JP2013180553A - Scatter prevention member having viscous adhesive layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a scatter prevention member having a viscous adhesive layer which can instantaneously solidify substances to be adhered, can re-paste the substances to be adhered, is excellent in processability such as cut-off in a sheet shape, not peeled off from the substance to be adhered even if exposed at a high-temperature atmosphere such as a fire, can exhibit scatter prevention performance even if exposed to combustion such as a fire when adhered to the substance to be adhered such as glass which is cracked by combustion, and is excellent in abrasion resistance.SOLUTION: A scatter prevention member having a viscous adhesive layer includes the viscous adhesive layer and a non-combustible base material, and the viscous adhesive layer has a viscous before being sintered and has an adhesion after being sintered, and includes a thermal function layer as at least one of outermost layers.

Description

  The present invention relates to an anti-scattering member with an adhesive layer. Specifically, the anti-scattering member with an adhesive layer having sinterability, the adhesive layer has adhesiveness before sintering, has adhesiveness after sintering, In addition, when it is attached to an adherend that breaks due to the burning of glass, etc., it can exhibit anti-scattering properties even when exposed to combustion during a fire, etc., and when used for flame retardant treatment of wood and plastic Relates to an anti-scattering member with an adhesive layer that exhibits excellent flame retardancy and is excellent in thermal functionality.

  A general glass scattering prevention film (for example, refer to Patent Document 1) is attached to prevent the glass from scattering due to crime prevention or impact. However, since such a conventional anti-scattering film uses PET or vinyl chloride as a raw material, it is vulnerable to fire and heat, and burns when exposed to a high-temperature atmosphere such as a fire.

  On the other hand, a non-combustible film can be attached to glass using a general pressure-sensitive adhesive (for example, see Patent Document 2). However, when exposed to a high temperature atmosphere such as a fire, the polymer component of the pressure-sensitive adhesive There exists a problem that it decomposes | disassembles and an incombustible film will peel from an adherend.

  A non-combustible film can be applied to glass using a sinterable adhesive typified by an aqueous dispersion of inorganic particles (see, for example, Patent Document 3), but it is difficult to reattach and is fixed after being applied. Since time and heat treatment are required until it is made, there is a problem that it cannot be fixed instantaneously. Further, there is a problem that it is difficult to cut out a sheet shape such as punching.

  In addition, there is a risk that float glass such as window glass is broken and scattered by heat such as fire. For this reason, if the member to be attached to the float glass such as the window glass does not peel off even in a high temperature atmosphere and does not burn out, it will be possible to express the scattering prevention even if it is exposed to combustion in the event of a fire, Very practical.

  Moreover, the glass scattering prevention film may be easily affected by temperature depending on the place of use. In such a situation, if heat insulation and heat shielding properties can be imparted to the glass scattering prevention film, for example, it becomes possible to develop heat retention against external temperature changes.

Japanese Patent Laid-Open No. 9-176337 Japanese Patent Laying-Open No. 2005-082775 JP 2002-173379 A

  The present invention can fix the adherends instantly, can reattach the adherends, can be cut out in a sheet shape, and is excellent in workability, and in a high-temperature atmosphere such as in a fire. Even when exposed to an adherend that is not peeled off from the adherend and is broken by the burning of glass or the like, it can exhibit anti-scattering properties even when exposed to combustion in the event of a fire, etc. It aims at providing the anti-scattering member with an adhesive layer which is excellent in property.

The anti-scattering member with an adhesive layer of the present invention is
Including an adhesive layer and a non-flammable substrate,
The adhesive layer has adhesiveness before sintering, has adhesiveness after sintering,
A thermal functional layer is included as at least one outermost layer.

  In preferable embodiment, the thickness of the said heat functional layer is 0.1 micrometer-200 micrometers.

  In a preferred embodiment, the thermal functional layer is a heat insulating layer.

  In a preferred embodiment, the heat insulating layer includes a hollow bead structure.

  In a preferred embodiment, the hollow bead structure is a glass bead.

  In a preferred embodiment, the thermal functional layer is a thermal barrier layer.

  In a preferred embodiment, the thermal barrier layer contains at least one selected from a pigment, a ceramic, a metal, and a microballoon.

  In preferable embodiment, the said heat shield layer is at least 1 sort (s) chosen from a coating layer, a sheet layer, a foil layer, a sputter layer, and a vapor deposition layer.

  In a preferred embodiment, the adhesive layer includes sinterable particles and a polymer component.

  In a preferred embodiment, the yield point of the sinterable particles is 250 ° C to 800 ° C.

  In a preferred embodiment, the sinterable particles are formed from at least one component selected from silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, and phosphorus oxide.

  In a preferred embodiment, the sinterable particles have an average particle size of 0.1 μm to 1000 μm.

  In preferable embodiment, the content rate of the said sinterability particle | grain is 1 to 80 weight% with respect to solid content of the said adhesive layer.

  In a preferred embodiment, the polymer component is at least one component selected from a rubber-based polymer, a silicone-based polymer, and an acrylic polymer.

  In a preferred embodiment, the material for forming the polymer component contains a photopolymerization initiator.

  In a preferred embodiment, the adhesive layer is obtained by photopolymerization.

  In preferable embodiment, the said nonflammable base material is an inorganic base material.

  In preferable embodiment, the said inorganic base material is a fibrous inorganic base material.

  In a preferred embodiment, the fibrous inorganic substrate is a glass cloth.

  In preferable embodiment, the scattering prevention member with an adhesive of this invention is a sheet form or a tape form, and thickness is 1 micrometer-1000 micrometers.

  According to the present invention, the adherends can be fixed instantaneously, the adherends can be reattached, and the sheet shape can be cut out, and the workability is excellent. Even when exposed to the bottom of the adherend, and when attached to an adherend that is broken by the combustion of glass or the like, it can exhibit anti-scattering properties even when exposed to combustion during a fire, An anti-scattering member with an adhesive layer that is excellent in thermal functionality can be provided. Since the anti-scattering member with an adhesive layer of this invention is excellent in thermal functionality, it is excellent in high temperature adhesiveness and high temperature adhesiveness.

It is an example of the schematic sectional drawing of the scattering prevention member with an adhesive layer of this invention. It is an example of the schematic sectional drawing of another scattering prevention member with an adhesive agent layer of this invention. It is the schematic of the method for evaluating the scattering prevention property of glass. It is the schematic of the method for evaluating high temperature adhesiveness and high temperature adhesiveness.

  The scattering prevention member with an adhesive layer of this invention contains an adhesive layer and a nonflammable base material.

  The adhesive layer has adhesiveness before sintering and has adhesiveness after sintering. Here, the anti-scattering member with an adhesive layer of the present invention means an anti-scattering member with an adhesive layer before sintering. That is, the anti-scattering member with an adhesive layer of the present invention is sticky as it is, and exhibits adhesiveness by sintering.

