JPH0948083A - Low-fuming flame-resistant decoration material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-fuming flame-resistant decoration material using a thermoplastic high molecular material which is substantially free from a halogen, which has the same self-extinguishing, non-dripping, scratch-resistant, pollution-resistant and decorative properties as or higher than a polyvinyl chloride resin decoration material, without using a polyvinyl chloride resin as a material for the decoration material. SOLUTION: In a flame-resistant decoration material made up basically of a surface layer and a back layer which are formed by a thermoplastic high molecular material which is substantially free from a halogen, a flame-retardant made of a hydrated metal compound and/or phosphorus compound and an expansive graphite are added to the rear layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a floor or wall surface of a building, a house or the like, or a floor or lining of a train, aircraft, bus, automobile, etc. More specifically, the present invention relates to a flame-retardant decorative material which is formed of a thermoplastic polymer material that does not contain halogen atoms such as chlorine and has excellent surface strength and design and which has low smoke emission.

[0002]

2. Description of the Related Art Conventionally, sheet materials made of vinyl chloride resin have been used for flooring materials and wall covering materials for buildings such as buildings and houses, and for flooring materials and lining materials for trains, aircraft, buses, automobiles, etc. Many decoration materials are used. The reason why vinyl chloride resin is used for such decoration materials is that vinyl chloride resin sheet has excellent surface strength and abrasion resistance, and that vinyl chloride resin sheet has excellent flame retardancy. .

[0003]

The above-mentioned decoration material made of vinyl chloride resin is advantageous in cost as well as the above-mentioned excellent performance, but harmful hydrogen chloride gas is generated during a fire or incineration process. In recent years, there is a danger that poisoning and suffocation due to hydrogen chloride gas will occur during a fire, and that a large amount of hydrogen chloride gas will be generated during incineration, which is unfavorable for environmental hygiene. Further, although the vinyl chloride resin is excellent in flame retardancy, there is also a problem in that if the sheet burns, the amount of smoke generated is large.

In order to solve the above-mentioned problems of the decorative material made of vinyl chloride resin, the present inventor has used ethylene-ethyl as a material of a flame-retardant decorative material containing no halogen atom and capable of being regenerated. Acrylic copolymer resin (hereinafter referred to as EEA), ethylene-methyl methacrylate copolymer resin (hereinafter referred to as EMMA), ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA), and other olefin copolymer resin, polypropylene (hereinafter referred to as PP) , Polyethylene (hereinafter referred to as PE), olefin resin such as polybutene-1 (hereinafter referred to as PB-1), ethylene-propylene elastomer (or rubber) (hereinafter referred to as TPO) were examined.

In order to impart flame retardancy to olefin resins, halogen compounds, aluminum or magnesium hydrated metal compounds, or nitrogen-containing compounds such as red phosphorus, carbon black, silicone resins and oils, and melamine resins. Etc. are used as a flame retardant material (flame retardant). Halogen compounds are problematic because they generate toxic substances such as hydrogen halide gas.If a hydrated metal compound is not added in a large amount, flame retardancy cannot be obtained.If a large amount is added, the scratch resistance of the decorative material deteriorates. Further, when a silicone resin or oil is added, the stain resistance deteriorates, and further, red phosphorus and carbon black cause a problem in that the sheet is colored, resulting in poor decorativeness and design. By combining these flame retardants, one having self-extinguishing property and non-drip property can be obtained, but it could not be used as a decorative material due to the above problems.

It is also conceivable that a sheet formed by blending the above flame retardant is coated with a thin film to give it a design property, but if the thickness of the film is less than 30 μm, the above-mentioned difficulty occurs. Although a sheet containing a combustible agent does not have sufficient low smoke emission, it can give a certain degree of flame retardancy, but the surface layer of 30 μm or less cannot hide the color of the base, and further, the floor material. It is not possible to obtain a decorative material having sufficient surface strength such as abrasion resistance and scratch resistance as a decorative material such as a wall covering material.

Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, and to use the vinyl chloride resin as a decorative material without using it, and to make it equal to or more than the vinyl chloride resin decorative material. , A flame-retardant decorative material with low smoke generation, which is excellent in self-extinguishing property, non-drip property, scratch resistance, stain resistance and decorative property,
It is provided by a thermoplastic polymer material which is substantially halogen-free.

[0008]

The above objects are achieved by the present invention described below. That is, the present invention provides a hydrated metal compound and / or a phosphorus compound in a flame-retardant decorative material basically composed of a front surface layer and a back surface layer formed of a thermoplastic polymer material containing substantially no halogen. A flame-retardant decorative material, characterized in that a flame-retardant agent comprising a compound and expansive graphite is added to the back surface layer.

The decorative material of the present invention shows excellent flame retardancy without using a halogen-containing resin such as vinyl chloride resin or a halogen compound-containing flame retardant, and contains halogen even if it is burned by a fire or the like. Since it does not generate harmful halogen gas, it exhibits lower smoke generation than vinyl chloride resin containing halogen.

[0010]

Next, the present invention will be described in more detail with reference to preferred embodiments. The decorative material of the present invention is basically composed of a front surface layer and a back surface layer. Both the front surface layer and the back surface layer are composed of a thermoplastic polymer material containing substantially no halogen atom. Conventionally, various methods for making a thermoplastic resin containing no halogen atom flame-retardant have been studied, but all of them are methods of making a flame-retardant by dispersing a flame-retardant agent in the entire resin compound. For example, when a phosphorus compound such as red phosphorus or a flame retardant such as carbon black is added, the resin is colored red or black, and it becomes impossible to form an arbitrary colored pattern as the surface layer of the decorative material. On the other hand, when a hydrated metal compound such as magnesium hydroxide or aluminum hydroxide is used as a flame retardant, since the resin is not colored by these flame retardants, it is possible to color the decorative material in any hue. If the flame retardant was not added in a large amount, the flame retardant effect could not be obtained, and if added in a large amount, the obtained decorative material was inferior in scratch resistance and was not suitable as a surface layer of the decorative material.

Therefore, the present inventor further researched for the purpose of providing a decorative material having low smoke emission and flame retardancy as a constituent of the entire decorative material without adding a flame retardant to the surface layer of the decorative material. As a result, the decorative material is basically composed of the front surface layer and the back surface layer, and by adding the specific flame retardant only in the back surface layer, the laminated body ( As a decorative material, it has been found that a decorative material having low smoke generation, excellent flame retardancy, self-extinguishing property and non-drip property can be obtained. That is, by adding a flame retardant composed of a hydrated metal compound and / or a phosphorus compound and expandable graphite to the back surface layer, it was possible to obtain excellent smoke emission as a laminate without adding a flame retardant to the surface layer. It was found to exhibit flame retardancy. The front surface layer and the back surface layer are not limited to single layers, and may have a laminated structure in which a plurality of sheets and the like are laminated.

When the back layer is a single-layer sheet or the like, a hydrated metal compound and / or a phosphorus compound and expansive graphite are added to the entire back layer so that the back layer has a laminated structure including a plurality of sheets. In this case, a hydrated metal compound and / or a phosphorus compound and expandable graphite are added to at least the back surface layer in contact with the front surface layer. The hydrated metal compound used in the present invention is not particularly limited as long as it is a substance that imparts a flame retardant action, and examples thereof include aluminum hydroxide and zinc borate.

The expansive graphite is, for example, scaly graphite that is oxidized by sulfuric acid, nitric acid, phosphoric acid, or the like.
For example, sulfuric acid intercalation compounds. In the present invention, among these expansive graphites, those that start to expand at a temperature of 300 to 400 ° C. and expand 50 times or more are preferable. These expandable graphites are preferably added to the back surface layer in a volume ratio of 2% or more.
When the back layer is a single layer, it is preferable to add 2% or more by volume ratio, and when the back layer is a multilayer, it is preferable to add 2% or more by volume ratio for the entire back layer. When the back surface layer is a multi-layer, the expansive graphite and the sheet to which the hydrated metal compound and / or the phosphorus compound are added are always laminated in the layer in contact with the front surface layer, and the expansive graphite is formed in the layer below that layer. Alternatively, a hydrated metal compound or a phosphorus compound may or may not be added, and expandable graphite may be added to the entire back surface layer in a volume ratio of 2% or more.

