JPH07241948A - Fire retardant polyolefinic laminate - Google Patents

Abstract

PURPOSE:To enhance the fire retardancy by providing a skin layer using a specific polypropylene resin indoor a polyolefinic elastomer and a foam layer composed of a specific resin compsn. CONSTITUTION:A laminate is constituted of a skin layer with a thickness of 0.1-1mm consisting of a polyolefinic elastomer and/or a polypropylene resin characterized by that a wt. average mol.wt. is 80000-50,0000 and a resin elution amt. up to 0 deg.C by a cross fractionation method is 25-75wt.% per the total amt. of a polypropylene resin and resin elution amts. within temp. ranges above 80-100 deg.C and above 100-125 deg.C are respectively 5-45, 2 45 and 2-40wt.% and a polyolefinic foam layer with a thickness of 0.5-5mm composed of a resin compsn. consisting of 0-85wt.% of a polypropylene resin and 100-15wt.% of a polyethylene resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having a skin material layer using a specific polypropylene resin and / or a polyolefin elastomer and a foam layer of a polyolefin resin. More specifically, it relates to a flame-retardant polyolefin-based laminate in which both the skin material layer and the foam layer contain a mixed flame-retardant compound composed of a nitrogen compound and a phosphorus compound.

[0002]

2. Description of the Related Art Conventionally, as an interior material for ceilings, doors, and instrument panels of automobiles, etc., a plasticized polyvinyl chloride resin (hereinafter referred to as plasticized PVC) layer whose surface is embossed or embossed is used. In general, a plasticized PVC layer formed by laminating a crosslinked foam layer and an interior aggregate layer on the plasticized PVC layer has been used. For example, in Japanese Patent Laid-Open No. 4-219230, a sheet layer made of a textured thermoplastic synthetic resin,
A laminate comprising a foam layer and a fiber layer using thermoplastic fibers containing PVC is disclosed. However, in recent years, the use of plasticized PVC containing chlorine has been restrained particularly in the automobile industry due to environmental issues and the like.

Therefore, in recent years, various thermoplastic elastomers have been used in place of plasticized PVC. For example, Japanese Patent Publication No. 1-14032 and Japanese Patent Publication No. 3-25346 disclose that a polyolefin-based resin
A blend with an ethylene-α-olefin copolymer rubber partially crosslinked with a peroxide is disclosed.
Further, JP-A-4-320838 and JP-A-4-320838.
Japanese Patent No. 334445 discloses a laminate composed of a layer made of a thermoplastic elastomer and a layer made of an ultrahigh molecular weight polyolefin. In JP-A-5-4307, a laminate composed of a layer made of a graft-modified polyolefin-based elastomer and a layer made of an ultra-high molecular weight polyolefin which are dynamically heat-treated in the presence of an organic peroxide and partially cross-linked. The body is disclosed.

However, since these laminated bodies are characterized by containing no halogen at all, the halogen-based flame retardants conventionally used cannot be used at all, and development of non-halogen flame retardants has recently been demanded. There is.

By the way, as flame retardants used conventionally, for example, brominated flame retardants and antimony trioxide composite flame retardants are often used. Generally, these halogen-based flame retardants have large effects, and in order to achieve flame retardancy with non-halogen flame retardants, they are disclosed in, for example, JP-A-49-5171 and JP-A-3-269029. As described above, attempts have been made to add inorganic substances such as magnesium hydroxide and basic magnesium carbonate. However, in order to impart sufficient flame retardancy to a material that is easily flammable such as polyolefin, it is necessary to add a large amount of the above-mentioned inorganic substances, in which case the polyolefin cannot be foamed or the skin material layer There is a problem that mechanical properties are deteriorated.

[0006]

SUMMARY OF THE INVENTION In the present invention, plasticized PVC provided by using a specific polypropylene resin and / or polyolefin elastomer
A mixed flame-retardant compound composed of a nitrogen compound and a phosphorus compound is formed on both layers of a laminate in which an alternative skin material layer and a foam layer made of a foam of a resin composition having a specific polyolefin resin blending ratio are laminated. The present invention is to provide a polyolefin-based laminate that can impart flame retardancy without impairing the desirable characteristics of the skin material layer and the foam layer by containing the.

[0007]

Thus, the flame-retardant polyolefin-based laminate of the present invention has, as the first layer, a polyolefin-based elastomer and / or a weight average molecular weight within the range of 80,000 to 500,000. The resin elution amount up to 0 ° C by the cross fractionation method is 25 to 75% by weight of the total polypropylene-based resin amount,
The resin elution amount in the temperature range of ℃ or below is 5 to 45% by weight of the total polypropylene resin amount,
The resin elution amount in the temperature range of 00 ° C or lower is 2 to 45% by weight of the total polypropylene resin amount, and the resin elution amount in the temperature range of 100 ° C to 125 ° C is 2 to 40% of the total polypropylene resin amount. It is made of polypropylene resin having a composition of wt% and has a thickness of 0.1.
A skin material layer having a thickness of 1 mm and a second layer having a polypropylene resin content of 0 to 85% by weight and a polyethylene resin content of 1
And a polyolefin-based foam layer having a thickness of 0.5 to 5 mm.

Each of the surface material layer and the foam layer contains a mixed flame retardant compound composed of a nitrogen compound and a phosphorus compound, and the mixed flame retardant compound is added to 100 parts by weight of the resin composition constituting each layer. 5-100 in the surface material layer
Parts by weight, and 25 to 100 parts by weight in the foam layer.

In a preferred embodiment, the flame-retardant polyolefin foam of the present invention has a structure in which the phosphorus compound is represented by the following formula (1) or (2).

[0010]

[Chemical 4]

(Wherein n is an integer of 20 or more,
A ¹ , A ² , and A ³ are the same or different,
Each independently, H, NH _2, or CONH _2. However, A ¹ , A ² , and A ³ are all H or C
It is never ONH ₂ . )

[0012]

[Chemical 5]

(In the formula, R ¹ is hydrogen or carbon atom 1
Is a linear or branched alkyl group or aryl group having 16 to 16, R ² is a hydroxyl group, hydrogen, or a linear or branched alkyl group having 1 to 16 carbon atoms, an alkoxy group, An aryl group or an aryloxy group, R ³ is hydrogen, or 1 to 16 carbon atoms.
Is a linear or branched alkyl group or aryl group having a number).

