyl.

[0067] The main chain structure of the photocrosslinkable curable resin is not particularly limited, and examples thereof include polyolefin resins, acrylic resins, epoxy resins, cyanoacrylate resins, etc. Examples of a method for introducing a photocrosslinkable group into the main chain include a method of polymerizing a monomer composition containing a photocrosslinkable group-containing monomer.

[0068] The photocrosslinkable group-containing monomer is not particularly limited, and examples thereof include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-(meth)acryloyloxybenzophenone, 4-[2-((meth)acryloyloxy)ethoxy]benzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, 4-(meth)acryloyloxyethoxy-4'-methoxybenzophenone, 4-(meth)acryloyloxy-4'-bromobenzophenone, and 4-(meth)acryloyloxyethoxy-4'-bromobenzophenone, with 4-(meth)acryloyloxybenzophenone and 4-[2-((meth)acryloyloxy)ethoxy]benzophenone being preferred. The photocrosslinkable group-containing monomer may be used alone or in combination of two or more. Note that (meth)acryloyloxy refers to methacryloyloxy or acryloyloxy.

[0069] (Elastomer) Examples of the elastomer include thermoplastic elastomers such as olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, and vinyl chloride-based elastomers.

[0070] (rubber) Examples of rubber include natural rubber, butyl rubber [synthetic rubber obtained by copolymerizing isobutylene with a small amount (preferably 1 to 3% by mass) of isobutylene], fluororubber, urethane rubber, silicone rubber, polychloroprene rubber, polybutadiene rubber, polyisoprene rubber, polyisobutylene rubber, styrene-butadiene rubber, butadiene-acrylonitrile rubber, nitrile rubber, and ethylene-propylene-diene copolymer, with butyl rubber being preferred.

[0071] The fire-resistant layer may contain an inorganic filler. The inorganic filler is not particularly limited as long as it is an inorganic filler that is generally used in producing a vinyl chloride resin molded body, and examples thereof include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawnnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mycelium, and montmorillonite. Examples of inorganic fillers include quartz, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconia titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dehydrated sludge, with calcium carbonate, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide being preferred. The inorganic fillers may be used alone or in combination of two or more.

[0072] The amount of inorganic filler added in the fire-resistant layer is preferably 3 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 30 parts by mass or more, more preferably 40 parts by mass or more, more preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and more preferably 70 parts by mass or more, per 100 parts by mass of the resin binder. The amount of inorganic filler added in the fire-resistant layer is preferably 300 parts by mass or less, more preferably 260 parts by mass or less, more preferably 250 parts by mass or less, more preferably 230 parts by mass or less, and more preferably 220 parts by mass or less, per 100 parts by mass of the resin binder. When the content of inorganic filler is 3 parts by mass or more, the fire resistance of the residue layer is improved, and the paper substrate can be more effectively prevented from reaching its ignition point and catching fire. When the content of inorganic filler is 300 parts by mass or less, the extensibility of the fire-resistant layer is improved, and even if the fire-resistant layer is deformed due to stress during use or transportation, or if the cardboard becomes wavy due to heating, the fire-resistant layer can be prevented from cracking or peeling off from the paper base material, and excellent fire resistance can be maintained.

[0073] The fire-resistant layer preferably contains an ethylene-vinyl acetate copolymer or a polymer having a hydrolyzable silyl group as a resin binder and calcium carbonate as an inorganic filler. When the fire-resistant layer contains glass frit, calcium carbonate, and an ethylene-vinyl acetate copolymer or a polymer having a hydrolyzable silyl group, the fire-resistant layer has improved elongation and fire resistance.

[0074] In the fire-resistant layer, the mass ratio of the resin binder content to the inorganic filler content (resin binder / inorganic filler) is preferably 0.2 or more, more preferably 0.3 or more, and more preferably 0.4 or more. In the fire-resistant layer, the mass ratio of the resin binder content to the inorganic filler content (resin binder / inorganic filler) is preferably 1.5 or less, more preferably 1.2 or less, more preferably 1.1 or less, more preferably 1.0 or less, and more preferably 0.9 or less. When the mass ratio of the resin binder to the inorganic filler (resin binder / inorganic filler) is within the above range, the elongation and fire resistance of the fire-resistant layer are improved.

