JP3499175B2 - Substantially colorless non-halogen flame-retardant polyolefin resin composition laminated sheet with excellent colorability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention relates to a substantially colorless non-
Halogen flame-retardant polyolefin resin composition laminated sheet
It is about. More specifically, the present invention
Is suitable for use in buildings, structures, etc.
Excellent in flexibility and mechanical properties, and emits halogen gas during combustion.
Virtually colorless non-halogen flame-retardant polio that does not generate
The present invention relates to a laminated sheet of a refin-based resin composition.
You. In the present invention, “substantially colorless” means colorless.
Effect on the resulting hue when applied and practical coloring
However, it includes a light color that is practically acceptable. Colorless
And a substantially colorless resin composition can be used in practically any color.
It can be colored freely without any trouble. [0002] 2. Description of the Related Art Conventional tents, sheet warehouses, architectural curing sheets
For sheet materials that make up buildings and structures such as buildings
In the process, a laminate of vinyl chloride resin and fiber fabric is used.
Used in vinyl chloride resin in recent years.
Because rogen is a source of toxic gas when burning,
Issues raised regarding waste disposal or fire safety
Have been. Due to this social background, halogen content
Various measures to reduce the amount as much as possible have been studied. Was
For example, as a substitute for vinyl chloride resin, Polyolefin
Non-halogen flame retardants (for example, metal
Hydrates, metal oxides, phosphorus-based flame retardants, etc.)
Halogen flame-retardant resins have been proposed (Japanese Unexamined Patent Publication No.
20348, JP-A-63-61055,
JP-A-63-128038, JP-A-63-1547
No. 60, JP-A-3-20342, etc.). However, in these methods, polyolefins are used.
Metal hydrate to provide sufficient flame retardancy to
(For example, magnesium hydroxide, aluminum hydroxide
Etc.) or metal oxides (eg antimony trioxide, acid
Magnesium oxide, titanium dioxide, etc.)
It is necessary to add a large amount of 0 to 300 parts by weight.
As a result of impairing the workability of the polyolefin resin composition,
Problems such as a significant decrease in the mechanical strength of the processed product
I am Especially when applied to sheet-like processed products
Not only the texture becomes hard, but also fatigue deterioration due to bending
And practical problems and flame retardancy.
Cannot be balanced. Therefore, the amount of the halogen-free flame retardant added is reduced.
To reduce red phosphorus and heat-expandable graphite,
A combination with a flame retardant has been proposed (Japanese Unexamined Patent Publication No. 1-4).
632, JP-A-6-184330, JP-A-6-184330
6-73251, JP-A-6-25476,
JP-A-8-302202). With these methods,
Advanced flame retardancy by reducing the amount of crab-free halogen-free flame retardants
Although it is possible to obtain the property, molded products by adding red phosphorus
Reddish brown coloration of molded products by adding heat-expandable graphite
Due to the black coloring, the flexibility of coloring of the molded product is impaired,
Can be used for applications that require color and toning
Was not. [0005] Further, red phosphorus is classified as a second-class dangerous substance under the Fire Service Law.
Not only does it require special care for handling,
The problem of the flame retardant effect decreasing over time due to hydrolysis,
Toxic phosphine gas is likely to be generated
The fact is that it is avoided in practice. In contrast,
Although heat-expandable graphite is highly safe, it does not
There is a problem of contaminating the machine.
There is a drawback that it takes time and effort to perform the ringing. Further, red phosphorus, heat-expandable graphite, etc. are used.
For imparting high flame retardancy to polyolefin resin without using
Combination of ammonium polyphosphate and metal oxide as a method
(JP-A-7-330968) and a phosphate compound
Combination with metal hydrate (Japanese Utility Model Laid-Open No. 6-29830),
Although these methods have been proposed, these methods
While keeping the amount of oxide and metal hydrate added low
There is also a composition that can obtain high flame retardancy
Has a fragile combustion ash residue of these metal compounds during combustion
However, due to the characteristics of ammonium polyphosphate and phosphate compounds
There are two types of difficulties to prevent the formation of certain pyrolysis foam layers.
Poor synergistic effect as a combination system with fuel
Was. [0007] SUMMARY OF THE INVENTION The present invention relates to
Using red phosphorus and heat-expandable graphite to solve the problem
Develops excellent flame retardancy and processability
Excellent in flexibility and mechanical strength, and also substantially colorless
Color-free, halogen-free flame-retardant polyolefin
It is intended to provide a laminated resin composition laminated sheet.
You. [0008] SUMMARY OF THE INVENTION
Color non-halogen flame-retardant polyolefin resin composition
Layer sheet is non-halogen for polyolefin resin.
-Based flame retardants and pyrolytic N_Two Compounding system containing gas generating agent
In the thermal decomposition N_Two During and after processing gas generating agent
In polyolefin resin without thermal decomposition foaming
By burning, non-halogen flame retardants and heat
Solvability N_Two Excellent flame retardant with synergistic effect with gas generant
It was found that it exhibited the nature and completed it. [0009] The substantially colorless excellent colorant of the present invention is provided.
Non-halogen flame-retardant polyolefin resin composition laminate
The sheet is a polyolefin resin and 100 parts by weight
10 to 200 parts by weight of a halogen-free flame retardant,
1 to 50 parts by weight of thermally decomposable N_Two Including a gas generating agent,
Substantially colorless non-halogen flame-retardant polyolefin-based tree
At least one sheet layer containing the fat composition;
At least one layer of fiber cloth laminated on the layer
A non-halogen flame retardant, wherein the degree of polymerization is 2
More than 00 ammonium polyphosphate, thermosetting resin coating
Particulate ammonium polyphosphate and melamine polyphosphate
At least one selected from the group consisting of
_Two When the gas generating agent is azodicarbonamide, 4,4'-O
Xybisbenzenesulfonyl hydrazide and dinitroso
At least one selected from pentamethylenetetramine
And at least 50% by weight of azodicarbonamide
And the sheet layer is a non-halogen flame-retardant polish.