In a preferred embodiment, the flame-retardant polyolefin-based laminate of the present invention has a structure in which the nitrogen compound is represented by the following formula (3).

[0015]

[Chemical 6]

(In the formula, R ^{4 to} R ⁶ are each independently hydrogen, or a hydroxyalkyl group having 1 to 16 carbon atoms, a dihydroxyalkyl group, a hydroxyaryl group or a dihydroxyaryl group.) The present invention will be described in detail.

The flame-retardant polyolefin-based laminate of the present invention comprises
A skin material layer as a first layer and a polyolefin-based foam layer as a second layer are laminated and formed.

The skin material layer in the present invention is formed using a polyolefin elastomer and / or a specific polypropylene resin.

As the above-mentioned polyolefin-based elastomer, an ethylene-α-olefin-based copolymer rubber dynamically partially cross-linked using a polyolefin-based resin, an organic peroxide and a polyfunctional monomer (for example, divinylbenzene). Those composed of a blend of and are preferably used. Specific examples thereof include "Milastomer" manufactured by Mitsui Petrochemical Co., Ltd. and "Sumitomo TPE" manufactured by Sumitomo Chemical Co., Ltd.

The specific polypropylene resin has a weight average molecular weight within the range of 80,000 to 500,000. Preferably 100,000-4
It is 50,000. This weight average molecular weight is 80,000
If it is less than 0, a problem occurs in the strength of the obtained laminate,
If it is more than 10,000, the extrudability and the forming extensibility when used as an interior material are insufficient.

The amount of resin eluted by the cross fractionation method used in the present invention is measured as follows. First, dissolve the polypropylene resin in o-dichlorobenzene at 140 ° C or the temperature at which the polypropylene resin is completely dissolved,
Cooling at a constant rate, a thin polymer layer is formed on the surface of an inert carrier prepared in advance in the order of increasing crystallinity and increasing molecular weight. Next, the temperature of the generated polymer layer is continuously or stepwise increased, and the concentrations of the components eluted in sequence are detected,
The composition distribution (crystallinity distribution) is measured <temperature rising elution fractionation>. At the same time, the molecular weight and molecular weight distribution of the component are measured by high temperature GPC. For example, the temperature rising elution fractionation (TREF = Temperature Rising Elutio
n Fractionation part and high temperature GPC (SEC = Size Ex
Cross-fractionation chromatograph device <CFC-T15, which is equipped with
Model OA: manufactured by Mitsubishi Petrochemical Co., Ltd.> can be used.

The polypropylene resin used for forming the skin material layer has a resin elution amount up to 0 ° C. of 25 to 7 of the total polypropylene resin amount by the cross fractionation method.
It is 5% by weight, preferably 30 to 75% by weight.
If this elution amount is less than 25% by weight, the flexibility and texture of the obtained skin material layer will be deteriorated, and if it is more than 75% by weight, the strength will be too strong and problems such as extensibility will occur.

The resin elution amount in the temperature range from 0 ° C. to 80 ° C. is 5 to 45% of the total polypropylene resin amount.
% By weight, preferably 8 to 43% by weight. When this elution amount is less than 5% by weight, the flexibility of the obtained skin material layer is lowered, and when it is more than 45% by weight, there is a problem in the extensibility.

The resin elution amount in the temperature range of higher than 80 ° C. and lower than 100 ° C. is 2 to the total polypropylene resin amount.
It is 45% by weight, preferably 2-40% by weight.
When the elution amount is less than 2% by weight, the extensibility of the obtained skin material layer is low, and when it is more than 45% by weight, the texture and the flexibility are deteriorated.

The resin elution amount in the temperature range of more than 100 ° C. and less than 125 ° C. is 2% of the total polypropylene resin amount.
˜40% by weight, preferably 2-35% by weight. When the elution amount is less than 2% by weight, the strength of the obtained skin material layer decreases, and when it exceeds 40% by weight, the texture and the flexibility are poor.

The above polypropylene-based resin is produced, for example, by the following multistage polymerization method. First, as a first step, polymerization is carried out in the presence of a titanium compound catalyst and an aluminum compound catalyst using a propylene monomer and optionally an α-olefin monomer other than propylene to obtain a first polypropylene resin. The polypropylene resin may be a propylene homopolymer, a propylene-ethylene copolymer, a propylene-α-olefin copolymer, or the like. In the second step, a titanium-containing polypropylene-based resin and an olefin monomer (for example, ethylene, propylene, or α-olefin) are copolymerized in the presence of the above-mentioned compound in the presence of the titanium compound catalyst and the aluminum compound catalyst. Let me
A second copolymer resin is obtained. The second copolymer resin obtained by this two-step reaction may be a propylene-ethylene copolymer, a propylene-α-olefin copolymer, or an ethylene-α-olefin copolymer. Similarly, a multi-step copolymerization reaction can be performed depending on the purpose. The α-olefin refers to a C ₄ or more aliphatic hydrocarbon compound, and examples thereof include 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl 1-pentene, and 1-octene. . The feature of this production method is that the polymerization is not completed in one step, but multi-step polymerization of two or more steps is performed. This allows multiple types of polymers to be built up in succession, producing blend-type copolymers at the molecular level, which is quite different from conventional polymer blends.

Generally, in the case of polymer blends, one way to improve flexibility and stretchability is to increase the molecular weight of the rubber component to be blended. In the case of the polypropylene-based resin used in the present invention, this rubber component corresponds to the components (propylene-ethylene, propylene-α-olefin, ethylene-
α-olefin), and since this component has a high molecular weight, it has a high melt viscosity. This rubber component can be finely dispersed in the polypropylene resin obtained in the first step by using the above-mentioned multistage polymerization method. However, in a blending method using an ordinary extruder or the like, when a rubber component having such a high molecular weight is used, the melt viscosity is high. Therefore, a resin having a finely dispersed morphology like the polypropylene resin used in the present invention is It cannot be made. Furthermore, in resins such as polypropylene-based block copolymers obtained by conventional reactions, the copolymerized ethylene, α-
The block component such as olefin is limited to about 50 wt% with respect to polypropylene as the main component due to its manufacturing process, and the content is usually up to 30 wt%. For this reason, it has been very difficult to realize flexibility such as plasticized PVC in polypropylene resin. However, when the above-mentioned method is used, the copolymerization component can be contained up to about 80 to 95% by weight, and a polypropylene resin having the same physical properties as plasticized PVC can be obtained.

