JP5443798B2 - Film or sheet formed from a flame retardant resin composition for building materials - Google Patents

Description

  The present invention relates to a resin composition for building materials having excellent flame retardancy, and interior materials such as wallpaper and building material sheets made of the resin composition.

  Flame retardant properties are required for building interior materials such as flooring and wallpaper, and those using vinyl chloride resin have been widely used. However, since a resin composition containing a halogen such as a vinyl chloride resin generates a large amount of smoke during combustion and a toxic gas such as an acidic gas or carbon monoxide, the use of a material containing no halogen is required. It has been demanded.

  In response to such a requirement, Patent Documents 1 to 3 propose using polyolefin-based resins instead of vinyl chloride resins. However, the vinyl chloride resin containing a large amount of halogen having flame retardancy was easy to make the flame retardant, but in the case of the polyolefin resin, a non-halogen flame retardant technology is required. For such problems, Patent Documents 1 to 3 propose the use of metal hydroxides and inorganic fillers such as aluminum hydroxide and magnesium hydroxide, but these metal hydroxides are difficult. Since a large amount of addition is required in order to express the combustion effect, the physical properties of the resin are affected, and when used as a thin material such as wallpaper, there is a significant problem in workability.

  Patent Document 4 proposes an intumescent flame retardant that exhibits flame retardancy by forming a surface expansion layer (Intumescent) during combustion and suppressing diffusion and heat transfer of decomposition products. However, it does not describe that it is particularly suitable for flame retardants of thin materials such as wallpaper, and that it does not suppress the generation of carbon monoxide, and does not describe the calorific value. It is not possible to obtain this knowledge.

  On the other hand, from the viewpoint of legal regulations, there is an increasing demand for flame retardants for interior materials such as wallpaper. As a result of the revision of the Building Standards Law, after June 1, 2000, a calorific value test using a corn calorimeter based on ISO 5660, which is highly reliable and accurate, was introduced as a flame retardancy evaluation method. The assessment of harmful gases and smoke emissions has also been reviewed.

For example, if the test result is
(1) The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less,
(2) There are no deformations such as through cracks and holes in the test specimen for 20 minutes after heating starts.
(3) The maximum heat generation rate exceeding 200 kw / m ² for 20 minutes after the start of heating does not continue for 10 seconds or more,
(4) When the average action stop time until the mouse stops the action after the start of heating is 6.8 minutes or more, the wallpaper as the test specimen is evaluated as “non-combustible material”.

The test result is
(1) The total calorific value for 10 minutes after the start of heating is 8 MJ / m ² or less,
(2) There is no deformation such as through cracks and holes in the test specimen for 10 minutes after the start of heating.
(3) The maximum heat generation rate exceeding 200 kw / m ² for 10 minutes after the start of heating does not continue for 10 seconds or more,
(4) When the average action stop time until the mouse stops the action after the start of heating is 6.8 minutes or more, the fiber wallpaper as the test specimen is evaluated as a “quasi-incombustible material”.

The test result is
(1) The total calorific value for 5 minutes after the start of heating is 8 MJ / m ² or less,
(2) There are no deformations such as through cracks and holes in the specimen for 5 minutes after the start of heating.
(3) If the maximum heat generation rate exceeding 200 kw / m ² for 5 minutes after the start of heating does not continue for 10 seconds or more, the fiber wallpaper as the test specimen is evaluated as a “flame retardant material”.

  Thus, there is a need for a flame-retardant interior material that is excellent in flame retardancy and has suppressed generation of harmful gases and the like.

JP-A-6-182916 JP-A-11-100456 JP 2004-277986 A JP 2003-26935 A

  Therefore, the object of the present invention is to suppress the generation of harmful gases such as carbon monoxide and acid gas and smoke, and has excellent flame retardancy such as low calorific value, and wallpaper made from the same, It is to provide interior materials such as seats.

The present invention (invention described in claim 1) per 100 parts by mass of the polyolefin resin, the following component (A) 5 to 40 parts by weight and the following component (B) 5 to 50 parts by mass, as a further component (C) A film or sheet formed from a flame retardant resin composition for building materials, characterized by comprising 0.01 to 15 parts by mass of layered silicate ,
The above object has been achieved by providing a film or sheet characterized in that the average carbon monoxide concentration in a calorific value test using a corn calorimeter based on ISO 5660 is less than 1 ppm and the thickness is 50 to 1000 μm. Is.
(A) component: (poly) phosphate compound represented by the following general formula (1) (B) component: (poly) phosphate compound represented by the following general formula (3)

（式中、ｎは１〜１００の数を表し、Ｘ¹はアンモニア又は下記一般式（２）で表されるトリアジン誘導体であり、ｐは０＜ｐ≦ｎ＋２を満たす数を表す。）

（式中、Ｚ¹及びＺ²は同一でも異なっていてもよく、−ＮＲ⁵Ｒ⁶基〔ここで、Ｒ⁵及びＲ⁶は同一でも異なっていてもよく、水素原子、炭素原子数１〜６の直鎖若しくは分岐のアルキル基又はメチロール基である〕、水酸基、メルカプト基、炭素原子数１〜１０の直鎖若しくは分岐のアルキル基、炭素原子数１〜１０の直鎖若しくは分岐のアルコキシ基、フェニル基及びビニル基からなる群より選ばれるいずれかの基である。）

(In the formula, n represents a number of 1 to 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and p represents a number satisfying 0 <p ≦ n + 2.)