  “Pressure-sensitive Adhesive” as used in the present invention is a kind of adhesion as defined in JIS, and is a temporary adhesion, which can be adhered only by applying a slight pressure. Say. In addition, since it has cohesive force and elasticity, it adheres strongly, but can be peeled off from a hard smooth surface. An adhesive is a soft solid and does not change state like an adhesive. Since the pressure-sensitive adhesive wets the adherends as they are and resists peeling, when the adherends are bonded together, the adhesive force that can withstand practical use can be instantly exhibited. That is, the pressure-sensitive adhesive has both a liquid property (fluidity) for getting wet to the adherend and a solid property (cohesive force) that resists peeling. Since the pressure-sensitive adhesive is a soft solid, the contact area with the adherend gradually increases by applying pressure or taking time. And since this softness can be maintained for a long time, it has the property of being peeled off when it is desired to peel off.

  The term “adhesive” as used in the present invention refers to the property that the surfaces of the same or different kinds of solids can be bonded and integrated as defined by JIS. The adhesive is a fluid liquid when the adherends are bonded together, and wets and becomes familiar with the adherends. Thereafter, it changes to a solid by heating or chemical reaction, and is firmly bonded at the interface between adherends to exert a force to resist peeling. That is, the adhesive wets with a liquid and adheres with a solid.

  The anti-scattering member with an adhesive layer of the present invention includes a thermal functional layer as at least one outermost layer. The anti-scattering member with an adhesive layer of the present invention may have the thermal functional layer as one outermost layer or both outermost layers.

  Any appropriate layer can be adopted as the thermal functional layer as long as it can exhibit thermal functionality. As such a heat functional layer, preferably, a heat insulating layer, a heat shielding layer, or the like is used.

  The thickness of the thermal functional layer is preferably 0.1 μm to 200 μm, more preferably 0.5 μm to 150 μm, and further preferably 1 μm to 100 μm. If the thickness of the thermal functional layer is within the above range, excellent thermal functionality can be exhibited, and excellent high-temperature tackiness and high-temperature adhesiveness can be exhibited.

  Any appropriate layer can be adopted as the heat insulating layer as long as the heat insulating effect is obtained.

  The thermal insulation layer preferably comprises a hollow bead structure. The hollow bead structure refers to a structure including a gas layer inside the beads. Examples of the gas layer include air, nitrogen, and a rare gas.

  Examples of such hollow bead structures include hollow ceramic beads, hollow silica beads, shirasu balloons, glass beads, and hollow styrene beads. Among these, glass beads are particularly preferable.

  More preferably, the heat insulating layer is a resin composition containing a hollow bead structure.

  The resin contained in such a resin composition is not particularly limited as long as it can hold a heat insulating material made of the hollow beads and can be molded into a predetermined shape. For example, polyolefin resin, acrylic resin, urethane resin, polyester resin, polystyrene, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyamide resin, epoxy resin, phenol resin, fluorine resin, and the like can be given.

  The heat insulating layer may further contain any appropriate additive depending on the purpose.

  Examples of the additive include a photopolymerization initiator, a silane coupling agent, a release agent, a curing agent, a curing accelerator, a diluent, an anti-aging agent, a denaturing agent, a surfactant, a dye, a pigment, and a discoloration preventing agent. UV absorbers, softeners, stabilizers, plasticizers, antifoaming agents and the like. The kind, number, and amount of additives that can be contained in the heat insulating layer can be appropriately set depending on the purpose.

  The thickness of a heat insulation layer becomes like this. Preferably they are 0.1 micrometer-200 micrometers, More preferably, they are 0.5 micrometer-150 micrometers, More preferably, they are 1 micrometer-100 micrometers. If the thickness of the heat insulating layer is within the above range, excellent heat insulating properties can be exhibited, and excellent high temperature tackiness and high temperature adhesive properties can be exhibited.

  Any appropriate layer can be adopted as the heat shielding layer as long as it can exhibit a heat shielding effect. Specifically, the heat shielding effect refers to an effect of suppressing the generation of thermal energy by reflecting most of infrared rays.

  The thermal barrier layer is preferably a layer having an average reflectance of 50% or more for light having an arbitrary wavelength in the range of 780 nm to 2100 nm.

  The heat shielding layer may be composed of only one layer or may be composed of two or more layers.

  The thermal barrier layer preferably contains any appropriate thermal barrier material. Examples of such a heat shielding material include pigments, ceramics, metals, and microballoons. Such a heat shielding material may be used alone or in combination of two or more.

  When the heat shielding material is particulate, the average particle diameter is preferably 0.005 to 10 μm, more preferably 0.01 to 1 μm. When the heat shielding material is in the form of particles, if the average particle diameter is within the above range, the heat shielding property of the heat shielding layer can be expressed at a high level.

  Any appropriate pigment can be adopted as the pigment. Examples of the pigment include inorganic pigments. Preferred examples of the inorganic pigment include white pigments such as titanium oxide, manganese dioxide, and cobalt oxide; and light color pigments using a white pigment in combination with other pigments.

  Any appropriate form of ceramic may be employed as the ceramic.

  Any appropriate metal can be adopted as the metal. Examples of the metal include aluminum and copper.

  A microballoon is a hollow fine particle having a cavity inside. Examples of the microballoon include a ceramic balloon made of glass or a titania composite. For example, glass beads are preferable.

  The thermal barrier layer may contain any appropriate additive. Examples of such additives include plasticizers, fillers, lubricants, heat stabilizers, antifogging agents, stabilizers, antioxidants, surfactants, resins, solvents, and the like.

  The thermal barrier layer can take any suitable form. The heat shielding layer is preferably at least one selected from a coating layer, a sheet layer, a foil layer, a sputtered layer, and a vapor deposition layer.

  When the heat-shielding layer is a coating layer, the heat-shielding layer can be formed by applying any appropriate heat-shielding paint.

  When the heat shielding layer is a sheet layer, examples of the heat shielding layer include a sheet layer containing a heat shielding material. Such a sheet layer may be formed by any appropriate forming method.

  When the heat shielding layer is a foil layer, examples of the heat shielding layer include a foil layer made of a metal foil such as an aluminum foil and a copper foil.

  When the thermal barrier layer is a sputter layer or a vapor deposition layer, it can be formed by any appropriate sputtering method or vapor deposition method.

  The thickness of the heat shield layer is preferably 0.1 μm to 100 μm, more preferably 1 μm to 100 μm. If the thickness of the heat-shielding layer is within the above range, excellent heat-shielding properties can be expressed, and excellent high-temperature tackiness and high-temperature adhesiveness can be expressed.

  The adhesive layer preferably includes sinterable particles and a polymer component.