Using a calender method, the polyolefin resin composition
Pyrolytic N_Two Do not use pyrolysis foam
At a temperature of 80 to 200 ° C.
Characterized by being formed from a film
It is. [0010] DETAILED DESCRIPTION OF THE INVENTION A substantially colorless non-woven fabric according to the present invention
Halogen flame-retardant polyolefin resin composition and substantial
Colorless non-halogen flame-retardant polyolefin resin group
Species of polyolefin resin used for composite laminate sheet
The class is not particularly limited, for example, ethylene-α-O
Lefin copolymer, low density polyethylene, medium density polyethylene
Tylene, high-density polyethylene, ethylene-vinyl acetate
Polymer, ethylene-acrylic acid copolymer, ethylene-a
Crylate ester copolymer, ethylene-methacrylic acid
Copolymer, ethylene-methacrylate copolymer
And mixtures of two or more of these.
Of course, these resins are substantially colorless. The polyolefin resin used in the present invention
Was produced by a radical polymerization method or an ionic polymerization method.
Things can be used. Polyethylene obtained by radical polymerization
Resin is ethylene alone or radical polymerized with ethylene
Obtained by copolymerization with a monomer capable of
Examples of monomers that can be combined include acrylic acid and metaac
Unsaturated carboxylic acids such as lylic acid and esterified products thereof;
Vinyl esters such as acid anhydrides and vinyl acetate;
I can do it. As an esterified product of unsaturated carboxylic acid
Are, for example, ethyl acrylate, methyl methacrylate,
Glycidyl acrylate and the like can be mentioned. These simple
Not only one type but also two or more types can be used. I
The polyethylene resin obtained by the on-polymerization method is ethylene
Alone or ethylene and α-olefin having 3 to 18 carbon atoms
Use transition metal solid catalyst or homogeneous metallocene catalyst
And polymerized as α-olefin
Is, for example, propylene, butene-1,4-methylpente
-1, hexene-1, octene-1, decene-1,
Kutadecene-1 or the like is used.
It is preferable to use an α-olefin. Also these
May be used alone or in combination of two or more.
No. The polyolefin resin used in the present invention
Among them, ethylene-vinyl acetate copolymer, ethylene-a
Crylic acid copolymer, ethylene-acrylate copolymer
Coalesce, ethylene-methacrylic acid copolymer, and ethylene
-Methacrylic acid ester copolymer is preferably used.
Wear. Further, these ethylene-based copolymers are
Melt-in either alone or in a blend of two or more
Dex is 0.5-20g / 10min, copolymerized monomer
Those having a content of from 5 to 30% by weight are preferred according to the invention
Can be used for Melt index is 0.5g / 10
If it is less than min, the forming process of the sheet of the present invention is extremely
It can be difficult. Higher than 20g / 10min
Not only does the resulting sheet have poor strength and heat resistance.
In addition, blocking may occur due to increased tackiness.
If the copolymerized monomer content is less than 5% by weight, a high
The wave weldability may be insufficient, and
If the combined monomer content is more than 30% by weight,
The tackiness may increase, making molding extremely difficult.
You. [0015] Substantially colorless used in the present invention
Pyrolytic N_Two Gas generating agent is azodicarbonamide
(A.D.C.A.), dinitrosopentamethylenetetra
Min (DPT), 4,4'-oxybisbenzenes
One or two of rufonyl hydrazide (OBSH)
And 50% by weight or more of azodicarbo.
It consists of amide. This thermally decomposable N_Two From gas
The raw material is 1 part per 100 parts by weight of the polyolefin resin.
５０50 parts by weight, preferably 1-30 parts by weight
You. Pyrolytic N_Two 50% by weight or more of the gas generating agent
Azodicarbonamide is occupied by heat-decomposable N
_Two The generator comprises only azodicarbonamide.
You may. Azodicarbonamide is a pyrolysis gas
(N_Two , CO, CO_Two , NH_Three ) Besides urazole, bi
Nitrogen-containing decomposition of urea, isocyanuric acid, siamide, etc.
By-products of solids and sublimates,
And sublimates are non-halogen flame retardants used in the present invention
Express high flame retardancy by synergistic effect with
The effect is especially good for ammonium polyphosphate and thermosetting resin coating.
Granulated ammonium polyphosphate, melamine polyphosphate
Which phosphate compounds and their derivatives
Is exerted to a higher degree. Further, the heat-decomposable N_TwoDecomposition aid for gas generating agent
Zinc oxide, oxidized
Inorganic such as lead, tribasic lead sulfate, dibasic lead phosphite
Salt, lead stearate, barium stearate, stearie
Metal soap such as calcium phosphate, and an appropriate amount of urea
Can be used to control the rate of pyrolysis during combustion
it can. The non-halogen flame retardant used in the present invention
Is ammonium polyphosphate, thermosetting resin-coated
One of ammonium phosphite and melamine polyphosphate
Or two or more kinds of the polyolefin resin 10
It is used in an amount of 10 to 200 parts by weight per 0 parts by weight. Poliri
Ammonium phosphate having a degree of polymerization of 200 or more is used.
And the surface of the ammonium polyphosphate particles
Min-based resin, urea resin, triazine resin, phenol tree
Coated with thermosetting resin such as fat and hardly soluble in water
Also, melamine polyphosphate is used. Polylin
If the polymerization degree of ammonium acid is less than 200,
Ammonium phosphite becomes water-soluble and halogen-free
A laminate obtained by laminating a flame-retardant polyolefin resin composition
The water resistance of the sheet may be reduced, or the durability of the flame retardant effect may be poor.
Become unsuitable for outdoor use.
is there. Non-halogen flame retardant used in the present invention
As the degree of polymerization of 600 surface-treated with melamine resin
~ 1200 granular ammonium polyphosphate is preferably used.
Can be used. In the present invention, the non-halogen flame retardant
That can be used as a virtually colorless flame retardant in combination with the agent
Aluminum hydroxide, magnesium hydroxide
Cium, calcium hydroxide, barium hydroxide, dihydroxide
Ruconium, basic magnesium carbonate, dolomite, ha
Of hydrotalcite, zinc hydroxystannate, tin oxide
Hydrates and hydrates of inorganic metal compounds such as borax
No. Aluminum oxide is also used as the metal oxide.