(In the formula, Z ¹ and Z ² may be the same or different, and —NR ⁵ R ⁶ group [wherein R ⁵ and R ⁶ may be the same or different; 6 linear or branched alkyl group or methylol group], hydroxyl group, mercapto group, linear or branched alkyl group having 1 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms. , Any group selected from the group consisting of a phenyl group and a vinyl group.)

（式中、ｒは１〜１００を表し、Ｙ¹は〔Ｒ¹Ｒ²Ｎ（ＣＨ₂）_mＮＲ³Ｒ⁴〕、ピペラジン又はピペラジン環を含むジアミンであり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、それぞれ、水素原子、又は炭素原子数１〜５の直鎖若しくは分岐のアルキル基であり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は同一の基であっても異なってもよく、ｍは１〜１０の整数であり、ｑは０＜ｑ≦ｒ＋２を満たす数を表す。）

(Wherein r represents 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ ], piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ And R ⁴ are each a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ may be the same or different. Well, m is an integer of 1 to 10, and q represents a number satisfying 0 <q ≦ r + 2.)

In the present invention (invention of claim 2), as the component (A), n in the general formula (1) is 2, p is 2, X ¹ is melamine (Z ¹ in the general formula (2)). And Z ² is —NH ₂
The film or sheet of Claim 1 using the melamine pyrophosphate which is) is provided.
Further, the present invention (invention described in claim 3), as the component (B), according to claim 1 or 2 q in the general formula (3) is 1, Y ¹ uses polyphosphoric acid piperazine piperazine The film or sheet is provided.
The present invention (invention according to claim 4) provides the film or sheet according to claim 3, wherein the piperazine polyphosphate is piperazine pyrophosphate.

Also, the present invention (invention according to claim 5) is one in which component (C) to provide a film or sheet according to claim 4 is talc.
Moreover, this invention (invention of Claim 6 ) provides the film or sheet | seat of any one of Claims 1-5 formed by mix | blending zinc oxide as (D) component further. .

Further, the present invention (invention according to claim 7) is either one of the claims 1-6, characterized in that the maximum concentration of carbon monoxide in the calorific value test with a cone calorimeter conforming to ISO5660 is 20ppm or less 1 The film or sheet described in the item is provided.

Further, the present invention (invention according to claim 8) is a layer of a film or sheet according to any one of claims 1 to 7 provides a interior material characterized by having at least one layer It is.
Further, the present invention (invention according to claim 9) is a layer of a film or sheet according to any one of claims 1 to 7 is provided a picture, characterized in that it comprises at least one layer is there.
Further, the present invention (invention according to claim 10) is to provide a building material sheet, characterized in that it consists of a film or sheet of any one of claims 1-7.

  According to the present invention, the generation of harmful gases such as carbon monoxide and acid gases and smoke is suppressed, and the resin composition for building materials having excellent flame retardancy such as a low calorific value, and wallpaper, sheet and the like comprising the same Interior material can be provided.

Hereinafter, the resin composition for flame-retardant building materials of the present invention will be described in detail.
First, the polyolefin resin used for the resin composition for flame-retardant building materials of the present invention will be described.
The polyolefin resin used in the present invention is a polymer mainly composed of ethylene and / or propylene. Examples of the ethylene polymer include ethylene homopolymers such as high pressure polyethylene, linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE); ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), Examples thereof include ethylene copolymers such as ethylene-ethyl methacrylate copolymer and ethylene-vinyl alcohol copolymer. The propylene-based polymer is usually a propylene homopolymer obtained by polymerizing propylene using a known α-olefin stereoregular catalyst such as a Ziegler-Natta catalyst; propylene and other propylene-based polymers and a random copolymer with an α-olefin (for example, ethylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1, etc.), specifically, a propylene homopolymer (Polypropylene), ethylene-propylene copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 terpolymer, and the like. A commercially available product may be used as the polyolefin resin.

Next, (A) component used for the resin composition for flame-retardant building materials of this invention is demonstrated.
The (poly) phosphate compound represented by the above general formula (1) used as the component (A) in the resin composition for flame retardant building materials of the present invention is (poly) phosphoric acid and ammonia or the above general formula ( It is a salt with the triazine derivative represented by 2).

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z ¹ and Z ² in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the linear or branched alkoxy group having 1 to 10 include groups derived from these alkyl groups. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ in the —NR ⁵ R ⁶ group that can be taken by Z ¹ and Z ² include, for example, the alkyls listed above. Examples of the group include those having 1 to 6 carbon atoms.

  Specific examples of the triazine derivative represented by the general formula (2) include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2, 4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5 -Triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy- Examples include 1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like.