  FIG. 1 is an example of a schematic cross-sectional view of the anti-scattering member with an adhesive layer of the present invention. The scattering prevention member 1000 with an adhesive layer of the present invention includes an adhesive layer 100, a nonflammable substrate 200, and a thermal functional layer 300, and the adhesive layer 100 is sintered in the polymer component 10. Particles 20 are dispersed. The anti-scattering member with an adhesive layer of the present invention may have a plurality of adhesive layers, may have a plurality of nonflammable substrates, or a plurality of thermal functional layers. You may have. For example, as shown in FIG. 2, the anti-scattering member with an adhesive layer 1000 of the present invention may include an adhesive layer 100 on both surfaces of the non-flammable substrate 200. In FIG. 2, the thermal functional layer 300 is included as one outermost layer.

  The content ratio of the sinterable particles in the adhesive layer is preferably 1% by weight to 80% by weight, more preferably 5% by weight to 70% by weight, based on the solid content of the adhesive layer. %, More preferably 10% to 60% by weight, and particularly preferably 20% to 50% by weight. When the content ratio of the sinterable particles in the adhesive layer is within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high-temperature atmosphere such as a fire can be sufficiently exhibited.

  The sinterable particles in the adhesive layer preferably include two or more types of sinterable particles having different yield points. When the sinterable particles in the adhesive layer contain two or more kinds of sinterable particles having different yield points, the adhesive layer can exhibit very excellent heat resistance.

  The yield point of the sinterable particles in the adhesive layer is preferably 250 ° C to 800 ° C, more preferably 250 ° C to 700 ° C, still more preferably 250 ° C to 600 ° C, and particularly preferably. Is 250 ° C to 500 ° C. When the yield point of the sinterable particles in the adhesive layer is within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high-temperature atmosphere such as in a fire can be sufficiently exhibited.

  Among the two or more types of sinterable particles having different yield points, the yield point of the sinterable particles having the lowest yield point is preferably 250 ° C to 800 ° C, more preferably 250 ° C to 700 ° C. More preferably, it is 250 to 600 ° C, and particularly preferably 250 to 500 ° C. When the yield point of the sinterable particles having the lowest yield point falls within the above range, the adhesive layer can exhibit much more excellent heat resistance.

  Any appropriate sinterable particles can be adopted as the sinterable particles in the adhesive layer. Such sinterable particles are preferably inorganic particles having sinterability, and more preferably, silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, phosphorus oxide. Sinterable particles formed from at least one component selected from By adopting such sinterable particles, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as in a fire can be sufficiently exhibited.

  The average particle diameter of the sinterable particles in the adhesive layer is preferably 0.1 μm to 1000 μm, more preferably 0.5 μm to 500 μm, still more preferably 1 μm to 300 μm, and particularly preferably. 2 μm to 150 μm. When the average particle diameter of the sinterable particles in the adhesive layer is within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as in a fire can be fully exhibited. .

  The polymer component in the adhesive layer preferably contains an antioxidant. When the polymer component in the adhesive layer contains an antioxidant, the adhesive layer can exhibit very excellent heat resistance.

  The content ratio of the antioxidant in the adhesive layer is preferably 0.1% by weight to 10% by weight, more preferably 0.3% by weight, based on the solid content of the adhesive layer. -8% by weight, more preferably 0.5% by weight to 6% by weight, and particularly preferably 0.7% by weight to 5% by weight. When the content ratio of the antioxidant falls within the above range, the adhesive layer can exhibit much more excellent heat resistance. The antioxidant may be only one kind or two or more kinds.

  Any appropriate antioxidant can be adopted as the antioxidant. As such an antioxidant, Preferably, at least 1 sort (s) chosen from a phenolic antioxidant, an amine antioxidant, an aminoether antioxidant, and a phosphorus antioxidant is mentioned.

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4 -N-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL-α-tocopherol, steari monocyclic phenolic compounds such as β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4, 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-) -T-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis [3- (3-t-butyl-4-hydride) Xyl-5-methylphenyl) propionate], triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl); ) Isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate Tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4- Tricyclic phenolic compounds such as hydroxybenzyl) benzene; tetracyclic [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] tetracyclic phenolic compounds such as methane; bis (3,5-di -T-butyl-4-hydroxybenzylphosphonate ethyl) phosphorus-containing phenol compounds such as calcium and bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) nickel;

  Examples of amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, Polycondensate of 6,6-tetramethylpiperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [ {6- (1,1,3 3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6 , 6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6 , 6-Tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-pepyridyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-butyl malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5, 5-tetramethylpiperazinone (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl- 4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl -3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6 , 6-Pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1, 2,3,4-butanetetracarbo Sylate, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6 Chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine And 1,2-dibromoethane condensate, N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl and the like.

  Examples of amino ether antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-he Tyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-nonyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-dodecyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite. , Cyclic neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl Tris (dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite, tris Such as 2,4-di -t- butyl-phenyl) phosphite.

  The polymer component in the adhesive layer preferably has a crosslinked structure. When the polymer component in the adhesive layer has a cross-linked structure, the adhesive layer can exhibit excellent heat resistance.

  The crosslinked structure can be constructed by any appropriate method. The cross-linked structure is preferably constructed by including a cross-linkable monomer in all monomer components constituting the polymer component. In this case, the content ratio of the crosslinkable monomer in all the monomer components constituting the polymer component is preferably 2.0% by weight to 60% by weight, more preferably 3.0% by weight to 57% by weight. More preferably, the content is 5.0% to 55% by weight, particularly preferably 7.0% to 53% by weight, and most preferably 8.0% to 50% by weight. When the content ratio of the crosslinkable monomer is within the above range, the adhesive layer can exhibit much more excellent heat resistance.

  The crosslinkable monomer may be only one type or two or more types.

  As the crosslinkable monomer, any appropriate crosslinkable monomer can be adopted as long as it is a monomer capable of constructing a crosslinked structure. Such a crosslinkable monomer is preferably a crosslinkable monomer having at least one functional group selected from an acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a vinyl group, and an amino group. Specific examples of such a crosslinkable monomer include, for example, a polyfunctional monomer described later.

  The content ratio of the polymer component in the adhesive layer is preferably 20% to 99% by weight, more preferably 30% to 95% by weight, based on the solid content of the adhesive layer. More preferably 40 to 90% by weight, particularly preferably 50 to 80% by weight. When the content ratio of the polymer component in the adhesive layer is within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as in a fire can be sufficiently exhibited.

  As the polymer component in the adhesive layer, any appropriate polymer component can be adopted as long as it is a polymer component capable of expressing tackiness. Such a polymer component is preferably at least one component selected from a rubber-based polymer, a silicone-based polymer, and an acrylic polymer. The polymer component in the adhesive layer may be only one type or two or more types.

  As the rubber polymer, any appropriate rubber polymer capable of exhibiting adhesiveness can be adopted.

  As the silicone polymer, any appropriate silicone polymer that can exhibit adhesiveness can be adopted.