System, magnesium oxide, barium oxide, titanium oxide, acid
Zinc oxide, tin oxide, zirconium oxide, molybdenum oxide
, Antimony oxide, zirconium-antimony complex acid
And metal complex oxides such as oxides. More gold
Genus carbonates include zinc carbonate, calcium carbonate, and carbonate carbonate.
Lium, magnesium carbonate, and magnesium carbonate-mosquito
Lucium and the like. Furthermore, as boric acid compounds
Is zinc borate, zinc metaborate, barium metaborate
And aluminum borate. These non-halogen flame retardants may be used alone or in combination.
May be used in combination of two or more. These non-halogen flame retardant
Aluminum hydroxide, magnesium hydroxide
, Zinc borate, antimony oxide, and zirconium-
Antimony composite oxides have a high flame retardant effect and are economical
Is also advantageous. Also, these non-halogen flame retardant particles
The diameter varies depending on the type of the compound.
In the case of minium or magnesium hydroxide, the average particle size is 2
Those having a particle size of 0 μm or less, particularly 10 μm or less have good workability and
It is preferable in terms of dispersibility. Further used in the present invention
Non-halogen flame retardant is the surface of non-halogen flame retardant particles
The stearic acid, oleic acid, palmitic acid, etc.
Fatty acids or their metal salts, paraffin wax, polyet
Tylene wax or their modified products, organic borane,
Coated with organic titanate or silane coupling agent
Or it is preferably a surface-treated or modified product
No. Halogen-free flame-retardant polyolefin resin of the present invention
In the composition, the non-halogen flame retardant is a polyolefin.
10 to 200 parts by weight based on 100 parts by weight of resin
Used in the amount added. The substantially colorless non-halogen flame retardant of the present invention
The reactive polyolefin-based resin composition is optionally halogenated.
Atom-free additives such as antistatic agents, antioxidants
Agents, weathering stabilizers such as hindered amine compounds, ultraviolet
A line absorber, a lubricant, a coloring agent, and the like can be added. Ma
The obtained halogen-free flame-retardant polyolefin resin
Within the range that does not impair the properties of the composition and the laminated sheet.
Add inorganic filler to reduce production cost
They can be used together. This inorganic filler includes silicone
Mosquito, talc, clay, glass powder, silicone pow
And the like. The halogen-free flame-retardant polyolefin of the present invention
The resin composition is substantially colorless. This substantially
Colorless, as described above, colorless and, in this resin composition
Effect on the hue obtained when practical coloring is applied
However, it includes a light color that is practically acceptable. This pale
The colors are, for example, the color of unbleached cotton cloth,
Color, unbleached Japanese paper color, ivory color (such as pale yellow)
Include. Halogen-free flame-retardant polyolefin of the present invention
Since the resin composition is substantially colorless,
It can be freely colored to hue and color density. The substantially colorless non-halogen flame retardant of the present invention
Polyolefin-based resin composition and laminated sheet thereof
There are no particular restrictions on the method for producing the
Evenly disperse and mix each component to be included in the fat composition
Any method is acceptable. The mixing method for this is as follows.
In the above range, a known method such as a Banbury mixer is used.
After melt-kneading using a kneader, kneader or twin-screw kneader
Granulation method or using a Banbury mixer
Make a high-concentration master batch for
Blender, tumble mixer, or Henschel Miki
Dry blending using a mixer like sir,
After mixing and melt mixing with a single screw extruder or twin screw extruder, etc.
A method of kneading and granulating can be employed. The substantially colorless non-halogen flame retardant of the present invention
From the conductive polyolefin-based resin composition
When forming the lum, heat-decomposable N_Two Gas generating agent is filled
Non-halogenated without thermal decomposition foaming during molding
Can be retained in a flame-retardant polyolefin resin composition.
Is necessary. For this reason, the film for sheet of the present invention
The method of forming the film is such that the film forming temperature is T-
Curry which may be lower temperature than die method and inflation method
The under method is used. Halogen-free flame retardant powder of the present invention
Calendars are used for the production of polyolefin resin laminated sheets.
According to the method, substantially colorless within the temperature range of 80 to 200 ° C
Of non-halogen flame-retardant polyolefin resin composition
A film is formed and laminated to the fiber fabric. The substantially colorless non-halogen flame retardant of the present invention
Substrate used for the conductive polyolefin resin composition laminated sheet
Colorless non-halogen flame-retardant polyolefin resin group
The thickness of the product film may be 80 to 800 μm
Preferably, it is particularly preferably 130 to 450 μm.
No. If the thickness is thinner than this range, molding will be difficult and
When laminated with fiber fabric, the unevenness of the fiber fabric surface
Thermo-compression of the film causes the film to break, impairing waterproofness
Can not be used for outdoor tents and seats
Sometimes. If the thickness is larger than the above range,
Not only makes it difficult to process, but also heavy and inflexible.
And handling may be poor. The substantially colorless non-halogen flame retardant of the present invention
Can be used for laminated sheet of conductive polyolefin resin composition
The fiber cloth may be any of a woven cloth, a knitted cloth and a non-woven cloth.
There is no particular limitation on the weave structure of the fabric, but using plain weave
Good because of the excellent balance of physical properties of the flame retardant sheet
Good. Russell knitted weft insertion tricot
The nonwoven fabric is preferably a nonwoven fabric using long fibers.
More preferably, spunbond nonwoven fabric and the like can be used. Ma
In addition, the warp and weft of the base fabric are made of synthetic fibers, natural fibers,
Of synthetic fibers or mixed fibers consisting of two or more of these
Although it may be woven by any of them, workability and versatility
Considering polypropylene fiber, polyethylene fiber
Fiber, polyvinyl alcohol fiber, polyester fiber,
Lamide fiber, acrylic fiber, polyurethane fiber,
Are synthetic fibers such as these mixed fibers, long fiber yarn, short fiber
Fiber spun yarn, split yarn, tape yarn, etc.