  Among the (poly) phosphate compounds represented by the general formula (1), as the component (A), a salt of (poly) phosphoric acid and melamine or an ammonium polyphosphate compound is preferable, and (poly) phosphoric acid And melamine salts are particularly preferably used.

Examples of the salt of (poly) phosphoric acid and melamine include melamine polyphosphate such as melamine orthophosphate and melamine pyrophosphate. Among these, n in the above general formula (1) is 2, p Is particularly preferably melamine pyrophosphate wherein X ¹ is melamine. For example, in the case of melamine pyrophosphate, the salt of (poly) phosphoric acid and melamine is obtained by reacting sodium pyrophosphate and melamine by adding hydrochloric acid at an arbitrary reaction ratio and neutralizing with sodium hydroxide. Can be obtained.

  As said ammonium polyphosphate compound, what carried out various treatments to ammonium polyphosphate simple substance and ammonium polyphosphate, and what has ammonium polyphosphate as a main component (henceforth a compound which has ammonium polyphosphate as a main component) Said). Examples of the ammonium polyphosphate alone include Exolite-AP422, Exolite-AP750 manufactured by Clariant, Foschek-P / 30, Foschek-P / 40, manufactured by Monsanto, and Sumisafe-P, manufactured by Sumitomo Chemical Co., Ltd. Commercial products can be used.

  As a compound having ammonium polyphosphate as a main component, the surface of ammonium polyphosphate is coated with a material in which ammonium polyphosphate is coated or microencapsulated with a thermosetting resin, or with a melamine monomer or other nitrogen-containing organic compound. And those that have been treated with a surfactant or silicon, and those that have been made slightly soluble by adding melamine or the like in the process of producing ammonium polyphosphate. Commercially available products of such compounds include Clariant's Exolit-AP462, Sumitomo Chemical Co., Ltd. Sumisafe-PM, Budenheim's Buddit-3167, FR Cross-C30, FR Cross-C60, and the like. Can be mentioned.

Next, (B) component used for the resin composition for flame-retardant building materials of this invention is demonstrated.
The (poly) phosphate compound represented by the general formula (3) used as the component (B) in the resin composition for flame-retardant building materials of the present invention is represented by (poly) phosphoric acid and Y ^1. It is a salt with diamine. The diamine represented by Y ¹ is a diamine containing R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ , piperazine or a piperazine ring.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R ^{1 to} R ⁴ include those described above as specific examples of the alkyl group represented by Z ¹ and Z ² . The thing of 1-5 carbon atoms is mentioned. Examples of the diamine containing a piperazine ring include compounds in which one or more of the 2, 3, 5, and 6 positions of piperazine are substituted with an alkyl group (preferably having 1 to 5 carbon atoms); The compound which substituted the amino group of 4th-position with the alkyl group (preferably C1-C5 thing) substituted by the amino group is mentioned.

Examples of the diamine represented by Y ¹ in the general formula (3) include N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, and N, N′-diethyl. Ethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylene Diamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis ( 2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) pi Rajin, and the like. As these compounds, all commercially available products can be used.

Among the (poly) phosphate compounds represented by the general formula (3), the component (B) includes a salt of (poly) phosphoric acid and piperazine, that is, piperazine orthophosphate, piperazine pyrophosphate, etc. Piperazine polyphosphate is preferred. Among these, piperazine polyphosphate in which q in the general formula (3) is 1 and Y ¹ is piperazine is preferable, and piperazine pyrophosphate is particularly preferable.

  For example, in the case of piperazine pyrophosphate, the salt of (poly) phosphoric acid and piperazine is easily obtained as a poorly water-soluble precipitate by reacting piperazine and pyrophosphoric acid in water or in an aqueous methanol solution. When (poly) phosphate piperazine is used, it may be a salt obtained from polyphosphoric acid and piperazine made of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and other polyphosphoric acids. In this case, the structure of the raw material polyphosphoric acid is not particularly limited.

  In the resin composition for flame retardant building materials of the present invention, the blending amount of the component (A) is set to 100 parts by mass of the polyolefin resin from the viewpoint of suppressing the generation of flame retardant (total calorific value) and carbon monoxide. On the other hand, it is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, even more preferably 10 to 25 parts by mass, and 15 to 25 parts by mass. Most preferred.

  The blending amount of the component (B) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyolefin resin from the viewpoint of suppressing the generation of flame retardancy (total calorific value) and carbon monoxide. Is preferable, 1-40 mass parts is further more preferable, 5-40 mass parts is more preferable, 15-35 mass parts is still more preferable, and 20-30 mass parts is the most preferable.

  Furthermore, the total amount of the component (A) and the component (B) that are flame retardant components is preferably 1 to 90 parts by mass, and 5 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin component. Part is more preferable, 25-60 mass parts is still more preferable, and 35-55 mass parts is the most preferable. If it is less than 1 part by mass, it is difficult to obtain a sufficient flame retarding effect, and if it exceeds 90 parts by mass, the properties as a resin may be deteriorated.

  In addition, the blending ratio (mass basis) of the component (A) and the component (B) is (A) / (B) = from the viewpoint of suppressing flame retardancy (total calorific value) and generation of carbon monoxide. The ratio is preferably 20/80 to 50/50, and more preferably (A) / (B) = 30/70 to 50/50.