  As the acrylic polymer, any appropriate acrylic polymer capable of exhibiting adhesiveness can be adopted. The acrylic polymer can be preferably formed from a monomer component essentially comprising an acrylic monomer. The content of the acrylic monomer in the total monomers that can be used to form the acrylic polymer is preferably 50% to 100% by weight, more preferably 55% to 98% by weight, and even more preferably. It is 60 to 95% by weight, particularly preferably 65 to 93% by weight. Only one type of acrylic monomer may be used, or two or more types may be used.

  As an acryl-type monomer, Preferably, the (meth) acrylic-acid alkylester which has an alkyl group is mentioned. Only one (meth) acrylic acid alkyl ester having an alkyl group may be used, or two or more may be used in combination. “(Meth) acryl” means “acryl” and / or “methacryl”.

  Examples of (meth) acrylic acid alkyl ester having an alkyl group include (meth) acrylic acid alkyl ester having a linear or branched alkyl group, (meth) acrylic acid alkyl ester having a cyclic alkyl group, and the like. Is mentioned. In addition, the (meth) acrylic acid alkyl ester here means monofunctional (meth) acrylic acid alkyl ester.

  Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( (Meth) acrylic acid decyl, (meth) acrylic acid isodecyl, (meth) a Undecyl silylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester having 1 to 20 carbon atoms, such as octadecyl acid, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate. Among these, Preferably, it is a (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in the alkyl group, and more preferably a (meth) acrylic acid alkyl ester having 2 to 10 carbon atoms in the alkyl group. .

  Examples of the (meth) acrylic acid alkyl ester having a cyclic alkyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

  A polyfunctional monomer can be used as a monomer component that can form an acrylic polymer. Any appropriate multifunctional monomer can be adopted as the multifunctional monomer. By employing a polyfunctional monomer, a crosslinked structure can be imparted to the acrylic polymer. Only 1 type may be used for a polyfunctional monomer and it may use 2 or more types together.

  Examples of the polyfunctional monomer include 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and (poly) ethylene glycol. Di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester Acrylate, urethane acrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol (meth) acrylate, 2-hydroxyethyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl ether 2-isocyanatoethyl acrylate, isocyanate ethyl (meth) acrylate, isocyanate (meth) acrylate, triglycidyl isocyanurate, (meth) acrylic acid, monohydroxy phthalate Ethyl (meth) acrylate, hexahydroxyphthalic acid monohydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, 1,4-butanediol diglycidyl Ether, 1,2-ethanediol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenyl Methane triisocyanate, methyl triisocyanate silane, tetraisocyanate silane, polyisocyanate, oxalic acid, Ronic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, 1,2,3-propanetricarboxylic acid, ethylene glycol, diethylene glycol, propylene glycol, dipropylene Glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2,4-butanetriol, polyoxypropylenetriol, trimethylolethane, tri Methylolpropane, aminomethanol, 2-aminoethanol, 3-amino-1-propanol, diethanolamine, triethanolamine, N, N-di-n-butylethanolamine, ethylenediamine, hexamethylenediamine, tolylene Mines, hydrogenated tolylenediamine, diphenylmethanediamine, hydrogenated diphenylmethanediamine, tolidineamine, naphthalenediamine, isophoronediamine, xylenediamine, hydrogenated xylenediamine, vinylamine, 2- (2-thienyl) vinylamine, 1- (allyloxy) vinylamine , Allyl alcohol, 1,3-butadiene monoepoxide, 1-vinyl-3,4-epoxycyclohexane and the like. Among these, acrylate-based polyfunctional monomers are preferable because of high reactivity, and 1,9-nonanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are more preferable. 4-hydroxybutyl acrylate glycidyl ether.

  As a monomer component capable of forming an acrylic polymer, a polar group-containing monomer can be used. Any appropriate polar group-containing monomer can be adopted as the polar group-containing monomer. By adopting the polar group-containing monomer, it becomes possible to improve the cohesive strength of the acrylic polymer or to improve the adhesive strength of the acrylic polymer. Only 1 type may be used for a polar group containing monomer, and it may use 2 or more types together.

  Examples of polar group-containing monomers include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and other carboxyl group-containing monomers or anhydrides thereof (such as maleic anhydride); (meth) acrylic Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, vinyl alcohol, allyl alcohol, etc .; (meth) acrylamide, N, N-dimethyl Amide group-containing monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, (meth) acrylic acid Zimechi Amino group-containing monomers such as aminoethyl and t-butylaminoethyl (meth) acrylate; Glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; Cyano groups such as acrylonitrile and methacrylonitrile Containing monomer: N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, N- Heterocycle-containing vinyl monomers such as vinyl oxazole; (meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; monomers containing sulfonic acid groups such as sodium vinyl sulfonate ; 2-phosphoric acid group-containing monomers such as hydroxyethyl acryloyl phosphate; and the like; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide. The polar group-containing monomer is preferably a carboxyl group-containing monomer or an anhydride thereof, and more preferably acrylic acid.

  As a monomer component capable of forming an acrylic polymer, other copolymerizable monomers can be used. Any appropriate other copolymerizable monomer can be adopted as the other copolymerizable monomer. By employing other copolymerizable monomers, it becomes possible to improve the cohesive strength of the acrylic polymer or to improve the adhesive strength of the acrylic polymer. Other copolymerizable monomers may be used alone or in combination of two or more.

  Other copolymerizable monomers include, for example, (meth) acrylic acid alkyl esters such as (meth) acrylic acid esters having an aromatic hydrocarbon group such as phenyl (meth) acrylate; vinyl such as vinyl acetate and vinyl propionate Esters; aromatic vinyl compounds such as styrene and vinyltoluene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; methoxyethyl (meth) acrylate, (meth) (Meth) acrylic acid alkoxyalkyl monomers such as ethoxyethyl acrylate; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate; cyclohexyl Maleimide, imide group-containing monomers such as isopropyl maleimide; fluorine-containing (meth) acrylate; 2-methacryloyloxy isocyanate group-containing monomers such as acryloyloxyethyl isocyanate silicon atom-containing (meth) acrylate; and the like.

  The weight average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably 400,000 to 3,000,000. The weight average molecular weight of the acrylic polymer can be determined by a gel permeation chromatography method (GPC method).

  The adhesive layer may contain any appropriate other component in addition to the above-mentioned antioxidant within the range not impairing the effects of the present invention, in addition to the sinterable particles and the polymer component. Such other components may contain only 1 type, and may contain 2 or more types.

  Other components include, for example, other polymer components, softeners, anti-aging agents, curing agents, plasticizers, fillers, thermal polymerization initiators, photopolymerization initiators, ultraviolet absorbers, light stabilizers, colorants ( Pigments and dyes), solvents (organic solvents), surfactants (eg, ionic surfactants, silicone surfactants, fluorosurfactants, etc.), crosslinking agents (eg, polyisocyanate crosslinking agents, silicones) System crosslinking agents, epoxy crosslinking agents, alkyl etherified melamine crosslinking agents, etc.). In addition, a thermal polymerization initiator and a photoinitiator may be contained in the material for forming a polymer component.

