JPH0966580A - Metal resin laminate composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide various properties such as rigidity, heat insulation by laminating aluminum plates on both side surfaces of a core material sheet made of composition having specific physical properties by a product obtained by incorporating the ingredient for satisfying a specific relational expression with polyolefin as a base material. SOLUTION: A is polyolefin used as a base material, B is styrene thermoplastic elastomer, C is ammonium polyphosphate, D is one or more types of triazine nitrogen-containing organic compound to satisfy formulae 1 to 3. Aluminum plates are laminated on both side surfaces of a core material sheet molded by composition having melting fluidity index [MI (190 deg.C, 2.16kgf) of the resin layer of the product obtained thereby or MFR (230 deg.C 2.16kgf0] is 0.5 to 10.0g/10min. The formula 1: component B = 3 to 30wt.%. The formula 2: by weight of the components [component D/component C] = 0.05 to 4, formula 3: component C + component D = 5 to 30wt.% [component A + component B + component C + component D = 100wt.%]. Accordingly, amount of smoking and the melting resin discharge at the time of fire contact are small, and it can be used for interior and exterior finish materials.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated composite having a flame-retardant property (hereinafter sometimes referred to as a laminated body of the present invention) composed of a polyolefin core sheet and a thin metal plate. . More specifically, the present invention relates to a laminated composite suitable as an interior / exterior material for buildings, vehicles, etc., which hardly emits black smoke or toxic gas even when contacted with flames or high heat during a fire.

The laminate of the present invention, while exhibiting the characteristics of a metal on its surface, has been improved in specific strength by the contribution of the resin forming the inner layer. As a result, rigidity, increase in heat distortion temperature, heat insulation, and weather resistance are achieved. It has various characteristics such as heat resistance, soundproofing and cold workability.

[0003]

2. Description of the Related Art Recently, performance as a flame-retardant material has begun to be required for a laminated body in which a polyolefin resin core sheet is sandwiched between metal plates. As the flame retardancy, for example, JIS A1321 “Flame retardancy test for interior materials for construction and construction method” is known, and in order to be used as a flame retardant material for interior building materials, an additional test to the test is Grade 2A. Required to pass.

[0004] There are several methods for making the core sheet flame-retardant, but the most widely used measure is to incorporate a flame retardant into a polyolefin resin. As the flame retardant, a halogen-based flame retardant composed of a combination of an organic halogen compound or the like and a flame retardant auxiliary such as antimony trioxide, an organic phosphorus-based flame retardant, or a metal hydroxide which is an inorganic filler exhibiting a flame retardant effect. Inorganic flame retardants and the like can be mentioned.

However, the above-mentioned laminate flame-retarded with a halogen-based flame retardant causes a large amount of black smoke from the core material layer upon contact with a flame, and is toxic and corrosive halogen gas (halogen vapor). Is caused, which causes a problem that the human body and other devices are adversely affected.

The laminate using the organic phosphorus flame retardant exhibits a flame retarding effect even if the amount of the flame retardant added is small, but the addition of the agent causes the melt flow index [MI] of the core sheet to be increased.
(190 ° C; 2.16 kgf) or MFR (230
℃; 2.16kgf)] is indispensable, and it becomes very difficult to pelletize or sheet the resin composition.

Further, with the inorganic flame retardant composed of metal hydroxide such as magnesium hydroxide or aluminum hydroxide, black smoke and toxic gas are hardly generated due to contact with the flame. However, for example, as used in the invention described in JP-A-6-316031, it is necessary to add a large amount of an inorganic flame retardant in order to provide sufficient flame retardancy, and the fluidity is lowered so that the resin composition Pelletization or sheeting becomes difficult, and the lightness, which is a characteristic of composite materials, is impaired.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have passed the additional test second grade A in JIS A1321 "Flame resistance test for building interior materials and construction methods" which is flame retardancy required for interior and exterior materials. In order to obtain a laminated body,
As a result, as described above, no black smoke is generated when contacting the flame, which is a problem left over in the conventional technique, and no toxic and corrosive halogen gas is generated. It has succeeded in obtaining a metal resin laminate capable of exhibiting the flame retardancy of No. 1 and having a relatively high melt fluidity index and passing the additional test second grade A in JIS A1321.