  Furthermore, in the flame-retardant building material resin composition of the present invention, a layered silicate is blended as the component (C) from the viewpoint of suppressing the generation of flame retardancy (total calorific value) and carbon monoxide. Is preferred. The layered silicate used as the component (C) is a layered silicate mineral and may have a cation between layers.

  The layered silicate is not particularly limited, for example, smectite clay minerals such as saponite, montmorillonite, hectorite, beidellite, stevensite, nontronite, talc, vermiculite, halloysite, swelling Sex mica etc. are mentioned. In the present invention, among these, it is preferable to use saponite or talc from the viewpoint of suppressing the generation of flame retardant (total calorific value) and carbon monoxide, particularly from the viewpoint of economics such as price. It is preferable to use talc.

  Examples of the saponite include Smecton SA (manufactured by Kunimine Kogyo Co., Ltd.), and examples of the montmorillonite include Sven (Hojun), Sven E (Hojun), Sven N-400 (Hojun). ), Sven No. 12 (Hojun Co., Ltd.) and the like, and examples of talc include fine powder talc MAICRO ACE series manufactured by Nippon Talc Co., Ltd., such as MAICRO ACE P-4, and ultrafine powder manufactured by Nippon Talc Co., Ltd. Examples include the talc SG series and the nano ace series manufactured by Nippon Talc Co., Ltd.

  The layered silicate in the present invention may be a natural product or a synthetic product. Moreover, these layered silicates may be used independently or 2 or more types may be used together.

  The cations that may be present between the layers of the layered silicate are metal ions such as sodium and calcium existing on the crystal surface of the layered silicate. Since these metal ions have a cation exchange property with a cationic substance, various substances having a cationic property such as an organic cation, a (quaternary) ammonium cation, a phosphonium cation, etc. It can be inserted (intercalated) between crystal layers.

The cation existing between the layers of the layered silicate used in the present invention may be a metal ion, or a part or all thereof may be an organic cation, a (quaternary) ammonium cation, or a phosphonium cation. good.
Examples of the metal ions include sodium ions, potassium ions, calcium ions, magnesium ions, lithium ions, nickel ions, copper ions, and zinc ions.
Examples of organic cations or quaternary ammonium cations include lauryl trimethyl ammonium cation, stearyl trimethyl ammonium cation, trioctyl methyl ammonium cation, distearyl dimethyl ammonium cation, di-cured tallow dimethyl ammonium cation, distearyl dibenzyl ammonium cation, etc. Can be mentioned.
These cations may be present alone or in combination of two or more.

  The amount of the component (C) layered silicate is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 12 parts by mass with respect to 100 parts by mass of the polyolefin resin. If the blending amount is less than 0.01 parts by mass, the flame retardancy (total calorific value) and the effect of suppressing the generation of carbon monoxide are small, and if it exceeds 15 parts by mass, the uniformity and the resin properties may be reduced. is there.

  Moreover, it is preferable to mix | blend zinc oxide as (D) component further to the resin composition for flame-retardant building materials of this invention. Zinc oxide may be surface-treated. Examples of zinc oxide include one type of zinc oxide (manufactured by Mitsui Kinzoku Kogyo Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Kinzoku Kogyo Co., Ltd.), nano fine 50 (ultrafine particle oxidation with an average particle size of 0.02 μm). Commercially available products such as zinc (manufactured by Sakai Chemical Industry Co., Ltd.) and nanofine K (ultrafine zinc oxide coated with zinc silicate having an average particle size of 0.02 μm: Sakai Chemical Industry Co., Ltd.) can be used. (D) It is preferable that the compounding quantity of the zinc oxide as a component is 0.01-10 mass parts with respect to 100 mass parts of polyolefin resin, and it is further more preferable that it is 0.1-5 mass parts.

  In the production of the resin composition for flame retardant building materials of the present invention, the timing of mixing the components (A) and (B) and, if necessary, the components (C) and (D) in the polyolefin resin is not particularly limited. . For example, two or more types selected from the components (A) to (D) may be pre-packed and then blended into the polyolefin resin, or each component may be blended with the polyolefin resin. Also good. In the case of making one pack, each component may be pulverized and mixed in advance, or may be pulverized after mixing each component in advance. It can mix | blend similarly when mix | blending resin and other arbitrary components other than the polyolefin-type resin mentioned later.

Moreover, you may mix | blend polycarbodiimide with the resin composition for flame-retardant building materials of this invention as an arbitrary component from a water-resistant point.
Examples of the polycarbodiimide that can be used in the present invention include (co) polymers using at least one selected from polyvalent isocyanate compounds. Specific examples of the polyvalent isocyanate include, for example, hexamethylene diisocyanate, xylene diisocyanate, cyclohexane diisocyanate, pyridine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, and p-phenylene diisocyanate. M-phenylene diisocyanate, 1,5-naphthylene diisocyanate and the like. As the polycarbodiimide, Carbodilite HMV-8CA and Carbodilite LA-1 manufactured by Nisshinbo Industries, Ltd. are preferable from the viewpoint of water resistance.