[0075] In the fire-resistant layer, the mass ratio of the glass frit content to the inorganic filler content (glass frit / inorganic filler) is preferably 0.05 or more, more preferably 0.08 or more, and more preferably 0.09 or more. In the fire-resistant layer, the mass ratio of the glass frit content to the inorganic filler content (glass frit / inorganic filler) is preferably 3.0 or less, more preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, and more preferably 1.0 or less. When the mass ratio of the glass frit content to the inorganic filler content (glass frit / inorganic filler) is within the above range, the elongation and fire resistance of the lower layer are improved.

[0076] The fire-resistant layer may contain a plasticizer. The plasticizer is not particularly limited as long as it is a plasticizer that is generally used when producing a molded article of a vinyl chloride resin, and examples thereof include phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); fatty acid ester plasticizers such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA); and epoxidized ester plasticizers such as epoxidized soybean oil. Plasticizers include polyester plasticizers such as adipic acid esters and adipic acid polyesters; trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TO™) and triisononyl trimellitate (TINT™); phosphate ester plasticizers such as trimethyl phosphate (TMP) and triethyl phosphate (TEP); and polyalkylene glycols such as polyethylene glycol and polypropylene glycol, with polyalkylene glycols being preferred and polypropylene glycol being more preferred. The plasticizers may be used alone or in combination.

[0077] The content of the plasticizer in the fire-resistant layer is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and more preferably 30 parts by mass or more, per 100 parts by mass of the resin binder. The content of the plasticizer in the fire-resistant layer is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and more preferably 55 parts by mass or less, per 100 parts by mass of the resin binder. When the content of the plasticizer is 20 parts by mass or more, the elongation of the fire-resistant layer is improved. When the content of the plasticizer is 100 parts by mass or less, the adhesion between the fire-resistant layer and the paper substrate is improved.

[0078] The fire-resistant layer may contain, as necessary, a tackifier, a foaming flame retardant, a heat stabilizer, a lubricant, a processing aid, a thermal decomposition type foaming agent, an antioxidant, an antistatic agent, a pigment, and the like, within the range that does not impair the physical properties of the fire-resistant layer.

[0079] The tackifier is not particularly limited and examples thereof include petroleum resins and rosin-based tackifiers, with petroleum resins being preferred because they enable the fire-resistant layer to be more firmly laminated and integrated onto the paper substrate. The tackifiers may be used alone or in combination of two or more.

[0080] The petroleum resin is not particularly limited, and examples thereof include C5 petroleum resin, C9 petroleum resin, C5C9 petroleum resin, dicyclopentadiene petroleum resin, etc. The petroleum resin is preferably unhydrogenated because it allows the fire-resistant layer to be more firmly laminated and integrated onto the paper substrate, but may be partially or completely hydrogenated. The petroleum resin may be used alone or in combination of two or more types.

[0081] C5 petroleum resins are petroleum resins made from the C5 fraction of petroleum, C9 petroleum resins are petroleum resins made from the C9 fraction of petroleum, and C5C9 petroleum resins are petroleum resins made from both the C5 and C9 fractions of petroleum. Examples of C5 fractions include cyclopentadiene, isoprene, and pentane. Examples of C9 fractions include styrene, vinyltoluene, and indene.

[0082] The rosin-based tackifier is not particularly limited, and examples thereof include natural rosin and esterified products of natural rosin (rosin ester resins), with rosin ester resins being preferred. The rosin-based tackifiers may be used alone or in combination of two or more.

[0083] The natural rosin is not particularly limited, and examples thereof include tall rosin, gum rosin, wood rosin, etc. The natural rosins may be used alone or in combination of two or more kinds.

[0084] The rosin ester resin is not particularly limited, and examples thereof include rosin glycerin ester, rosin pentaerythritol ester, rosin methyl ester, rosin ethyl ester, rosin butyl ester, rosin ethylene glycol ester, etc. The rosin ester resins may be used alone or in combination of two or more.

[0085] The content of the tackifier in the fire-resistant layer is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass or more, per 100 parts by mass of the resin binder. The content of the tackifier in the fire-resistant layer is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the resin binder. When the content of the tackifier is 0.5 parts by mass or more, the fire-resistant layer can be more firmly laminated and integrated onto the paper substrate. When the content of the tackifier is 200 parts by mass or less, the elongation of the fire-resistant layer is improved.

