JP4829555B2 - Non-combustible resin composition and non-combustible resin film laminate - Google Patents

Description

The present invention relates to a non-combustible resin composition and a non-combustible resin film laminate that can obtain a non-combustible resin film having high incombustibility and excellent calendar molding processability, and excellent weather resistance and translucency. About.

Sheet materials used for membrane materials for architectural structures, membrane materials for tent warehouses, facades, flexible containers, etc., as well as mechanical properties such as weather resistance, water resistance, abrasion resistance, flexibility and tensile strength, as well as the use site In some cases, flame retardancy is required to prevent the spread of fire in the event of a fire as stipulated in the Building Standards Law. For this reason, as a sheet material, a sheet-like fiber such as polyester fiber or glass fiber, which is coated with a flame-retardant resin, is usually used. Conventionally, as a flame-retardant resin for coating, a soft polyvinyl chloride resin, a polytetrafluoroethylene resin, or the like has been used.

However, when a soft polyvinyl chloride resin is used, the contained plasticizer or flame retardant oozes out to the surface layer over time, so that the adhesion of the surface increases and dirt in the atmosphere adheres, There was a problem that flexibility, weather resistance, incombustibility, and the like deteriorated. In addition, when a polytetrafluoroethylene resin is used, there are problems that flexibility, mechanical strength, and the like are lowered and moldability is poor.

On the other hand, polymer materials used for industrial applications have recently been desired to be converted to materials that do not place a burden on the environment, that is, environmentally adaptable materials, due to waste plastic treatment and environmental hormone problems. Specifically, for example, conversion from a polyvinyl chloride resin to a polyolefin resin has been studied due to problems such as generation of dioxins upon combustion and toxicity of a plasticizer.

Thus, in recent years, there has been an increasing demand for so-called eco-materials that use thermoplastic resins such as polyolefin resins in order to convert to environmentally friendly materials, but thermoplastic resins are the most combustible resins. Therefore, it is the most difficult task to develop flame retardancy.

In order to solve such problems, at present, a large amount of flame retardant is often used by being kneaded into a thermoplastic resin. Among these, halogen-containing flame retardants are frequently used because they have a high flame-retarding effect and relatively little deterioration in moldability and mechanical strength of molded articles. However, when a halogen-containing flame retardant is used, a large amount of halogen-based gas is generated during molding or combustion, which may corrode equipment or adversely affect the human body. Therefore, a so-called non-halogen flame retardant treatment method that does not use a halogen-containing compound is strongly desired.

In contrast, for example, Patent Document 1 and Patent Document 2 disclose metal compounds such as aluminum hydroxide, magnesium hydroxide, and basic magnesium carbonate as flame retardants that do not contain halogen and do not generate toxic gas during combustion. Has been disclosed, and flame retardancy is controlled by the type, combination and blending amount of the flame retardant.

However, in order to impart sufficient flame retardancy to the flammable thermoplastic resin, it is necessary to add a large amount of flame retardant, and a resin composition containing a large amount of flame retardant is molded into a film or the like. Depending on the combination of various flame retardants and the resin, the flame retardant may be deposited on the film surface, or the film may become yellowish or sticky due to the decomposition or degradation reaction of the resin. There was a problem that the performance would be lowered.
JP-A-57-165437 JP-A-61-36343

In view of the above situation, the present invention provides a non-combustible resin composition and a non-combustible resin composition that can obtain a non-combustible resin film having high incombustibility and excellent calendering processability, and excellent weather resistance and translucency. It aims at providing a conductive resin film laminated body.

式（１）中、Ｒ ^１ 及びＲ ^２ は、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表わし、ｍ及びｎは０又は１〜４の整数を表わす。

なお、本明細書において、不燃性樹脂フィルム積層体とは、建築基準法施行令１０８条の２に準拠した発熱性試験を行った場合に、５０ｋＷ／ｍ^２の輻射加熱条件下で２０分間加熱し燃焼した時の総発熱量が８ＭＪ／ｍ^２未満、２００ｋＷ／ｍ^２を超える発熱時間が１０秒未満であり、かつ、発熱性試験後のサンプル（供試体）に亀裂や穴開き等が観察されないフィルム積層体を意味する。
以下に本発明を詳述する。 The present invention includes 100 parts by weight of an oxygen-containing thermoplastic resin, 5 to 50 parts by weight of melamine cyanurate, 0.1 to 50 parts by weight of layered silicate, 5 to 100 parts by weight of a flame retardant, and antioxidant as a molding processing aid. Non-flammable resin composition containing 1 to 10 parts by weight of an agent and / or lubricant , wherein the oxygen-containing thermoplastic resin is an ethylene- (meth) acrylate alkyl copolymer, an ethylene- (meth) acrylic acid copolymer. It is at least one selected from the group consisting of a polymer, an ethylene-vinyl acetate copolymer and an ethylene-vinyl alcohol copolymer, and the melamine cyanurate is surface-treated with silica particles, The layered silicate is montmorillonite and / or swellable mica having an average particle diameter of 0.01 to 3 μm, and the flame retardant has an average particle diameter of 0.5 to 10 μm. m and surface treated with at least one selected from the group consisting of a silane coupling agent, a titanium coupling agent and stearic acid, and / or magnesium hydroxide, A mixture of a phosphorus-based antioxidant that is a cyclic organophosphorus compound represented by the following formula (1) and a phenol-based antioxidant that is a compound represented by the following formula (2): Is a non-flammable resin composition having a blending weight ratio of 1: 6 to 1: 1 .

In formula (1), R ¹ and R ² represent a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and m and n represent 0 or an integer of 1 to 4.

