KR20170058533A - A flame retardant tile for a ship comprising a biodegradable polymer resin - Google Patents

Abstract

The present invention relates to a flame-retardant tile for a ship and, more specifically, to a flame-retardant tile for a ship capable of realizing various appearances by providing a printing layer, being environmentally friendly because a base layer and a transparent layer of the flame-retardant tile for a ship includes biodegradable resin, and having excellent flame retardancy and safety by reducing smoke density and toxic gas generated by combustion of resin during a fire.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame retardant tile for a ship including a biodegradable polymer,

The present invention relates to a marine flame retardant tile, and more particularly, to a marine flame retardant tile having a printed layer, which can realize various external appearance, and a base layer and a transparent layer of the marine flame retardant tile include environmentally friendly biodegradable resins, And more particularly, to a flame retardant tile for ships which is safe and has excellent flame retardancy by reducing smoke density and toxic gas.

In general, ships are made of a steel structure by connecting blocks made of steel. Like the land-based structures, these floors are covered with flooring.

Such a flooring material may be applied to a steel plate to apply a compound for sound insulation to maintain the outer shape of the steel plate forming the structure, but in most cases, the floor formed on the ship is finished by installing a separate flooring material on the floor.

 The marine flooring according to the related art includes a core material 110 made of a rocky material having a predetermined height as shown in FIG. 1, and a closure member 120 covering an upper part of the core material 110 . The marine floor material 100 is advantageous in cost saving by finishing the marine floor provided with the core member 110 with excellent thermal insulation and sound insulation and filling the interior with the closure member 120 with the closure member 120. However, the marine flooring 100 according to the prior art as described above is limited in its appearance.

On the other hand, flame retardancy is the most excellent for flooring materials using rubber material, but it is expensive and has limitations in appearance.

In addition, it may be considered to apply PVC decorative deco tiles which are low in price and can realize various appearance to ship flooring. However, since it generates many toxic gas such as hydrogen chloride (HCl) gas during combustion and has a high smoke density, , The conventional decorative PVC tiles could not be applied as flooring for ships.

Especially, in recent years, there has been a lot of interest in fire safety due to a fire accident due to a fire accident. In the case of using a PVC decorative tile on a ship, the amount of smoke is high when a fire occurs, Or a secondary disaster such as asphyxiation in the event of fire suppression occurs, so that it is difficult to apply it as a marine flooring material.

Therefore, there is a demand for development of marine flame retardant tiles which can realize various appearance, eco-friendly, safe, and excellent in flame retardancy by reducing smoke density and toxic gas generated by combustion of resin during a fire.

As an example of a conventional marine flooring material, Korean Patent Laid-Open Publication No. 10-2011-0123920 is available.

KR 10-2011-0123920 A (11 Nov 2011)

In order to solve the above-described problems, the present invention is to provide a flame retardant tile having a base layer and a transparent layer which are environmentally friendly, including a biodegradable resin, and have a smoke density And a flame retardant tile for marine which is safe and has excellent flame retardancy by reducing toxic gas.

To achieve the above object, the present invention provides a marine flame retardant tile comprising: a base layer; A printing layer formed on the base layer; And a transparent layer formed on the print layer.

The flame retardant tile for marine of the present invention has a print layer, and thus has a different appearance from a conventional marine flooring material.

In addition, the marine flame retardant tile of the present invention has an effect of being environment-friendly by forming the base layer and the transparent layer with the biodegradable resin composition, reducing the smoke density and toxic gas generated by the combustion of the resin during fire, and being excellent in safety and in flame retardancy.

1 is a perspective view of a conventional marine floor material.
2 is a schematic cross-sectional view of a marine flameproof tile of the present invention.
3 is a schematic cross-sectional view of a specific embodiment of a marine flame-retardant tile of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

2 is a schematic cross-sectional view of a marine flameproof tile of the present invention. As shown in FIG. 2, the present invention includes a base layer 20; A printed layer (30) formed on the base layer (20); And a transparent layer (40) formed on the print layer (30).