[0009]

That is, the laminated body of the present invention has a constitution defined in the following "basic constitution" and "improved constitution 1" to "improved constitution 5". : [Basic configuration] The following components (B), (C) and (D) are based on the polyolefin (A) as a base material and the following relational expression (1)
And (2) and (3) are contained so as to be satisfied, and the melt fluidity index [MI (190 ° C; 2.16 kgf) or MFR (2
30 ° C; 2.16 kgf)], 0.5 g / 10 min
A metal-resin laminated composite obtained by laminating aluminum plates on both sides of a core sheet formed by molding a composition that is larger and 10.0 g / 10 min or less. (A): Polyolefin (B): Styrene-based thermoplastic elastomer (C): Ammonium polyphosphate (D): One or more triazine-based nitrogen-containing organic compounds; (1) Component (B) = 3 to 30% by weight and (2) Weight ratio of the components to each other [component (D) / component (C)]
= 0.05 to 4 and (3) Component (C) + Component (D) = 5 to 30 wt% [Component (A) + Component (B) + Component (C) + Component (D) = 100
weight%]

[Improved constitution 1] The polyolefin has the following 1
The metal-resin laminated composite according to the "basic constitution", which is selected from at least one species. I. Ethylene homopolymer, b. A copolymer of an ethylene main component and one or more α-olefins having 3 or more carbon atoms or polar monomers, c. A homocrystalline polymer of propylene, and d. A crystalline copolymer of a propylene main component and one or more kinds of ethylene or α-olefins having 1 or more butenes or polar monomers.

Further, a modified resin obtained by copolymerizing or grafting an unsaturated carboxylic acid such as maleic anhydride, acrylic acid or fumaric acid, or a derivative such as an acid anhydride or ester with the above resin, or the above resin with ionizing radiation. A modified resin that has been treated or cross-linked with a cross-linking agent can also be used depending on the application.

The fluidity index of the resin layer is MI (190 ° C .; 2. ° C.) for ethylene homopolymers and copolymers of ethylene main component and α-olefin having 3 or more carbon atoms or one or more polar monomers. 16 kgf) is a MF homocrystalline polymer, and MF for a crystalline copolymer of a propylene main component and one or more of ethylene or 1-butene or more α-olefins or polar monomers.
R (230 ° C; 2.16 kgf) is applied.

The thickness of the polyolefin resin of the present invention is 1
mm or more and 8 mm or less, preferably 2 mm or more and 5 m
m or less. If the thickness is less than 1 mm, the laminated composite will be largely warped and deformed, which is not preferable. When the thickness exceeds 8 mm, the outflow of the resin becomes large due to the contact with the flame.

In the present invention, various fillers (or reinforcing agents) may be added to the above polyolefin resin to the extent that flame retardancy is not substantially reduced. Examples of the filler used include fibrous fillers such as glass fibers, carbon fibers and vinylon fibers, flake fillers such as mica and talc, spherical fillers such as glass beads, and amorphous fillers such as calcium carbonate and wood chips.

The surface of these fillers (or reinforcing agents) is preferably subjected to a treatment for imparting an affinity to the resin to be blended. As such processing,
For example, addition of unsaturated carboxylic acid or its acid anhydride,
Examples thereof include unsaturated amine addition and rubbery coating.

In addition to these fillers, a filler,
Coloring agents, deterioration inhibitors, antistatic agents, lubricants and the like can be added.

[Improved Structure 2] A homopolymer and / or a copolymer in which the nitrogen-containing organic compound has a monomer structure represented by [Chemical Formula 2] as a unit structure, a reaction product of cyanuric chloride and a diamine, The metal resin laminate according to "basic constitution" and "improved constitution 1", which is a reaction product of ethylene urea and aldehyde and a reaction product of ethylene thiourea and aldehyde.