[0086] The intumescent flame retardant is not particularly limited, and examples thereof include ammonium phosphate, ammonium polyphosphate, and aluminum phosphite. Ammonium polyphosphate and aluminum phosphite are preferred, as they further improve the fire resistance of the fire-resistant layer, and aluminum phosphite is more preferred. The intumescent flame retardants may be used alone or in combination of two or more.

[0087] The content of the intumescent flame retardant in the fire-resistant layer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and more preferably 38 parts by mass or more, per 100 parts by mass of the resin binder. The content of the intumescent flame retardant in the fire-resistant layer is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, more preferably 60 parts by mass or less, and more preferably 49 parts by mass or less, per 100 parts by mass of the resin binder. When the content of the intumescent flame retardant is 20 parts by mass or more, the fire resistance of the fire-resistant layer is improved. When the content of the intumescent flame retardant is 90 parts by mass or less, the elongation of the fire-resistant layer is improved.

[0088] The fire-resistant layer preferably contains glass frit and an intumescent flame retardant. By using the glass frit and the intumescent flame retardant in combination, the fire-resistant layer can be endowed with excellent elongation and fire resistance.

[0089] In the fire-resistant layer, the mass ratio of the intumescent flame retardant content to the glass frit content (intumescent flame retardant / glass frit) is preferably 0.1 or more, more preferably 0.2 or more, and more preferably 0.3 or more. In the fire-resistant layer, the mass ratio of the glass frit content to the intumescent flame retardant content (glass frit / intumescent flame retardant) is preferably 1 or less, more preferably 0.9 or less, more preferably 0.8 or less, and more preferably 0.7 or less. When the mass ratio of the glass frit content to the intumescent flame retardant content (glass frit / intumescent flame retardant) is within the above range, the elongation and fire resistance of the fire-resistant layer are improved.

[0090] When the resin binder in the fire-resistant layer contains a hydrolyzable silyl group, it preferably contains a silanol condensation catalyst. The silanol condensation catalyst is not particularly limited, and examples thereof include dibutyltin diacetylacetonate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octoate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) oxide, and dibutyltin oxybisethoxysilicate and other organic tin compounds; tetra-n-butoxy titanate, tetraisopropoxy titanate, and other organic titanium compounds, with organic tin compounds being preferred. The silanol condensation catalyst may be used alone or in combination of two or more.

[0091] A fire-resistant composition is prepared by uniformly mixing a resin binder, glass frit, and optional additives in a known manner, and the fire-resistant composition is applied to a paper substrate in a known manner and then cured as necessary, thereby forming a fire-resistant layer on the paper substrate. The curing of the curable resin may be performed in a known manner depending on the type of curable resin (for example, by supplying moisture, irradiating with light such as ultraviolet light, or by heating).

[0092] The method for mixing the resin binder and the glass frit with the additives contained as necessary is not particularly limited, and examples thereof include a method in which the mixture is supplied to a mixing device such as a single-screw extruder or a twin-screw extruder and melt-kneaded.

[0093] [Laminate] The laminate A is constructed by integrally laminating fire-resistant layers C, C on at least one surface (preferably both surfaces) of a paper substrate B. In detail, as shown in Fig. 3, the fire-resistant layer C of the laminate A is integrally laminated over the entire surface of at least one surface of the paper substrate B. As shown in Fig. 4, the fire-resistant layer C of the laminate A is preferably integrally laminated over the entire surface of both surfaces of the paper substrate B.

[0094] When the paper substrate B is corrugated cardboard 1, fire-resistant layers C, C are laminated integrally onto the outer surfaces of both side components that make up the outermost layer of the corrugated cardboard 1. In the corrugated cardboard 1 shown in Figure 1, fire-resistant layers C, C are laminated integrally onto the outer surfaces of both side liners 3, 3. In the corrugated cardboard 1 shown in Figure 2, fire-resistant layers C, C are laminated integrally onto the outer surfaces of liners 3, 3 that make up the outermost layer of the laminate A. When the component that makes up the outermost layer of the corrugated cardboard is core raw paper that is bent into a corrugated cross section, the fire-resistant layer C is laminated integrally onto the outer surface of the core raw paper.