In the present invention, the base layer 20 is formed of a resin composition containing a poylajctic acid (PLA) resin, an inorganic flame retardant, and a filler so as not to deteriorate physical properties as a tile while being environmentally friendly and excellent in flame retardancy.

The PLA resin is a biodegradable resin prepared by fermenting vegetable starch, for example, with lactic acid fermentation. When the flame retardant tile for ships is manufactured using such a PLA resin, it is environmentally friendly. Since the emission of toxic gas and the smoke density in case of fire are small, It is effective. The content of the PLA resin in the resin composition forming the base layer 20 is preferably 5-25 wt%, and more preferably 10-20 wt%. When the content of PLA resin is less than 5% by weight, the effect of inhibiting toxic gas emission and smoke density is insignificant in the case of fire and fire, and in case of exceeding 25% by weight, disadvantage of PLA resin having poor dimensional stability and narrow processing temperature and operating temperature range It may cause deterioration of the physical properties of the marine flame-retardant tile. Therefore, the above-mentioned range is preferable.

The inorganic flame retardant may be at least one selected from the group consisting of metal hydroxides such as magnesium hydroxide, aluminum hydroxide, barium hydroxide and calcium hydroxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, Metal oxides such as tin oxide, nickel oxide, copper oxide and tungsten oxide; metal powders such as aluminum, iron, copper, nickel, titanium, manganese, tin, zinc, molybdenum, cobalt, bismuth, chromium, tungsten, antimony, And carbonates such as magnesium carbonate, calcium carbonate and barium carbonate, and any one or more of these may be used in combination. It is preferable to use metal hydroxides which have a small amount of fuming when burning and emit water (H ₂ O) at a high temperature, and it is particularly preferable to use aluminum hydroxide or magnesium hydroxide. The content of the inorganic flame retardant in the resin composition forming the base layer is preferably 10-40 wt%, and more preferably 15-25 wt%. When the content of the inorganic flame retardant is less than 10% by weight, the flame retardancy effect is insignificant. When the content is more than 40% by weight, the workability and the property of the flame retardant tile for marine use may be deteriorated.

The filler may be one or more selected from the group consisting of calcium carbonate, talc, fly ash, blast furnace slag, and combinations thereof. It is preferable to use calcium carbonate as a filler because it is advantageous in terms of cost and versatility, and heat resistance and durability can be enhanced. The content of the filler in the resin composition forming the base layer is preferably 30-70 wt%, more preferably 40-65 wt%. If the content of the filler is less than 30% by weight, the tile price rise, heat resistance and durability may be deteriorated, and if it exceeds 70% by weight, the workability may be deteriorated.

In the present invention, the resin composition for forming the base layer 20 may further include a thermoplastic polyurethane resin for flame retardancy and processability. The thermoplastic polyurethane resin in the resin composition forming the base layer 20 is preferably 1-15% by weight, and more preferably 1-10% by weight. If the content of the thermoplastic polyurethane resin is less than 1%, it is difficult to impart flexibility to the tile due to the characteristics of the PLA resin. If the content exceeds 15% by weight, it may be flexible, but it may cause dimensional stability and fuming property. desirable.

Further, in the present invention, the resin composition for forming the base layer 20 may further include at least one selected from a plasticizer, a processing aid, and a lubricant for processability.

A benzoate-based, citrate-based or phosphate-based plasticizer may be used as the plasticizer, and the content of the plasticizer in the resin composition forming the base layer may be 1-5% by weight.

An acrylic copolymer may be used as the processing aid for improving workability and melt strength. The content of the processing aid in the resin composition forming the base layer may be 1-5% by weight.

The lubricant may be used to prevent the resin composition for forming the base layer from adhering to the calender or the press during processing such as calender molding or press molding of the base layer, and higher fatty acids such as stearic acid may be used. The content of the lubricant in the resin composition forming the base layer may be 0.01-1% by weight.