In this specification, the non-combustible resin film laminate is heated for 20 minutes under a radiant heating condition of 50 kW / m ² when a heat generation test based on Article 108-2 of the Building Standard Law Enforcement Ordinance is performed. The total calorific value when burned is less than 8 MJ / m ² , the heat generation time exceeding 200 kW / m ² is less than 10 seconds, and cracks and holes are observed in the sample after the exothermic test (specimen) Means a film laminate that is not.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have found that an oxygen-containing thermoplastic resin, a melamine cyanurate, a layered silicate, a flame retardant, and an incombustible resin composition containing an antioxidant and / or a lubricant as a molding processing aid. However, it has been found that it has extremely high incombustibility and excellent calender molding processability, and that the obtained incombustible resin film is also excellent in weather resistance and translucency, thereby completing the present invention.

The nonflammable resin composition of the present invention contains an oxygen-containing thermoplastic resin.
Examples of the oxygen-containing thermoplastic resin include ethylene- (meth) acrylic acid alkyl copolymers, ethylene- (meth) acrylic acid copolymers, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers. At least one selected from the group consisting of

When a copolymer having an ethylene component is used as the oxygen-containing thermoplastic resin, a component derived from a substance copolymerized with ethylene, that is, an alkyl (meth) acrylate, (meth) acrylic acid, vinyl acetate or vinyl alcohol The preferable lower limit of the content of the component derived from the above is 10% by weight, and the preferable upper limit is 50% by weight. If it is less than 10% by weight, the nonflammability of the nonflammable resin composition may be insufficient, and if it exceeds 50% by weight, molding (film formation) of the nonflammable resin composition may be difficult. Later films may cause blocking. A more preferred lower limit is 10% by weight, and a more preferred upper limit is 30% by weight.

The oxygen-containing thermoplastic resin has a preferred lower limit of oxygen content of 3% by weight and a preferred upper limit of 20% by weight. If it is less than 3% by weight, the nonflammability may be insufficient. If it exceeds 20% by weight, molding of the nonflammable resin composition becomes difficult or the surface becomes sticky, and dust adheres. May cause problems such as A more preferred lower limit is 5% by weight, and a more preferred upper limit is 15% by weight.

The oxygen-containing thermoplastic resin has a preferred lower limit for the weight average molecular weight of 5,000 and a preferred upper limit of 5 million. A more preferable lower limit is 20,000, and a more preferable upper limit is 300,000.
The preferred lower limit of the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.1, and the preferred upper limit is 80. A more preferred lower limit is 1.5, and a more preferred upper limit is 40.

The nonflammable resin composition of the present invention contains melamine cyanurate.
By containing the above melamine cyanurate, a polymerization reaction occurs under high heat during combustion, and a sintered body is formed at an early stage during combustion. In addition to supplying oxygen from the outside, flammability generated by combustion Since the gas can be shut off, it is possible to suppress the heat generation rate of the obtained non-combustible resin film and to exhibit excellent combustion prevention performance.

The melamine cyanurate is preferably surface-treated with silica particles. The surface treatment method using silica particles is not particularly limited, and examples thereof include treatment with silica sol, treatment with silica slurry, and the like, and treatment with silica sol is more preferable. In the surface treatment using other than silica particles, the resin may be colored or the molding processability may be lowered due to the interaction with the resin, the filler, the molding processing aid and the like.

The lower limit of the content of the melamine cyanurate is 5 parts by weight and the upper limit is 50 parts by weight with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. If it is less than 5 parts by weight, the nonflammability standard cannot be satisfied. When the amount exceeds 50 parts by weight, although nonflammability is sufficiently obtained, the density (specific gravity) of the obtained nonflammable resin film is increased, and workability and workability are reduced due to increase in weight and decrease in flexibility. Moreover, the translucency of a film will also fall remarkably. A preferred lower limit is 10 parts by weight and a preferred upper limit is 40 parts by weight.

The nonflammable resin composition of the present invention contains a layered silicate.
By containing the layered silicate, the sintered body is formed at an early stage during combustion, and not only the supply of oxygen from the outside but also the combustion gas generated by the combustion can be cut off. It is possible to suppress the heat generation rate of the non-combustible resin film and to exhibit excellent combustion prevention performance.

Examples of the layered silicate include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, vermiculite, halloysite, and swellable mica (swellable mica). Among these, montmorillonite and / or swellable mica is preferably used. These layered silicates may be natural products or synthetic products. Moreover, these layered silicates may be used independently and may use 2 or more types together.

When montmorillonite and / or swellable mica is used as the layered silicate, the preferable lower limit of the average particle diameter is 0.01 μm, and the preferable upper limit is 3 μm. If it is less than 0.01 μm, the particles dispersed in the resin are likely to re-aggregate, and the translucency of the resulting non-flammable resin film may be lowered. When it exceeds 3 μm, the dispersibility may be lowered, and the translucency of the obtained noncombustible resin film may be significantly lowered.

As the layered silicate, it is preferable to use smectite clay minerals and swelling mica having a large shape anisotropy defined by the following formula (1). By using a layered silicate having a large shape anisotropy, the obtained non-combustible resin film has more excellent mechanical properties.
Shape anisotropy = Area of crystal surface (A) / Area of crystal side surface (B) (1)
In the formula, the crystal surface (A) means the layer surface, and the crystal side surface (B) means the layer side surface.

It does not specifically limit as a shape of the said layered silicate, It is preferable that average length is 0.01-3 micrometers, thickness is 0.001-1 micrometer, and aspect-ratio is 20-500. More preferably, the average length is 0.05 to 2 μm, the thickness is 0.01 to 0.5 μm, and the aspect ratio is 50 to 200.

The lower limit of the content of the layered silicate is 0.1 parts by weight and the upper limit is 50 parts by weight with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. If it is less than 0.1 part by weight, it becomes difficult to form a sintered body during combustion, so that the nonflammability becomes insufficient. If it exceeds 50 parts by weight, the density (specific gravity) of the noncombustible resin composition increases, and the workability and workability deteriorate due to the increase in weight and the decrease in flexibility. A preferred lower limit is 1 part by weight and a preferred upper limit is 20 parts by weight.