[0018]

Embedded image

(In the formula, both X and Z ¹ are structures bonded to the triazine skeleton through a nitrogen atom, and X is --N
An alkylamino group or a morpholino group represented by a group of HR ¹ or —NR ² R ³ and a piperidine group, R ¹ ,
R ² and R ³ are linear or branched alkyl groups having 1 to 6 carbon atoms (R ¹ and R ² may be the same or different). Or X is -NHR ^4, a hydroxyalkyl amino group represented by group -NR ⁵ R ⁶ R ^4,
R ⁵ and R ⁶ are linear or branched hydroxyalkyl groups having 2 to ⁶ carbon atoms (R ⁵ and R ⁶ may be the same or different). Z ¹ is a divalent piperazine group,
Or formula -HN (CH ₂₎ (where m is an integer from 2 to 6) _m NH- group represented by, or the formula -NR ⁷ (CH _{2) l}
A group represented by R ⁸ N- (l is an integer from 2 to 6), one or both of R ^7, R ⁸ is a hydroxyethyl group. )

The nitrogen-containing organic compound contained in the polymer layer forming the laminate of the present invention means a high temperature such as a flame in the presence of the above-mentioned ammonium polyphosphate (C) in the polyolefin (A). As a result of thermal decomposition caused by contact with a non-flammable gas such as water vapor, carbon dioxide or nitrogen, a mixture of one or more, two or more kinds of organic compounds and a carbonaceous residue and 2 It includes any product obtained by reacting one or more species with each other.

[Improved Construction 3] A styrene-based thermoplastic elastomer is copolymerized with styrene and butadiene or isoprene by anionic polymerization method, cationic polymerization method, coordination polymerization method, radical polymerization method, solution polymerization method, emulsion polymerization method or the like. In the block copolymer, the weight ratio of styrene / butadiene or isoprene is 10-50 / 50-9.
The metal-resin laminated composite according to "basic constitution", "improved constitution 1" and "improved constitution 2", which has a characteristic of 0.

[Improved Structure 4] The aluminum plate is made of aluminum or aluminum alloy and has a plate thickness of 50 to 10.
The metal-resin laminated composite according to the "basic constitution" and "improved constitution 1" to "improved constitution 3", which is a plate or foil having a thickness of 00 µm, preferably 150 to 1000 µm, and more preferably 200 to 1000 µm.

These aluminum plates have a plate thickness of 50 μm.
If it is less than 1, the flame-retardant effect of the core sheet is not sufficiently exerted, and 1
If it is thicker than 000 μm, the lightness, which is a characteristic of the composite laminate, is impaired. Also, it is preferable that the inner surface (adhesive surface with resin) of these aluminum plates is subjected to anticorrosion treatment such as chromate or alumite due to the problem of corrosiveness, but treatment of the outer surface (outer surface of the product) such as coating. -It is not limited depending on the presence or absence of anticorrosion treatment.

[Improved Construction 5] The core resin layer has a foaming ratio of 1.
The metal-resin laminated composite according to "basic constitution" and "improved constitution 1" to "improved constitution 4", which is a non-foamed body or a foamed body of 0 to 5.0 times.

[0025]

In the laminated composite having the above structure, the viscosity of the resin itself is improved by adding the styrene-based elastomer to the core material sheet to prevent the resin from flowing out due to the contact with the flame, and to reduce the amount of the resin. With the combination of flame retardant, JIS A
It becomes possible to satisfy the standard required by the additional test 2nd class A in 1321 "Flame retardancy test of interior materials for construction method".

The core sheet according to the present invention has its MI [(190 ° C .; 2.16 kgf)] or MFR in a product state.
[(230 ° C; 2.16kgf)] is 10.0g / 1
It is desirably 0 min or less, preferably 2.0 g / 10 min or less. The reason is that by improving the fluidity of the base material itself, it is possible to reduce the amount of the styrene-based thermoplastic elastomer added to prevent the molten resin from flowing out. However, 0.5g / 10mi
Those less than n may pass the additional test second grade A in JIS A1321 without adding a styrene elastomer.

The styrene elastomer according to the present invention is
The effect was observed with a copolymer of styrene and butadiene or a copolymer of styrene and isoprene. If these are less than 3% by weight, sufficient viscosity improving effect is not seen,
Even if added more than 30% by weight, no further effect is observed. 10 to 20% by weight in terms of flame retardant effect and cost
Is preferred.