The thickness of the base layer may be 1 to 5 mm.

In the present invention, the print layer 30 formed on the base layer 20 serves to impart various print patterns to the resulting flame retardant tile for marine use. The printing layer 30 is formed on the surface of the white sheet 31 in various ways such as transfer printing, gravure printing, screen printing, offset printing, rotary printing or flexographic printing after the white sheet 31 is formed And can be formed by giving a printed pattern 32 (see Fig. 3). The white sheet 31 is a white sheet, which improves the adhesion between the base layer 20 and the printed pattern 32 or the pattern formed on the white sheet while the pattern is clearly visible. Can be implemented. The thickness of the white sheet 31 may be 0.1-0.3 mm, but is not limited thereto. The print layer 30 may be formed using a transparent sheet or a colored sheet other than the white sheet 31. [

Alternatively, the printing layer 30 can be formed directly on the base layer 20 by transfer printing, gravure printing, or screen printing. In this case, the printing layer is an ink layer formed by printing, and is so thin that it is difficult to measure its thickness. Therefore, its thickness is so small that it does not affect the total thickness of the marine flame retardant tile obtained according to the present invention, Can be ignored.

Since the print layer 30 imparts a pattern through printing and gives a good appearance and a design effect to the aesthetics, the flame retardant tile for marine of the present invention overcomes the limitation of the appearance of the conventional marine flooring Various marine flame retardant tiles can be realized.

In the present invention, the transparent layer 40 formed on the print layer 30 protects the print pattern and the pattern of the print layer 30 and provides the flame retardant tile for marine with flame retardancy.

In the present invention, the transparent layer 40 is a transparent film made of a resin composition containing a biodegradable polymer resin and a phosphorus-based flame retardant.

The biodegradable polymer resin is not particularly limited as long as it is biodegradable, and it is preferable that the biodegradable polymer resin is selected from the group consisting of PLA (Poly Lactic Acid) resin, polyglycolic acid resin, polycaprolactone resin, aliphatic polyester resin, polyhydroxybutyric acid resin and D- Among these resins, at least one of them is preferable. At this time, the biodegradable resin is most preferably a PLA resin exhibiting properties similar to those of a commercial resin such as polypropylene (PP) or polyethylene terephthalate (PET) resin. The content of the biodegradable resin in the resin composition forming the transparent layer 40 is preferably 40-75 wt%, more preferably 50-70 wt%. When the content of the biodegradable polymer resin is less than 40% by weight, the effect of preventing environmental toxicity and toxic gas emission and smoke density is small. When the biodegradable polymer resin content exceeds 75% by weight, the properties of the flame retardant tile for marine use may be deteriorated. .

The phosphorus flame retardant may be selected from the group consisting of a phosphate compound, a phosphonate compound, a phosphinate compound, and a phosphazene compound.

Specific examples of the phosphate compound include triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri Bis (diphenylphosphine) phosphate, bis (diphenylphosphine) phosphate, bis (diphenylphosphine) ), Resorcinol bis (2,6-ditertiarybutylphenylphosphate), and hydroquinone bis (2,6-dimethylphenylphosphate). These may be used singly or in combination of two or more.

Specific examples of the phosphonate compound include aluminum methyl methylphosphonate and cyclic phosphonate. These phosphonate compounds may be used singly or in combination of two or more thereof. have.

Specific examples of the phosphinate compound include aluminum diethylphosphinate and aluminum methylethylphosphinate. These compounds may be used singly or in combination of two or more. .

A specific example of the above phosphazene compound is hexaphenoxy tricyclophosphazene.

As the phosphorus flame retardant, it is preferable to use a phosphate compound having compatibility (transparency, plasticity, etc.) with the biodegradable polymer compound, more preferably resorcinol bis (diphenylphosphate), bisphenol A-bis Diphenyl phosphate) is preferably used in view of volatility and cost competitiveness.