The nonflammable resin composition of the present invention contains a flame retardant.
The flame retardant is not particularly limited as long as it can impart flame retardancy to the obtained non-flammable resin film. For example, metal hydroxide, metal oxide, phosphorus flame retardant, silicone flame retardant, etc. Non-halogen flame retardants. Of these, metal hydroxides are preferred.

As the metal hydroxide, for example, aluminum hydroxide and / or magnesium hydroxide surface-treated with at least one selected from the group consisting of a silane coupling agent, a titanium coupling agent and stearic acid is preferably used. It is done. Of these, silane coupling agent treatment is preferably used. When the surface treatment is performed using a surface treatment agent other than the above, the resin may be colored or the molding processability may be lowered due to the interaction with the resin, the filler, the molding processing aid and the like.

The above metal hydroxides (including surface-treated metal hydroxides) are endothermic and dehydrated under high heat during combustion, thereby reducing the temperature of the combustion field by absorbing heat and releasing water molecules. Exhibits the effect of extinguishing fire Further, by using two or more kinds of metal hydroxides in combination, the endothermic dehydration reaction starts at different temperatures, so that a higher flame retardant effect can be obtained.
Since the nonflammable resin composition of the present invention contains the layered silicate, the flame retardancy effect by the metal hydroxide is increased. This is because the flame retardant effect due to the film formation during the combustion of the layered silicate and the flame retardant effect due to the endothermic dehydration reaction of the metal hydroxide occur in concert, and each flame retardant effect is promoted. .

The minimum with the preferable average particle diameter of the said metal hydroxide is 0.5 micrometer, and a preferable upper limit is 10 micrometers. If it is less than 0.5 μm, the particles dispersed in the resin are likely to re-aggregate, and the translucency of the resulting non-flammable resin film may be lowered. If it exceeds 10 μm, the dispersibility may be reduced, and the molding processability and translucency of the resulting non-combustible resin film may be significantly reduced.

The content of the flame retardant is 5 parts by weight for the lower limit and 100 parts by weight for the upper part with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. Incombustibility falls that it is less than 5 weight part. When the amount exceeds 100 parts by weight, nonflammability is sufficiently obtained, but the density (specific gravity) of the obtained nonflammable resin film is increased, and workability and workability are reduced due to an increase in weight and a decrease in flexibility. A preferred lower limit is 20 parts by weight and a preferred upper limit is 60 parts by weight.

The nonflammable resin composition of the present invention contains an antioxidant and / or a lubricant as a molding processing aid. By containing the antioxidant and / or lubricant, molding processability can be improved.

As said antioxidant, it is a mixture of phosphorus antioxidant and phenolic antioxidant, Comprising weight ratio of phosphorus antioxidant and phenolic antioxidant is 1: 6 to 1: 1. Some are preferably used. If the blending weight ratio is outside the above range, the synergistic effect of the phosphorus antioxidant and the phenolic antioxidant cannot be obtained, and discoloration occurs due to the thermal deterioration of the resin.

As the phosphorus-based antioxidant, a cyclic organic phosphorus compound represented by the following formula (1) is preferable. As the cyclic organic phosphorus compound, for example, 9,10-dihydro-9-oxa-10 phosphaphenanthrene- 10-oxide; 1-chloro (or bromine, fluor), 1,3-dichloro (or dibromo, difluoro), 1,3,7-trichloro (or tribromo, trifluoro), 1-methyl, 1,3-dimethyl, 1,3,7-trimethyl, 1-tert-butyl, 3-tert-butyl, 1-cyclohexyl, 3- (α-methylbenzyl, 1-phenyl, 3-phenyl, 1- (4-methylphenyl), 3 -Cyano, 1-methyl-3-chloro (or bromine), 1-methyl-3,7-dichloro (or dibromo), 1,3,7-trimethyl-2,6-dic (Or dibromo), 1-phenyl-3-chloro (or bromine), 1-chloro (or bromine) -3-benzyl, 1-chloro-3-bromo, 1,3-dibromo-7-chloro, etc. The cyclic organophosphorus compound of following formula (1) which has group on a biphenyl skeleton is mentioned.

式（１）中、Ｒ^１及びＲ^２は、ハロゲン原子、アルキル基、シクロアルキル基、アリール機、アラルキル基又はアルケニル基を表わし、ｍ及びｎは０又は１〜４の整数を表わす。

In formula (1), R ¹ and R ² represent a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and m and n represent 0 or an integer of 1 to 4.

As said phenolic antioxidant, the compound shown by following formula (2) is preferable. (2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate) is used.
When an antioxidant other than these is used, the dispersibility of the antioxidant in the oxygen-containing thermoplastic resin is lowered, and partial thermal deterioration may occur.

As the lubricant, stearyl acid phosphate is preferably used. Examples of the stearyl acid phosphate include compounds represented by the following formula (3) and the following formula (4). These may be used alone or in combination of two or more.

The lower limit of the content of the antioxidant and / or lubricant is 1 part by weight and the upper limit is 10 parts by weight with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. When the amount is less than 1 part by weight, the resin is discolored due to thermal deterioration of the resin, or the resin is sticky and adheres to the metal surface of a forming apparatus such as a rolling roll or an extrusion screw. If it exceeds 10 parts by weight, the moldability will be improved, but the amount of organic components will increase, so it will not be possible to meet the standards for nonflammability. A more preferred lower limit is 2 parts by weight, and a more preferred upper limit is 5 parts by weight.

The non-flammable resin composition of the present invention preferably further contains a flame retardant aid.
By containing the flame retardant aid, the oxygen index of the obtained non-flammable resin film is improved, and the maximum heat generation rate can be significantly reduced.