More preferably, among the backside layers having a multilayer structure,
It is particularly preferable to stack the expansive graphite and the hydrated metal compound and / or the phosphorus compound so that the total thickness of the layers not added is not larger than the total thickness of the layers added. If expandable graphite is added to the back layer in a volume ratio of 2% or more, the decorative material can be made flame-retardant even if the surface layer does not contain a flame retardant, and if it is 2% or more, the number of parts to be added is However, since the flame retardant effect cannot be obtained even if added in an amount of 30% or more, it is preferable to use it in the range of 2 to 30% in terms of volume ratio from the viewpoint of cost.

The hydrated metal compound added to the back surface layer is
From the viewpoint of flame retardancy, it is preferable to add 30 parts by weight or more, preferably 30 to 200 parts by weight to 100 parts by weight of the thermoplastic polymer material of the back surface layer. When the phosphorus compound is added, it is preferable that the content of the phosphorus element in the phosphorus compound is in the range of 3 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic polymer material. As the phosphorus compound, it is possible to use generally commercially available ones, for example, polyphosphoric acid salts such as red phosphorus and ammonium polyphosphate whose surface is coated with a resin, triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, Examples thereof include phosphoric acid ester-based plasticizers such as diphenyl 2-ethylhexyl phosphate.

Further, in the present invention, a tin compound may be further added as a flame retardant in order to further improve flame retardancy and low smoke generation. The tin compound is not particularly limited as long as it is a tin compound having a flame retardant action, and examples thereof include zinc hydrated tin compound (ZnSn (OH) ₆ ), zinc stannate (ZnSn).
O ₃ ), tin oxide (SnO ₂ ), hydrated tin compound (SnO
₂ × H ₂ O).

In the present invention, the most preferable combination of flame retardants is a combination of expandable graphite, a hydrated metal compound and a tin compound, or a combination of expandable graphite, a phosphorus compound and a tin compound, As a result, a decorative material excellent in both flame retardancy and low smoke generation is provided, which is particularly preferable. Further, in the present invention, it is possible to obtain a decorative material having low smoke generation and excellent flame retardancy without adding a flame retardant to the surface layer of the decorative material, but the decorative property of the surface of the decorative material, scratch resistance It is of course possible to add a known flame retardant in an amount that does not impair the properties and stain resistance.

The thermoplastic polymer material constituting the surface layer and back surface layer of the decorative material of the present invention is not particularly limited as long as it is a polymeric material substantially free of halogen atoms, but it is used as a decorative material. Is preferably polypropylene (PP),
Linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE), low density polyethylene (LD
PE), polybutene (PB) and other α-olefin resins, ethylene-ethyl acrylate copolymer resin (EE
A), ethylene-vinyl acetate copolymer resin (EVA), ethylene-methyl methacrylate copolymer resin (EMMA),
Ethylene-copolymer such as ethylene-methyl acrylate copolymer resin (EMA), or terpolymer, or thermoplastic synthetic resin such as ethylene-ionomer of ethylene and acrylic acid, rubber elasticity at room temperature Is a polymeric material that plastically deforms due to temperature rise,
It may be a thermoplastic elastomer consisting of a hard phase and a soft phase, for example, the hard phase is polyethylene, polypropylene,
Olefinic thermoplastic elastomer whose soft phase is olefinic rubber, polyester is hard phase, polyester thermoplastic elastomer whose soft phase is polyether, other urethane thermoplastic elastomer, or hydrogenated styrene-butadiene rubber, hard phase Examples thereof include styrene and a styrene-based thermoplastic elastomer whose soft phase is butadiene, vinyl isoprene, or the like, or those obtained by hydrogenating these.

These thermoplastic synthetic resins and thermoplastic elastomers may be used alone or as a blend of several kinds of resins and elastomers. In addition, plasticizers, stabilizers, inorganic fillers, organic fillers,
Various commonly used additives such as a lubricant, an ultraviolet absorber, a foaming agent, a coloring agent, an antioxidant and a gelation accelerator can be appropriately mixed and used.