As such a manufacturing method, for example, there is a method described in JP-A-4-224809. In this method, as a titanium compound, for example, titanium trichloride and magnesium chloride are co-ground, and this is orthotitanic acid n
A spherical solid titanium catalyst having an average particle diameter of 15 μm, which is obtained by treating with —butyl, 2-ethyl-1-hexanol, ethyl p-toluate, silicon tetrachloride, diisobutyl phthalate, or the like, is used. In this method, a silicon compound, especially diphenyldimethoxysilane, is added as an electron donor to the polymerization tank, and ethyl iodide is further added. Further, JP-A-3-97747 discloses that a titanium compound obtained by treating an adduct of magnesium chloride and alcohol with titanium tetrachloride and an electron donor is used. In addition to these methods, for example, JP-A-4-96912, JP-A-4-96907, JP-A-3-174410, and JP-A-2-170803.
No. 2, 170, 802 and No. 3, 20543.
No. 9, JP-A-61-42553 and the like describe such a manufacturing method. In producing the polypropylene resin forming the flame-retardant polyolefin-based laminate of the present invention, any known method as described above can be used. Examples of actual resins obtained by such a production method include "PER" manufactured by Tokuyama Soda Co., Ltd. and "Cataloy" manufactured by Highmont Co., Ltd. (polypropylene resin polymerized by the Cataloy process; Profax). Any of these can be used in the present invention.

The skin material layer has a thickness of 0.1 to 1 m.
m, and preferably 0.15 to 0.8 mm. If the thickness is not within this range, the desired strength and texture of the skin material layer cannot be obtained.

The above skin material layer is a mold T that is generally used.
Any die can be molded and optionally coextruded. In this case, a feed block die, a multi-manihole die, a multi-throttle die and the like can be exemplified, and any one may be used.

The skin material layer is a coat hanger type T die, or a feed block die of 5 layers of 3 types, 2
By using a multilayer extrusion die such as a two-layer multi-manifold type die, a single layer or a polypropylene-based resin specified by a cross fractionation method, which is used as a skin material layer in the present invention, is specified. If necessary, it can be multi-layered or can be coated with another olefin resin. Moreover, when extruding, the surface of the skin material layer may be subjected to embossing, graining, or the like, if necessary.

Further, the skin material layer in the present invention is coated with a top coat made of an acrylic resin or a urethane resin in order to improve the scratch resistance of the skin, and a skin is used as long as the non-halogen flame retardancy is not hindered. Printing can be coated to enhance the design of the material layer.

The foam layer as the second layer in the present invention is a foam of a resin composition comprising 0 to 85% by weight of a polypropylene resin and 100 to 15% by weight of a polyethylene resin.

When the foam layer is formed using a polypropylene resin, the polypropylene resin used may be a propylene homopolymer, a propylene-based copolymer, or a mixture thereof. Further, in order to improve the foaming suitability (control [UP] the resin melt viscosity during foaming), this polypropylene resin is
It may have a broad molecular weight distribution or have a long-chain branched structure introduced.

As the above copolymer, 85% propylene was used.
Examples thereof include a propylene-ethylene copolymer and a propylene-α-olefin copolymer which are contained in an amount of not less than wt%. In this case, as the α-olefin, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like are exemplified.

The polypropylene-based resin preferably has a melt index (hereinafter abbreviated as "MI";
Measured according to ASTM D1238) is 0.2 to 20. When the MI of the polypropylene resin is less than 0.2, it becomes difficult to form the foam layer into a sheet, and when the MI is more than 20, the heat resistance becomes poor.

The polyethylene resin used in the foam layer may be a polyethylene homopolymer, a copolymer containing ethylene as a main component, or a mixture thereof. As the polyethylene homopolymer, linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ultra low density polyethylene (VLDPE, U)
LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), etc. are illustrated.

Examples of the above-mentioned copolymer include ethylene-α-olefin copolymer containing 80% by weight or more of ethylene. In this case, as the α-olefin,
Examples include propylene, 1-butene, 1-pentene, 1-heptene, 1-hexene, 1-octene and the like.

Further, as the copolymer other than α-olefin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the like may be used alone or in combination.

The polyethylene resin is preferably
Its MI is 0.1-40. When the MI is less than 0.1, a problem occurs in appearance when the foam layer is formed into a sheet, and when the MI exceeds 40, a problem occurs in strength.

In the foam layer in the present invention, the amount of the polypropylene resin present is 0 to 85% by weight, and when it exceeds 85% by weight, the flexibility of the foam layer is lost, which is not preferable.

The foam used to form the foam layer in the present invention must have a sufficient degree of crosslinking in order to obtain sufficient strength and moldability. This degree of crosslinking is
It is represented by the xylene extraction residue value at 120 ° C. The foam preferably has a xylene extraction residue value in the range of 20 to 80% by weight. When the xylene extraction residual value is less than 20% by weight, air bubbles melt and flow during the lamination of the foam layer, which makes it difficult to laminate. When it exceeds 80% by weight, the foam layer obtained has poor flexibility. .

The above-mentioned foam may be crosslinked depending on the heat resistance of the finally obtained foam layer, the foaming method and the like. As a general cross-linking method, a method of thermally decomposing a radical generator such as a peroxide mixed in a resin to cross-link, cross-linking by irradiation of ionizing radiation, in the presence of a polyfunctional monomer as a cross-linking aid Examples thereof include crosslinking with peroxides or ionizing radiation, and silane crosslinking.

When the foam is crosslinked, a crosslinking aid may be used. The cross-linking aid used in the present invention may be any polyfunctional monomer as long as it causes a cross-linking reaction by an electron beam, radiation, or a peroxide, and two or more kinds thereof are mixed and used. May be. As typical examples thereof, aromatic or aliphatic compounds containing one or more vinyl groups or allyl groups in one molecule, and compounds containing one or more acryloyloxy groups or methacryloyloxy groups. Is mentioned.