Ammonium polyphosphate (C) according to the present invention
And the nitrogen-containing organic compound (D) have a weight ratio of component (D) /
Component (C) = 0.05-4, preferably 0.1-0.6
Set to the range of. When the weight ratio is below the lower limit of 0.05 or considerably above the upper limit of 4, the flame retardant-containing weight composition hardly develops the desired flame retardancy. A laminated body which is laminated and adhered by sandwiching it from both sides with the above thin plate is also unlikely to exhibit the desired flame retardancy. Moreover, component (D)
In addition to the request to keep the ratio of / component (C) within the above range, the sum of the amounts of both components, that is, component (C) + component (D), is 5 to 30% by weight of the composition, preferably 10 to 20% by weight
[Component (A) + Component (B) + Component (C) + Component (D) =
100% by weight]. If the lower limit of the range is less than 5% by weight, the flame retardancy becomes insufficient. On the other hand, when the upper limit is more than 30% by weight, not only the flame retardance is insufficient but also the polymer flows out.

As a method of joining the core material polyolefin resin forming the metal-resin laminated composite of the present invention and the metal plate layer, a method using an ordinary adhesive or a method using an adhesive polyolefin resin can be mentioned. Each is described below. Method using ordinary adhesive: Epoxy compound type or urethane compound (isocyanate) type, the thickness of the adhesive layer is 0.5 ~ 50μ
About m is sufficient.

Method using adhesive polyolefin resin:
Examples thereof include those obtained by grafting an unsaturated carboxylic acid or an acid anhydride thereof to a polyolefin resin. This is formed into a sheet of 20 to 100 μm, preferably 30 to 80 μm, and used. This method is desirable in terms of productivity.

[Metal-resin Laminated Composite Preparation Procedure] The metal-resin laminated composite of the present invention can be prepared, for example, by the following procedure: [Core sheet] A flame-retardant polyolefin resin composition constituting the core sheet is prepared. To obtain, a mixture of the above-mentioned polyolefin (A) with a styrene-based thermoplastic elastomer (B) and ammonium polyphosphate (C) and at least one nitrogen-containing organic compound (D) is mixed with a suitable stirring and mixing apparatus such as Henschel. Charge into a mixer (trade name), super mixer, tumbler mixer, etc.

After the stirring and mixing after the charging is continued for 1 to 10 minutes, the obtained mixture is further melt-kneaded by using a roll kneader or a screw extruder, and then granulated (pelletized). The pellets are formed into a sheet having an arbitrary film thickness by an appropriate means such as a hot press or an extruder equipped with a T-die to obtain a core sheet of a metal resin laminate.

When the core sheet is made of foam, the foam sheet has more excellent heat insulation and sound insulation capabilities, and at the same time leads to weight reduction of the laminate itself. The foamed sheet can be prepared by a known method such as adding a chemical foaming agent to the polyolefin mixture or directly injecting a gas into the molten resin.

[Preparation of Laminated Body] The above-mentioned thin metal plates are placed on both sides of the core material sheet with the above-mentioned adhesive polyolefin resin interposed therebetween and hot pressed, and the respective layers are thermocompression bonded. Thus, the metal resin laminate of the present invention is obtained.

[Alternative Method 1 (Use of Adhesive Polyolefin Resin (Continuous Film)]] The above flame-retardant core material sheet is prepared by an extruder equipped with a T-die, and the above-mentioned adhesive polyolefin resin is formed from both sides thereof. The sheets are laminated, and the above-mentioned thin metal plates are further laminated from both sides thereof, and the layers are laminated while being continuously supplied while being continuously supplied between the nip composed of a pair of laminating rolls that rotate in opposition. Is
Then, the metal-resin laminated composite of the present invention is integratedly manufactured by a take-off machine equipped with multi-stage rolls. In this method, it is important that the laminating roll has a sufficient temperature and pressing force to join the thin metal sheet and the flame-retardant core material sheet via the adhesive polyolefin sheet layer.

Although a manufacturing method using a hot press can be adopted as a modified form of the alternative method 1, it is not suitable for the integrated manufacturing, and therefore exerts its power on the contrary when the integrated manufacturing is difficult. That is, the present invention can be flexibly adapted to a production mode in which specifications such as the use of a core material sheet and / or a metal sheet and / or the use of an adhesive or the use of an adhesive polyolefin resin layer are required for every several products.