The surface layer and the back layer of the decorative material of the present invention are basically composed of the above-mentioned thermoplastic synthetic resin and / or thermoplastic elastomer, and are made of polyester fiber, nylon fiber, chemical fiber such as glass fiber, hemp and the like. It is also possible to laminate a fiber base material such as a woven fabric or a non-woven fabric made of natural fibers such as wool on the lowermost layer or the intermediate layer of the back surface layer in order to prevent the expansion and contraction of the decorative material and to improve the dimensional stability. .

The front surface layer and the rear surface layer are formed by heating and softening a sheet or film formed from a thermoplastic synthetic resin and / or a thermoplastic elastomer containing substantially no halogen as described above, or chips and flakes, and pressing. It has a single layer structure such as an inlaid structure or a laminated structure. The sheet or film is formed by a calender molding method, an extrusion molding method, a press molding method, or the like.

When the decorative material of the present invention is used as a floor material, it is preferable that the decorative material is formed into a long shape having a thickness of 1 to 5 mm and a width of 1 to 2 m, but is not limited to this. Depending on the place, the thickness and size are appropriately determined and molded. The method for laminating the front surface layer and the back surface layer, or the method for laminating the sheets of the respective layers when the back surface layer is a multi-layer, includes calender molding or extrusion molding, and at the same time laminating a sheet prepared in advance by heat fusion, The formed sheets can be laminated by heat fusion by heating and pressing with a laminator, or the sheets can be laminated with an adhesive by a known laminating method such as a dry lamination method. Also, when used as wall coverings, ceiling materials, automobile leather, etc., they can be laminated in the same manner, and the sheet thickness is 0.1 to 1 mm.
It is molded in the range of. The width and length of the sheet are appropriately set according to the application.

When the surface layer constituting the decorative material of the present invention is also made flame-retardant, the thickness of the surface layer is 2 / the thickness of the back surface layer.
It is preferably 5 or less, and when used as a flooring material, the surface layer preferably has a thickness of 0.1 mm or more from the viewpoint of abrasion resistance. Also, in the case of wall coverings and other decorative materials, if the surface layer is too thin, the color of the back surface layer can be seen through the surface layer, hindering the design of the surface, and the surface layer can be easily peeled off by scratching. Therefore, the thickness of the surface layer is preferably 50 μm or more, and more preferably 100 μm or more.

It is also possible to form an arbitrary printed pattern on the surface layer of the decorative material of the present invention, to color the surface layer, or to perform various surface treatments on the surface layer. When forming a print pattern on the surface layer, form an arbitrary print pattern by a known printing means such as direct printing by gravure printing, screen printing or transfer printing with a transfer paper on which the print pattern is formed. Can be done. A well-known treating agent can be used when the surface treatment is applied to the surface layer, and examples thereof include a urethane treating agent and an acrylic treating agent. What kind of treatment does not include halogen such as vinyl chloride resin. Agents may be used. The coating method of the treating agent can be carried out by a known means such as gravure coating or spraying. Further, it is possible to form the surface layer only with a transparent layer, laminate a printed transparent sheet, or laminate a colored sheet with a transparent sheet.

Further, in order to further reduce the smoke generation amount of the decorative material of the present invention, it is possible to crosslink the entire decorative material.
The cross-linking method can be carried out, for example, by irradiating with an electron beam, by irradiating with ultraviolet rays, or by compounding a chemical substance (cross-linking agent) capable of cross-linking each thermoplastic polymer material.

[0026]

Next, the present invention will be described more specifically with reference to examples and comparative examples. (Formation of Flame Retardant-Containing Sheet) Based on the composition of Table 1, the width of the sheet which becomes the back surface layer of the decorative material with a test roll is 300 m.
m, the thickness was appropriately adjusted and molded, and when the thickness was 1.0 mm or more, the sheets were laminated by heat fusion to form a back layer sheet.