Examples of the crosslinking aid include divinylbenzene, diallylbenzene, divinylnaphthalene, trimethylolpropane trimethacrylate, ethylvinylbenzene, 1,9-nonanediol dimethacrylate, 1-nonanealcohol monomethacrylate, 1,6.
-Hexanediol methacrylate, 2,2-bis [4
-(Acryloxydiethoxy) phenyl] propane,
1,2,4-benzenetricarboxylic acid triallyl ester, 1,2-benzenedicarboxylic acid diallyl ester,
1,3-benzenedicarboxylic acid diallyl ester, 1,
4-benzenedicarboxylic acid diallyl ester, and related homologs thereof.

The above-mentioned cross-linking aid is usually added in a proportion of 0.05 to 10 parts by weight with respect to 100 parts by weight of the resin composition forming the foam layer. If the amount is less than 0.05 parts by weight, crosslinking is insufficient, a homogeneous foam cannot be obtained, and the strength at high temperature becomes insufficient. If the blending ratio of the cross-linking aid exceeds 10 parts by weight, the cross-linking density becomes too high, which causes a problem in moldability.

When the ratio of the polyethylene resin to the resin composition forming the foam layer exceeds 80% by weight, the crosslinking aid may be omitted. This is because the polyethylene resin is self-crosslinking, and a sufficient crosslinked product can be obtained by applying a crosslinking means such as electron beam irradiation without a crosslinking aid.

The radical generator may be any of those generally used, and examples thereof include benzoyl peroxide, octanoyl peroxide, decanoyl peroxide, acetyl peroxide, tertiary butyl peroxyisobutyrate and cumene hydroperoxide. To be

Examples of the silane crosslinking agent used for the silane crosslinking include trimethoxyvinylsilane, triethoxyvinylsilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane and the like can be mentioned. Further, such a silane cross-linking agent is actually a radical generator such as the above-mentioned peroxide, and is grafted to a resin composition for forming a foam layer,
Crosslinking is carried out by hydrogen bonding with water, steam or the like. In this case, some cross-linking of the polyolefins caused by the peroxide is also included.

The above-mentioned foam is mixed in a polymer-forming body by, for example, mixing a substance that generates a gas when the resin composition for forming the foam layer is heated, and heating the substance, gasifying it by decompression, or decomposing it. It is produced by creating bubbles in the.

Here, as the foaming agent serving as a gas generating source,
Carbon dioxide, difluorodichloromethane, etc., which is a gas at room temperature and pressure but is used in the state of being dispersed and dissolved in resin,
Butane, pentane, methanol, which gasifies when heated,
Water, etc., and thermally decomposable organic foaming agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide, and 4,4-oxybis (benzenesulfonyl hydrazide), which generate decomposition gas upon heating. .

The blending ratio of the above pyrolyzable organic foaming agent is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the above resin composition. When the blending ratio of the foaming agent is less than 1 part by weight,
If a predetermined expansion ratio cannot be obtained and the amount exceeds 40 parts by weight, a uniform foam cannot be obtained, for example, giant bubbles are partially formed.

The foam layer in the present invention preferably has an apparent density in the range of 0.02 to 0.2 g / cm ³ . That is, the expansion ratio is 5 to 50 times (c
m ³ / g). This expansion ratio is preferably 10-
It is 40 times. If the density of the foam is more than 0.2 g / cm ³ , the cushioning property of the laminate cannot be obtained, and
If it is less than 02 g / cm ³ , cell breakage occurs during lamination of the foam layer, resulting in poor extensibility.

The foam layer has a thickness of 0.5 to 5 m.
m, preferably 1 to 4 mm. If the thickness of the foam layer is not within this range, the cushioning property when the laminate is used as an interior material is lacking.

The above foam layer is prepared by first kneading the components constituting the resin composition forming this layer using a kneading device such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, or a roll. Then, the composition can be formed into a sheet, and the obtained sheet-shaped molded product is irradiated with ionizing radiation to be crosslinked, and heated and foamed in a hot air oven. These irradiation and foaming operations may be carried out continuously or batchwise. Examples of the ionizing radiation include electron rays, γ rays, X rays, neutron rays, etc., and electron rays are most preferably used, and the irradiation dose is generally in the range of 1 to 10 Mrad.

As a method for producing the flame-retardant polyolefin-based laminate of the present invention, for example, by the method described above, the skin material layer as the first layer is extruded, and at the same time as the second layer is formed on the skin material layer. There may be mentioned a method of laminating the foam layers of and thermocompression bonding.

The flame-retardant polyolefin-based laminate of the present invention comprises
A mixed flame retardant compound containing a nitrogen compound and a phosphorus compound is contained, and 5 to 100 parts by weight of the mixed flame retardant compound in the surface material layer, and a foam layer, relative to 100 parts by weight of the resin composition forming each layer. It is contained in a proportion of 25 to 100 parts by weight. When the added amount of the mixed flame retardant compound is less than the minimum amount of each (that is, less than 5 parts by weight in the surface material layer and less than 25 parts by weight in the foam layer), the required flame retardancy cannot be obtained. , Greater than maximum parts by weight (ie more than 100 parts by weight in the facing layer and 10 in the foam layer).
If it is more than 0 parts by weight), the uniformity and the expansion ratio of the foam layer of the second layer will be insufficient, and the skin material layer as the first layer will also have problems in extensibility and surface property. Further, in order to exhibit the required flame retardancy in the polyolefin-based laminate, it is preferable that the flame retardant compound is 20 parts by weight or more based on 100 parts by weight of the resin composition of the skin layer, and the resin of the foam layer. It is contained in an amount of 30 parts by weight or more based on 100 parts by weight of the composition.

In the flame-retardant polyolefin laminate of the present invention, the mixed flame-retardant compound consisting of the above-mentioned nitrogen compound and phosphorus compound must be added to both the skin material layer and the foam layer. The ratio of the amount added to the skin material layer to the amount added to the foam layer is preferably within the range of 0.1 to 4. More preferably, it is used at about 0.1 to 2.

If the ratio of the above-mentioned mixed flame-retardant compound consisting of a nitrogen compound and a phosphorus compound to each layer is outside this range, the main flame-retardant evaluation (JIS D
1201) does not provide sufficient flame retardancy. Further, if the above-mentioned mixed flame retardant compound is not added to the skin material layer even in a small amount, a situation may occur in which only the skin material layer burns when it comes into contact with a flame.

