JPS6280033A - Incombustible heat-insulating composite material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a non-combustible thermal insulation composite material having a basic laminated structure consisting of a steel plate, a foam, a water glass layer and a glass fiber mat insulation material. Roofing materials, interior walls,
It relates to composite materials useful for applications that require a high degree of non-combustible heat insulation and mechanical strength, such as exterior walls.

(Prior art) Conventionally, composite materials made by laminating foam on steel plates have superior insulation properties and workability compared to inorganic non-combustible insulation materials, and have no problem with moisture absorption. It is used as a building material for roofs, etc. However, since the foam of this conventional laminated composite material is flammable and generates a large amount of heat, it does not meet the standards for noncombustible materials stipulated in Ministry of Construction Notification No. 1828, and its use is prohibited. It was limited.

Utility Model Publication No. 58-175 was developed as a noncombustible heat insulating material with good handling properties by improving the drawbacks, heat insulation properties, and corrosion caused by moisture absorption of conventional noncombustible heat insulating composite materials made of laminated materials of steel plates and foam.
Publication No. 036 proposes a laminated non-combustible heat insulating material made of a foam and a steel plate in which the amount of flammable resin based on the foam is limited by using a foam with an expansion ratio of, for example, 200 times or more. ing.

However, since the amount of resin in the foam used in this noncombustible heat insulating material is too small, its mechanical strength is insufficient, and the foam is easily broken or cells are destroyed during folding plate processing. Moreover, commercially produced crosslinked polyolefin resin foams usually have an expansion ratio of about 5 to 40 times, so the foam with an ultra-high expansion ratio of 200 times as proposed in this proposal is It is difficult to stably produce it using the continuous crosslinking foaming process that is used industrially, and as a result, it is expensive, which is a practical limitation.

(Problems to be Solved by the Invention) An object of the present invention is to provide a noncombustible heat insulating composite material that overcomes the drawbacks of the conventional noncombustible heat insulating composite materials and has excellent noncombustibility, heat insulation properties, mechanical strength, and no moisture absorption. There is something to do. Still another object is to provide a method for manufacturing such a noncombustible heat insulating composite material industrially and at a low cost.

(Means for Solving the Problems) The object of the present invention is to achieve the invention described in the claims above, that is, to achieve the invention in which the halogenated flame retardant is contained in an amount of 2 to 30% by weight and the inorganic filler is contained in an amount of 10 to 50% by weight. Contains 0.02
Apparent density of ~0.06 CI/cm3 and 0.5-2.
This can be achieved by a non-combustible heat insulating composite material comprising a steel plate on the non-sliced surface of a polyolefin foam having a thickness of 5 rnm and a glass fiber mat insulation material provided on the sliced surface of the foam via a water glass layer.

The steel plate constituting the composite material of the present invention is not limited to steel, and examples include galvanized iron plates, colored iron plates, PVC steel plates, etc., which are certified as noncombustible materials and are used. However, the thickness of this steel plate (
dl) is the relationship with the foam thickness (d2), that is, the ratio of the foam thickness (d2) to the steel plate thickness (dl) (d1/d2>, where this ratio is at least 0.3 or more. Normally, d1 is in the range of 0.2 to 1.5 mm, preferably 0.6 to 1.2 mm.

Further, the foam constituting the composite material of the present invention is made of a nonflammable polyolefin resin containing a halogen flame retardant and an inorganic filler, and has an apparent density of 0.02 to 0°06C1/cm3 and a It is necessary that the crosslinked foam has a thickness of .5 to 2.5 mm.

Here, the polyolefin resin is necessarily a polyolefin homopolymer 1 which essentially contains an olefin, a polyolefin copolymer, and a blend thereof.
More specifically, ethylene, propylene, butene-1
There are homopolymers of α-olefins such as , 4-methyl-pentene-1, and copolymers based on these monomers, and these monomers include vinyl compounds such as vinyl acetate and acrylic esters, butadiene, and isoprene. Non-polymer copolymers containing at least one type of conjugated diene compound such as conjugated diene compounds as a copolymerization component, and thermoplastic resin compositions containing the above-mentioned polymers as a substantial main component can be mentioned.

When blending a large amount of flame retardant and/or inorganic filler into the foam to create a flexible foam with a high expansion ratio, use a low-crystalline thermoplastic resin, such as a crystallinity of 40% by density method. % or less of rubbery thermoplastic resin or modified polyolefin resin as the main component, preferably 50% by weight or more.