(Table 1)

(Molding of Non-Flame Retardant Sheet) Next, based on the composition of Table 2 below, a sheet to be a surface layer was formed into a width of 300 mm by a test roll, and the thickness of each sheet was appropriately adjusted to form a non-flame retardant sheet. . (Table 2)

(Note 1) Ethylene-ethyl acrylate copolymer resin (Note 2) Polypropylene resin (Note 3) Styrene-vinyl isoprene-styrene ternary copolymer resin (Note 4) Ultra low density polyethylene resin (Note 5) Hydrogen Added styrene-butadiene rubber The flame-retardant-containing sheet obtained from Table 1 and the non-flame-retardant sheet obtained from Table 2 are heated and melted to form a laminated sheet having a thickness of 2.0 mm to obtain a decorative material of the present invention. . The 0.5 mm thick sheet formed according to Table 2 was used as the surface layer of the decorative material.

Example 1 A non-flame retardant sheet of Formulation 7 formed to a thickness of 0.5 mm was laminated on the surface of a flame retardant-containing sheet of Formulation 1 formed to a thickness of 1.5 mm to obtain a thickness of 2. A 0 mm decorative material of the present invention was molded. Example 2 A non-flame retardant sheet of compound 7 molded to a thickness of 0.5 mm was laminated on the surface of a flame retardant-containing sheet of compound 2 molded to a thickness of 1.5 mm, and a book having a thickness of 2.0 mm was laminated. The decorative material of the invention was molded. Example 3 A 2.0 mm thick book was prepared by laminating a 0.5 mm thick molded non-flame retardant sheet on the surface of a blended 3 flame retardant containing sheet molded to a thickness of 1.5 mm. The decorative material of the invention was molded.

Example 4 A non-flame-retardant sheet of compound 7 molded to a thickness of 0.5 mm was laminated on the surface of a flame retardant-containing sheet of compound 4 molded to a thickness of 1.5 mm to obtain a thickness of 2.0 mm. The decorative material of the present invention was molded. Example 5 A flame retardant-containing sheet of Formulation 1 formed to a thickness of 1.5 mm was laminated on a non-flame retardant sheet of Formulation 8 formed to a thickness of 0.2 mm, and a thickness of 0. A non-flame retardant sheet of compound 7 molded to 3 mm is laminated to a thickness of 2.0 mm.
The decorative material of the present invention was molded.

Example 6 A flame-retardant-containing sheet of formulation 1 formed into a thickness of 0.4 mm was used as the lowermost layer, and a non-flame-retardant sheet of formulation 8 formed into a thickness of 0.2 mm thereon, thickness 1. A flame retardant-containing sheet of Formulation 1 molded to 0 mm and a non-flame retardant sheet of Formulation 7 molded to 0.4 mm thickness were sequentially laminated to form a decorative material of the present invention having a total thickness of 2.0 mm. Example 7 Printing using an acrylic resin as a main component that does not contain a flame retardant so that the thickness after drying is 25 μm on the entire surface of the flame retardant-containing sheet of Formulation 1 molded to a thickness of 1.5 mm. The decorative material of the present invention was formed by coating a paint to form a printed pattern.

Comparative Example 1 A non-flame-retardant sheet of Compound 7 having a thickness of 0.5 mm was laminated on the surface of a flame-retardant-containing sheet of Compound 5 having a thickness of 1.5 mm, and a thickness of 2.0 mm. The decorative material of Comparative Example was molded. Comparative Example 2 A non-flame retardant sheet of Compound 7 molded to a thickness of 0.5 mm was laminated on the surface of a flame retardant-containing sheet of Compound 6 molded to a thickness of 1.5 mm, and a Comparative Example having a thickness of 2.0 mm. The decorative material of was molded.

Comparative Example 3 A non-flame retardant sheet of Formulation 7 formed to a thickness of 1.0 mm was laminated on the surface of a flame retardant-containing sheet of Formulation 1 formed to a thickness of 1.0 mm, and a thickness of 2.0 mm. The decorative material of Comparative Example was molded. The following tests were conducted on the flame retardancy and smoke generation properties of these decorative materials. (Combustion test) A combustion test was conducted using each of the above decorative materials as test pieces, and the results are shown in Table 3. The flame-retardant test method for decorative materials is US Federal Aviation Administration (FAA) PART25 Annex PART-1 (12 seconds & 60 seconds vertical combustion test)
It was carried out according to 25.853b.