[Alternative Method 2] For a core material sheet and / or a metal sheet made of flame-retardant polyolefin formed by an extruder equipped with a T-die or a hot press, the following 3
After any one of the coating modes is applied, the metal thin plates are laminated from both sides of the core sheet and then sandwiched by a pair of opposing lamination rolls to obtain the metal-resin laminated composite of the present invention.・ Apply adhesive to both sides of the core sheet. -Apply adhesive to the surfaces to be bonded on both metal thin plates to be laminated on both sides of the core sheet. -Apply the adhesive to one side of the core material sheet, and apply the adhesive to the surface to be adhered of the thin metal plate to be adhered to the surface where the adhesive is not applied.

[0038]

EXAMPLES The present invention will be specifically described below with reference to Examples and, if necessary, Comparative Examples. However, the scope of the present invention is not limited to the examples. An embodiment in which additions and / or changes and the like which can be easily made by those skilled in the art are made in the following examples is also within the scope of the present invention. [Test Method and Conditions in Examples] (1) Preparation Method of Flame-Retardant Polyolefin Core Material Sheet After pellets of the flame-retardant polyolefin resin obtained in each Example and each Comparative Example are melt-kneaded, T-die method (Die temperature: 180 ° C.) A flame-retardant polyolefin resin sheet (length 220 mm × width 220 mm × thickness 3 mm) was prepared. In addition, in some of the comparative examples, it is difficult to prepare a smooth sheet by the T-die method. For this, a core sheet was prepared by hot pressing (180 ° C.) for 5 minutes. (2) Method for producing laminated body The obtained flame-retardant polyolefin sheet is used as a core sheet, and a predetermined adhesive polyolefin resin film (layer thickness 30 μm) is laid on both sides thereof, and a metal thin plate is placed thereon. By thermocompression bonding (140 ° C. × 5 min) with a hot press, a laminate having a predetermined size (length 220 mm × width 220 mm × thickness 3 mm) was prepared. A test piece was obtained by piercing (25 mm in diameter) the laminate using a hole saw. (3) Flowability index of polyolefin resin Pellets MI (190 ° C .; 190 ° C .; using pellets obtained by cutting the obtained flame-retardant polyolefin sheet)
2.16 kgf) or MFR (230 ° C .; 2.16 k
gf) was measured (according to JIS K7210). (4) Evaluation of smoke emission coefficient and flame retardancy Evaluation of smoke emission coefficient and flame retardancy in experimental examples (general term for examples and comparative examples) is based on JIS A1321 building interior materials and flame retardancy test method of construction method. The grade 2 A in the additional test was used to evaluate the pass or fail. Further, the degree of outflow of the molten resin from the test piece under the test conditions was observed and added as a reference for evaluation.

Example 1 High density polyethylene [abbreviation: HDPE-1; density 0.960 g / cc; MI (190 ° C; 2.16 kg) as a constituent of a polyolefin resin (abbreviation "component (A)")
f) 1.80 g / 10 min] 75% by weight and styrene-
Butadiene block copolymer (abbreviation "Component (B)")
[Brand name: Califlex (manufactured by Shell Chemical Co.)] 15% by weight of ammonium polyphosphate (abbreviated as "component (C)")
[Brand name: Exolit 442 (manufactured by Hoechst)] and a nitrogen-containing organic compound (abbreviation “component (D)”) [2-piperazinyl-4-morpholino-1,3,5-triazine homopolymer] (D ) / (C) = 0.3 (weight ratio) combined [(C) + (D)] 10% by weight and charged into a high-speed stirring mixer (Henschel mixer: trade name).

Furthermore, the sum of the above components [(A) + (B)
+ (C) + (D)] 100 parts by weight, as various additives, n-octadecyl-β- (4′-hydroxy-
0.03 parts by weight of 3 ', 5'-di-t-butylphenyl) propionate and 0.1 part by weight of calcium stearate were also charged into a Henschel mixer (trade name) and stirred and mixed for 3 minutes.