[0095] The fire-resistant layer C of the laminate A is composed of a resin binder and glass frit in a predetermined ratio, and has excellent elongation and fire resistance.

[0096] Since the fire-resistant layer C has excellent elongation, even if the laminate A is deformed due to stress applied thereto during use or transportation of the laminate A, the fire-resistant layer C smoothly follows the deformation of the laminate A, reducing the occurrence of damage such as cracks in the fire-resistant layer C.

[0097] Therefore, in the event of a fire, it is possible to generally prevent flames from reaching the paper substrate through cracks in the fire-resistant layer C, and the spread of fire can be effectively prevented.

[0098] As the paper substrate B is heated, it often deforms into a wavy cross-section. However, even in such cases, the fire-resistant layer C has excellent extensibility, so it does not peel off from the paper substrate and remains laminated and integrated onto the surface of the paper substrate, thereby generally preventing flames from penetrating between the fire-resistant layer C and the paper substrate B, causing the paper substrate to burn and spread the fire.

[0099] The fire-resistant layer C of the laminate A burns due to the heat of a fire and generates a non-combustible residue layer, but before combustion, it absorbs the heat generated during a fire, and the resin binder constituting the fire-resistant layer C acts to bind the glass frits together. In the generated residue layer, the glass frits are firmly bound together, preventing the paper substrate B from burning and effectively preventing the spread of fire.

[0100] As described above, the fire-resistant layer C has excellent heat absorption ability in the event of a fire, and therefore prevents the paper substrate B from heating up and reaching the ignition point, thereby effectively preventing the spread of fire due to the burning of the paper substrate B of the laminate A.

[0101] In the fire-resistant layer C of the laminate A, the glass frits bond together due to heat during a fire, and the resin binder burns, generating a non-combustible residue layer. Because the residue layer is thickened by the bonding of the glass frits, it prevents the paper substrate from being overheated and igniting, and effectively prevents the laminate A from burning and spreading.

[0102] The residue layer generated by the combustion of the fire-resistant layer C has glass frits firmly bonded together, and therefore can effectively block flames in the event of a fire and effectively prevent the fire from spreading.

[0103] Thus, the fire-resistant layer C of the laminate A has both excellent elongation and fire resistance. Therefore, due to its excellent elongation, the fire-resistant layer C of the laminate A can follow changes in the shape of the paper substrate and maintain a stable laminated and integrated state with the paper substrate without causing cracks, both before a fire, such as during use or transportation, and during a fire, and can smoothly absorb applied external forces to prevent damage such as cracks. Furthermore, in the event of a fire, the fire-resistant layer C of the laminate A can effectively block the flames and absorb the heat during a fire to prevent the paper substrate from igniting and the fire from spreading.

[0104] When the paper substrate B of laminate A is cardboard, and the liner to which the fire-resistant layer C is laminated is used as a No. 3 dumbbell test piece as specified in JIS K6250, the elongation when a tensile test is conducted in accordance with JIS K6251 at 50 mm / min in an atmosphere of 23°C and 50% relative humidity is preferably 50% or more, more preferably 60% or more, more preferably 65% ​​or more, more preferably 70% or more, and more preferably 75% or more. When the elongation is 50% or more, the fire-resistant layer of laminate A can follow changes in the shape of the paper substrate and maintain a stable laminated and integrated state without cracking, both before a fire during use or transportation, and during a fire, and can smoothly absorb applied external forces to prevent damage such as cracking. When the paper substrate B of the laminate A is cardboard, and the liner to which the fire-resistant layer C is laminated is used as a No. 3 dumbbell test piece as specified in JIS K6250, the elongation when subjected to a tensile test in accordance with JIS K6251 at 23°C and 50% relative humidity at 50 mm / min is preferably 600% or less, more preferably 500% or less, more preferably 450% or less, more preferably 400% or less, more preferably 350% or less, more preferably 300% or less, more preferably 250% or less, and more preferably 200% or less.