As the flame retardant aid, for example, silicone / acrylic composite rubber is preferably used.
The silicone-acrylic composite rubber reacts with an oxygen-containing thermoplastic resin having an active group to promote char formation (charification), or when a glassy inorganic compound film is formed, a protective material As a result, the thermal decomposition of the oxygen-containing thermoplastic resin is suppressed.

The content of the silicone-acrylic composite rubber is preferably 0.1 parts by weight and preferably 20 parts by weight with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. If it is less than 0.1 part by weight, the oxygen index of the obtained noncombustible resin film may not be sufficiently improved, or the maximum heat generation rate may not be sufficiently reduced. If it exceeds 20 parts by weight, the density (specific gravity) of the noncombustible resin film may increase, the mechanical strength or the like may decrease, or the flexibility may be poor. A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 15 parts by weight.

It is preferable that the nonflammable resin composition of the present invention further contains an ultraviolet absorber and / or a light stabilizer as a weather resistant prescription agent. Weather resistance can be improved by containing the said ultraviolet absorber and / or light stabilizer.

The content of the weather resistance prescription agent is preferably 0.1 parts by weight and preferably 2 parts by weight with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. If it is less than 0.1 part by weight, discoloration or embrittlement of the film may occur due to light deterioration. When the amount exceeds 1 part by weight, although the weather resistance is improved, the amount of organic components increases, so it may not be possible to satisfy the standard of nonflammable performance. A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 1 part by weight.

As the ultraviolet absorber, for example, a benzotriazole compound can be suitably used.
The benzotriazole-based compound is not particularly limited, and examples thereof include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-t-octylphenol) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 (2H-benzotriazol-2-yl) phenol], 2 (2′hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″) , 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-5-acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy- 5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-acryloylethylphenyl) -5-chloro-2H-benzotriazole, and the like.

As the light stabilizer, for example, a hindered amine compound can be preferably used.
The hindered amine compound is not particularly limited, and examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2 succinate. , 2,6,6-tetramethylpiperidine polycondensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6 , 6-Tetramethyl-4-piberidylbenzoate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -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) and the like.

It is preferable that the nonflammable resin composition of the present invention further contains a fluorescent whitening agent and / or an inorganic pigment as a hue adjusting agent. By including the fluorescent whitening agent and / or inorganic pigment, the hue can be easily adjusted.

The inorganic pigment is not particularly limited, and examples thereof include titanium oxide, bengara, chrome yellow, cobalt green, ultramarine blue, and cobalt blue. Of these, titanium oxide is preferably used when whiteness is important.

The content of the fluorescent brightening agent or inorganic pigment is preferably 0.1 parts by weight and preferably 5 parts by weight with respect to 100 parts by weight of the oxygen-containing thermoplastic resin. If it is less than 0.1 part by weight, a sufficient hue adjusting effect may not be obtained. If it exceeds 10 parts by weight, the hue adjusting effect can be sufficiently obtained, but the moldability of the non-flammable resin composition may be lowered or the flexibility may be poor. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 5 parts by weight.

Moreover, as for the nonflammable resin composition of this invention, the preferable minimum of MFR (melt mass flow rate) measured by 210 degreeC and the load 2.16kg is 0.5 g / 10min, and a preferable upper limit is 5 g / 10min. Since fluidity | liquidity will deteriorate that it is less than 0.5 g / 10min, thickness nonuniformity may arise between the center and edge part of the film obtained, for example. If it exceeds 5 g / 10 min, it may be difficult to obtain a film having a certain thickness because the fluidity is too good.

The non-flammable resin film is preferably formed by a calendar forming method. Specific examples include, for example, oxygen-containing thermoplastic resins, melamine cyanurate, layered silicates, flame retardants, molding processing aids, and additives such as flame retardant aids, weathering prescription agents, and hue modifiers as necessary. It is preferable to manufacture a nonflammable resin film by preparing a resin composition to be rolled and rolling it using a calendar molding method. By using the calendar molding method, the thickness accuracy and productivity of the film can be improved.

The method for preparing the resin composition used for the production of the noncombustible resin film is not particularly limited. For example, a direct kneading method in which raw materials are directly kneaded; a layered silicate having a predetermined blending amount or more in an oxygen-containing thermoplastic resin; A master batch is prepared by kneading a flame retardant, molding processing aid, flame retardant aid, hue adjusting agent, etc., and then an oxygen-containing thermoplastic resin is blended in the prepared master batch so that each component has a predetermined blending amount. And a master batch method for dilution.

Furthermore, in the nonflammable resin film formed from the nonflammable resin composition by the calendar molding method, a preferable lower limit of the thickness is 50 μm, and a preferable upper limit is 400 μm. If it is less than 50 μm, the mechanical strength of the film, such as tensile strength and tear strength, may decrease. If it exceeds 400 μm, the organic component weight will increase and the total calorific value will increase. May not be possible. A more preferable lower limit is 100 μm, and a more preferable upper limit is 300 μm.

When molding a non-combustible resin film by the calendar molding method, when the rolling process is performed for 30 minutes using a metal roll heated to the melting point of the oxygen-containing thermoplastic resin +50 to 100 ° C., before and after the rolling process. The upper limit of the color difference (ΔE) of the film is preferably 10. If the color difference exceeds 10, the resulting non-combustible resin film has yellowing, and the appearance may be significantly impaired.
Further, if the heating temperature of the metal roll is less than the melting point of the oxygen-containing thermoplastic resin + 50 ° C., it becomes difficult to obtain a film having a certain thickness because the resin fluidity is low, and if it exceeds + 100 ° C., the resin deteriorates and deteriorates. May happen.