As the phosphorus compound used in the present invention, it is desirable to use a compound represented by the following formula (1) or (2).

[0061]

[Chemical 7]

(Where n is an integer of 20 or more,
A ¹ , A ² , and A ³ are the same or different,
Each independently, H, NH _2, or CONH _2. However, A ¹ , A ² , and A ³ are all H or C
ONH ₂ ).

Examples of the phosphorus compound represented by the above formula (1) include ammonium polyphosphate and polyphosphoric acid amide. With regard to ammonium polyphosphate, a free-flowing powdery substance having a degree of polymerization of about 200 to 1,000 and a surface coated with a melamine / formaldehyde resin or the like, which is hardly soluble in water, can also be used.

[0064]

[Chemical 8]

(In the formula, R ¹ is hydrogen or a linear or branched alkyl group or aryl group having 1 to 16 carbon atoms, and R ² is a hydroxyl group, hydrogen, or 1 to 16 carbon atoms. It is a linear or branched alkyl group having 16 groups, an alkoxy group, an aryl group or an aryloxy group, and R ³ is hydrogen or 1 to 1 carbon atoms.
A linear or branched alkyl or aryl group having 6).

The compound represented by the above formula (2) includes methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid, t-butyl. Phosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid , Diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, and the like. These may be used alone or in combination of two or more kinds.

Further, in the present invention, in addition to the above phosphorus compound, red phosphorus and the like can be used if necessary. Further, it can be used in combination with the above phosphorus compound. Commercially available red phosphorus may be used, but from the viewpoint of moisture resistance and safety (spontaneous ignition during kneading), red phosphorus particles whose surfaces are coated with a resin are preferable.

The nitrogen-containing compound used in the present invention is preferably a compound represented by the following formula (3).

[0069]

[Chemical 9]

(In the formula, R ^{4 to} R ⁶ are each independently
Hydrogen or a hydroxyalkyl group having 1 to 16 carbon atoms, a dihydroxyalkyl group, a hydroxyaryl group or a dihydroxyaryl group).

Examples of the compound that can be used as the nitrogen-containing compound include isocyanuric acid, mono (hydroxymethyl) isocyanurate, bis (hydroxymethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, mono (dihydroxymethyl). ) Isocyanurate, bis (dihydroxymethyl) isocyanurate, tris (dihydroxymethyl) isocyanurate, mono (2-hydroxyethyl) isocyanurate, bis (2-hydroxyethyl) isocyanurate,
Tris (2-hydroxyethyl) isocyanurate, Tris (1,2-dihydroxyethyl) isocyanurate, Tris (3-hydroxypropyl) isocyanurate, Tris (2,3-dihydroxypropyl) isocyanurate, Tris (4-hydroxybutyl) ) Isocyanurate, tris (3,4-dihydroxybutyl) isocyanurate, tris (8-hydroxyoctyl) isocyanurate, tris (4-hydroxyphenyl) isocyanurate, tris (2,4-dihydroxyphenyl)
Examples thereof include isocyanurate and tris (2,3-dihydroxyphenyl) isocyanurate.

The mixed flame retardant compound of the nitrogen compound and the phosphorus compound in the present invention is such that the mixing ratio of both is phosphorus compound: nitrogen compound = 90 to 50:10 to 50.
It is preferable to use the above range. If the mixing ratio of both compounds is not within this range, the synergistic effect between both compounds will be insufficient, and it will be difficult to obtain the required flame retardancy.

Further, according to the present invention, the foamability of the foam layer as the second layer and the foamability of the foam layer as the second layer constituting the flame-retardant polyolefin laminate are not impaired. In addition to the mixed flame retardant compound, a flame retardant aid such as hydrated metal hydroxide may be added to the extent that the physical properties thereof are not deteriorated. The hydrated metal hydroxide may be a known one, and examples thereof include aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate and dawsonite.

The amount of these flame retardant aids to be added varies depending on the amount of the main flame retardant compounded, but is preferably 100 parts by weight or less relative to 100 parts by weight of the resin composition which is each layer constituting the laminate. If it exceeds this range, high flame retardancy is obtained, but the mechanical properties of each layer are deteriorated and it cannot be used.

The skin material layer and the foam layer constituting the flame-retardant polyolefin-based laminate of the present invention may contain an antioxidant, a stabilizer, a pigment, a metal damage inhibitor, etc. depending on the purpose. it can.

The above-mentioned antioxidant is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin composition forming each layer.

As the above-mentioned stabilizer, known ones of phenol type, phosphorus type, sulfur type and amine type can be used. Specific examples of the compound as this stabilizer include:
Tris (3,5-di-t-butyl-
4-hydroxybenzyl) isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4)
-Hydroxyphenyl) propionate] methane, propyl gallate and the like, in the phosphorus system, triphenylphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2-methylenebis (4,4). 6-di-t-butylphenyl) octyl phosphite, etc., such as dilauryl-3,3′-thiodipropionic acid ester in the sulfur system, bis [2-methyl-4-ester
(3-n-dodecanylthiopropionyloxy) -5-
t-Butylphenyl] sulfide, lauryl stearyl-3,3′-thiodipropionic acid ester and the like. These may be used alone or in combination of two or more.

Further, in the present invention, a filler, an antistatic agent, a stabilizer and a crosslinker are added to both the skin material layer and the foam layer as long as the physical properties of the resin composition of each layer constituting the laminate are not impaired. Agents, lubricants, softeners, pigments and the like may be added.

The flame-retardant polyolefin-based laminate of the present invention comprises
Further, a layer of interior aggregate may be laminated.

As the above-mentioned interior aggregate, for example, a molded body obtained by impregnating an acrylonitrile-butadiene-styrene resin, a polyolefin resin, a phenol resin, or the like with a wood material molded into a fixed shape; a polypropylene resin, a polyester Examples of the molded article include a composite of a system resin and paper.