Examples of such rubbery thermoplastic resins or modified polyolefin resins include vinyl acetate containing 6 to 35 wt.
Ethylene-vinyl acetate copolymer with a content density of 0.910-, -0.970, ethylene-edyl acrylate copolymer (preferably ethyl acrylate with a content of 5.
(containing 20% by weight), ethylene-α-olefin copolymer (preferably containing 5 to 30% by weight of α-olefin with a density of less than 0.910), thermoplastic polybutadiene resin (preferably syndiotactic 1
゜2-Polybutadiene with 90% 1,2-bonds
Thermoplastic styrene-butadiene comonopolymer resin (preferably containing 10 to 50% styrene), chlorinated polyethylene (preferably containing 25% chlorine)
Examples of the α-olefin include olefins having 3 to 8 carbon atoms such as propylene and butene.

Among these low-crystalline thermoplastic resins, ethylene-
Vinyl acetate copolymer, ethylene-α-olefin (0
3 to Ca) type copolymers are preferred, and ethylene-vinyl acetate type copolymers are more preferred.

In addition, for the purpose of improving the extrusion moldability of the resin composition used for manufacturing the foam of the present invention, polyethylene with good fluidity, for example, a melt flow rate of 50 to 200 C1/10 min. Low density polyethylene and the like can be added and blended as appropriate.

Further, the halogenated flame retardants to be blended into the composite material of the present invention include halogenated aliphatic, halogenated aromatic and halogenated alicyclic flame retardants, preferably brominated flame retardants. , one or more of these may be used.

Specific examples of these flame retardants include decabromodiphenyl ether, hexabromobenzene, and "Fireguard" 3000. "Fire Guard" 7000, "Dechloran Plus" 25, CITEX"-BT93, ESB
-400,5R-TBA-400,5R-TBA400
P-1, EBR-700, EBR-734, etc., but in particular, bisphenol A/decabromobisphenol A/epichlorohydrin glycidyl ether condensate (e.g., EBR-700, etc.), bisphenol A-based brominated epoxy resin, or Prepolymers and crosslinked products thereof are preferred.

In addition to these flame retardants, flame retardant aids such as antimony trioxide, zinc flate, and red phosphorus, other types of flame retardants such as phosphorus compounds, heat stabilizers, weathering agents, plasticizers, and pigments are used in combination. It is of course possible to do so.

However, these flame retardants are preferably incorporated in the foam of the present invention in an amount of 2 to 30% by weight, preferably 4 to 25% by weight, and when the amount is less than 2% by weight,
The flame retardant effect becomes insufficient and it becomes difficult to suppress the amount of heat generated in the sealing test. On the other hand, if it exceeds 30% by weight, the amount of smoke emitted during combustion increases, which is not preferable.

Next, as inorganic fillers, calcium carbonate, magnesium carbonate, talc, clay, zirconium oxide, bentonite, attapulgite, barium III, zinc borate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, oxidized Examples include tin hydrate, and one or more of these may be blended, preferably with an average particle size of 0.01 to 50.
It is preferably 0.1 to 20 microns, more preferably 0.5 to 10 microns.

In particular, inorganic compounds such as aluminum hydroxide and basic magnesium carbonate that contain bound water or a hydroxyl group that thermally decomposes to generate moisture in their molecules and have a moisture release temperature of 250° C. or higher are particularly preferred.

It goes without saying that these inorganic fillers may be treated with higher fatty acids, higher fatty acid salts, silane coupling agents, titanate surface treatment agents, etc. prior to mixing with the resin.

However, these inorganic fillers are
It is best to mix within the range of ~50% by weight; if it is less than 10%, it will be difficult to suppress the amount of heat generated when the foam burns, and if it exceeds 50%, it will be difficult to produce the foam. This is not preferable because it tends to cause gas buildup during foaming in the process, making it difficult to produce a foam with a high expansion ratio. - containing such flame retardants and inorganic fillers;
The polyolefin resin foam of the present invention having closed cells with an apparent density of 0.02 to 0.06 C1/cm3, preferably a sheet-like foam, is coated with a water glass layer on its sliced surface. It is important that the fiberglass mat insulation is laminated and the steel plate is laminated on its non-sliced side.

Here, the non-sliced surface refers to the foam surface itself obtained through the foam manufacturing process, and the sliced surface refers to the foam surface itself obtained through the foam manufacturing process.
This refers to the surface formed by cutting this foam with a sharp knife.

The non-combustible heat insulating composite material of the present invention is characterized in that steel plates are laminated and bonded together in contact with the non-sliced surface of the foam, and a glass fiber mat heat insulating material is formed on the sliced surface via a hydraulic lath layer. At the point.