In addition, when molding a non-combustible resin film by the calendar molding method, when the rolling process is performed for 30 minutes using a metal roll heated to the melting point of the oxygen-containing thermoplastic resin +50 to 100 ° C., the surface of the metal roll A preferable upper limit of the difference in reflectance (R) is 10%. When the difference in reflectance on the surface of the metal roll exceeds 10%, fillers, stabilizers, additives, etc. blended in the resin, and products that are oxidized, decomposed, combined, deteriorated, etc. Since it is considered that the surface is adhered or accumulated (plate-out), the roll releasability of the resin is significantly lowered, and a film having a predetermined thickness may not be taken out from the roll.

The non-combustible resin film obtained by using the non-combustible resin composition of the present invention is laminated on one or both sides of a glass cloth having a warp density and a weft density of 15 to 45/25 mm, thereby providing a non-combustible resin film. A laminate can be obtained. The nonflammable resin film laminate obtained in this way is also one aspect of the present invention.

The glass cloth has a lower limit of warp density and weft density of 15/25 mm and an upper limit of 45/25 mm. When it is less than 15 pieces / 25 mm, the mechanical strength such as tensile strength and tear strength of the non-combustible resin film laminate of the present invention is lowered. When it exceeds 45/25 mm, the translucency is lowered.

The glass cloth has a preferable lower limit of the diameter of the single fiber of 3 μm and a preferable upper limit of 10 μm. If it is less than 3 μm, the mechanical strength such as weather resistance, abrasion resistance and tensile strength may be lowered. When it exceeds 10 μm, the translucency is lowered, and when used as a sheet material for an internally illuminated signboard, the designability and sharpness may be lowered.

The preferable lower limit of the thickness of the glass cloth is 100 μm, and the preferable upper limit is 400 μm. If it is less than 100 μm, the mechanical strength may be insufficient, and the nonflammable performance of the nonflammable resin film laminate may be insufficient. When it exceeds 400 μm, flexibility may be lowered.

The minimum with the preferable weight of the said glass cloth is 150 g / m < ² >, and a preferable upper limit is 350 g / m < ² >. If it is less than 150 g / m ² , sufficient mechanical strength such as flexibility and tensile strength may not be obtained. When it exceeds 350 g / m ² , the weight is too large, and workability and the like may be deteriorated.

As said glass cloth, in order to improve a flame retardance, what processed the surface by flame retardants, such as a polyphosphate carbamate, may be used. Although it does not specifically limit as a coating amount of flame retardants, such as the said polyphosphate carbamate, A preferable minimum is 20 g / m < ² > as a solid content, and an upper limit is 70 g / m < ² >. If it is less than 20 g / m ² , the flame retardancy may be insufficient, and if it exceeds 70 g / m ² , the fiber itself becomes hard and the flexibility required for the non-flammable resin film laminate decreases. Sometimes.

In the incombustible resin film laminate of the present invention, the preferred lower limit of the total light transmittance measured by a method according to JIS K 7105 is 15%. If it is less than 15%, the design properties, sharpness, etc. of the film material for tents and internally illuminated electric signboards may be insufficient. A more preferred lower limit is 18%.

The non-combustible resin film laminate of the present invention has a maximum heat generation when heated and burned for 20 minutes under a radiant heating condition of 50 kW / m ² in a combustion test “combustion test method for building materials” in accordance with ASTM E 1354. It is preferable that the speed is 350 kW / m ² or less, the total heat generation amount is less than 8 MJ / m ² , and the heat generation speed exceeding 200 kW / m ² is less than 10 seconds. If it is out of the above range, sufficient incombustible performance may not be exhibited. More preferably, the maximum heat generation rate is 300 kW / m ² or less, the total heat generation amount is 7 MJ / m ² or less, and the heat generation rate exceeding 200 kW / m ² is 8 seconds or less.

The non-flammable resin film laminate of the present invention preferably has self-extinguishing properties. Without self-extinguishing properties, practicality may be insufficient.

As a method for producing the incombustible resin film laminate of the present invention, for example, after producing an incombustible resin film containing an oxygen-containing thermoplastic resin, a layered silicate and a flame retardant by calender roll molding or the like, a thermocompression bonding roll The method (laminate method) etc. which laminate | stack a nonflammable resin film and glass cloth etc. are mentioned.

In order to improve the adhesion between the glass cloth and the non-combustible resin film, the glass cloth is subjected to a sticking (surface contact) process or a surface treatment as necessary to improve the adhesion between the glass cloth and the non-combustible resin film. Also good. In addition, these processes may be performed independently and may use 2 or more types together. Moreover, you may go to the single side | surface of a glass cloth, and may carry out to both surfaces.

The sticking (contacting) adhesive used for performing the sticking (contacting) process is not particularly limited as long as it has excellent adhesion between the glass cloth and the noncombustible resin film. For example, an elastomer (rubber) ) System adhesive (contact) adhesive, acrylic resin system adhesive (contact) adhesive, polyvinyl ether system adhesive (contact) adhesive, silicone system adhesive (contact) adhesive, ethylene-vinyl acetate system adhesive (contact) adhesive, There are ethylene-ethyl acrylate-based (contact) adhesives, urethane-based (contact) adhesives, and double-sided adhesive (contact) adhesive sheets (double-sided adhesive (contact) adhesive tapes) made of these adhesives. Can be mentioned. These sticky (contact) adhesives may be used alone or in combination of two or more.

The surface treatment agent used for performing the surface treatment is appropriately selected according to the use environment and application, and is not particularly limited, and examples thereof include a water repellent and a silane coupling agent. These surface treatment agents may be used alone or in combination of two or more.

The water repellent is not particularly limited, and examples thereof include a fluorine water repellent and a silicone water repellent.
The fluorine-based water repellent is not particularly limited as long as it has a perfluoroalkyl group. For example, AG-955 (Asahi Glass Co., Ltd.), AG-970 (Asahi Glass Co., Ltd.), Dick Guard F-90 (Large) Nippon Ink Co., Ltd.). Moreover, it does not specifically limit as a silicone type water repellent, For example, Drypon 600 (made by Nikka Chemical Co., Ltd.), PolonT (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned. These water repellents may be used independently and may use 2 or more types together.