Also to these interior aggregates, the mixed flame-retardant compound used in the present invention may be added if necessary.
In particular, when a polyolefin resin (particularly polypropylene resin) is used as an aggregate, for example, in a cold press mold having a shape as an automobile interior material, the melted polyolefin resin is extruded into the lower mold, and the skin material is placed here. A multilayer sheet in which a layer and a foam layer are laminated, and a method of integrating the interior aggregate layer by pressing at the same time, similarly from the foam layer side to the flame-retardant polyolefin-based laminate, and melted A method of pressing a polyolefin resin while injection molding is being studied.

In molding by such a press,
It is desirable to add the mixed flame retardant compound used in the present invention to the extent that the moldability is not hindered.

The skin material layer and the foam layer obtained as described above are excellent in flexibility, heat resistance, moldability and flame retardancy, respectively, and the foam layer also has foamability and cushioning property. Excel. Therefore, by laminating these, it is possible to provide a flame-retardant polyolefin-based laminate having flame retardancy and having the above-mentioned properties, and further by laminating layers of various interior aggregates, a laminate suitable for interior The body can also be provided.

[0084]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The skin material layers, foam layers, and laminates obtained in the examples and comparative examples of the present invention were evaluated by the methods described below.

(Skin material layer) 1. Appearance: Visual swelling, surface roughening during surface texturing,
When no gloss or the like was confirmed, it was rated as O, and when even a slight amount was recognized, it was rated as X.

2. Texture: judged by the feel.

3. Extensibility / heat resistance: 10 mm x 150 m
A strip-shaped sample of m was observed for elongation behavior at 80 ° C. with a tensilon (manufactured by Orientec Co.) equipped with a constant temperature bath,
It was judged by the appearance at 100% elongation. The case where the surface roughness or the necking phenomenon appears was marked with x, and the case where there was no change was marked with o.

(Foam layer) 1. Appearance: A case where surface bubble breakage and surface irregularities were not confirmed at all by visual observation was rated as O, and other cases were rated as X.

2. Magnification: Measured according to JIS K7112, and the reciprocal thereof was taken as the magnification (cm ² / g).

3. Degree of cross-linking: 0.1 g of a polyolefin resin foam was taken, the bubbles were crushed, and the mixture was kept in 50 ml of xylene at a temperature of 120 ° C. for 24 hours, and then the dry weight (g) of the residue permeated through a 200-mesh wire net It was measured and calculated by the following formula.

Degree of crosslinking (% by weight) = (dry weight of residue /
0.1 g) × 100 (laminate) 1. Flame retardancy: Based on JIS D1201, the flame retardancy of the laminate was evaluated and judged as easy flammability, slow flammability, and self-extinguishing property.

2. Formability: Cylindrical female die for vacuum forming (diameter 100 mm, H / D = 0.3, corner R = 1)
0φ, H; depth (cm) of molded product, D: diameter (cm) of molded product) and heated to 150 to 160 ° C.,
When there was no problem such as tearing, swelling, or surface property, molding was possible, and when any one problem occurred, it was evaluated as X.

(Example 1) <Foam layer> The ethylene component to be copolymerized was 3.6% by weight.
And 100 parts by weight of a resin composition consisting of 70% by weight of polypropylene having a weight average molecular weight of 430,000 and 30% by weight of linear low-density polyethylene (density 0.920), and trimethylolpropane tri 1.5 parts by weight of methacrylate and 1.5 parts by weight of 1,9-nonanediol dimethacrylate, thermal decomposition type foaming agent 1
2 parts by weight, 2,6-di-t-butyl-as an antioxidant
0.3 parts by weight of p-cresol and 0.3 parts by weight of dilaurylthiodipropionate, 0.5 parts by weight of methylbenzotriazole as a metal damage inhibitor, 24.5 parts by weight of ammonium polyphosphate and tris () as flame retardants. The mixture containing 10.5 parts by weight of 2-hydroxyethyl) isocyanurate was extruded using a twin-screw extruder to obtain a sheet layer having a thickness of 1.1 mm. Further, the sheet layer is irradiated with ionizing radiation at an acceleration voltage of 800 kV to 2.0 Mrad.
After irradiation and crosslinking, the crosslinked sheet layer was continuously supplied to a vertical hot air foaming furnace to foam. The foaming conditions were maintained at 270 ° C. with hot air and an infrared heater, and foaming was carried out at atmospheric pressure. The obtained foam layer had an expansion ratio of 22.4 times and a thickness of 2.5 mm. The resin composition of this foam layer is shown in Table 1 below.

<Skin material layer> 80% by weight of a thermoplastic polyolefin-based elastomer (Milastomer 9020N: manufactured by Mitsui Petrochemical Co., Ltd.) and polypropylene (block PP)
MI = 2.0: manufactured by Chisso Corporation) 14 parts by weight of ammonium polyphosphate and 6 parts by weight of tris (2-hydroxyethyl) isocyanurate as a flame retardant were further added to 100 parts by weight of a resin composition consisting of 20% by weight. Polypropylene having a resin temperature of 230 ° C. in a 50φ extruder and a weight average molecular weight of 365,000, and the resin elution amount at each temperature by the cross fractionation method is the value shown in 5 in Table 2 below. Resin (Cataloy NKS-
25P: manufactured by Highmont Co.) was coextruded in two layers at a resin temperature of 230 ° C. by a 65φ extruder. The multi-layer extruder used here has a capacity of 50 in addition to the above two extruders.
Since an extruder of φ was provided and a T die mold and a feed block were provided, in the production of the two-layer sheet of this example, one extruder of 50φ was stopped. The resins for the skin layer are shown in Table 2 below.

The above foam layer is immediately laminated on the side of the catalloy layer of the extruded and melted skin material layer, which is then passed through a pair of rolls and fused to be laminated and integrated. 1. Simultaneously, the surface material layer is subjected to texturing using a chevrolet, and the surface material layer 0.2 mm + foam layer 2.
A 5 mm sheet-shaped flame-retardant polyolefin-based laminate was obtained. Among the skin material layers constituting the obtained laminate, the layer of milastomer component was 0.05 mm and the catalloy layer was 0.15 mm.

Further, the obtained sheet-like laminate was placed in a cold press mold (mold temperature: about 60 ° C.), and the resin temperature was about 170 ° C. on the lower mold, and polypropylene was used as an interior aggregate. After supplying the resin, pressure was applied to obtain an interior laminate. The composition of the obtained laminate is shown in Table 3 below.
Shown in.