  Any appropriate thermal polymerization initiator can be adopted as the thermal polymerization initiator. Examples of such thermal polymerization initiators include peroxide polymerization initiators such as hydrogen peroxide, benzoyl peroxide, and t-butyl peroxide; 2,2′-azobis-2-methylpropioaminate 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-N, N′-dimethyleneisobutylaminate, 2,2′-azobisisobutyronitrile, 2,2 And azo polymerization initiators such as' -azobis-2-methyl-N- (2-hydroxyethyl) propionamide; Only one type of thermal polymerization initiator may be used, or two or more types may be used in combination. Such a thermal polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent. Examples of such a reducing agent include ionized salts such as sulfites, hydrogen sulfites, iron, copper, and cobalt salts; amines such as triethanolamine; reducing sugars such as aldose and ketose;

  The content ratio of the thermal polymerization initiator in the adhesive layer is preferably 5 parts by weight or less, more preferably 0 with respect to the monomer component used to form the polymer component of the adhesive layer. 0.01 parts by weight to 5 parts by weight, and more preferably 0.05 parts by weight to 3 parts by weight.

  Arbitrary appropriate photoinitiators can be employ | adopted as a photoinitiator. Examples of such photopolymerization initiators include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime systems. Examples include photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators. Only 1 type may be used for a photoinitiator and it may use 2 or more types together.

  Examples of the ketal photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals), etc.). It is done. Examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (for example, trade name “Irgacure 184” (manufactured by Ciba Specialty Chemicals), etc.), 2,2-diethoxyacetophenone, 2,2- Examples include dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4- (t-butyl) dichloroacetophenone. Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the acylphosphine oxide photopolymerization initiator include trade name “Lucirin TPO” (manufactured by BASF). Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. . Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

  The content ratio of the photopolymerization initiator in the adhesive layer is preferably 5 parts by weight or less, more preferably 0 with respect to the monomer component used to form the polymer component of the adhesive layer. 0.01 parts by weight to 5 parts by weight, and more preferably 0.05 parts by weight to 3 parts by weight.

  The adhesive layer has tackiness before sintering. The adhesive layer has a peel rate of 50 mm / min, a peel angle of 180 °, and an adhesive force at 23 ° C. of preferably 0.1 N / 10 mm to 15 N / 10 mm before the sintering. Preferably they are 0.5N / 10mm-10N / 10mm, More preferably, they are 1N / 10mm-8N / 10mm, Especially preferably, they are 2N / 10mm-6N / 10mm. When the adhesive strength is within the above range, the adherends can be fixed instantly, the adherends can be reattached, and the sheet can be cut out in a sheet shape. Can exhibit high tackiness. A specific method for measuring the adhesive strength will be described later.

  The adhesive layer has sinterability. Arbitrary appropriate temperature can be employ | adopted for sintering temperature according to the kind and quantity of sinterable particle | grains contained in an adhesive agent layer.

  The scattering prevention member with an adhesive layer of this invention contains a nonflammable base material.

  In the present invention, the “nonflammable substrate” refers to a substrate containing at least a component that may remain as an incombustible after combustion (sometimes referred to as “nonflammable component”). . As such an incombustible component, any component that can remain as an incombustible material after combustion may be used. For example, a component that remains as an incombustible material after combustion in the same form without any reaction during combustion ( (Sometimes referred to as “non-reactive non-flammable components”), or components that can react as a non-combustible material during combustion and remain as non-combustible materials after combustion (“reactive non-combustible component”) Or the like)). In addition, the reactive incombustible component is not a non-combustible material itself, but a component that can be reacted by heat or the like during combustion to become a non-combustible material. Other components may be related.

  The non-flammable base material may be a base material composed only of non-flammable components, and the non-flammable component and the component that is burned down by the reaction during combustion and the like and does not remain after combustion ("burnable component" May be referred to)).

Specifically, the non-combustible substrate includes the following.
(1) A base material composed only of non-reactive nonflammable components.
(2) The base material comprised by the composition containing a non-reactive type nonflammable component and a burnout component.
(3) A substrate composed only of reactive noncombustible components.
(4) A base material composed of a composition containing a reactive nonflammable component and a burnable component.
(5) The base material comprised only from the non-reactive nonflammable component and the reactive nonflammable component.
(6) The base material comprised by the composition containing a non-reactive nonflammable component and a reactive nonflammable component, and a burnout component.

  An incombustible component may be used independently and may be used in combination of 2 or more type.

  Each component such as a non-reactive nonflammable component or a reactive nonflammable component may be used alone or in combination of two or more.

  The burnout component may be used alone or in combination of two or more.

  Examples of the incombustible component include glass cloth, glass fiber, metal net, metal fiber, layered clay mineral, silica particle, metal particle, silicone, and siloxane polymer. As the incombustible component, a glass cloth, a glass fiber, a metal net, and a metal fiber product are particularly preferable in that the incombustible material can exhibit high toughness after combustion. That is, when a non-combustible base material containing a non-combustible component such as glass cloth, glass fiber, metal net, or metal fiber material is used, the anti-scattering member with an adhesive layer has a high level of anti-glass scattering property. It can be demonstrated.

  The burnout component includes any suitable polymer component such as, for example, polymer particles. Examples of such polymer components include acrylic resins; urethane resins; polyethylene (PE), polypropylene (PP), ethylene-propylene copolymers, ethylene-vinyl acetate copolymers (EVA), and the like α- Olefin resin containing olefin as monomer component; Polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); Vinyl acetate resin; Polyphenylene sulfide (PPS); Polyamide (nylon) Amide resins such as wholly aromatic polyamide (aramid); polyimide resins; polyether ether ketone (PEEK); epoxy resins; oxetane resins; vinyl ether resins; natural rubber; Such a polymer component may be used independently and may be used in combination of 2 or more type.

  As the nonflammable substrate, any appropriate substrate can be adopted as long as it is a nonflammable substrate. For example, an inorganic base material, an organic inorganic composite base material, etc. are mentioned. As the nonflammable substrate, an inorganic substrate is preferable.

  Any appropriate inorganic substrate can be adopted as the inorganic substrate. Preferably, it can permeate | transmit liquid substances, such as a monomer and a syrup-like polymer. Examples of such an inorganic base material include inorganic base materials having voids such as a fibrous inorganic base material and a network-like inorganic base material.

  Examples of the form of the fibrous inorganic substrate include woven fabric and nonwoven fabric.

  Specific examples of the fibrous inorganic base material include glass cloth, asbestos, carbon fiber, and fibrous metal oxide.

  Specific examples of the network-like inorganic base material include a metal net.

  Arbitrary appropriate thickness can be employ | adopted for the thickness of an inorganic base material with the kind. For example, it is preferably 1 μm to 500 μm.

