JP4577086B2 - Flame retardant flooring - Google Patents

Description

  The present invention relates to a flame retardant floor material, and more particularly, in a floor material mainly composed of a modified epoxy resin that does not generate a toxic gas during combustion, the flame resistance of which the wear resistance, which is a drawback thereof, is improved. Regarding flooring.

  Conventionally, polyurethane resin (hereinafter referred to as “PU”) is used for flooring materials such as ships and buildings in order to provide good adhesion and rust prevention to steel plates and the like that constitute the base of the floor, and to ensure good habitability. Tile and cast type flooring materials made of polyvinyl chloride resin (hereinafter abbreviated as PVC resin) have been used. However, a floor material made of PU resin generates toxic gas such as cyan gas when burned. Further, although the tile made of PVC resin has flame retardancy, it has a defect that toxic gas such as chlorine gas, hydrogen chloride gas, and cyan gas is generated during combustion, like PU resin. Therefore, any floor material composed of these resin compositions has a high risk of toxic gas being generated in the event of a fire, leading to a fatal accident. For this reason, development of floor materials that can be substituted for these has been required for disaster prevention.

  In order to solve such problems, Patent Document 1 proposes a flame retardant flooring composition mainly composed of a modified epoxy resin that is self-digestible and does not generate a halogen-based toxic gas during combustion. ing. However, since this flame retardant flooring composition has low wear resistance, practically, a urethane resin coating is applied to the flooring surface to ensure wear resistance.

However, by applying a urethane resin coating, although it is a small amount, cyan gas is generated, and a safe flame-retardant flooring that does not generate any toxic gas has not been established yet.
Japanese Patent Laid-Open No. 4-120121

  An object of the present invention is a flooring material mainly composed of a modified epoxy resin that does not generate toxic gas during combustion, and has flame resistance with excellent wear resistance while preventing generation of toxic gas during combustion. To provide flooring.

  The flame retardant flooring of the present invention that achieves the above object is based on 100 parts by weight of the modified epoxy resin, 8 to 25 parts by weight of a phosphorus-based flame retardant, 75 to 100 parts by weight of aluminum hydroxide, and 25 of a curing agent. It is a flame retardant flooring material in which a coating material composed of an acrylic resin, a silicon compound, an organopolysiloxane resin and a silane coupling agent is applied to a floor base material composed of a resin composition containing ˜90 parts by weight.

  The flame retardant flooring of the present invention is composed of a floor base material and a paint applied to the surface thereof. The floor base material is mainly composed of a modified epoxy resin, a phosphorus flame retardant, aluminum hydroxide and a curing agent. Therefore, it has excellent flame retardancy and does not generate toxic gas during combustion. In addition, the paint applied to the surface of the floor base material is composed of acrylic resin, silicon compound, organopolysiloxane resin and silane coupling agent, so no toxic gas is generated during combustion and wear resistance It has excellent characteristics. The flame retardant flooring of the present invention has such a structure, does not generate any toxic gas at the time of combustion, has excellent characteristics of flame retardancy and wear resistance, It is useful as a flooring material for buildings and buildings.

  The floor base material constituting the flame retardant flooring of the present invention uses a modified epoxy resin as a base resin. By using the modified epoxy resin, cyan gas is not generated like PU resin, and chlorine gas, hydrogen chloride gas, and cyan gas are not generated like PVC resin. In addition, the modified epoxy resin used in the present invention is not only inferior to PU resin or PVC resin, but also exhibits resilience and / or durability, adhesion to a steel plate, and characteristics such as imparting rust prevention to the steel plate. Or it needs to have flexibility.

  As such a modified epoxy resin, for example, an epoxy resin modified with a urethane prepolymer which is a reaction product of an isocyanate compound and a polyol (hereinafter referred to as a urethane modified epoxy resin), an epoxy resin modified with various rubbers (hereinafter referred to as a urethane prepolymer) , Rubber-modified epoxy resins), epoxy resins modified with alkyl glycidyl ethers having side chains (hereinafter referred to as side-chain modified epoxy resins), epoxy resins modified with alkyl glycidyl ethers (hereinafter referred to as alkyl glycidyl ether-type epoxies). And an epoxy resin modified with a diglycidyl carboxylic acid composed of a carboxylic acid such as dimer acid (hereinafter referred to as a diglycidyl ester type epoxy resin), and more preferably an alkyl glycidyl ester. It is preferable to use ether type epoxy resin.