The test piece has a size of 2.0 inches × 12.0 inches, both sides of which are fixed by metal frames, and is vertically mounted. And the lower part of the test piece is 0.75 from the flame.
Hang it in an inch and apply it to a 1.5 inch flame for 12 seconds. The measurement items were combustion length, afterflame, and burning flame of drip. (Method of measuring smoke amount) The method was performed based on the test method of ASTM F814-83. As the test device, an NBS smoke emission measuring device was used. Test piece 3 inches × 3 inches Evaluation method It was represented by smoke density (Ds value) at 4 minutes. Ds = V / AL × log10 (100 / T) V: chamber volume A: sample surface area L: optical path length T: transmittance

Table 3 (measurement results)

The evaluation criteria for "evaluation of flame retardancy and smoke generation" are as follows:
The maximum burning length was 8 inches or less on average, the afterflame was 15 seconds or less on average, the burning of drip material was 5 seconds or less on average, and the smoke amount was 150 or less at a Ds value of 4 minutes. "Evaluation of concealing property of surface layer" The concealing property of the surface layer was judged with the naked eye, ◯: the color of the back surface layer was concealed, △: the color of the back surface layer was slightly transparent in the lightly colored portion of the surface Visible, x: It was evaluated that there was no hiding property at all.

"Evaluation of abrasion resistance of surface layer" The abrasion resistance of the surface layer was measured by a Taber abrasion test (JIS A1453). Measurement conditions Load: 15 kg Rotational speed: 500 rotations Wearing wheel: H-22 Evaluation Criteria O: The back surface layer is completely invisible after the test. Δ: The back surface layer is slightly transparent after the test. X: The back surface layer is abraded after the test.

[0039]

EFFECTS OF THE INVENTION The decorative material of the present invention has the constitution of (claim 1), and expandable graphite, a hydrated metal compound, a phosphorus compound and tin are added to the back surface layer without adding a flame retardant to the surface layer. By adding at least one of the three compounds, low smoke emission and excellent flame retardant effect as a constituent of the decorative material, and since no halogen-based resin or flame retardant is used, the environment is improved. Moreover, since no flame retardant is added to the surface layer, it is possible to freely apply a color or pattern, and it is possible to provide a decorative material having excellent stain resistance and scratch resistance.

According to the constitution of (Claim 2), in addition to the effect of the constitution of Claim 1, a decorative material excellent in self-extinguishing property and low smoke emission can be obtained. With the configuration of (Claim 3), in addition to the effect of Claim 1, a flame retardant effect can be obtained without adding expansive graphite to the entire back surface layer of the decorative material, which is economically significant. (Claim 4)
With this structure, the decorative material is more excellent in self-extinguishing property and low smoke emission. With the structure of (Claim 5), the surface layer has a thickness of 50 μm or more and a thickness of 2/5 or less of the thickness of the back surface layer, so that the surface has hiding property, abrasion resistance, scratch resistance, and the like. It is possible to obtain a decorative material having improved performance, low smoke generation, and excellent flame retardancy.

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Claims (5)

[Claims] 1. A hydrated metal compound and / or a phosphorus compound in a flame-retardant decorative material basically composed of a front surface layer and a back surface layer formed of a thermoplastic polymer material containing substantially no halogen. And a flame-retardant material composed of expansive graphite is added to the back surface layer. 2. The flame-retardant decoration material according to claim 1, wherein a tin compound is further added to the back surface layer. 3. The back surface layer is composed of a plurality of laminated structures, and at least the back surface layer in contact with the front surface layer contains a hydrated metal compound and / or
Alternatively, the flame-retardant decoration material according to claim 1, wherein a flame-retardant material including a phosphorus compound and expandable graphite is added. 4. The flame-retardant decoration material according to claim 3, wherein a tin compound is further added to at least the back surface layer in contact with the front surface layer. 5. The flame-retardant decorative material according to claim 1, wherein the thickness of the front surface layer is 50 μm or more and 2/5 or less of the thickness of the back surface layer.