  Arbitrary appropriate components, such as a forming material component of an adhesive layer, may be contained in the void portion of the inorganic base material.

  Arbitrary appropriate forms can be employ | adopted for the scattering prevention member with an adhesive bond layer of this invention. Examples of the form of the anti-scattering member with an adhesive layer of the present invention include a sheet form and a tape form. When the form of the anti-scattering member with an adhesive layer of the present invention is a sheet, it can be used as an adhesive sheet. The scattering prevention member with an adhesive layer of the present invention may have a form in which a sheet or tape is wound into a roll. Moreover, the anti-scattering member with an adhesive layer of the present invention may have a form in which sheets or tapes are laminated.

  When the scattering prevention member with an adhesive layer of the present invention is in a sheet form, the thickness is preferably 1 μm to 1000 μm, more preferably 5 μm to 500 μm, still more preferably 10 μm to 300 μm, and particularly preferably. Is 20 μm to 200 μm. If the thickness of the anti-scattering member with an adhesive layer of the present invention is within the above range, the handleability as an anti-scattering member with an adhesive layer is excellent.

  The scattering prevention member with an adhesive layer of the present invention can be produced by any appropriate method.

  The anti-scattering member with an adhesive layer of the present invention is preferably produced by laminating an adhesive layer, a non-combustible base material, and a thermal functional layer, or an adhesive layer forming material and an incombustible material. A method of manufacturing an adhesive layer by forming the adhesive layer by a curing reaction after laminating the adhesive substrate and the thermal functional layer, and a forming material for the adhesive layer, a nonflammable substrate, and a forming material for the thermal functional layer. Examples of the method include a method in which an adhesive layer and a heat functional layer are formed by lamination reaction after being laminated.

  As a preferable production method of the pressure-sensitive adhesive layer in the anti-scattering member with an adhesive layer of the present invention, for example, a polymerizable composition containing a monomer component used for forming a polymer component and any appropriate photopolymerization initiator A polymerizable syrup is prepared by polymerizing a part of the polymer, and sinterable particles are added to the polymerizable syrup and dispersed uniformly, and then coated on any appropriate substrate (separator, etc.) The method of irradiating and photopolymerizing (curing) is mentioned. The anti-scattering member with an adhesive layer of the present invention can be produced by laminating a nonflammable substrate on the pressure-sensitive adhesive layer thus obtained. Moreover, in the preferable manufacturing method of the said adhesive layer, the scattering prevention member with an adhesive layer of this invention can be manufactured by using a nonflammable base material as a base material to apply.

  Arbitrary appropriate conditions can be employ | adopted about conditions, such as a light source in the case of light irradiation, irradiation energy, an irradiation method, and irradiation time.

  Examples of active energy rays used for light irradiation include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron rays, and ultraviolet rays. Preferably it is an ultraviolet-ray.

  Examples of irradiation with active energy rays include irradiation with a black light lamp, a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, and the like.

  Heating may be performed during the polymerization. Any appropriate heating method can be adopted as the heating method. Examples of the heating method include a heating method using an electric heater, a heating method using electromagnetic waves such as infrared rays, and the like.

  As the heat insulating layer, an available film or sheet-like heat insulating layer may be used as it is, or may be produced by any appropriate method. When producing a heat insulation layer, Preferably, it can produce by apply | coating the resin composition (for example, resin composition containing a hollow bead structure etc.) which is a forming material, and drying as needed. When applying the resin composition as a forming material, any appropriate solvent may be added as necessary.

  Arbitrary appropriate means can be employ | adopted as a means to apply | coat a resin composition. Examples of such means include gravure coating, spray coating, dip coating, and the like.

  When drying after apply | coating a resin composition, the heating temperature for drying becomes like this. Preferably it is 30 to 180 degreeC, More preferably, it is 50 to 150 degreeC. The heating time for drying is preferably 10 seconds to 10 minutes.

  In producing the heat insulating layer, after applying the resin composition, it may be cured by ultraviolet irradiation, heating or the like, if necessary. For example, when a resin composition containing an ultraviolet curable resin is used, it is preferably cured by ultraviolet irradiation, and when a resin composition containing a thermosetting resin is used, it is preferably cured by heating.

  The heat insulation layer may be aged for a required time after production. By aging, the peel strength of the coated film can be improved.

  When the heat-shielding layer is a coating layer, the heat-shielding layer can be formed by applying any appropriate heat-shielding paint. Specifically, for example, the thermal barrier layer is formed by applying a thermal barrier coating on the surface of the non-flammable substrate in the laminate of the adhesive layer and the non-flammable substrate. After applying the thermal barrier paint, it is dried if necessary. As the thermal barrier coating, a commercially available thermal barrier coating may be used, or any appropriate thermal barrier and other additives as required may be mixed with any appropriate solvent. As the solvent, for example, an organic solvent and water are preferable. As the solvent, only one kind of solvent may be used, or a mixed solvent of two or more kinds of solvents may be used. In the case of mixing the heat shielding material and, if necessary, other additives and the solvent, the heat shielding material may be mixed in a powder state, or may be mixed in a slurry form or a sol form.

  Arbitrary appropriate means can be employ | adopted as a means to apply a thermal-insulation coating material. Examples of such means include gravure coating, spray coating, dip coating, and the like. After applying the thermal barrier paint, the coated product can be dried as necessary. The heating temperature for drying is preferably 50 to 200 ° C. The heating time for drying is preferably 10 seconds to 60 minutes. After drying, aging may be performed for a required time. By aging, the peel strength of the coated film can be improved.

  When the heat shielding layer is a sheet layer, the sheet layer can be formed by any appropriate forming method. Specifically, for example, a sheet-like material is formed by any appropriate forming method, and the sheet-like material is pasted on the surface of the non-combustible substrate in the laminate of the adhesive layer and the non-combustible substrate. Match.

  When the heat shielding layer is a foil layer, specifically, for example, a foil-like material such as a metal foil is prepared in advance, and the surface of the incombustible substrate in the laminate of the adhesive layer and the incombustible substrate The foil-like material is bonded together.

  When the thermal barrier layer is a sputter layer, for example, it can be formed by any appropriate sputtering method.

  When the thermal barrier layer is a vapor deposition layer, it can be formed by any appropriate vapor deposition method, for example.

  The production of the heat insulating layer can be performed at any appropriate timing when the anti-scattering member with an adhesive layer of the present invention is produced.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The separators and cover separators used in each of the following examples were each a biaxially stretched polyethylene terephthalate film (trade name “MRN38”, Mitsubishi Chemical Polyester Film) with a thickness of 38 μm, on which one side was subjected to a silicone-based release treatment. Used). When performing various evaluations, the separator and the cover separator were appropriately peeled off.