The preferable lower limit of the content of the water repellent is 0.01% by weight in terms of solid content and the preferable upper limit is 10% by weight with respect to the weight of the glass cloth substrate. By setting it within the above range, sufficient water resistance can be obtained in addition to sufficient adhesive strength between the noncombustible resin film and the glass cloth. A more preferred lower limit is 0.03% by weight, and a more preferred upper limit is 5% by weight.

The silane coupling agent is not particularly limited. For example, vinyl methoxy silane, vinyl triethoxy silane, vinyl tris (β-methoxy ethoxy) silane, γ-aminopropyl trimethoxy silane, γ-aminopropyl methyl dimethoxy silane, γ -Aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyl Trimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopro Pyrmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, γ-methacryloxypropylmethyldimethoxysilane, γ -Methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, β- (3,4 epoxy cyclohexyl) -ethylenetrimethoxysilane, γ-glycidoxypropyltrimethoxy Examples include silane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

In the nonflammable resin film laminate of the present invention, a protective layer made of a protective layer forming resin may be formed on one side or both sides.
The resin for forming the protective layer is not particularly limited, and examples thereof include a fluorine resin, an acrylic resin, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, an ethylene-vinyl acetate-vinyl alcohol terpolymer. It is done. These protective layer forming resins may be used alone or in combination of two or more.

The method for forming the protective layer on one side or both sides of the non-combustible resin film laminate of the present invention is not particularly limited. For example, a method for laminating a protective sheet made of the protective layer forming resin, or the protective layer formation described above. For example, a method of coating a resin (water) solution.

The use of the non-combustible resin film laminate of the present invention is not particularly limited, and examples thereof include membrane materials for building membrane structures, membrane materials for tent warehouses, facades, flexible containers, internally illuminated signboards, and the like. Especially, it is used suitably for the interior lighting type electrical signboard for which high translucency and nonflammability are desired.

In order to describe the present invention in more detail, examples will be given below, but the present invention is not limited to these examples.

Example 1
In a small extruder (“TEX30”, manufactured by Nippon Steel Works), 100 parts by weight of ethylene-ethyl acrylate copolymer (“A4250”, oxygen content: 8% by weight, manufactured by Nippon Polyolefin Co., Ltd.), silica particles Surface-treated melamine cyanurate ("MC-640", manufactured by Nissan Chemical Industries) 20 parts by weight, swellable fluorine mica ("Somasif ME-100", manufactured by Corp Chemical) 10 parts by weight, silane coupling agent 25 parts by weight of aluminum hydroxide having an average particle size of 0.5 to 10 μm treated by the above (“Hijilite 42HSTV”, Showa Denko Co., Ltd.), and a phosphorous antioxidant having the structure of the above formula (1) as an antioxidant ("HCA", manufactured by Sanko Chemical Co., Ltd.) 0.2 parts by weight and a phenolic antioxidant having the structure of the above formula (2) ("Sumilyzer GS (F)", Sumitomo 0.5 parts by weight (manufactured by Gakusha), 0.5 parts by weight of stearyl acid phosphate (“LBT-100”, manufactured by Sakai Chemical Co., Ltd.) as a lubricant were filled, melted and kneaded at a set temperature of 180 ° C., and extruded. The strand was pelletized with a pelletizer. Next, the obtained pellets were formed into a sheet by performing a rolling process with a metal roll heated to 180 ° C. for 30 minutes using a two-mixing roll forming machine (“B010”, manufactured by Toyo Seiki Seisakusho), and having a thickness of 150 μm. A non-combustible resin film was prepared.

(Example 2)
A nonflammable resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that the amount of aluminum hydroxide (“Hijilite-42HSTV”) was changed to 60 parts by weight.

(Example 3)
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that the addition amount of melamine cyanurate (“MC-640”) was 5 parts.

Example 4
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that the amount of melamine cyanurate (“MC-640”) added was 40 parts by weight.

(Example 5)
150 μm in thickness in the same manner as in Example 1 except that 10 parts by weight of montmorillonite (“New Sven D”, manufactured by Toyoshun Mining Co., Ltd.) was used instead of 10 parts by weight of the swellable fluorine mica “Somasif ME-100”. A non-combustible resin film was prepared.

(Example 6)
Example 1 except that 25 parts by weight of magnesium hydroxide (“Kisuma 5J”, manufactured by Kyowa Chemical Co., Ltd.) having an average particle diameter of 0.8 μm was used instead of 25 parts by weight of aluminum hydroxide (“Heidilite-42HSTV”). Similarly, a non-combustible resin film having a thickness of 150 μm was produced.

(Example 7)
A non-combustible resin film having a thickness of 150 μm was prepared in the same manner as in Example 1 except that the amount of the swellable fluorine mica “Somasif ME-100” was 1 part by weight.

(Example 8)
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that the amount of the swellable fluorine mica “Somasif ME-100” was 20 parts by weight.

(Comparative Example 1)
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that melamine cyanurate “MC-640” was not used.

(Comparative Example 2)
A non-flammable resin film having a thickness of 150 μm was prepared in the same manner as in Example 1 except that melamine cyanurate “MC-640” and swellable fluorine mica “Somasif ME-100” were not used.

(Comparative Example 3)
Instead of 25 parts by weight of aluminum hydroxide (“Heidilite-42HSTV”), 25 parts by weight of aluminum hydroxide having an average particle diameter of 65 μm (“B-30”, manufactured by Sakai Kogyo Co., Ltd.) surface-treated with a silane coupling agent is used. A non-combustible resin film was produced in the same manner as in Example 1 except that it was. In addition, the thickness of the obtained nonflammable resin film was 400 micrometers.