  In the case of using polycarbodiimide, the blending amount is preferably 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin from the viewpoint of water resistance. More preferred is 0.5-3 parts by mass. If it is less than 0.01 part by mass, the water resistance may be insufficient, and if it exceeds 10 parts by mass, the properties of the resin may be deteriorated.

  Moreover, you may mix | blend a foaming agent with the resin composition for flame-retardant building materials of this invention as an arbitrary component. In particular, when producing a wallpaper or sheet having a foamed resin layer foamed to give a three-dimensional design (volume feeling), the resin composition for flame-retardant building materials of the present invention containing a foaming agent is preferably used. be able to. A foamed resin layer is formed by containing a foaming agent in the resin layer and foaming the resin layer by placing it under a foaming temperature and pressure condition. As a method for producing the foamed resin layer, a method may be adopted in which a non-foamed sheet is once formed from a resin composition to which a foaming agent has been added in advance, and then the temperature is raised to change to a foamed resin sheet. The method of obtaining a foamed resin sheet directly from the added resin composition may be used.

Usable foaming agents are appropriately selected from chemical foaming agents and gas foaming agents (physical foaming agents) based on the molding method and molding temperature of the foamed resin sheet.
Chemical blowing agents include azo compounds such as azodicarbonamide and azobisisobutyronitrile, hydrazide compounds such as benzosulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), dinitrosopentamethylenetetramine And nitroso compounds, or a mixture thereof. These chemical foaming agents decompose by themselves depending on molding conditions and generate gas that contributes to foam molding. Moreover, you may use a foaming adjuvant with these foaming agents as needed. Examples of the foaming aid include zinc compounds such as zinc oxide and zinc stearate, and organic acids such as salicylic acid, phthalic acid, and oxalic acid.

Examples of the gas foaming agent (physical foaming agent) include halogenated hydrocarbons such as carbon dioxide and difluorodichloromethane, and hydrocarbons such as butane, pentane, hexane, cyclobutane, and cyclohexane. These physical foaming agents themselves become gas depending on molding conditions, and contribute to foam molding. As the gas foaming agent (physical foaming agent), carbon dioxide gas, butane gas, chlorofluorocarbon gas and the like are suitable.
One type of foaming agent may be used, or a plurality of types may be used in combination.

  Moreover, you may mix | blend resin other than polyolefin resin with the resin composition for flame-retardant building materials of this invention. As the resin other than the polyolefin-based resin, either a thermoplastic resin or a thermosetting resin can be used. A thermoplastic resin is preferable from the viewpoint of moldability, but a halogen-containing resin is not preferable from the viewpoint of non-halogen. Specific examples of resins other than polyolefin resins include polyester resins, polylactic acid resins, polyamide resins, polystyrene resins, polyacetal resins, polyurethane resins, aromatic and aliphatic polyketone resins, polyphenylene sulfide resins, polyetheretherketone resins, polyimides. Resin, thermoplastic starch resin, polystyrene resin, acrylic resin, AS resin, ABS resin, AES resin, ACS resin, AAS resin, vinyl ester resin, polyurethane resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, poly Ether sulfone resin, phenoxy resin, polyphenylene oxide resin, poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, polyvinyl alcohol resin, unsaturated polyester Ether resins, melamine resins, phenolic resins and urea resins.

In addition to the polyolefin resin, other acrylic rubbers, diene rubbers (for example, polybutadiene, polyisoprene), copolymers of diene and vinyl monomers (for example, styrene-butadiene random copolymers, styrene-butadiene blocks) Copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene , Butadiene-acrylonitrile copolymer), polyisobutylene, copolymer of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether rubber, epic Rohidoringomu, etc. may also be mentioned. Furthermore, those having various degrees of crosslinking, those having various microstructures such as cis structure, trans structure, etc., those having vinyl groups, or those having various average particle diameters (in the resin composition) In addition, a multi-layered polymer called a so-called core-shell rubber composed of a core layer and one or more shell layers covering the core layer, and adjacent layers made of different polymers can be used. A core-shell rubber containing a silicone compound can also be used.
The various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers, graft copolymers and the like.
Resins other than polyolefin resins may be used alone or in combination of two or more. In the case of using a resin other than the polyolefin-based resin, the blending amount thereof is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polyolefin-based resin. The following.

Moreover, you may mix | blend a fluorine-type drip inhibitor with the resin composition for flame-retardant building materials of this invention. However, when a fluorine-based anti-drip agent is added, care must be taken because it tends to cause a decrease in the melt flow rate (MFR) of the resin.
Specific examples of the fluorine anti-drip agent include, for example, fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, sodium perfluoromethanesulfonate, and potassium perfluoro-n-butanesulfonate. Perfluoroalkanesulfonic acid alkali metal salt compounds or perfluoroalkanesulfonic acid alkali compounds such as perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, and perfluoro-2-ethylhexanesulfonic acid calcium salt Examples include earth metal salts. These may be used alone or in combination of two or more. Similarly, silicon rubbers can be blended as other anti-drip agents.