The water glass layer formed on the sliced surface of the foam of the present invention has the general formula: M20'n5i02 (where M is an alkali metal such as L+, Na, or a quaternary ammonium group, and n is 0. (is a rational number from 5 to 4) is a water-soluble alkali metal silicate represented by:

Specific examples of such water glasses include liquid water glasses that are commercially available as No. 1 to No. 4 water glasses, and these water glasses contain hardening agents such as monolithium to silicofluoride and aluminum phosphates. Examples include those containing an appropriate amount of glyoxal sulfate or its ε-caprolactone.

Further, as described above, the steel plates to be laminated on the foam of the present invention include galvanized iron plates, colored iron plates, PVC steel plates, etc. In the present invention, the thickness (dl) of this steel plate and the foam The ratio (dl/d2) to the thickness (d2) of the foam is 0.3 or more, preferably 0°5 or more, and the foam thickness (d2)
) is 0.5 to 2.5 mm, preferably 1.0 to 2.0 m
It is necessary to be within the range of .

That is, when the above ratio (d1/d2) is less than 0.3, the heat absorption effect of the steel plate in the noncombustible heat insulating composite material of the present invention is too small, and the calorific value in the base material test exceeds the standard value. Therefore, it is not desirable.

Moreover, if the thickness (d2) of the foam is smaller than Q, 5 mm, the heat insulating effect of the non-combustible heat insulating material of the present invention will be lowered, which is not preferable, and if it exceeds 2.5 mm, the composite material will easily burn, and the This is not preferable because it will no longer satisfy the standard values of the material test.

In the noncombustible heat insulating composite material of the present invention, a glass fiber mat heat insulating material is laminated on the water glass layer, and the glass fiber mat heat insulating material may include long glass fibers, cut fibers, or their fiber waste entangled with each other. In some cases, the surface of these glass fiber sheets may be coated with various non-woven fabrics, or the glass fibers may be bonded together with resin. Commercially available products include ``Super Felton'' (manufactured by Diasu Co., Ltd.), ``Fujimat'' (manufactured by Fuji Jushi Co., Ltd.), and ``Zifunen'' (manufactured by Tsukisui Kagaku Co., Ltd.).

In the noncombustible thermal insulation composite material in which this glass fiber mat insulation material is laminated on the water glass layer, the thickness (d3) of the glass fiber mat insulation material is 3. Qmm or more, preferably 4.
It is desirable that the thickness is □ mm or more, and if this thickness is less than 3 mm, the thickness of the composite material as a whole will become thinner, and the number of composite materials in the test specimen for base material testing will have to be increased. As a result, the amount of foam increases, which is undesirable because the calorific value exceeds the base material test standard.

Generally speaking, in the non-combustible heat insulating composite material of the present invention, a steel plate or a glass fiber mat insulating material surface of another non-combustible heat insulating composite material of the present invention is laminated on the glass fiber mat heat insulating material surface and bonded together. It can be made into a multilayer laminated composite material, which has both sides made of steel plates and can be used not only for the inner walls of buildings but also for the outer walls.

The method for manufacturing the non-combustible heat insulating composite material of the present invention involves fusing the non-sliced surface of the aforementioned polyolefin resin foam to a steel plate or heat-pressing the non-sliced surface with a small amount of adhesive applied. - Form a laminate in which steel plates are laminated and bonded to the non-sliced surface of the foam, then apply water glass to the sliced surface of the foam, and apply Nocorus fiber pine 1-insulating material to the water glass coated surface. It can be manufactured by laminating and bonding under heat and pressure. The amount of coating of the above hydraulic lath is 15 to 100 ml on the sliced surface of the foam and 1 to 100 g on the glass fiber pine.
There are no particular limitations, as long as the heat insulating material exhibits sufficient adhesive strength and is applied within a range that poses no practical problems.

(Effects of the Invention) The noncombustible heat insulating composite material of the present invention comprising a steel plate, a specific foam, a hydraulic lath layer, and a glass fiber insulation material obtained in this way has the following properties: (1) Fire protection that passes the provisions of the Building Standards Act and noncombustible material standards Has performance.

(2) Excellent heat insulation properties and anti-condensation properties.

(3) Those provided with glass fiber mat insulation have moisture resistance that completely prevents corrosion of steel plates, despite having water retention properties.

Therefore, the noncombustible heat insulating composite material of the present invention is lightweight and has excellent processability and handling, and can be widely used as various roofing materials by folding plates, and as noncombustible heat insulating materials for interior walls, exterior walls, and other buildings. can do.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the present invention, the apparent density and expansion ratio of the foam are values measured by the following measuring method, and the noncombustible material test was conducted according to the measuring method described below.