The obtained mixture was extruded (bore diameter: 45 mm).
After melt-kneading (200 ° C.) in the medium, it was extruded into pellets. The obtained pellets were melt-kneaded, and a resin sheet was obtained by a T-die method (die temperature; 180 ° C.). Adhesive polyolefin film on both sides of the resin sheet [Product name:
Cranbetter (made by Kurashiki Spinning Co., Ltd.)], and aluminum thin plates (layer thickness:
200 μm; sandwiched by abbreviated name “AL”) and hot pressed (140
The metal resin laminate of the present invention [total thickness 3 mm; AL // HDPE // AL] was prepared by pressurizing and pressing (5 min) at (° C.). After making a hole of a predetermined size in the laminate with a hole saw, a flame retardancy test (based on JIS A1321) was performed. Table 1 shows the results.

Examples 2 and 3 Pellets prepared using the above components (A), (B), (C) and (D) were added to a chemical blowing agent azodicarbonamide (abbreviated as "component (E)" in the table). [Brand name: Vinyl Hall (manufactured by Eiwa Chemical Industry Co., Ltd.)] 0.3 parts by weight was added, and liquid paraffin was used for attachment. This was formed into a film with an extruder, and a laminated sheet was prepared in the same manner as in Example 1 using the obtained foamed sheet having a foaming ratio of about 1.8 times, and subjected to a flame retardancy test (above Example 2). . In addition, the amount of the above component (E) was adjusted, and a foamed sheet having a foaming ratio of about 3.0 was used in Example 3.
As a result, a flame retardancy test was performed. Table 1 shows the results.

Examples 4 to 6 and Comparative Examples 1 to 3 The total amount of the styrene-butadiene block copolymer as the component (B) added and the total amount of the ammonium polyphosphate and the nitrogen-containing organic compound as the component (C). That is, (C) + (D)
A flame retardant test was conducted by preparing a laminate in the same manner as in Example 1 except that the amount was changed to the amount shown in Table 1. Table 1 shows the results.

Comparative Examples 4 to 6 The ammonium polyphosphate as the component (C) and the nitrogen-containing organic compound as the component (D) were not added, and the addition amount of the styrene-butadiene block copolymer as the component (B) was changed. A laminate was prepared in the same manner as in Example 1 except that the amount shown in Table 1 was changed, and a flame retardancy test was conducted. Table 1 shows the results.

Comparative Examples 7 and 8 Component (C), ammonium polyphosphate, and component (D), the nitrogen-containing organic compound, were blended in the amounts shown in Table 1 to give component (B), styrene. A laminate was prepared in the same manner as in Example 1 without adding the butadiene block copolymer, and the flame retardancy test was conducted. Table 1 shows the results.

[0046]

[Table 1]

Examples 7 to 9 and Comparative Example 9 The total ratio [(D) / (C)] of ammonium polyphosphate as the component (C) and the nitrogen-containing organic compound as the component (D).
A flame retardant test was conducted by preparing a laminate in the same manner as in Example 1 except that the amount was changed to the amount shown in Table 2. The results are shown in Table 2.

Examples 10 to 13 As shown in Table 2, the kind of the nitrogen-containing organic compound which is the component (D) is 2-piperazine-4-N, N-bis (β-hydroxyethyl) amino-, respectively. Other than the homopolymer of 1,3,5-triazine, the reaction product of cyanuric chloride and ethylenediamine, the reaction product of ethylene urea and formaldehyde, and the reaction product of ethylene thiourea and formaldehyde. A laminate was prepared in the same manner as in Example 1 and a flame retardancy test was conducted. The results are shown in Table 2.

[0049]

[Table 2]

Examples 14 and 15 Laminates were prepared by using aluminum thin plates having a total thickness of 50 μm and 1000 μm as the thin metal plates to be placed on both sides of the laminate, and the flame retardancy test was conducted. went. Table 3 shows the results.

Example 16 Lamination was carried out in the same manner as in Example 1 except that the styrene-isoprene block copolymer [trade name: Califlex (manufactured by Shell Chemical Co.)] was used as the styrene thermoplastic elastomer which is the component (B). A body was prepared and a flame retardancy test was conducted.
Table 3 shows the results.