Of these, tensile strength, tear strength, and heat-resistant
Polyester multifilament with excellent loop properties
Thread (long fiber thread) yarn, polyamide multifilament
(Long fiber yarn) yarn, mixed fiber of these, composite fiber, etc.
It is preferable to use a plain-woven fiber fabric formed from. These fiber fabric base fabrics and substantially colorless
Halogen-retardant polyolefin resin composition film
In the laminate with, the film is laminated on one side of the base fabric
May be stacked on both sides,
Considering the durability of the application, both sides of the base fabric are substantially colorless
Non-halogen flame-retardant polyolefin resin composition
It is preferable that the layers are laminated. Also, the method of lamination
As an alternative, an adhesive layer may be provided between the film and the base cloth.
Alternatively, they may be laminated without an adhesive. Substantially of the present invention
Colorless non-halogen flame-retardant polyolefin resin composition
The base fabric used to manufacture the laminated sheet and the substantially colorless non-woven fabric
Rogen flame-retardant polyolefin resin composition film
The lamination method is to process the film by calendering
After that, the film by thermocompression with a laminator
And laminating the base cloth. In the present invention
Colorless non-halogen flame-retardant polyolefins
The production of the laminated sheet of the resin composition is carried out by the calendar method.
And the polyester fiber
The method of thermocompression bonding with plain weave fabric is efficient and economical.
More preferred. At this time, the weave structure of the plain weave
Woven fabric does not impair the flame retardant effect,
Is well-balanced and preferably used. The polyester used for the plain woven fabric is
Flame-retardant polyester containing phosphorus compounds
Fibers can also be used. [0029] The present invention will be more specifically explained by the following examples.
As will be explained, the scope of the present invention is limited by these examples.
Absent. [0030]Example 1 Ethylene-vinyl acetate copolymer resin⁽¹⁾(Trademark: Ebate
To-K-2010: Sumitomo Chemical Co., Ltd .: Vinyl acetate content
25wt%, melt flow rate 3g / 10min, density
0.95) 100 parts by weight of melamine as a flame retardant
Resin coating type ammonium polyphosphate⁽⁷⁾
(Trademark: Hostafram AP-745 (EXOLIT I
FR-23): Clariant: polymerization degree n = 1000)
40 parts by weight and pyrolytic N_TwoAzodica as gas generating agent
Rubonamide (A.D.C.A.)^{(Four )}(Trademark: Uniho
AZ L-10: Otsuka Chemical Co., Ltd .: Decomposition temperature 199
° C: gas generation amount 240 ml / g) 10 parts by weight and lubricant⁽⁹⁾
As zinc stearyl phosphate (trademark: JP-5
18ZN: Johoku Chemical Co., Ltd.) 1.0 parts by weight and ultraviolet absorption
Absorbent^(Ten)(Trademark: Tinuvin P: Ciba Specialty
Chemicals Co., Ltd.) 0.3 parts by weight and white pigment⁽⁸⁾(quotient
Mark: High Conc Master HCM2060: Dainichi Seika
140 parts by weight of a compound containing 5 parts by weight.
Kneading for 10 minutes with a hot roll (2 rolls) set to ℃
Then, a film having a thickness of 0.2 mm is
And under-roll molding. The oxygen index (LO
I) was 36.3 (JIS K-7201).
The UL-94 vertical flammability test score was V-0.
Was. Roll kneading of the kneading composition and calendering
-No stickiness or plate-out observed in molding
It was good. Next, 0.2 mm obtained from the kneaded composition was used.
Of the polyester fiber plain weave fabric (25
0 denier polyester multifilament: Yarn density vertical
25 yarns / 2.54 cm x 24 wefts / 2.54 cm)
Thermocompression bonding with a laminator set at 130 ° C
0.5mm thick, weight 540g / m^TwoNonha
A logen flame-retardant polyolefin resin sheet was obtained. this
According to JIS L-1091 (A-2 method category 3) for sheets
The results of the 45 degree flameproof test were acceptable. Also obtained
The hue of the mixed sheet is vivid,
Was. Table 1 shows the test results. [0032]Example 2 In the composition of Example 1, the azodicarbonamide was
(A.D.C.A.) ^(Four)Reduced to 5 parts by weight
And dinitrosopentamethylenetetramine (D.
P. T)^(Five)(Trademark: Cellular D: Eiwa Chemical Industry
(Co.): Decomposition temperature 205 ° C: Gas generation amount 242 ml / g)
5 parts by weight, heat-decomposable N_TwoTotal gas generating agent
Except that the blending amount was 10 parts by weight,
Preparation of a resin composition and a laminated sheet thereof in the same manner as in 1.
Then, the same evaluation as in Example 1 was performed. The resulting file
Lum has an oxygen index (LOI) of 35.0,
The result of the UL-94 vertical flammability test was V-0. Ma
Roll kneading of the kneading composition and calendering
Good without stickiness and plate out
there were. The thickness obtained from this kneading composition is 0.5 mm,
540 g / m^TwoNon-halogen flame retardant polyolefin
JIS L-1091 (A-2 method classification)
The result of the 45 degree flameproof test according to 3) was passed. Ma
The hue of the obtained film is determined by the pigment contained in it.
The white color was bright. Table 1 shows the test results. [0033]Example 3 In the same manner as in Example 1, the resin composition, its film and
The laminated sheet was prepared and evaluated. However, ethylene-vinegar
Instead of 100 parts by weight of vinyl acetate copolymer resin, ethylene
Tyl methacrylic acid copolymer resin⁽²⁾(Trademark: Acklift
WH-202: Sumitomo Chemical Co., Ltd .: Methyl methacryl
Luric acid content 20 wt%: melt flow rate 2 g / 10 min
 , Density 0.95) 100 parts by weight,
(White)⁽⁸⁾Pigment (blue) instead of 5 parts by weight⁽¹⁷⁾(Trademark: C
Icon Master HCM1615: Dainichi Seika
5 parts by weight were used. Oxygen finger of the resulting film
The number (LOI) is 37.8 and UL-94
The result of the direct flammability test was V-0. Also, this kneading
Adhesion in roll kneading and calendering of the composition
The properties and plate-out were not observed and were good. this
0.5 mm in thickness and 540 g / weight obtained from the kneading composition
m^TwoHalogen-free flame-retardant polyolefin resin sheet
According to JIS L-1091 (A-2 method category 3)
The result of the flameproof test passed. Also obtained sea
The hue of the paint is vivid blue in the blended pigment.