A. Apparent density and expansion ratio Measure the weight and thickness of the foam cut into a size of 10 cm x 10 cm, and calculate the weight per unit volume (g/Cm3) by dividing the weight by the volume of the foam. and the apparent density. The reciprocal of this apparent density was taken as the expansion ratio of the foam.

B. Noncombustible Material Test Jl5-A-1321-1975, "Testing Methods for Flame Retardancy of Building Interior Materials and Construction Methods" A base material test was conducted.

The criteria for determining the measurement results are as follows.

Regarding the surface test, time and temperature area during combustion (tdθ
) and smoke generation coefficient (CA), in the base material test, the temperature (T'C) exceeding the set temperature in the furnace (750'C) was taken, and if the value was within the following range, it was passed.

tdθ('C-m1n><O CA≦30 T ('C) <50 Examples 1-6, Comparative Examples 1-3 Density is 0.940. Melt flow rate (M.

■) is 30-35% by weight of ethylene-vinyl acetate copolymer containing 14% by weight of vinyl acetate of 4 g/10 min, M,
5 to 10% by weight of low density foraethylene with I of 200g/10 minutes, 30 to 40% by weight of aluminum hydroxide, bisphenol A-based brominated epoxy resin prepolymer (SR-rB
A400P-1 > 10% by weight and azodicarbonamide 8~12゛ were blended using a Henschel Mikina, melted and kneaded using a pressurized Nigu, and then 30mmφ
Pelletized using a twin screw extruder.

Using this pellet as a raw material, a 3Qmmφ extruder was used to
A sheet with a thickness of 2 mm was prepared by melt extrusion at 40'C.

This sheet was irradiated with an electron beam of 5 Mrad using an electron beam irradiation device to cause crosslinking. The obtained crosslinked sheet was heated to 230°C.
Heating and foaming in a heating and melting vine of 1 to 5 to a thickness of 5 to
A foam having a thickness of 5 mm and an expansion ratio of 20 to 40 times was obtained.

Slice one side of this foam to a thickness of 0.5~3.
A foam having a sliced surface and a non-sliced surface of Qmm was prepared. A heated galvanized iron plate (thickness: 0.6 to 1.2 mm) was laminated on the non-sliced surface of this foam, heat-sealed, and wound up with a roll. Next, water glass was applied to the sliced surface of the foam laminated with the galvanized iron plates, and while blowing hot air, the glass fiber mat insulation material was laminated while being compressed with a hot roll to create a composite material.

A surface test and a base material test were conducted on the obtained noncombustible heat insulating composite material of the present invention. The results are as follows: glass fiber mat insulation material (Comparative Example 1), composite material (Comparative Example 2) where the thickness of the iron plate is outside the range specified by the present invention, and (d1/d2) ratio is within the range specified by the present invention. The results are shown in Table 1 along with the measurement results for the other composite material (Comparative Example 3).

By the way, as a result of a surface test of the laminate obtained by simply laminating and heat-sealing the above-mentioned galvanized iron plate (thickness 0.6 mm) on the non-sliced surface of the foam, it showed a value of tdθ 01CA < 30, indicating that it was difficult to Flammability was grade 1, which was rare.

As shown in Table 1, the non-combustible thermal insulation composite material of the present invention is
While both the surface test and the base material test fully satisfied the standards as a noncombustible material, the thickness of the glass fiber mat insulation material (Comparative Example 1) was outside the range specified by the present invention. (Comparative Example 2) and composite material (Comparative Example 3) whose (d1-d2) ratio is outside the range specified in the present invention, the furnace temperature in the base material test significantly exceeded the standard value. Therefore, it was unsuitable as a noncombustible heat-insulating composite material.

Claims (2)

[Claims] (1) Contains 2-30% by weight of halogen flame retardant and 10-50% by weight of inorganic filler, 0.02-0.06g/
A steel plate is placed on the non-sliced surface of a polyolefin resin foam having an apparent density of cm^3 and a thickness of 0.5 to 2.5 mm, and a glass fiber mat insulation material is placed on the sliced surface of the foam via a water glass layer. A non-combustible thermal insulation composite material. (2) In claim 1, the thickness of the steel plate (d
_1) and the thickness of the polyolefin resin foam (d_2)
(d_1/_2) is at least 0.3 or more, and the thickness of the glass fiber mat insulation material is at least 3.
A non-combustible heat insulating composite material with a thickness of 0 mm.