[Synthesis Example 1] (Preparation of photopolymerizable syrup (A))
As monomer components, 2-ethylhexyl acrylate: 90 parts by weight, acrylic acid: 10 parts by weight, photopolymerization initiator (trade name “Irgacure 651”, manufactured by BASF): 0.05 part by weight, and photopolymerization initiator (trade name) "Irgacure 184" (manufactured by BASF): Nitrogen gas after stirring 0.05 parts by weight in a four-necked separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube until uniform Was carried out for 1 hour to remove dissolved oxygen. Thereafter, ultraviolet light was irradiated from the outside of the flask with a black light lamp to polymerize, and when the viscosity reached an appropriate level, the lamp was turned off and nitrogen blowing was stopped to partially polymerize at a polymerization rate of 3.5%. A photopolymerizable syrup (A) as a composition was prepared.

[Synthesis Example 2] (Preparation of anti-scattering member with adhesive layer (A))
Photopolymerizable syrup (A) obtained in Synthesis Example 1: 100 parts by weight of 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight and phosphoric acid frit (VY0144, manufactured by Takara Standard Co., Ltd.) Bending point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A glass cloth (manufactured by Unitika, trade name: E10T-4W, thickness: 100 μm) was placed on the coated surface to form a laminate.
On the obtained laminate, a cover separator is bonded in a form in which the release treatment surface is in contact, a black light lamp is used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) are irradiated from both sides for 5 minutes to be cured, It was set as the sheet-like adhesive agent layer scattering prevention member (A).

[Synthesis Example 3] (Preparation of anti-scattering member with adhesive layer (B))
Photopolymerizable syrup obtained in Synthesis Example 1 (A): 100 parts by weight of 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight and enamel frit (CY0098M1, manufactured by Takara Standard Co., Ltd., yield point) : 500 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A glass cloth (manufactured by Unitika, trade name: E10T-4W, thickness: 100 μm) was placed on the coated surface to form a laminate.
On the obtained laminate, a cover separator is bonded in a form in which the release treatment surface is in contact, a black light lamp is used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) are irradiated from both sides for 5 minutes to be cured, It was set as the scattering prevention member (B) with a sheet-like adhesive layer.

[Example 1]
The cover separator on the glass cloth side of the anti-scattering member with adhesive layer (A) obtained in Synthesis Example 2 is peeled to expose the glass cloth side, and a heat insulating paint (acrylic resin emulsion paint containing glass beads, A trade name “Suncoat Thermoshield” (manufactured by Nagashima Special Paint Co., Ltd.) was applied onto the exposed surface and dried at 100 ° C. for 5 minutes to obtain a sheet-like anti-scattering member (1) with an adhesive layer. The thickness of the heat insulation layer was 20 μm.
The evaluation results are shown in Table 1.

[Example 2]
The cover separator on the glass cloth side of the anti-scattering member with adhesive layer (B) obtained in Synthesis Example 3 is peeled to expose the glass cloth side, and a heat insulating paint (acrylic resin emulsion paint containing glass beads, The product name “Suncoat Thermoshield” (manufactured by Nagashima Special Paint Co., Ltd.) was applied onto the exposed surface and dried at 100 ° C. for 5 minutes to obtain a sheet-like adhesive member with an adhesive layer (2). The thickness of the heat insulation layer was 20 μm.
The evaluation results are shown in Table 1.

Example 3
The cover separator on the glass cloth side of the anti-scattering member with adhesive layer (A) obtained in Synthesis Example 2 is peeled off to expose the glass cloth side, and a heat-insulating paint (manufactured by Nippon Special Paint Co., Ltd., Parathermo) ) Was applied onto the exposed surface and dried at 100 ° C. for 5 minutes to obtain a sheet-like adhesive member with anti-adhesive layer (3). The thickness of the heat shield layer was 20 μm.
The evaluation results are shown in Table 1.

Example 4
The cover separator on the glass cloth side of the anti-scattering member with adhesive layer (B) obtained in Synthesis Example 3 is peeled off to expose the glass cloth side, and a heat-insulating paint (manufactured by Nippon Special Paint Co., Ltd., Parathermo) ) Was applied on the exposed surface and dried at 100 ° C. for 5 minutes to obtain a sheet-like anti-scattering member with an adhesive layer (4). The thickness of the heat shield layer was 20 μm.
The evaluation results are shown in Table 1.

Example 5
The cover separator on the glass cloth side of the anti-scattering member with adhesive layer (A) obtained in Synthesis Example 2 is peeled off to expose the glass cloth side, and a highly transparent heat insulating film (produced by Lintec Corporation, heat cut “IR −50HD ”) was pasted onto the exposed surface to obtain a sheet-like anti-scattering member (5) with an adhesive layer. The thickness of the highly transparent heat insulating film was 78 μm.
The evaluation results are shown in Table 1.

[Comparative Example 1]
The anti-scattering member with adhesive layer (A) obtained in Synthesis Example 2 was used as the anti-scattering member with adhesive layer (C1).
The evaluation results are shown in Table 1.

<Evaluation of glass shatter prevention>
As shown in FIG. 3, the anti-scattering member with an adhesive layer obtained in Examples / Comparative Examples was cut into 100 mm × 100 mm squares and attached to 100 mm × 100 mm square, 3 mm thick float glass, and the laminate and did. This laminate was placed horizontally so that the anti-scattering member with an adhesive layer was on top and the glass was on the bottom, and heat of about 700 ° C. was applied to the entire surface using a cone calorie tester. After 5 minutes, the laminate was removed from the corn calorie tester, returned to room temperature (23 ° C.) and stood vertically. It was evaluated whether or not the broken glass collapsed due to thermal expansion.
○: Broken glass does not collapse.
X: Broken glass collapses.

<Evaluation of high-temperature tackiness and high-temperature adhesiveness>
(High temperature tack test * 1)
The anti-scattering member with an adhesive layer obtained in Examples and Comparative Examples was cut out to 30 mm × 50 mm, bonded to a glass plate of 30 mm × 30 mm, and the anti-scattering member with an adhesive layer protruded 20 mm from the glass plate. A test specimen was prepared. The test body was affixed to a stainless steel jig as shown in FIG. 4, and further fixed between stainless steel plates using fixing screws.
The test body fixed to the jig was placed in an electric furnace maintained at 200 ° C., and allowed to stand in a high temperature atmosphere for 10 minutes under the condition of a temperature increase rate of 15 ° C./min. Thereafter, the test body is taken out, the adhesion state of the test body and the glass plate is visually observed, ○ when the test body and the glass plate are not peeled, Δ when the peeling of the test body and the glass plate is less than half, The case where the test body and the glass plate were peeled off by half or more was evaluated as x.
(High temperature adhesion test * 2)
Using the anti-scattering member with an adhesive layer obtained in Examples and Comparative Examples, a test specimen was prepared and fixed to a jig in the same manner as in the high temperature tack test * 1. Then, it put into the electric furnace hold | maintained at 700 degreeC, and left still in a high temperature atmosphere for 10 minutes on the conditions of the temperature increase rate of 20 degrees C / min. Then, the test specimen is taken out, the adhesion state of the test specimen and the glass plate is visually observed, and the case where the test specimen and the glass plate are not peeled is evaluated as ◯, and the case where the test specimen and the glass plate are peeled is evaluated as × did.