[0105] The bending strength of the liner of cardboard 1 is 0.0001N / mm 2 More than 0.0002N / mm is preferable. 2 More preferably, 0.0003N / mm 2 The bending strength of the liner of the cardboard 1 is preferably 0.1000 N / mm 2 Preferably less than 0.0500N / mm 2The following is more preferable. When the bending strength of the liner of the corrugated cardboard 1 is within the above range, stress applied to the laminate A can be smoothly absorbed during use or transportation of the laminate A before a fire occurs, and the laminated state between the fire-resistant layer and the paper substrate can be stably maintained without causing cracks in the fire-resistant layer. Furthermore, in the event of a fire, stress applied to the laminate by heating can also be smoothly absorbed, and the laminated state between the fire-resistant layer and the paper substrate can be stably maintained, which can generally prevent flames from penetrating between the fire-resistant layer and the paper substrate, causing the paper substrate to burn and spread the fire. The bending strength of the liner of the corrugated cardboard 1 refers to a value measured in accordance with JIS K7171.

[0106] When the paper substrate B of the laminate A is cardboard, the bending strength of the liner to which the fire-resistant layer C is laminated is 0.0001 N / mm 2 More than 0.0002N / mm is preferable. 2 More preferably, 0.0003N / mm 2 The bending strength of the liner of the cardboard 1 is preferably 0.1000 N / mm 2 Preferably less than 0.0500N / mm 2 The following is more preferable. When the bending strength of the liner onto which the fire-resistant layer C is laminated is within the above range, stress applied to the laminate A can be smoothly absorbed in a state before a fire occurs, such as during use or transportation of the laminate A, and the laminated state between the fire-resistant layer and the paper substrate can be stably maintained without causing cracks in the fire-resistant layer. Furthermore, in the event of a fire, stress applied to the laminate by heating can also be smoothly absorbed, and the laminated state between the fire-resistant layer and the paper substrate can be stably maintained, which can generally prevent flames from penetrating between the fire-resistant layer and the paper substrate, causing the paper substrate to burn and spread the fire. The bending strength of the liner onto which the fire-resistant layer C is laminated is a value measured in accordance with JIS K7171.

[0107] The corrugated cardboard 1 has a core raw paper 2 bent into a corrugated cross section disposed between adjacent liners 3, 3. In the event of a fire, the corrugated cardboard 1 heats up and stress is applied to the cardboard 1, but the corrugated core raw paper absorbs the stress by changing the degree of bending, allowing the laminated state of the fire-resistant layer and the paper substrate to be stably maintained. This generally prevents flames from penetrating between the fire-resistant layer and the paper substrate, causing the paper substrate to burn and spread.

[0108] As described above, the laminate A has excellent elongation and fire resistance, and therefore can be suitably used as a building material, and in particular as a partition wall material for dividing spaces in a building.

[0109] The laminate A is constructed by laminating a fire-resistant layer onto at least one surface of a paper base material, and can be easily cut into the desired shape using general-purpose cutting means such as a cutter or knife, making it suitable for use in applications other than the above-mentioned building components. [Example]

[0110] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0111] The following raw materials were used in producing the laminates of the Examples and Comparative Examples.

[0112] [Resin binder] Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product name "Ultrathene 726") Silicone resin with hydrolyzable silyl groups (modified silicone resin, manufactured by Kaneka Corporation under the trade name "MS Polymer S303," hydrolyzable silyl groups: dimethoxysilyl groups)

[0113] [Glass frit] Glass frit (Takara Standard Co., Ltd., product name "VY0144", melting temperature: 400°C)

[0114] [Tackifier] C9 petroleum resin (unhydrogenated, manufactured by Tosoh Corporation, product name "Petcol 120")

[0115] [Foaming flame retardant] Aluminum phosphite (manufactured by Taihei Chemical Co., Ltd., product name "APA100")

[0116] [Inorganic filler] Calcium carbonate (Bihoku Powder Co., Ltd. product name "BF300")

[0117] [Plasticizer] Polypropylene glycol (AGC product name "E3020")

[0118] [Silanol condensation catalyst] Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., product name "U220H")

[0119] [Dehydrating agent] Vinyltrimethoxysilane

[0120] [Paper substrate] Liner (Oji Materia product name "OFK210", pulp content: 99% by mass or more, basis weight: 210g / m 2 , Density: 0.6g / m 3 , Bending strength: 0.0013N / mm 2 , used as a structural material (liner) for cardboard)

[0121] (Examples 1 to 5, Comparative Examples 1 and 2) The resin binder, glass frit, tackifier, intumescent flame retardant, inorganic filler, plasticizer, silanol condensation catalyst, and dehydrating agent in the amounts shown in Table 1 were uniformly mixed to prepare a fire-resistant composition.