Examples 17 to 19 As the component (A) polyolefin resin, HDPE-
2 [density 0.953; MI 0.70 g / 10 min],
Propylene homocrystalline polymer [abbreviation: PP-1; density 0.910 g / cc; MFR (230 ° C .; 2.16 kg
f) 2.30 g / 10 min] and HDPE-3 [density 0.964; MI 7.50 g / 10 min] were used, but the addition amount of the styrene-based elastomer as the component (B) was changed to Example 17, respectively. Example 18 and Example 1
As No. 9, a laminated body was prepared in the same manner as in Example 1 and a flame retardancy test was conducted. Table 3 shows the results.

Comparative Example 10 HDPE-as the polyolefin resin as the component (A)
4 [Density 0.960; MI 0.50 g / 10 min] was used, and a flame retardancy test was conducted in the same manner as in Example 1 except that the component (B) styrene elastomer was not added. . Table 3 shows the results.

Comparative Examples 11 and 12 PP-2 was used as the component (A) polyolefin resin.
[Density 0.900 g / cc; MFR 16.0 g / 10 m
in] and HDPE-5 [density 0.952; MI15.
0 g / 10 min] and changing the addition amount of the styrene-based elastomer as the component (B) as Comparative Examples 11 and 12, respectively, a laminate was prepared and a flame retardancy test was conducted. Table 3 shows the results.

[0055]

[Table 3]

[Experimental Findings] (1) From Table 1 showing the results of the flame retardancy test obtained in Examples 1 to 6 and Comparative Examples 1 to 8, the following can be observed. -The laminated body of Example 1 passed in terms of smoke generation and flame retardancy, and the amount of molten resin spilled out was very small.

The laminated bodies of Examples 2 and 3 passed the flame retardance as in Example 1. That is, it is judged that the present resin composition can maintain the flame retardant performance regardless of foaming / non-foaming. However, since the rigidity of the core sheet is extremely reduced, the expansion ratio is practically 5.0 times or less.

The laminated bodies of Examples 4 to 6 passed the flame retardance as in Example 1. In contrast, Comparative Examples 1 to
The laminate of No. 3 failed in flame retardancy. That is, by adding the styrene elastomer as the component (B), the viscosity of the resin itself is improved, and the total blending amount of the ammonium polyphosphate as the component (C) and the nitrogen-containing organic compound as the component (D) [ Component (C) + component (D)] can be reduced. At this time, the range of the added amount of the component (B) is 3 to 30% by weight, and the range of the sum of the component (C) and the component (D) [component (C) + component (D)] is 5 to 30% by weight. It is valid.

The laminates of Comparative Examples 4 to 8 failed in terms of flammability. That is, only the styrene-butadiene block copolymer which is the component (B) or the ammonium polyphosphate which is the component (C) and the nitrogen-containing organic compound which is the component (D) alone impart sufficient flame retardancy. Is difficult

(2) From Table 2 showing the results of the flame retardancy test obtained in Examples 7 to 13 and Comparative Example 9, the following can be observed. -Like the example 1, the laminated bodies of Examples 7 to 9 passed the flame retardancy. That is, the ratio [component (D) / component (C)] of component (C) and component (D) in the flame-retardant olefin polymer composition constituting the core layer of the laminate of the present invention is 0.1 to 0.1.
Good flame retardancy can be obtained at 3.0.

The laminate of Comparative Example 9 fails in flame retardancy. The cause is that the ratio [component (D) / component (C)] of the component (C) and the component (D) is out of the range of the present invention 5.0.
Required for points set to.

The laminated bodies of Examples 10 to 13 were acceptable in terms of flame retardance as in Example 1. That is, the nitrogen-containing organic compound which is the component (D) is a homopolymer formed from a unit structure, a reaction product of cyanuric chloride and a diamine, or a reaction product of ethylene urea and formaldehyde or ethylene thiourea. Good results are obtained with reaction products with formaldehyde.

(3) Examples 14 to 19 and Comparative Example 10
From Table 2 showing the results of the flame retardancy test obtained in Nos. 12 to 12, the following can be observed. The laminated bodies of Examples 14 and 15 passed the flame retardance as in Example 1. That is, the aluminum thin plates placed on both sides of the laminate are effective in the range of 50 μm to 1000 μm.

The laminated body of Example 16 passed the flame retardancy test as in Example 1. That is, even if a styrene-isoprene block copolymer is used as the styrene elastomer as the component (B), sufficient flame retardancy can be exhibited.