(Example 2) <Foam layer> By the same method as in Example 1 except that 35 parts by weight of Hostaflam AP745 (phosphorus compound: nitrogen compound = 72: 28 manufactured by Hoechst) was used as a flame retardant. A foam layer having a thickness of 2.0 mm was obtained. The resin composition of this foam layer is shown in Table 1.

<Surface material layer> The weight average molecular weight is 220,0.
100, polypropylene resin (PER-R210E manufactured by Tokuyama Soda Co., Ltd.) having a resin elution amount at each temperature by the cross fractionation method having a value shown by 3 in Table 2 below.
20 parts by weight of Hostafram AP745 as a flame retardant was added to parts by weight, and an extruder (caliber 90 mm, L / D = 2) was added.
In 8), the mixture was melt-kneaded at 240 ° C. and extruded into a sheet with a thickness of 0.3 mm using a T-die to obtain a skin material layer.
The resin of this skin material layer is shown in Table 2. The above foam layer was laminated as it was, and the surface of the skin material layer was simultaneously subjected to the embossing treatment at about 55 ° C. using a Chevrolet roll.

Further, as an automobile door interior aggregate, an adhesive (polyester adhesive (Hybon; manufactured by Hitachi Chemical Polymer Co., Ltd.) and isocyanate (Desmodur M) are used in which wood chips are molded into a door shape with phenolic resin.
R; manufactured by Sumitomo Bayer Urethane Co., Ltd.) is used, and a laminate of a skin material layer and a foam layer is preheated to 150 ° C., and heated and pressed under the conditions of 80 ° C. and 3 Kg / cm ^2. By molding, an interior laminate was obtained. The composition of the obtained interior laminate is shown in Table 3 below.

(Examples 3 to 6 and Comparative Examples 1 to 5) The compositions of Examples 3 to 6 and Comparative Examples 1 to 5 are shown in Table 3 (Examples 3 to 6) and Table 4 (below). Comparative Example 1
5).

Here, in Example 3, the obtained flame-retardant polyolefin laminate was placed in a cold press mold (mold temperature of about 60 ° C.), and a resin temperature of about 170 was set on the lower mold.
After supplying a polypropylene resin as an interior aggregate at 0 ° C., pressure was applied to obtain an interior laminate.

Here, in Comparative Example 3, after the skin material layer and the foam layer were laminated, a wood piece was molded into a door shape with a phenolic resin as an interior aggregate for an automobile door, and an adhesive was used. Is applied, and a laminate of the skin material layer and the foam layer is preheated to 150 ° C. and heated and pressed under the conditions of 80 ° C. and 3 Kg / cm ² to obtain an interior laminate. Was given.

Example 7 <Foam layer> Low density polyethylene having a density of 0.92 g / cm ² and MI = 3.4 (YK-40 manufactured by Mitsubishi Petrochemical Co., Ltd.)
7 parts by weight of a thermal decomposition type foaming agent, 0.3 parts by weight of 2,6-di-t-butyl-p-cresol as an antioxidant and 0 of dilaurylthiodipropionate per 100 parts by weight of a resin composition consisting of 0.3 parts by weight, 0.5 parts by weight of methylbenzotriazole as a metal damage inhibitor, 24.5 parts by weight of ammonium polyphosphate and 10.5 parts by weight of tris (2-hydroxyethyl) isocyanurate as a flame retardant, Further cumene hydroperoxide 1.0
Parts by weight were added, and these mixture compositions were extruded using a twin-screw extruder at a temperature (155 ° C.) at which peroxide did not decompose to obtain a sheet layer having a thickness of 1.1 mm. Furthermore, the sheet layer was made into pellets with a pelletizer. The obtained pellets are put into a mold capable of sealing up to a thickness of 2.0 mm so that the filling rate is 90% or more, and the crosslinked sheet is heated with a hot press heated to 180 ° C. for 10 minutes under a pressure of 150 kg / cm ^2. Layered. The obtained crosslinked sheet layer was put in an oven and allowed to freely foam at a temperature of 250 ° C. for 5 minutes. The obtained foam layer had a foaming ratio of 28 times and a thickness of 3.5 mm. The resin composition of this foam layer,
The results are shown in Table 1 below.

<Skin material layer> The same resin composition as in Example 5 (resin 5 in Table 2; Catalloy NKS-025P).
In addition, 25 parts by weight of Hostaflam AP745 as a flame retardant was added to PCM-30 (manufactured by Ikegai Kihan Co., Ltd.) and T
Using a die, at about 230 ° C, width 200 mm, thickness 0.
Extruded as a 3 mm sheet layer, laminated on the above polyethylene foam layer as it is, and about 5
At 5 ° C., the surface material layer was simultaneously subjected to graining. However, the size of the foam layer in this case was 250 mm in width and 500 mm in length, and 10 sheets of this were prepared to prepare a flame-retardant polyolefin-based laminate. The composition of the obtained laminate,
The results are shown in Table 3 below.

(Example 8) <Foam layer> The foam layer of this example was formed by using the resin having the same composition as in Example 1 and the same method as in Example 1, The same flame retardant as in Example 1 was added. The obtained foam layer had an expansion ratio of 22.4 times and a thickness of 2.5 mm.

<Surface material layer> 50% by weight of a polyolefin thermoplastic elastomer (Milastomer 9020N: manufactured by Mitsui Petrochemical Co., Ltd.) and a polyolefin thermoplastic elastomer (Milastomer 8030N: manufactured by Mitsui Petrochemical Co., Ltd.) 5
A mixture of 100 parts by weight of a resin composition consisting of 0% by weight and 14 parts by weight of ammonium polyphosphate and 6 parts by weight of tris (2-hydroxyethyl) isocyanurate as a flame retardant was added to the mixture at a resin temperature of 23 by an extruder.
It was extruded at 0 ° C. to obtain a skin material layer having a thickness of 0.2 mm.
The foam layer was laminated as it was, and the surface of the skin material layer was simultaneously subjected to the embossing process by using the embossing roll.

Further, the obtained sheet-like laminate was placed in a cold press mold (mold temperature: about 60 ° C.), and the resin temperature was about 170 ° C. on the lower mold, and polypropylene was used as an interior aggregate. After supplying the resin, pressure was applied to obtain an interior laminate. The composition of the obtained laminate is shown in Table 3 below.
Shown in.