[0122] The obtained fire-resistant composition was applied to one side of a liner to form a coating layer at the coating thickness shown in Table 1. The coating layer on the liner was left to stand for 7 days in an atmosphere at a temperature of 25°C and a relative humidity of 50%, crosslinking and curing the silicone resin having a hydrolyzable silyl group, and the fire-resistant layer was laminated and integrated onto one side of the liner to produce a laminate.

[0123] The elongation, bending strength, fire resistance and adhesiveness of the resulting laminate were measured in the following manner, and the results are shown in Table 1.

[0124] The volume expansion ratio and residual hardness of the fire-resistant layer of the obtained laminate were measured in the following manner. The results are shown in Table 1.

[0125] (growth rate) The laminate was cut into No. 3 dumbbell test pieces as specified in JIS K6250. These dumbbell test pieces were subjected to a tensile test at 50 mm / min in an atmosphere of 23°C and 50% relative humidity in accordance with JIS K6501 to measure the elongation percentage.

[0126] (bending strength) The bending strength of the liner and the liner with the fire-resistant layer laminated and integrated (the entire fire-resistant layer and liner) was measured in accordance with JIS K7171. The bending strength of the liner is shown above. The bending strength of the liner with the fire-resistant layer laminated and integrated (the entire fire-resistant layer and liner) is shown in the "Bending strength (fire-resistant layer + liner)" column in Table 1.

[0127] (Fire resistance 1) The fire resistance of the fire-resistant layer was evaluated as follows. The fire-resistant composition was applied to one side of a liner at a surface coating thickness of 1.5 mm to form a coating layer. The coating layer on the liner was left to stand for 24 hours in an atmosphere of 25°C and 50% relative humidity. When a silicone resin having a hydrolyzable silyl group was included, the silicone resin having a hydrolyzable silyl group was crosslinked and cured, and the fire-resistant layer was laminated and integrated onto one side of the liner to produce a laminate.

[0128] A gas burner was used as the fire source. The flame temperature of the gas burner was 1000°C ± 30°C. The gas burner was positioned so that its nozzle was 100 mm away from the surface of the fireproof layer in a direction perpendicular to the surface. The gas valve and air valve of the gas burner were adjusted so that the overall flame length of the gas burner was 80 mm and the height of the reducing flame (the distance between the gas burner and the laminate) was 40 mm, thereby keeping the flame size constant.

[0129] The fire-resistant layer of the laminate was heated with the flame of a gas burner for 20 minutes, but the test was terminated when the flame penetrated the fire-resistant layer of the test specimen in its thickness direction, even if the 20 minutes had not yet elapsed. A: No holes or cracks were formed in the fireproof layer of the test specimen, and the flame did not penetrate the fireproof layer. If B: Holes and / or cracks were formed in the fireproofing layer of the test specimen, allowing the flame to penetrate the fireproofing layer. If there

[0130] (Fire resistance 2) The fire-resistant layer of the laminate was heated with the flame of a gas burner in the same manner as in the measurement conditions for fire resistance 1 above, except that the height of the reducing flame (the distance between the gas burner and the laminate) was 35 mm, and the time until the fire-resistant layer was penetrated by the flame of the gas burner was measured.

[0131] (Adhesiveness) The fire resistance of the fire-resistant layer was evaluated as follows. The fire-resistant composition was applied to one side of a liner at a surface coating thickness of 1.5 mm to form a coating layer. The coating layer on the liner was left to stand for one week in an atmosphere of 25°C and 50% relative humidity. When a silicone resin having a hydrolyzable silyl group was included, the silicone resin having a hydrolyzable silyl group was crosslinked and cured, and the fire-resistant layer was laminated and integrated onto one side of the liner to produce a laminate.

[0132] (Volume expansion ratio) The fire-resistant composition prepared as described above was molded into a rectangular parallelepiped molded body measuring 100 mm long x 100 mm wide x 2.0 mm thick. The molded body was left to stand for 7 days in an atmosphere of 25°C and 50% relative humidity to crosslink and harden the silicone resin having hydrolyzable silyl groups, thereby preparing a test specimen.