A silicone oil may be blended in the flame retardant building material resin composition of the present invention in order to suppress secondary aggregation during blending and to improve water resistance.
Silicone oil having a methylpolysiloxane structure includes only a dimethylpolysiloxane structure, a structure including both a dimethylpolysiloxane structure and a methylhydrogenpolysiloxane structure, and only a methylhydrogenpolysiloxane structure. Things. Moreover, you may use what carried out 1 or more types of modification | denaturation selected from epoxy modification, carboxyl modification, carbinol modification, and amino modification as said silicone oil.

  Examples of silicone oils that can be used in the present invention include KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.) having a methyl hydrogen structure of 100%, and HMS having a part of methyl hydrogen structure. -151 (manufactured by Gelest), HMS-071 (manufactured by Gelest), HMS-301 (manufactured by Gelest), DMS-H21 (manufactured by Gelest), and the like. 2000 (Shin-Etsu Chemical Co., Ltd.), KF-102 (Shin-Etsu Chemical Co., Ltd.), carboxyl modified products, for example, X-22-4015 (Shin-Etsu Chemical Co., Ltd.), carbinol modified products, For example, X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.) and examples of amino-modified products include KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.). It is.

Moreover, you may mix | blend a silane coupling agent with the resin composition for flame-retardant building materials of this invention. A silane coupling agent is a compound having an organic functional group and a hydrolyzable group, and is represented by, for example, A— (CH ₂ ) _k —Si (OR) ₃ . A is an organic functional group, k represents a number of 1 to 3, and R represents a methyl group or an ethyl group. Examples of the organic group of A include an epoxy group, a vinyl group, a methacryl group, an amino group, and a mercapto group. As the silane coupling agent, those having an epoxy group are particularly preferable.

  Moreover, it is also preferable to mix | blend a reinforcing agent with the resin composition for flame-retardant building materials of this invention. As the reinforcing material, fibrous, plate-like, granular, or powdery materials that are usually used for reinforcing thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber and other inorganic fibrous reinforcements, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, Organic fiber reinforcements such as kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper waste, waste paper and wool, glass flakes, non-swellable mica, graphite, metal foil ,ceramic Zeolite, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, Examples include plate-like and granular reinforcing materials such as aluminum silicate, silicon oxide, gypsum, nobaclite, dosonite, and clay. These reinforcing materials may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or with a coupling agent such as aminosilane or epoxysilane. It may be processed.

  Moreover, you may mix | blend a crystal nucleating agent with the resin composition for flame-retardant building materials of this invention. As the crystal nucleating agent, those generally used as polymer crystal nucleating agents can be used without particular limitation, and any of inorganic crystal nucleating agents and organic crystal nucleating agents can be used. Specific examples of inorganic crystal nucleating agents include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, and oxidation. Examples thereof include metal salts of neodymium and phenylphosphonate. These inorganic crystal nucleating agents may be modified with an organic substance in order to enhance the dispersibility in the composition.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, etc., organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid amide , Carboxylic acid amides such as ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), benzylidenesorbitol and its derivatives, sodium-2,2′-methylenebis (4 , 6-di-t-butylphenyl) phosphate, phosphorus compound metal salts, and 2,2-methylbis (4,6-di-t-butylphenyl) sodium.

  Moreover, you may further mix | blend a plasticizer with the resin composition for flame-retardant building materials of this invention. As the plasticizer, those generally used as polymer plasticizers can be used without particular limitation, and examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and the like. An epoxy-type plasticizer etc. can be mentioned.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol, and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of polyvalent carboxylic acid ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellit Trimellitic acid ester such as tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipine Adipic acid esters such as benzylbutyl diglycol acid, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid Butyl, and sebacic acid esters such as di-2-ethylhexyl sebacate, and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols. And a polyoxyalkylene glycol such as a propylene oxide addition polymer, a tetrahydrofuran addition polymer of a bisphenol, or a terminal blocking compound such as a terminal epoxy-modified compound, a terminal ester-modified compound, and a terminal ether-modified compound.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are other so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, and paraffins.
When using a plasticizer, it may be used alone or in combination of two or more.

  In addition, the flame retardant building material resin composition of the present invention further includes, as necessary, a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, and the like. It is also preferable to stabilize the resin composition by adding.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl- 4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-) Cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tertiary) Butyl-m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) Benzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxy) Benzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-) Tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3- Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undeca And triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. The amount of the phenolic antioxidant used is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4- Ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritertiarybutylphenyl) pentaerythritol Diphosphite, bis (2,4-dicumylphenyl) pe Taerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6 Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl ) Oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. The amount of these phosphorus antioxidants used is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate). The amount of these thioether antioxidants to be used is preferably 0.001 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferred.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxy). 2-hydroxybenzophenones such as benzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'- Trioctylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis 2- (2′-hydroxyphenyl) such as 4-tert-octyl-6- (benzotriazolyl) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole ) Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5- Benzoates such as di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyl Substituted oxanilides such as oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano- Cyanoacrylates such as methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s -Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2 , 4-ditertiarybutylphenyl) -s-triazine and the like. The amount of the ultraviolet absorber used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2 , 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl). Di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di Tributyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2 , 2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl -4-piperidylamino) Xanthane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2, , 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like. The amount of these hindered amine light stabilizers used is preferably 0.001 to 30 parts by mass and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Further, the resin composition for flame retardant building materials of the present invention includes a triazine ring-containing compound, a metal hydroxide, a phosphate ester flame retardant, a condensed phosphate ester flame retardant, and a phosphate flame retardant as necessary. Addition of inorganic phosphorus flame retardant, silicon flame retardant, other inorganic flame retardant aid, other organic flame retardant aid, hydrotalcite, antistatic agent, metal soap, filler, pigment, lubricant, etc. May be.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimeramine and the like can be mentioned.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.