Was. Table 1 shows the test results. [0034]Example 4 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, ethylene-acetic acid
Instead of 100 parts by weight of vinyl copolymer resin, ethylene-methyl
Rumethacrylic acid copolymer resin⁽²⁾Using 100 parts by weight,
Further, azodicarbonamide (ADCA)^(Four)Arrangement
The combined amount was reduced to 5 parts by weight, and 4,4'-oxybis
Benzenesulfonyl hydrazide (OBSH)⁽⁶⁾
(Trademark: Neoserbon: Eiwa Chemical Co., Ltd .: Decomposition temperature
159 ° C: 125ml / g of gas generation) 5 parts by weight
Combined with pyrolytic N_TwoThe total amount of the gas generating agent is 10 wt.
Part, and pigment (white)⁽⁸⁾Pigment instead of 5 parts by weight
(Blue)⁽¹⁷⁾5 parts by weight were used. Oxygen in the resulting film
The index (LOI) is 34.6 and UL-94
The result of the vertical flammability test was V-0. Also,
Roll kneading of the kneading composition and, in the calendar molding,
Adhesion and plate-out were not observed and were good.
0.5 mm in thickness and 540 in weight obtained from this kneading composition
g / m^TwoNon-halogen flame-retardant polyolefin resin
According to JIS L-1091 (A-2 method category 3)
The results of the 45 degree flameproof test were acceptable. Also obtained
The hue of the colored sheet is bright blue due to the pigment used in the formulation.
It was easy. Table 1 shows the test results. [0035]Example 5 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, ethylene-acetic acid
50 parts by weight of 100 parts by weight of the vinyl copolymer resin
Instead of ultra low density polyethylene resin⁽³⁾(Trademark: J
ILEX LLBF1350: melt flow rate 0.5
g / 10min: density 0.92) 50 parts by weight were used. Profit
The oxygen index (LOI) of the film obtained was 35.9.
The UL-94 vertical flammability test score was V-0.
there were. Roll kneading of the kneading composition and curling
Adhesiveness and plate out were observed in undermolding
Not good. The thickness obtained from this kneaded composition
0.5mm, weight 540g / m^TwoNon-halogen flame retardant po
JIS L-1091 for polyolefin resin sheet
The result of the 45 degree flameproof test by (A-2 method category 3) passed.
Met. The hue of the obtained sheet was blended.
The white by the pigment was vivid. Table 1 shows the test results.
You. [0036]Example 6 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, ethylene-acetic acid
50 parts by weight of 100 parts by weight of vinyl copolymer resin
Ultra low density polyethylene resin⁽³⁾Using 50 parts by weight,
Azodicarbonamide (A.D.C.A.)^(Four)Amount of
Was reduced to 5 parts by weight, and dinitrosopentamethylene was added.
Tetramine (DPT)^(Five)Add 5 parts by weight,
Pyrolytic N_TwoThe total amount of the gas generating agent is 10 parts by weight.
Was. The oxygen index (LOI) of the obtained film was 34.
3 and the result of UL-94 vertical flammability test is V
−0. In addition, roll kneading of this kneading composition and
Adhesive and plate out in calendering
Was not observed and was good. Obtained from this kneading composition
Thickness 0.5mm, weight 540g / m^TwoHalogen-free
JIS L-10 of flammable polyolefin resin sheet
The result of the 45 degree flameproof test according to 91 (A-2 method category 3)
It passed. The hue of the obtained sheet is
The white color of the pigment was bright. Table 1 shows the test results
Show. [0037]Example 7 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, azodicarbon
Amide (A.D.C.A.)^(Four)10 parts by weight
To 20 parts by weight. Oxygen index of the obtained film
(LOI) is 38.4 and UL-94 vertical
The result of the flammability test was V-0. Also, this kneading group
Roll kneading and calender molding
The properties and plate-out were not observed and were good. this
0.5 mm in thickness and 540 g / weight obtained from the kneading composition
m^TwoHalogen-free flame-retardant polyolefin resin sheet
According to JIS L-1091 (A-2 method category 3)
The result of the 5 degree flameproof test was passed. In addition, the obtained
The hue of the sheet is bright white with the blended pigment.
Was. Table 1 shows the test results. [0038]Example 8 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Increased from 40 parts by weight to 80 parts by weight
Weighed. The resulting film has an oxygen index (LOI) of 4
4.2 and UL-94 vertical flammability test results
Was V-0. Roll kneading of the kneading composition
In addition, adhesive and plate out
No problem was observed. Obtained from this kneaded composition
0.5mm thickness, weight 545g / m^TwoNon-halogen
JIS L-1 of flame-retardant polyolefin resin sheet
Result of 45 degree flameproof test according to 091 (A-2 method category 3)
Passed. The hue of the obtained sheet is
The white color of the resulting pigment was vivid. Table 1 shows the test results.
Shown in [0039]Example 9 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Melamine polyphosphate 4 instead of 40 parts by weight
0 parts by weight, and a pigment (white)⁽⁸⁾Instead of 5 parts by weight
Pigment (red)⁽¹⁸⁾(Trademark: High Conc Master HCM11
74: 5 parts by weight of Dainichi Seika Kogyo Co., Ltd. was used. Obtained
The film has an oxygen index (LOI) of 34.3,
The UL-94 vertical flammability test score was V-0.