[0133] The test piece was placed in an electric furnace and heated at 600°C for 30 minutes, after which the thickness of the test piece was measured. The volume expansion ratio was calculated based on the following formula: Volume expansion ratio (times) = thickness of test piece after heating / thickness of test piece before heating

[0134] (residual hardness) The heated test piece for which the volume expansion ratio was measured was fed into a compression tester (Kato Tech Co., Ltd., "Finger Feeling Tester") and compressed to 0.25 cm. 2 The specimen was compressed with an indenter at a speed of 0.1 cm / sec, and the stress at break was measured.

[0135] Examples 6 to 9 A corrugated board was prepared in which liners (pulp content: 99% by mass or more) having the basis weight, thickness, and bending strength shown in Table 2 and core base paper (pulp content: 99% by mass or more) bent and formed into a corrugated cross section were alternately laminated together, with the outermost layers of both being made of liners. The basis weight and thickness of the corrugated board are shown in Table 2. The thickness of the corrugated board refers to the thickness of the corrugated board in the layering direction of the core base paper and liner.

[0136] The number of liners and core raw papers that make up the cardboard is shown in Table 1. For example, a cardboard box with three liners and two core raw papers has the structure shown in Figure 2.

[0137] The fire-resistant composition prepared in Example 1 was used. The fire-resistant composition was applied to the outer surfaces of both liners, which would become the outermost layers of cardboard 1, to a thickness of 0.5 mm to form a coating layer. The coating layer on the liner was left to stand for 24 hours in an atmosphere of 25°C and 50% relative humidity to crosslink and harden the silicone resin having a hydrolyzable silyl group, and the fire-resistant layers were laminated and integrated onto the outer surfaces of both liners to prepare a laminate.

[0138] The resulting laminate was measured for fire resistance 1 and 2, and the results are shown in Table 2. Note that fire resistance 2 was measured for one of the fire-resistant layers in the laminate.

[0139] The outermost liner with the integrated fire-resistant layer was peeled off from the obtained laminate, and the liner with the integrated fire-resistant layer was cut into a No. 3 dumbbell test piece as specified in JIS K 6250. The dumbbell test piece was subjected to a tensile test at 50 mm / min in an atmosphere of 23°C and 50% relative humidity in accordance with JIS K 6251 to measure the elongation.

[0140] The outermost liner on which the fire-resistant layer was laminated was peeled off from the obtained laminate, and the bending strength of the liner on which the fire-resistant layer was laminated (the entire fire-resistant layer and liner) was measured in accordance with JIS K7172, and the results are shown in the "Bending strength (fire-resistant layer + liner)" column in Table 2.

[0141] [Table 1]

[0142] [Table 2] [Explanation of symbols]

[0143] 1 cardboard box 2 Core paper 3 Liner A laminate B Paper base material C Refractory layer

Claims

1. A paper substrate; A laminate characterized by having a fire-resistant layer laminated integrally on at least one surface of the paper substrate and containing 100 parts by mass of a resin binder and 6 to 200 parts by mass of glass frit.

2. The paper substrate is Core paper and 2. The laminate according to claim 1, which is a corrugated board comprising a liner laminated and integrated onto at least one surface of the core raw paper.

3. 3. The laminate according to claim 1, wherein the resin binder of the fire-resistant layer contains at least one resin selected from the group consisting of ethylene-vinyl acetate copolymer, synthetic resin having a hydrolyzable silyl group, epoxy resin, vinyl chloride resin, and butyl rubber, or a cured resin thereof.

4. 3. The laminate according to claim 1, wherein the resin binder contains a synthetic resin having a hydrolyzable silyl group and / or an ethylene-vinyl acetate copolymer.

5. The laminate according to claim 2, characterized in that the liner to which the fire-resistant layer is laminated and integrated has an elongation of 50% or more when used as a No. 3 dumbbell test piece specified in JIS K6250 and subjected to a tensile test at 50 mm / min in an atmosphere of 23°C and 50% relative humidity in accordance with JIS K6251.

6. A partition wall member comprising the laminate according to claim 1 or 2.

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