  Examples of the phosphate ester flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl Diphenyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- ( t-butylphenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropyl phosphate) Sulfonyl) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

  Examples of the above-described condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.

  Examples of the other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and hydrotalcite, and surface-treated products thereof. As these inorganic flame retardant aids, for example, TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite) : Kyowa Chemical Industry Co., Ltd.), Alkamizer 4 (Zinc-modified hydrotalcite: Kyowa Chemical Industry Co., Ltd.) and other commercial products can be used. Moreover, as said other organic type flame retardant adjuvant, a pentaerythritol is mentioned, for example.

  Among the optional components other than the components (A) to (D), when a flame retardant or a flame retardant aid is used, the blending amount thereof is not particularly limited as long as the effects of the present invention are not impaired. However, the total content is preferably 15 parts by mass or less with respect to 100 parts by mass of the polyolefin resin.

  In addition, the flame retardant building material resin composition of the present invention may include, for example, a crosslinking agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a fluorescent agent, an antifungal agent, a bactericidal agent, and a metal as necessary. Additives usually used for synthetic resins, such as an inactive agent, a release agent, a processing aid, an antioxidant, and a light stabilizer, can be blended as long as the effects of the present invention are not impaired.

  When blending optional components other than the components (A) to (D) (excluding resins other than polyolefin-based resins), the blending amount is not particularly limited as long as the effects of the present invention are not impaired. However, the total content is preferably 15 parts by mass or less with respect to 100 parts by mass of the polyolefin resin.

  The flame retardant building material resin composition of the present invention can be used as an interior material after being formed into a film or sheet by a conventionally known method. The film or sheet formed from the resin composition for flame-retardant building materials of the present invention can be used alone or in combination with other materials as interior materials such as wallpaper and flooring. For example, in the case of wallpaper, the resin composition for flame retardant building materials may be formed into a film or sheet to form a resin layer, which is then adhered and laminated to paper or the like as a base material by a conventional method. From the viewpoint of ensuring sufficient flame retardancy, the film or sheet (resin layer) formed from the resin composition for flame retardant building materials of the present invention preferably has a thickness of 50 to 2000 μm, more preferably 50 to 1000 μm, Most preferably, it is 50-500 micrometers. The said interior material should just have at least 1 layer of resin layers formed from the resin composition for flame-retardant building materials of this invention, and may have 2 or more layers of this resin layer. When it has two or more resin layers formed from the resin composition for flame-retardant building materials of this invention, it is desirable that the thickness of each resin layer is said preferable range. Moreover, interior materials other than wallpaper can also be produced according to the above.

  The flame retardant building material resin composition of the present invention is suitable for building materials, particularly interior materials, because it has a reduced total calorific value and generation of harmful gases, especially in the form of films, sheets, and plates. The effect can be exhibited particularly when the shape is made. Specifically, it is suitable as a material for wallpaper, wall materials, floor materials, ceiling boards, decorative boards, decorative sheets, films for building materials, sheets for building materials, and the like.

  The film or sheet formed from the above-described resin composition for flame-retardant building materials of the present invention can also be used as the above-described film for building materials or sheet for building materials. The film for building materials or the sheet for building materials may have various functions such as anti-slip properties, moisture-proof (humidity control) properties, sound-proof (sound insulation) properties, and heat insulation properties. The building material film or the building material sheet can be used in the same manner as conventionally known. For example, as described above, the building material film or the building material sheet can be used as an interior material alone or laminated and used in combination with other materials. It can also be applied to the inside of walls, ceilings, floors, etc., as sheets, soundproof sheets, heat insulation sheets and the like.

  Moreover, the resin composition for flame-retardant building materials of the present invention is characterized in that generation of carbon monoxide during smoke generation or combustion is suppressed. For example, regarding the generation of carbon monoxide, the building material obtained from the resin composition for flame retardant building materials of the present invention has a maximum carbon monoxide concentration of 20 ppm or less, particularly less than 1 ppm, in a corn calorimeter test according to ISO 5660. It is preferable that the harmfulness of the combustion gas is suppressed to the level of. In addition, the building material obtained from the flame retardant building material resin composition of the present invention has reduced combustion gas toxicity to an average carbon monoxide concentration of less than 1 ppm in a test using a cone calorimeter in accordance with ISO 5660. It is preferable.