(Example 9) <Foam layer> The foam layer of this example was formed by using the resin having the same composition as in Example 1 and the same method as in Example 1, The same flame retardant as in Example 1 was added. The obtained foam layer had an expansion ratio of 22.4 times and a thickness of 2.5 mm.

<Surface material layer> 60% by weight of a thermoplastic polyolefin elastomer (Milastomer 8030N: manufactured by Mitsui Petrochemical Co., Ltd.), a weight average molecular weight of 240,000, and a resin elution amount at each temperature by a cross fractionation method. In the same manner as in Example 8 except that a resin composition obtained by blending with 40% by weight of a polyprene resin (manufactured by Highmont Co., Ltd .: Catalloy FX7083) having a value shown by 6 in Table 2 below was used. A skin material layer having a thickness of 0.2 mm was obtained. The foam layer was laminated as it was, and the surface of the skin material layer was simultaneously subjected to the embossing process by using the embossing roll.

Further, as an automobile door interior aggregate, an adhesive was applied to a wood piece formed of a phenolic resin in the shape of a door, and an adhesive was applied thereon, and a laminate of a skin material layer and a foam layer was formed thereon. The interior laminate was obtained by preheating to 80 ° C. and heat-pressing under conditions of 80 ° C. and 3 Kg / cm ² . The composition of the obtained interior laminate is shown in Table 3 below.

Table 1 below shows the resin composition of the foam layers used in the examples and comparative examples of the present invention, and Table 2 shows the kinds of the resin of the skin material layer.

[0113]

[Table 1]

[0114]

[Table 2]

Table 3 below shows the compositions of the skin material layer and the foam layer used in the examples of the present invention. Regarding the type of the skin material layer in the table, the examples in which two resins are described were formed by laminating the two resins except for Example 9. The skin layer of Example 9 was obtained by blending the two listed resins.

[0116]

[Table 3]

The following flame retardants were used as the flame retardants in the table: a) Ammonium polyphosphate: tris (2-hydroxyethyl) isocyanurate = 7: 3 b) Hostaflam AP745 (manufactured by Hoechst) c) t-Butylphosphonic acid: tris (2-hydroxyethyl) isocyanurate = 8: 2 d) t-Butylphosphonic acid: bis (2-hydroxyethyl)
Isocyanurate = 6: 4 e) Aluminum hydroxide.

Table 4 below shows the compositions of the skin material layer and the foam layer used in the comparative examples of the present invention. Regarding the type of skin material layer in the table, the examples in which two resins are described were formed by laminating the two resins.

[0119]

[Table 4]

As the flame retardant in the table, the same flame retardant as in the examples of Table 3 was used.

Table 5 below shows the evaluation results of the laminates in the examples of the present invention.

[0122]

[Table 5]

Table 6 below shows the evaluation results of the laminates in the comparative examples of the present invention.

[0124]

[Table 6]

As described above, by using the present invention, a laminate having excellent flame retardancy which does not impair the desirable characteristics of the skin material layer and the foam layer can be obtained.

[0126]

According to the present invention, a skin material layer provided by using a specific polypropylene resin and / or a polyolefin elastomer and serving as a substitute for plasticized PVC, and a resin having a specific proportion of the polyolefin resin. In both layers of the laminate laminated with a foam layer made of a foam of the composition, by containing a specific amount of a mixed flame retardant compound consisting of a nitrogen compound and a phosphorus compound, in some cases,
By further laminating the interior aggregate layer, it is possible to provide a polyolefin-based laminate capable of imparting flame retardancy without impairing the desirable properties of the skin material layer and the foam layer and a laminate suitable for interior use. .

Claims (3)

[Claims] 1. A polyolefin-based elastomer as a first layer and / or a weight average molecular weight of 80,000.
The amount of resin elution up to 0 ° C by the cross fractionation method is within the range of up to 500,000
5 to 75% by weight, the resin elution amount in the temperature range of more than 0 ° C and 80 ° C or less is 5 to 45% by weight of the total polypropylene resin amount, and in the temperature range of more than 80 ° C and 100 ° C or less. The resin elution amount is 2 to 45% by weight of the total polypropylene resin amount, and exceeds 100 ° C and 125 ° C.
As a second layer, a skin material layer made of polypropylene resin having a composition in which the amount of resin elution in the following temperature range is 2 to 40% by weight of the total polypropylene resin amount and the thickness thereof is 0.1 to 1 mm. , A polypropylene resin 0 to 85% by weight and a polyethylene resin 100 to 15% by weight of a resin composition foam having a thickness of 0.5 to 5 mm.
A flame-retardant polyolefin-based laminate having a foam layer which is a layer containing a mixed flame-retardant compound composed of a nitrogen compound and a phosphorus compound in each of the surface material layer and the foam layer. With respect to 100 parts by weight of the constituent resin composition,
A flame-retardant polyolefin-based laminate in which the mixed flame-retardant compound is contained in the surface material layer in an amount of 5 to 100 parts by weight, and in the foam layer in an amount of 25 to 100 parts by weight. 2. The flame-retardant polyolefin-based laminate according to claim 1, wherein the phosphorus compound is represented by the following formula (1) or (2): (In the formula, n is an integer of 20 or more, A ¹ , A ² , and A ³ are the same or different and each is independently H, NH ₂ , or CONH ₂ . ¹ ,
A ² and A ³ are not all H or CONH ₂ . ) [Chemical 2] (In the formula, R ¹ is hydrogen or a linear or branched alkyl group or aryl group having 1 to 16 carbon atoms, and R ² is a hydroxyl group, hydrogen, or 1 to 16 carbon atoms. A linear or branched alkyl group, an alkoxy group, an aryl group or an aryloxy group, wherein R ³ is hydrogen, or a linear or branched alkyl group or aryl group having 1 to 16 carbon atoms. It is.) 3. The flame-retardant polyolefin-based laminate according to claim 1, wherein the nitrogen compound is represented by the following formula (3): (In the formula, R ^{4 to} R ⁶ are each independently hydrogen, or a hydroxyalkyl group having 1 to 16 carbon atoms, a dihydroxyalkyl group, a hydroxyaryl group or a dihydroxyaryl group.)