The content of the phosphorus-based flame retardant in the resin composition forming the transparent layer 40 is preferably 10-30% by weight, and more preferably 10-25% by weight. If the content of the phosphorus flame retardant is less than 10% by weight, the flame retardancy and plasticity are deteriorated. If the content is more than 30% by weight, the properties of the flame retardant tile for marine use may be deteriorated.

In the present invention, the resin composition for forming the transparent layer 40 may further contain at least one selected from the group consisting of a processing aid, an epoxy resin, an antiblocking agent, a lubricant, and other additives in order to improve transparency, processability and storage property.

The processing aid may be an acrylic copolymer for enhancing transparency, processability and melt strength. The content of the processing aid in the resin composition forming the transparent layer may be 10-30% by weight, preferably 15-25% by weight .

The epoxy resin is added for transparency, and the content of the epoxy resin in the resin composition forming the transparent layer may be 0.1-5 wt%.

The anti-blocking agent is added to prevent blocking of the film which is in contact with each other when the film is wound up after processing, and at least one selected from silica, diatomaceous earth, kaolin and talc can be used, The content of the anti-blocking agent in the resin composition may be 0.1-5 wt%.

The lubricant may be used to prevent the resin composition for forming a transparent layer from adhering to the calender or the press during processing such as calender molding or press molding of the transparent layer 40, and higher fatty acids such as stearic acid may be used. The content of the lubricant in the resin composition forming the transparent layer may be 0.1-5 wt%.

Other additives may be antioxidants, antistatic agents, ultraviolet stabilizers, moisture release agents and the like, and the content of other additives in the resin composition forming the transparent layer may be 0.1-5 wt%.

The thickness of the transparent layer may be 0.1 to 1 mm.

Since the transparent layer 40 of the present invention includes a phosphorus flame retardant, it forms a char on the surface during burning, generates radicals by pyrolysis, captures H radicals or OH radicals, .

The base layer 20 of the marine flameproof tile of the present invention may further include an optional layer 10 (FIG. 3). The base layer 10 protects the bottom of the flame-retardant tile, blocks moisture from the floor, and maintains the overall curling balance of the upper and lower tiles. The base layer 10 may be constructed to include a PVC resin or a PLA resin and a filler (i.e., calcium carbonate).

The thickness of the easy layer 10 may be 0.1-3 mm.

Further, the marine flame-retardant tile of the present invention may optionally further include a surface treatment layer (not shown) on the uppermost layer.

That is, the surface treatment layer can be formed on the transparent layer 40, and functions to prevent initial contamination, that is, adhesion of contaminants to the surface of the tile, and to improve scratch resistance and abrasion resistance. The surface treatment layer may be formed by coating a coating solution in which a thermosetting or photocurable compound is dissolved in a solvent. However, in the case of a thermosetting compound, when heat is applied to form a surface treatment layer, the physical properties of other layers located below the heat treatment layer, particularly, the transparent layer 40 and the base layer 20 can be changed, It is more preferable to use a compound. In this case, the curable compound may be a monomer or oligomer having at least one functional group such as an unsaturated bond group capable of performing a crosslinking reaction, and examples thereof include urethane acrylate, epoxy acrylate, polyether acrylate, Dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like can be used, but they are exemplified by And the present invention is not intended to be limited thereto. In the present invention, these can be used singly or as a mixture of two or more kinds of them as a photo-curable compound. The coating liquid containing the photo-curing compound generally contains a photopolymerization initiator in addition to the photo-curable compound and the solvent. If necessary, various additives may be added to the coating solution in the range of not changing the physical properties of the hard coating layer such as a light stabilizer and a leveling agent . The surface treatment layer has a surface hardness of 7H or more as measured by pencil hardness, and it may be a surface hardness of the surface of the plastic film being excellent, more preferably in a range of 7H to 8H. The photocurable compound constituting the surface treatment layer may preferably be a conventional photocurable urethane acrylate.