Was. Roll kneading of the kneading composition and calendering
-No stickiness or plate-out observed in molding
It was good. The thickness obtained from this kneading composition is 0.5
mm, weight 540g / m^TwoNon-halogen flame retardant polyole
According to JIS L-1091 (A-2)
The result of the 45 degree flameproof test according to method category 3) was a pass.
Was. Also, the hue of the obtained sheet is
The resulting red was vivid. Table 2 shows the test results. [0040]Example 10 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Reduced the blending amount from 40 parts by weight to 20 parts by weight
Measure and add 20 parts by weight of melamine polyphosphate
And pigment (white)⁽⁸⁾Pigment (red) instead of 5 parts by weight
⁽¹⁸⁾5 parts by weight were used. Oxygen index of the obtained film
(LOI) is 35.1 and UL-94 vertical
The result of the flammability test was V-0. Also, this kneading group
Adhesive in roll kneading of product and calendering
Also, no plate-out was observed, which was favorable. This mix
0.5 mm in thickness and 540 g / m in weight obtained from the kneading composition
^TwoHalogen-free flame-retardant polyolefin resin sheet
According to JIS L-1091 (A-2 method category 3)
The result of the 5 degree flameproof test was passed. In addition, the obtained
The hue of the plate is vivid in red due to the blended pigment.
Was. Table 2 shows the test results. [0041]Example 11 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Reduced the blending amount from 40 parts by weight to 20 parts by weight
Measure and freshly add magnesium hydroxide⁽¹²⁾(Trademark: Kisuma 5
A: 50 parts by weight of Kyowa Chemical Industry Co., Ltd. was additionally blended.
The resulting film has an oxygen index (LOI) of 38.8.
Yes, and the result of UL-94 vertical flammability test is V-0
Met. Roll kneading of the kneading composition and
Adhesiveness and plate out are recognized in render molding
Not good. The thickness obtained from this kneaded composition
0.5mm, weight 550g / m^TwoNon-halogen flame retardant po
JIS L-1091 for polyolefin resin sheet
The result of the 45 degree flameproof test by (A-2 method category 3) passed.
Met. The hue of the obtained sheet was blended.
The white by the pigment was vivid. Table 2 shows the test results.
You. [0042]Example 12 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Reduced the blending amount from 40 parts by weight to 20 parts by weight
Weigh and freshly add antimony trioxide⁽¹³⁾(Trademark: Atox
S: Nippon Seiko Co., Ltd. (50 parts by weight) was additionally blended. Get
The resulting film has an oxygen index (LOI) of 37.6.
The UL-94 vertical flammability test score was V-0.
there were. Roll kneading of the kneading composition and curling
Adhesion and plate out were observed in undermolding
Not good. The thickness obtained from this kneaded composition
0.5mm, weight 550g / m^TwoNon-halogen flame retardant po
JIS L-1091 for polyolefin resin sheet
The result of the 45 degree flameproof test by (A-2 method category 3) passed.
Met. The hue of the obtained sheet was blended.
The white by the pigment was vivid. Table 2 shows the test results.
You. [0043]Example 13 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Reduced the blending amount from 40 parts by weight to 20 parts by weight
Weigh and freshly aluminum borate⁽¹⁴⁾(Trademark: Albora
PF03: 50 parts by weight of Shikoku Chemical Industry Co., Ltd.
Was blended. The oxygen index (LOI) of the obtained film is
37.9, and the UL-94 vertical flammability test was completed.
The result was V-0. Also, roll mixing of the kneading composition
In kneading and calendering, adhesive and plate
No out was recognized and it was good. Obtained from this kneading composition
0.5mm thickness, weight 540g / m^TwoNon-halogen
JIS L- for flame-retardant polyolefin resin sheet
Results of 45 degree flameproof test according to 1091 (A-2 method category 3)
The result was a pass. The hue of the obtained sheet is
The white by the combined pigment was vivid. Show test results
It is shown in FIG. [0044] [0045] [0046] [0047]Comparative Example 1 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾The formulation of 40 parts by weight was omitted. Obtained
The film has an oxygen index (LOI) of 18.4 and UL
The results of the -94 vertical flammability test were NR (V-0, V-1,
V-2). Also, this kneading
0.5 mm thickness and 510 g / m weight obtained from the composition^Two
Of non-halogen flame-retardant polyolefin resin sheet,
45 degrees according to JIS L-1091 (A-2 method category 3)
The flame test failed. Table 3 shows the test results. [0048]Comparative Example 2 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. Where N_TwoGas generating agent
A. D. C. A^(Four)The blending of 10 parts by weight was omitted. Get
The resulting film has an oxygen index (LOI) of 24.8.
The UL-94 vertical flammability test score was V-2.