(Comparative Example 4)
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that aluminum hydroxide (“Hijilite-42HSTV”) was not used.

(Comparative Example 5)
A non-combustible resin film having a thickness of 150 μm was prepared in the same manner as in Example 1 except that aluminum hydroxide (“Hydelite-42HSTV”) and swellable fluorine mica “Somasif ME-100” were not used.

(Comparative Example 6)
Example in which 25 parts by weight of melamine cyanurate “MC-640” was used instead of 25 parts by weight of melamine cyanurate (“MC-610”, manufactured by Nissan Chemical Industries, Ltd.) not subjected to surface treatment with silica particles In the same manner as in Example 1, a nonflammable resin film was produced. In addition, the thickness of the obtained nonflammable resin film was 450 micrometers.

Example 9
Instead of 100 parts by weight of the ethylene-ethyl acrylate copolymer “A4250”, 100 parts by weight of ethylene-vinyl acetate copolymer (“Ultrasen # 634”, oxygen content: 6% by weight, manufactured by Tosoh Corporation) was used. A nonflammable resin film having a thickness of 150 μm was produced in the same manner as in Example 1 except that.

(Example 10)
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 9 except that the addition amount of the phosphorus-based antioxidant “HCA” was 0.5 parts by weight as the antioxidant.

(Example 11)
A non-combustible resin film having a thickness of 150 μm was produced in the same manner as in Example 9 except that the addition amount of the phenolic antioxidant “Sumilyzer GS (F)” was 1.2 parts by weight as the antioxidant.

(Comparative Example 7)
150 μm in thickness in the same manner as in Example 9 except that 100 parts by weight of polyethylene resin (“HB530”, manufactured by Nippon Polychem) was used instead of 100 parts by weight of the ethylene-vinyl acetate copolymer “Ultrasen # 634”. A non-combustible resin film was prepared.

(Comparative Example 8)
In place of 0.2 part by weight of the phosphorus-based antioxidant “HCA” as an antioxidant, the phosphorus-based antioxidant (“Irganx1222”, manufactured by Ciba Specialty Chemicals) which is not the structure (organocyclic phosphorus compound) according to claim 10 A noncombustible resin film was produced in the same manner as in Example 9 except that the amount was 0.2 parts by weight. In addition, the thickness of the obtained nonflammable resin film was 400 micrometers.

(Comparative Example 9)
In place of 0.5 parts by weight of the phenolic antioxidant “Sumilyzer GS (F)” as an antioxidant, a phenolic antioxidant having no structure according to claim 11 (“ADK STAB AO-80”, Asahi Denka Kogyo Co., Ltd.) Product) A nonflammable resin film was produced in the same manner as in Example 9 except that the amount was 0.5 parts by weight. In addition, the thickness of the obtained nonflammable resin film was 450 micrometers.

(Comparative Example 10)
As the antioxidant, except that the phenolic antioxidant “Sumilyzer GS (F)” and the phosphorus antioxidant “HCA” were changed to the phenolic antioxidant “ADK STAB AO-80” and the phosphorus antioxidant “Irganx1222”, respectively. Produced a nonflammable resin film in the same manner as in Example 9. In addition, the thickness of the obtained nonflammable resin film was 500 micrometers.

(Comparative Example 11)
A nonflammable resin film was produced in the same manner as in Example 9 except that stearyl acid phosphate “LBT-100” was not used as a lubricant. In addition, the thickness of the obtained nonflammable resin film was 400 micrometers.

(Evaluation)
The following evaluation was performed about the nonflammable resin film obtained in Examples 1-11 and Comparative Examples 1-11. In addition, about the nonflammable resin film obtained by the comparative examples 3, 6, and 8-11 which were not able to produce the 150-micrometer-thick nonflammable resin film, translucency evaluation and nonflammable performance evaluation were not performed. The results are shown in Tables 1 and 2.

(1) Evaluation of roll molding processability In the examples and comparative examples, the following items were evaluated when the nonflammable resin film was molded.

(1-1) The reflectivity (R) of the metal roll surface before and after the plate-out rolling process is measured using a metal reflectometer (Ure-30, manufactured by USHIO INC.), And the presence or absence of plate-out is determined according to the following criteria. It was evaluated with.
R difference exceeds 10%: With plate out R difference within 10%: No plate out

(1-2) Roll releasability In the rolling process, whether or not a film with a predetermined thickness can be taken out from the roll was evaluated according to the following criteria.
1 point: The film cannot be removed even if the thickness is 400 μm or more. 2 points: The film can be removed if the thickness is 400 μm or more. 3 points: The film can be removed if the thickness is about 400 μm. 4 points: The film is about 200 μm thick. 5 points can be taken out: Film can be taken out easily even with a thickness of about 200 μm

(1-3) The color difference (ΔE) of the film before and after the color change rolling step was measured with a color difference meter (CR-400, manufactured by Konica Minolta). When ΔE is 5 or less, it is considered that there is no problem in appearance.

(1-4) MFR (Melt Mass Flow Rate)
The MFR (melt mass flow rate) of the resin composition used was measured under the conditions of 210 ° C. and a load of 2.16 kg. In addition, when MFR is outside the range of 0.5 g / 10 min to 5 g / 10 min, it is considered that it is difficult to obtain a film having a constant thickness.

(2) Glass cloth (“KS2500” having a warp density of 44/25 mm, a weft density of 33/25 mm, a single fiber diameter of 9 μm, a twist number of 0 times / 25 mm, and a thickness of 180 μm using a thermo-compression roll with total light transmittance. The obtained non-combustible resin film was laminated on both surfaces of Kanebo Co., Ltd. to produce a non-combustible resin film laminate having a thickness of 400 μm.
About the obtained nonflammable resin film laminated body, the total light transmittance (%) of the nonflammable resin film laminated body was measured based on JISK7105 "The optical characteristic evaluation test method of a plastic".