The laminated body of Comparative Example 10 passed the flame retardancy test as in Example 1. That is, the melt fluidity index of the polyolefin resin used as the base material of the core sheet [MI (1
90 ° C; 2.16 kgf) or MFR (230 ° C;
2.16kgf)] is less than 0.5g / 10min,
Sufficient flame retardancy may be exhibited without adding a styrene elastomer.

The laminated bodies of Examples 17 to 19 passed the flame retardance as in Example 1. On the other hand, the laminates of Comparative Examples 11 and 12 failed in flame retardancy.
That is, the polyolefin resin used as the base material of the core sheet has a melt fluidity index [MI (190; 2.16 kg
f) or MFR (230 ° C; 2.16 kgf)] is 1
Effective at 0.0 g / 10 min or less.

[0067]

The flame-retardant laminated composite of the present invention has the following various effects. (1) The amount of smoke is small, and the outflow of the molten resin at the time of contact with flame is small. (2) The flame retardancy test can be passed even if the melt fluidity index is relatively high. (3) Can be used as interior and exterior materials for buildings, vehicles and public buildings.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 23/02 LCH C08L 23/02 LCH

Claims (4)

[Claims] 1. A polyolefin (A) is used as a base material and the following components (B), (C) and (D) are represented by the following relational expression (1).
And (2) and (3) are contained so as to be satisfied, and the melt fluidity index [MI (190 ° C; 2.16 kgf) or MFR (2
30 ° C; 2.16 kgf)], 0.5 g / 10 min
A metal-resin laminated composite obtained by laminating aluminum plates on both sides of a core sheet formed by molding a composition that is larger and 10.0 g / 10 min or less. (A): Polyolefin (B): Styrene-based thermoplastic elastomer (C): Ammonium polyphosphate (D): One or more triazine-based nitrogen-containing organic compounds; (1) Component (B) = 3 to 30% by weight and (2) Weight ratio of the components to each other [component (D) / component (C)]
= 0.05 to 4 and (3) component (C) + component (D) = 5 to 30% by weight [component (A) + component (B) + component (C) + component (D) = 100
weight%] 2. The metal resin laminated composite according to claim 1, wherein the polyolefin is selected from one or more of the following. Ethylene homopolymer, propylene homopolymer,
An ethylene copolymer, which is a copolymer of ethylene and an α-olefin having 3 or more carbon atoms or a polar monomer, and comprising 50% by weight or more of ethylene unit. 3. A homopolymer and / or copolymer in which the nitrogen-containing organic compound has a monomer structure represented by [Chemical Formula 1] as a unit structure, a reaction product of cyanuric chloride and a diamine, and ethylene urea. The metal resin laminated composite according to claim 1 or 2, which is a reaction product of an aldehyde and a reaction product of ethylenethiourea and an aldehyde. Embedded image (Wherein X and Z ¹ are both structures bonded to a triazine skeleton through a nitrogen atom, and X is an alkylamino group or a morpholino group represented by a group of —NHR ¹ or —NR ² R ³ , It is a piperidine group and R ¹ , R ² and R ³ are linear or branched alkyl groups having 1 to 6 carbon atoms (R ¹ and R ² may be the same or different) or X is -NHR ^4, a hydroxyalkyl amino group represented by group ^{-NR 5 R 6 R 4, R} 5, R
⁶ is a linear or branched hydroxyalkyl group having 2 to ⁶ carbon atoms (R ⁵ and R ⁶ may be the same or different). Z ¹ is a divalent piperazine group, a group represented by the formula —HN (CH ₂ ) _m NH— (m is an integer of 2 to 6), or a formula —NR ⁷ (CH ₂ ) ₁ R ⁸ N. −
Is a group represented by (1 is an integer of 2 to 6) and R
One or both of ⁷ and R ⁸ are hydroxyethyl groups. ) 4. A styrene-based thermoplastic elastomer, wherein styrene and butadiene or isoprene are anionic polymerization method, cationic polymerization method, coordination polymerization method, radical polymerization method,
A block copolymer copolymerized by a solution polymerization method, an emulsion polymerization method, or the like, and having a styrene / butadiene or isoprene weight ratio of 10 to 50/50 to 90. Item 3. A metal resin laminated composite according to item 3.