Was. Further, a thickness of 0.5 mm obtained from the kneaded composition,
Weight 540g / m^TwoHalogen-free flame retardant polyolefin
JIS L-1091 (A-2 law section)
The 45 degree flameproof test according to minute 3) failed. Test results
The results are shown in Table 3. [0049]Comparative Example 3 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, A. D. C. A
^(Four)10 parts by weight and ammonium polyphosphate^{(7 )}40 layers
Omit the mixing of parts by weight and add melamine polyphosphate⁽¹¹⁾To
40 parts by weight were additionally blended. Oxygen finger of the resulting film
The number (LOI) is 23.4, UL-94 vertical burning
The result of the sex test was V-2. Also, this kneading composition
0.5mm, weight 540g / m obtained from^TwoNon
JIS for halogen-retardant polyolefin resin sheet
  45 degree flameproof test according to L-1091 (A-2 method category 3)
The test failed. Table 3 shows the test results. [0050]Comparative Example 4 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, A. D. C. A
^(Four)10 parts by weight and ammonium polyphosphate⁽⁷⁾40 weight
Omit the mixing of parts and add magnesium hydroxide⁽¹²⁾10
0 parts by weight was additionally blended. Oxygen index of the obtained film
(LOI) is 24.6, UL-94 vertical flammability
The test score was V-2. In addition, this kneading composition
0.5mm thickness and 560g / m weight^TwoNonha
JIS for logen flame-retardant polyolefin resin sheet
45 degree flameproof test according to L-1091 (A-2 method category 3)
Was rejected. Table 3 shows the test results. [0051]Comparative Example 5 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, A. D. C. A
^(Four)10 parts by weight and ammonium polyphosphate⁽⁷⁾40 weight
Part of the formulation is omitted and antimony trioxide is newly added.⁽¹³⁾100
Additional parts by weight were added. Oxygen index of the obtained film
(LOI) is 22.9, UL-94 vertical flammability
The test score was V-2. In addition, this kneading composition
0.5mm thickness and 580g / m weight^TwoNonha
JIS for logen flame-retardant polyolefin resin sheet
45 degree flameproof test according to L-1091 (A-2 method category 3)
Was rejected. Table 3 shows the test results. [0052]Comparative Example 6 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, A. D. C. A
^(Four)10 parts by weight and ammonium polyphosphate⁽⁷⁾40 weight
Part of the composition is omitted and aluminum borate is newly added.⁽¹⁴⁾10
0 parts by weight was additionally blended. Oxygen index of the obtained film
(LOI) is 25.3, UL-94 vertical flammability
The test score was V-2. In addition, this kneading composition
0.5mm thickness and 550g / m weight^TwoNonha
JIS for logen flame-retardant polyolefin resin sheet
45 degree flameproof test according to L-1091 (A-2 method category 3)
Was rejected. Table 3 shows the test results. [0053]Comparative Example 7 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, ethylene-acetic acid
Vinyl copolymer resin⁽¹⁾Ethylene instead of 100 parts by weight
Methyl methacrylate copolymer resin⁽²⁾100 parts by weight
Used, ammonium polyphosphate⁽⁷⁾40 parts by weight of
Was increased to 250 parts by weight. Oxygen finger of the resulting film
The number (LOI) is 46.4, UL-94 vertical burning
The result of the sex test was V-0. However, this kneading composition
Plate-out and kneading in calendering of objects
Remarkably poor workability due to poor workability, etc.
Can produce flame-retardant polyolefin resin sheet
I didn't come. Therefore, JISL-1091 (A-2 method classification)
The 45 degree flameproof test according to 3) could not be evaluated. Test results
The results are shown in Table 3. [0054]Comparative Example 8 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, ethylene-acetic acid
Vinyl copolymer resin⁽¹⁾Ethylene instead of 100 parts by weight
Methyl methacrylate copolymer resin⁽²⁾100 parts by weight
A. D. C. A^(Four)From 10 parts by weight to 1
The amount was increased to 00 parts by weight. Oxygen index of the obtained film
(LOI) is 24.9, UL-94 vertical flammability
The test score was V-2. Karen of this kneading composition
In kneading, kneading is poor and workability is extremely poor.
Therefore, halogen-free flame-retardant polyolefin resin
A sheet could not be made. Therefore, JIS
45 degree flameproof test according to L-1091 (A-2 method category 3)
Could not be evaluated. Table 3 shows the test results. [0055]Comparative Example 9 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, A. D. C. A
^(Four)Omit 10 parts by weight and add red phosphorus ⁽¹⁵⁾(quotient
Mark: Novaled 120UF: Rin Kagaku Kogyo Co., Ltd.) 10
Parts by weight were added. The resulting film has an oxygen index (LO
I) is 34.3, which is a value of UL-94 vertical flammability test.
The result was V-0. Also obtained from this kneading composition
0.5mm thickness, weight 540g / m^TwoNon-halogen
JIS L-1 of flame-retardant polyolefin resin sheet
Passed the 45 degree flameproof test by 091 (A-2 method category 3)
However, the color of the sheet was
And it has the disadvantage of
Lack of color flexibility, emphasizing colorfulness and design
It was unsuitable for tent applications. Test results
Are shown in Table 4. [0056]Comparative Example 10 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, new red phosphorus
⁽¹⁵⁾10 parts by weight were added. Oxygen finger of the resulting film
The number (LOI) is 45.8, UL-94 vertical burning
The result of the sex test was V-0. Also, this kneading composition
0.5mm, weight 540g / m obtained from^TwoNon
JIS for halogen-retardant polyolefin resin sheet
  45 degree flameproof test according to L-1091 (A-2 method category 3)
The test passed, but the sheet color was colored with white pigment
Despite this, the disadvantage of coloring in reddish maroon
Yes, lacks the flexibility of coloring, colorful and design
However, it was unsuitable for tent applications where emphasis was placed.
Table 4 shows the test results. [0057]Comparative Example 11 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Omitting 40 parts by weight of compound
⁽¹⁵⁾10 parts by weight, and a pigment (white)⁽⁸⁾5 parts by weight
Instead of pigment (blue)⁽¹⁷⁾5 parts by weight were used. Obtained
The film has an oxygen index (LOI) of 23.4 and UL
The result of the -94 vertical flammability test was V-2. Also,
0.5 mm in thickness and 540 in weight obtained from this kneading composition
g / m^TwoNon-halogen flame-retardant polyolefin resin
According to JIS L-1091 (A-2 method category 3)
The 45 degree flameproof test failed. Also the sheet color
Is colored black-purple despite being colored by a blue pigment.
The disadvantage is that it lacks the flexibility of coloring,
Flameproof for tent applications where colorfulness and design are important
It was unsuitable including sex. Table 4 shows the test results.
You. [0058]Comparative Example 12 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, A. D. C. A
^(Four)The addition of 10 parts by weight is omitted, and heat-expandable graphite is newly added.
⁽¹⁶⁾(Trademark: GREP-EG: Tosoh Corporation) 20 weight
Parts were added. Oxygen index (LOI) of the obtained film
Is 31.5, the result of UL-94 vertical flammability test
Was V-0. Also obtained from this kneaded composition
0.5mm thick, weight 540g / m^TwoNon-halogen flame retardant
JIS L-109 of water-soluble polyolefin resin sheet
1 (A-2 method category 3) 45 degree flameproof test passed
However, plate out during calendar processing was remarkable,
Problems such as contamination of the heat roll of the processing machine to black
Was. In addition, the color of the sheet is
Has the disadvantage of being colored black-gray,
It lacks flexibility, and emphasis is placed on colorfulness and design.