(3) Total calorific value, exothermic time combustion test exceeding 200 kW / m ^{2 Based} on ASTM E 1354, a test piece (99 mm × 99 mm) of the non-combustible resin film laminate obtained in (2) is a cone calorimeter. Was irradiated with a 50 kW / m ² heat ray and burned. The total calorific value (MJ / m ² ) after heating and burning for 20 minutes and the exothermic time exceeding 200 kW / m ² were measured.

(4) Presence / absence of cracks and cracks After the nonflammable resin film laminate obtained in (2) was heated for 20 minutes, the presence or absence of holes and cracks penetrating the back surface was confirmed.
○: There are no holes or cracks penetrating the back surface.
X: There are holes and cracks penetrating the back surface.

As shown in Tables 1 and 2, it can be seen that the nonflammable resin films obtained in Examples 1 to 11 are excellent in moldability (calendar moldability) using a metal roll. Moreover, it turns out that the nonflammable resin film laminated body obtained by laminating | stacking with a glass cloth is excellent in nonflammable performance, and has a high total light transmittance.
On the other hand, the nonflammable resin films obtained in Comparative Examples 1 to 11 have poor moldability (calendar moldability) using a metal roll, and may be difficult to mold to a predetermined thickness (150 μm). Moreover, also about what was shape | molded by predetermined thickness, the nonflammable performance and the total light transmittance of the nonflammable resin film laminated body obtained by laminating | stacking with a glass cloth were low.

According to the present invention, a nonflammable resin film having high translucency and nonflammability and excellent in mechanical strength such as weather resistance, water resistance, abrasion resistance, flexibility and tensile strength can be obtained. A nonflammable resin composition and a nonflammable resin film laminate can be provided.

Claims (12)

100 parts by weight of an oxygen-containing thermoplastic resin, 5 to 50 parts by weight of melamine cyanurate, 0.1 to 50 parts by weight of a layered silicate, 5 to 100 parts by weight of a flame retardant, and an antioxidant and / or a molding processing aid A non-flammable resin composition containing 1 to 10 parts by weight of a lubricant ,
The oxygen-containing thermoplastic resin is an ethylene- (meth) acrylic acid alkyl copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-vinyl alcohol copolymer. At least one selected,
The melamine cyanurate is surface-treated with silica particles,
The layered silicate is montmorillonite and / or swellable mica having an average particle size of 0.01 to 3 μm,
The flame retardant has an average particle diameter of 0.5 to 10 μm and is surface-treated with at least one selected from the group consisting of a silane coupling agent, a titanium coupling agent and stearic acid, and / Or magnesium hydroxide,
The antioxidant is a mixture of a phosphorus-based antioxidant that is a cyclic organic phosphorus compound represented by the following formula (1) and a phenol-based antioxidant that is a compound represented by the following formula (2): A nonflammable resin composition, wherein a blending weight ratio of the phosphorus-based antioxidant and the phenol-based antioxidant is 1: 6 to 1: 1 .

In formula (1), R ¹ and R ² represent a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and m and n represent 0 or an integer of 1 to 4.

An MFR (melt mass flow rate) measured at 210 ° C. and a load of 2.16 kg is 0.5 to 5 g / 10 min, and a non-combustible resin film having a thickness of 50 to 400 μm can be molded by a calendar molding method. When the rolling process is performed for 30 minutes using a metal roll heated to the melting point of the oxygen-containing thermoplastic resin +50 to 100 ° C. in the calendar molding method, the color difference (ΔE) before and after the rolling process is 10 or less. The nonflammable resin composition according to claim 1, wherein the difference in surface reflectance (R) is 10% or less. The incombustible resin composition according to claim 1 or 2, wherein the oxygen-containing thermoplastic resin is an ethylene- (meth) acrylate alkyl copolymer or an ethylene-vinyl acetate copolymer. The incombustible resin composition according to claim 1, 2 or 3, wherein the oxygen-containing thermoplastic resin has an oxygen content of 3 to 20% by weight. The non-flammable resin composition according to claim 1, 2, 3 or 4 , wherein the lubricant is stearyl acid phosphate. Furthermore, 0.1-20 weight part of flame retardant adjuvants which consist of silicone acrylic composite rubber | gum are contained , The nonflammable resin composition of Claim 1, 2, 3, 4 or 5 characterized by the above-mentioned . Furthermore, 0.1-2 weight part of ultraviolet absorbers and / or light stabilizers are contained as a weather-resistant prescription agent , The nonflammable resin composition of Claim 1, 2, 3, 4, 5 or 6 characterized by the above-mentioned . . The nonflammable resin composition according to claim 7 , wherein the ultraviolet absorber is a benzotriazole compound. Furthermore, 0.1-5 weight part of fluorescent whitening agents and / or inorganic pigments are contained as a hue adjusting agent , The incombustible of Claim 1, 2, 3, 4, 5, 6, 7 or 8 characterized by the above-mentioned. Resin composition. The glass cloth having a warp density and a weft density of 15 to 45 pieces / 25 mm, and the glass cloth laminated on one side or both sides of the glass cloth according to claim 1, 2, 3, 4, 5, 6, 7, 8, or 9. A nonflammable resin film laminate comprising a nonflammable resin composition. The incombustible resin film laminate according to claim 10, wherein the total light transmittance measured by a method according to JIS K 7105 is 15% or more. In a combustion test in accordance with ASTM E 1354, the maximum heat generation rate when heated and burned for 20 minutes under a radiation heating condition of 50 kW / m ² is 350 kW / m ² or less, and the total heating value is less than 8 MJ / m ² , incombustible resin film laminate according to claim 10 or 11, wherein heating rates in excess of 200 kW / ^{m 2} is equal to or less than 10 seconds.