The thickness of the surface treatment layer may be 5 to 40 mu m.

The transparent layer 40, the white sheet 31, the base layer 20 and the base layer 10 of the marine flame retardant tile of the present invention can be formed by calendaring, casting, blow molding or extrusion molding .

Calendering is a molding method in which a sheet or a film is continuously produced by rolling a raw material between two or more rolls rotating in mutually opposite directions. Casting molding is a method in which a synthetic resin sol is laminated on a release paper having excellent heat resistance, Coating, and then lamination. In blow molding, the thermoplastic resin is heated and melted and continuously extruded from the extruder into a tube, and the parison is inserted into one or two or more molds to seal the top and bottom of the parison. In the extrusion molding, a thermoplastic plastic material is heated and melted by using an extruder to form a fluid state, and then a T die In the form of a film.

Preferably, in the case of calender molding, the content of additives such as additives can be freely controlled as compared with other production methods, and thus a flooring material having excellent flexibility, impact resistance, mechanical strength, workability, It is possible to further reduce the cost of the raw material, and therefore, it is preferable to produce it by the calender molding method.

Further, the respective layers of the marine flame-retardant tile can be formed by laminating them with heat and pressure using a plywood process or the like known in the art.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

(Preparation of transparent layer)

, 1% by weight of an anti-blocking agent, 1% by weight of a higher fatty acid, and 1% by weight of an additive, based on the total weight of the composition, 60% by weight of PLA resin, 18% by weight of resorcinolbis (diphenylphosphate) Kneaded with a Banbury mixer, and then subjected to primary and secondary mixing using a two-roll mill to prepare a composition for forming a transparent layer. Subsequently, the composition for the production of a transparent layer was calender molded at a temperature of 150 ° C to prepare a transparent layer (Film) having a thickness of 0.3 mm.

(Production of printing layer)

45 weight% of PLA resin, 9 weight% of ATBC, 7 weight% of acrylic copolymer, 1 weight% of stearic acid as high fatty acid, 31 weight% of diisocyanate, calcium carbonate and 7 weight% of titanium dioxide were kneaded by a Banbury mixer, The mixture was subjected to primary and secondary mixing using a two-roll mill. Then, the produced raw material was subjected to calender molding at a temperature of 150 캜 to produce a white sheet having a thickness of 0.15 mm. Further, printed patterns were formed on the surface of the white sheet through a gravure printing or transfer printing method to produce a printing layer.

(Base layer production)

12 wt% of PLA resin, 5 wt% of thermoplastic polyurethane resin, 3 wt% of plasticizer, 3 wt% of acrylic copolymer, 0.1 wt% of higher fatty acid, 56 wt% of calcium carbonate and 20.9 wt% of aluminum hydroxide were kneaded with a Banbury mixer Next, the base layer composition was prepared by primary secondary mixing using the two-rolls.

Subsequently, the base layer composition was calender molded at a temperature of 150 캜 to prepare a base layer having a thickness of 1.7 mm.

(Preparation of Easy Layer)

43 wt% of PLA resin, 5 wt% of ATBC, 6 wt% of acrylic copolymer, 1 wt% of stearic acid as high fatty acid, 43 wt% of calcium carbonate, 1 wt% of titanium dioxide, and 1 wt% of rosin were kneaded with a Banbury mixer Next, primary and secondary mixes were performed using the two-rolls. Then, the produced raw material was subjected to calender molding at a temperature of 140 to 180 DEG C to prepare an easy layer having a thickness of 0.25 mm.

The prepared transparent layer, the print layer, the base layer and the base layer were sequentially laminated, followed by heat and pressure using a laminating method to produce a flame retardant tile for marine use. 3 is a cross-sectional view of a marine flameproof tile according to the above embodiment.

Experimental Example  One

The flame propagation properties, smoke density and toxic gas of the flame retardant tile for marine of the above embodiment were measured and the test method thereof was as follows.