  The anti-scattering member with an adhesive layer obtained in the examples is capable of fixing the adherends instantly, reattaching the adherends, and cutting the sheet shape. In addition, when exposed to a high temperature atmosphere such as a fire, it does not peel off from the adherend, and when it is attached to an adherend that is broken by the burning of glass, etc. Even if exposed, it can exhibit anti-scatter properties. Moreover, since the anti-scattering member with an adhesive layer obtained in the Examples is excellent in thermal functionality, it can exhibit excellent high-temperature tackiness and high-temperature adhesiveness.

The anti-scattering member with an adhesive layer of the present invention can be instantly fixed to glass, can be reattached, and is not peeled off from an adherend even when exposed to a high temperature atmosphere such as in a fire. Therefore, the anti-scattering member with an adhesive layer of the present invention can effectively prevent glass scattering not only in applications that are not exposed to a high temperature atmosphere but also in applications that are exposed to a high temperature atmosphere. Available. Moreover, since the anti-scattering member with an adhesive layer of this invention shows the outstanding thermal functionality, it can be utilized suitably also in the use environment which is easy to be influenced by temperature.
The anti-scattering member with an adhesive layer of the present invention is, for example, as a building material, a wooden house such as a conventional shaft construction method or a framed wall construction method, a reinforced concrete construction house, a lightweight steel construction or a heavy steel construction steel construction house, a prefab General houses such as construction methods, super high-rise apartments, high-rise apartments, mid- and low-rise apartments, apartment buildings such as apartments, coffee shops, restaurants, office buildings, department stores, supermarkets, indoor parking lots, movie theaters, hotels, various sports facilities, gymnasiums , Concert halls, dome-shaped baseball stadiums, soccer fields, indoor soccer fields, indoor pools, exterior buildings for public buildings, exterior wall materials, exterior wall materials, interior wall materials, wall insulation materials, ceilings Materials, ceiling finishing materials, roofing materials, flooring materials, flooring materials, partition materials, bathroom wall materials, flooring materials and ceiling materials and their finishing materials, kitchen wall materials and flooring materials Well materials and their finishing materials, toilet wall materials, floor materials and ceiling materials and their finishing materials, pillar materials and pillar protection materials, interior materials and surface finishing materials for various doors such as toilets, interiors, entrances and fences, It can be suitably used for partition materials, curtains, particularly wall materials and ceiling materials of kitchens, and clean room partitions. In addition, interior materials or surface finishing materials of fire prevention equipment such as exhaust ducts, fire doors and fire shutters, furniture surface finishing materials such as tables, door surface finishing materials, window glass surface finishing materials, furniture surface finishing materials such as tables, It can be used for anti-scattering materials and surface finishing materials such as window glass, mirrors and tiles, surface finishing materials for signboards and electronic signage, and roll screens. Also, body protection materials for ships, aircraft, automobiles, railway vehicles, interior / exterior wall materials, ceiling materials, roofing materials, floor materials, surface protection materials for printed materials affixed inside and outside railway vehicles, and surface of inkjet media materials It can be used for a protective material, an external protective material or an internal protective material for a solar cell, a battery protective material such as a lithium ion battery, or an electric / electronic device member such as a partition inside an electric device. Furthermore, it can also be used as an ashtray peripheral tool, a surface finishing material of a trash can, a front panel of a pachinko machine, or a casing protective material.

DESCRIPTION OF SYMBOLS 10 Polymer component 20 Sinterable particle 100 Adhesive layer 200 Nonflammable base material 300 Thermal functional layer 1000 Anti-scattering member with an adhesive layer 2000 Glass plate 3000 Test body 4000 Fixing screw

Claims (20)

Including an adhesive layer and a non-flammable substrate,
The adhesive layer has adhesiveness before sintering, has adhesiveness after sintering,
Including a thermal functional layer as at least one outermost layer,
Anti-scattering member with adhesive layer.   The scattering prevention member with an adhesive layer according to claim 1, wherein the thermal functional layer has a thickness of 0.1 μm to 200 μm.   The scattering prevention member with an adhesive layer according to claim 1 or 2, wherein the thermal functional layer is a heat insulating layer.   The scattering prevention member with an adhesive layer according to claim 3, wherein the heat insulating layer includes a hollow bead structure.   The scattering prevention member with an adhesive layer according to claim 4, wherein the hollow bead structure is a glass bead.   The scattering prevention member with an adhesive layer according to claim 1 or 2, wherein the thermal functional layer is a thermal barrier layer.   The scattering prevention member with an adhesive layer according to claim 6, wherein the heat shielding layer contains at least one selected from a pigment, ceramic, metal, and microballoon.   The scattering prevention member with an adhesive layer according to claim 6 or 7, wherein the heat shielding layer is at least one selected from a coating layer, a sheet layer, a foil layer, a sputter layer, and a vapor deposition layer.   The said adhesive layer is a scattering prevention member with an adhesive layer in any one of Claim 1-8 containing a sinterable particle | grain and a polymer component.   The scattering prevention member with an adhesive layer according to claim 9, wherein a yield point of the sinterable particles is 250C to 800C.   The sinterable particle is formed from at least one component selected from silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, and phosphorus oxide. Anti-scattering member with an adhesive layer.   The scattering prevention member with an adhesive layer according to any one of claims 9 to 11, wherein an average particle diameter of the sinterable particles is 0.1 µm to 1000 µm.   With the adhesive agent layer in any one of Claim 9-12 whose content rate of the said sinterability particle | grain is 1 weight%-80 weight% with respect to solid content of the said adhesive agent layer. Anti-scattering member.   The scattering prevention member with an adhesive layer according to any one of claims 9 to 13, wherein the polymer component is at least one component selected from a rubber-based polymer, a silicone-based polymer, and an acrylic polymer.   The scattering prevention member with an adhesive layer according to any one of claims 9 to 14, wherein the material for forming the polymer component contains a photopolymerization initiator.   The scattering prevention member with an adhesive layer according to any one of claims 1 to 15, wherein the adhesive layer is obtained by photopolymerization.   The scattering prevention member with an adhesive layer according to any one of claims 1 to 16, wherein the non-combustible substrate is an inorganic substrate.   The scattering prevention member with an adhesive layer according to claim 17, wherein the inorganic base material is a fibrous inorganic base material.   The scattering prevention member with an adhesive layer according to claim 18, wherein the fibrous inorganic base material is a glass cloth. The scattering prevention member with an adhesive layer according to any one of claims 1 to 19, which has a sheet shape or a tape shape and has a thickness of 1 µm to 1000 µm.