Is not suitable for tent applications including workability.
Was. Table 4 shows the test results. [0059]Comparative Example 13 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, new heat expansion
Graphite⁽¹⁶⁾20 parts by weight were added. Of the resulting film
The oxygen index (LOI) is 47.3 and UL-94
The result of the direct flammability test was V-0. Also, this kneading
0.5 mm in thickness and 540 g / m in weight obtained from the composition^Two
Of non-halogen flame-retardant polyolefin resin sheet,
45 degree protection according to JISL-1091 (A-2 method category 3)
The flame test was passed, but the plate during calendering
Outing was remarkable, and the hot roll of the processing machine was stained black.
Also, despite the color of the sheet with the white pigment,
It has the disadvantage of being colored black-gray, and can be colored freely
It lacks character and is important for colorfulness and design.
However, it was unsuitable for the application of the application including the workability. Trial
Table 4 shows the test results. [0060]Comparative Example 14 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Omitting 40 parts by weight of compound
Tonic graphite⁽¹⁶⁾20 parts by weight, and a pigment (white)⁽⁸⁾
Pigment (blue) instead of 5 parts by weight⁽¹⁷⁾5 parts by weight were used. Profit
The resulting film has an oxygen index (LOI) of 25.1.
The UL-94 vertical flammability test score was V-2.
Was. Further, a thickness of 0.5 mm obtained from the kneaded composition,
Weight 540g / m^TwoHalogen-free flame retardant polyolefin
JIS L-1091 (A-2 law section)
The 45 degree flameproof test according to minute 3) failed. This mix
Plate out during calendering of kneading composition
In addition, the heat roll of the processing machine was stained black. Also the sheet
Is colored black-blue despite the color of the blue pigment
Which lacks the flexibility of coloring
For tent applications where colorfulness and design are important
It was unsuitable including the workability. Table 4 shows the test results.
Shown in [0061]Comparative Example 15 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Omitting 40 parts by weight and newly adding hydroxyl
magnesium⁽¹²⁾100 parts by weight and red phosphorus⁽¹⁵⁾10 parts by weight
And were added. Oxygen index (LOI) of the obtained film
Is 33.6, the result of UL-94 vertical flammability test
Was V-0. Also obtained from this kneaded composition
0.5mm thick, weight 565g / m^TwoNon-halogen flame retardant
JIS L-109 of water-soluble polyolefin resin sheet
1 (A-2 method category 3) 45 degree flameproof test passed
However, the kneadability of this kneaded composition during calendering
It was poor and the workability was extremely poor. Also, the sheet
The color is maroon, despite the color of the white pigment
But it lacks the flexibility of coloring.
For tent applications where colorfulness and design are important
Was unsuitable including the workability. Show test results
It is shown in FIG. [0062]Comparative Example 16 In the same manner as in Example 1, the resin composition, its film and its
Was prepared and evaluated. However, polyphosphoric acid
Monium⁽⁷⁾Omitting 40 parts by weight and newly adding hydroxyl
magnesium⁽¹²⁾100 parts by weight and heat-expandable graphite⁽¹⁶⁾2
0 parts by weight. Oxygen index of the obtained film
(LOI) is 34.2, UL-94 vertical flammability
The test score was V-0. In addition, this kneading composition
0.5mm thickness and 570g / m weight^TwoNonha
JIS for logen flame-retardant polyolefin resin sheet
45 degree flameproof test according to L-1091 (A-2 method category 3)
Passed, but when the kneaded composition was calendered
Is poor in kneading and plate-out is remarkable.
The hot roll of the machine was stained black. Also, the color of the sheet
Despite coloring with white pigment,
The drawback is that it lacks the flexibility of coloring.
Processability for tent applications where ruffle and design are important
And was unsuitable. Table 4 shows the test results.
You. [0063] [Table 1] [0064] [Table 2][0065] [Table 3] [0066] [Table 4][0067] According to the present invention, the laminated sheet according to the present invention can be used.
And the polyolefin-based
While giving the resin a high degree of flame retardancy,
Substantially colorless, so it can be colored to the desired hue
With excellent molding processability.
Type tent, sunshade tent, tent warehouse, curing sheet, etc.
For applications requiring flame retardancy, conventional vinyl chloride
It is extremely useful as a sheet to replace resin sheets.
You.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-10-7846 (JP, A) JP-A-7-145288 (JP, A) JP-A-2-160849 (JP, A) JP-A-7-145 89014 (JP, A) JP-A-10-100330 (JP, A) JP-A-10-225949 (JP, A) JP-A-9-194647 (JP, A) Japanese Utility Model Application Showa 50-47232 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08

Claims (1)

(57) [Claim 1] A polyolefin resin, 10 to 200 parts by weight of a halogen-free flame retardant, and 1 to 50 parts by weight of a thermally decomposable N ₂ gas with respect to 100 parts by weight of the polyolefin resin. And at least one sheet layer containing a substantially colorless non-halogen flame-retardant polyolefin-based resin composition, and at least one layer laminated on the sheet layer, and a base cloth made of a fiber cloth. wherein the non-halogenated flame retardant, a polymerization degree of 200 or more ammonium polyphosphate, ammonium thermosetting resin coated particulate polyphosphate, and at least one member selected from melamine polyphosphate, wherein the heat decomposable N ₂ gas The generator is a small one selected from azodicarbonamide, 4,4'-oxybisbenzenesulfonylhydrazide and dinitrosopentamethylenetetramine. Both comprise one, and is its 50 wt% or more of azodicarbonamide, said sheet layer, the halogen-free flame-retardant polyolefin resin composition, the calendar method, the thermally decomposable N ₂ gas generating agent 80-2 without thermal decomposition foaming
A substantially colorless, non-halogen, flame-retardant, polyolefin-based resin composition laminated sheet having excellent colorability, which is formed from a film obtained by forming at a temperature of 00 ° C.