The smoke density and toxic gas measurement method was performed by the ISO 5659-2 combustion chamber test method. The test results are shown in Table 1 below.

[Table 1]

As shown in Table 1, the marine flame-retardant tile according to the present invention meets all of the flame retardant performance standards of the International Maritime Organization (IMO) for classification, and includes a biodegradable resin composition, The smoke density and the toxic gas are reduced and the safety and the flame retardancy are excellent, and it is confirmed that various effects can be realized by providing the printing layer.

1: Flame retardant tile for ships
10: Easy layer 20: Base layer
30: print layer 31: white sheet 32: printed pattern
40: transparent layer 50: surface treated layer
100: Conventional marine flooring
110: core material
120: Closing member

Claims (18)

A base layer;
A printing layer formed on the base layer;
And a transparent layer formed on the printing layer. The method according to claim 1,
Wherein the base layer is formed of a resin composition comprising a poylajctic acid (PLA) resin, an inorganic flame retardant, and a filler. 3. The method of claim 2,
Wherein the resin composition forming the base layer comprises 5-25% by weight of a PLA resin, 10-40% by weight of an inorganic flame retardant, and 30-70% by weight of a filler. 3. The method of claim 2,
Wherein the inorganic flame retardant is one or more selected from among metal hydroxides consisting of magnesium hydroxide, aluminum hydroxide, barium hydroxide and calcium hydroxide. 3. The method of claim 2,
Wherein the resin composition forming the base layer further comprises at least one selected from a thermoplastic polyurethane resin, a plasticizer, a processing aid, and a lubricant. The method according to claim 1,
Wherein the base layer has a thickness of 1 to 5 mm. The method according to claim 1,
Wherein the print layer is formed by transfer printing, gravure printing, screen printing, offset printing, rotary printing, or flexographic printing on the surface of a white sheet to give a print pattern. The method according to claim 1,
Wherein the thickness of the printing layer is 0.01 mm to 0.3 mm. The method according to claim 1,
Wherein the transparent layer is formed of a resin composition comprising a biodegradable polymer resin and a phosphorus-based flame retardant. 10. The method of claim 9,
The biodegradable polymer resin may contain one or two selected from PLA (Poly Lactic Acid) resin, polyglycolic acid resin, polycaprolactone resin, aliphatic polyester resin, polyhydroxybutyric acid resin and D-3- By weight based on the total weight of the flame-retardant tile. 10. The method of claim 9,
Wherein the phosphorus flame retardant is one or a mixture of two or more selected from the group consisting of a phosphate compound, a phosphonate compound, a phosphinate compound, and a phosphazene compound. 12. The method of claim 11,
The phosphate compound may be selected from the group consisting of triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, Bis (diphenylphosphate), bis (diphenylphosphate), bis (diphenylphosphine), bis (diphenylphosphoryl) phosphate, bis (2,6-ditertiary butylphenylphosphate) or hydroquinone bis (2,6-dimethylphenylphosphate). 10. The method of claim 9,
Wherein the resin composition for forming the transparent layer is formed of a resin composition containing 40 to 75% by weight of a biodegradable polymer resin and 10 to 30% by weight of a phosphorus-based flame retardant. 10. The method of claim 9,
Wherein the resin composition forming the transparent layer further comprises at least one selected from the group consisting of a processing aid, an epoxy resin, an antiblocking agent, a lubricant, and other additives. 15. The method of claim 14,
The resin composition for forming the transparent layer contains 10-30% by weight of a processing aid, 0.1-5% by weight of an epoxy resin, 0.1-5% by weight of an antiblocking agent, 0.1-5% by weight of a lubricant, and 0.1-5% Flame retardant tile for marine features. The method according to claim 1,
Wherein the thickness of the transparent layer is 0.1 to 1 mm. The method according to claim 1,
And an easy layer below the base layer. The method according to claim 1,
And a surface treatment layer is further formed on the transparent layer.

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