EXAMPLES Hereinafter, although an Example etc. show this invention in detail, this invention is not restrict | limited at all by the following Examples. Examples 1 and 4 are reference examples.

[Examples 1-7 and Comparative Examples 1-4]
70 parts by mass of ethylene-vinyl acetate copolymer (EVA) (Ultrasen 515, manufactured by Tosoh Corporation), 0.1 part by mass of calcium stearate (lubricant), tetrakis [3- (3,5-ditertiarybutyl -4-hydroxyphenyl) methyl propionate] methane (phenolic antioxidant) 0.1 parts by mass and tris (2,4-di-tert-butylphenyl) phosphite (phosphorus antioxidant) 0.1 The ethylene-vinyl acetate copolymer resin composition obtained by blending parts by mass and the components shown in Table 1 below were blended and then extruded at 170 to 190 ° C. to produce pellets. The obtained pellets were press-molded at 190 ° C. to obtain 100 mm × 100 mm × 0.2 mm test sheets (Examples 1 to 7). Moreover, the test sheet | seat was similarly created using magnesium hydroxide as a comparative flame retardant (Comparative Examples 1-4). In addition, all the mixing | blendings of Table 1 are a mass part reference | standard.

(A) component and (B) component of Table 1 were manufactured with the following method.
[Production Example 1]
(A) Component: Melamine pyrophosphate Pyrophosphate and melamine were produced by reacting at a molar ratio of 1: 1.
[Production Example 2]
(B) Component: Piperazine pyrophosphate Pyrophosphate and piperazine were produced by reacting at a molar ratio of 1: 1.

About the test sheet | seat obtained above, the following flame retardance evaluation, smoke generation evaluation, and carbon monoxide density | concentration evaluation were performed.
<Flame retardance evaluation>
About the test sheet | seat obtained above, the calorific value test based on ISO5660 is done using a cone calorimeter (CONE III made by Toyo Seiki Seisakusho Co., Ltd.), and the heat release rate (Heat Release Rate) is set to 50 kW / m in the radiant heat condition. Measured at ² . Table 1 shows the total heat generation amount (MJ / m ² ), the maximum heat generation rate (kW / m ² ), and the maximum heat generation rate duration (seconds).
<Smoke generation evaluation>
Using the corn calorimeter, the smoke concentration was measured in the same manner. The maximum smoke density is shown in Table 1.
<Evaluation of carbon monoxide concentration>
The carbon monoxide concentration was measured using the corn calorimeter. Table 1 shows the maximum carbon monoxide concentration and the average monoxide concentration from the time of ignition until 150 seconds had elapsed.

Claims (10)

The following (A) component 5-40 mass parts and the following (B) component 5-50 mass parts with respect to 100 mass parts of polyolefin resin , Furthermore, as a (C) component, 0.01-15 mass parts of layered silicates A film or sheet formed from a flame retardant resin composition for building materials, characterized by comprising:
The film or sheet | seat characterized by the average carbon monoxide density | concentration in the calorific value test by the cone calorimeter based on ISO5660 being less than 1 ppm, and the thickness being 50-1000 micrometers.
(A) component: (poly) phosphate compound represented by the following general formula (1) (B) component: (poly) phosphate compound represented by the following general formula (3)

(In the formula, n represents a number of 1 to 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and p represents a number satisfying 0 <p ≦ n + 2.)

(In the formula, Z ¹ and Z ² may be the same or different, and —NR ⁵ R ⁶ group [wherein R ⁵ and R ⁶ may be the same or different; 6 linear or branched alkyl group or methylol group], hydroxyl group, mercapto group, linear or branched alkyl group having 1 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms. , Any group selected from the group consisting of a phenyl group and a vinyl group.)

(Wherein r represents 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ ], piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ And R ⁴ are each a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ may be the same or different. Well, m is an integer of 1 to 10, and q represents a number satisfying 0 <q ≦ r + 2.) As the component (A), melamine pyrophosphate in which n in the general formula (1) is 2, p is 2, and X ¹ is melamine (Z ¹ and Z ² in the general formula (2) are —NH ₂ ) is used. The film or sheet according to claim 1 to be used. The film or sheet according to claim 1 or 2, wherein piperazine polyphosphate in which q in the general formula (3) is 1 and Y ¹ is piperazine is used as the component (B).   The film or sheet according to claim 3, wherein the piperazine polyphosphate is piperazine pyrophosphate. The film or sheet according to claim 4 , wherein the component (C) is talc. Furthermore, the film or sheet | seat of any one of Claims 1-5 formed by mix | blending zinc oxide as (D) component. The film or sheet according to any one of claims 1 to 6 , wherein a maximum carbon monoxide concentration in a calorific value test using a corn calorimeter based on ISO 5660 is 20 ppm or less. An interior material comprising at least one layer comprising the film or sheet according to any one of claims 1 to 7 . A wallpaper comprising at least one layer comprising the film or sheet according to any one of claims 1 to 7 . A sheet for building materials, comprising the film or sheet according to any one of claims 1 to 7 .