  Preferred examples of the urethane-modified epoxy resin include Adeka Resin EPU-11, Adeka Resin EPU-15, and Adeka Resin EPU-6 manufactured by Asahi Denka Kogyo Co., Ltd.

  Preferable examples of the rubber-modified epoxy resin include acrylic rubber fine particle-dispersed epoxy resin (for example, Eposet manufactured by Nippon Shokubai Co., Ltd.).

  Preferable examples of the side chain modified epoxy resin include Araldite XB-4122 manufactured by Ciba-Geigy Corporation, Adeka Resin EP-4005 manufactured by Asahi Denka Kogyo Co., Ltd.

  Preferred examples of the alkyl glycidyl ether type epoxy resin include Adeka Glycilol ED-503 manufactured by Asahi Denka Kogyo Co., Ltd.

  Preferred examples of the diglycidyl ester type epoxy resin include Epicoat EP-871 and EP-872 manufactured by Yuka Shell Epoxy Co., Ltd.

  These modified epoxy resins can be used alone or in combination of two or more. Those containing a small amount of a urethane component, such as a urethane-modified epoxy resin, can reduce the amount of toxic gas generated when used in combination with other resins.

  The floor base material constituting the floor material of the present invention contains a phosphorus-based flame retardant as a flame retardant in the modified epoxy resin. Preferable examples of the phosphorus flame retardant include a phosphate ester flame retardant, a polyphosphate flame retardant, and a red phosphorus flame retardant. By blending a phosphorus-based flame retardant, flame retardancy can be imparted without impairing the feature of not generating a toxic gas during combustion of the modified epoxy resin.

  In this invention, the compounding quantity of a phosphorus flame retardant is 8-25 weight part with respect to 100 weight part of modified epoxy resins, Preferably it is 10-15 weight part. If the amount is less than 8 parts by weight, sufficient flame retardancy cannot be imparted to the resin composition. If the amount exceeds 25 parts by weight, the flame retardancy is good, but the physical properties of the cured product (flexibility, water resistance, etc.) ) Decreases.

  In the floor base material constituting the flooring of the present invention, aluminum hydroxide is further blended in the range of 75 to 100 parts by weight, preferably 80 to 90 parts by weight with respect to 100 parts by weight of the modified epoxy resin. Since aluminum hydroxide contains water of crystallization, it functions as a flame retardant aid that becomes water vapor during combustion and improves flame retardancy. If the blending amount of aluminum hydroxide is less than 75 parts by weight, the effect as a flame retardant aid is insufficient, and if it exceeds 100 parts by weight, the physical properties of the resulting cured resin are lowered and casting at the time of flooring molding Sex is reduced.

  The floor base material constituting the floor material of the present invention is further blended with a curing agent. Preferable examples of the curing agent include polyamidoamine, rubber-modified polyamidoamine, urethane-modified polyamidoamine, and aliphatic-modified polyamine.

  The compounding quantity of a hardening | curing agent is mix | blended in 25-90 weight part with respect to 100 weight part of modified epoxy resins, Preferably it is 40-80 weight part. When the blending amount of the curing agent is less than 25 parts by weight, the time required to complete the curing of the resin composition becomes too long, and when it exceeds 90 parts by weight, the pot life of the resin composition is too short. In addition, the flexibility of the flooring material is reduced, cracks and the like are easily generated, and the durability is deteriorated.

  Furthermore, the resin composition constituting the floor base material of the floor material of the present invention includes a color toner such as a pigment for imparting color to a normal epoxy resin composition, an inorganic filler, a diluent, an anti-aging agent, A plasticizer etc. can be mix | blended suitably.

  The coating material which comprises the flooring of this invention is apply | coated to the surface of the floor base material which consists of an epoxy resin composition, and improves the abrasion resistance of a flooring. The paint used in the present invention is a paint comprising an acrylic resin, a silicon compound, an organopolysiloxane resin, and a silane coupling agent.

  In the present invention, the acrylic resin is a copolymer resin containing acrylic acid or a methacrylic acid derivative as a main component, and is not particularly limited as long as it can be used as a base resin of a paint. it can. The acrylic resin preferably has a weight average molecular weight in the range of 2,000 to 50,000, more preferably 5,000 to 20,000, from the viewpoints of coating film hardness, scratch resistance, weather resistance and finish. is there.

  From the viewpoint of storage stability, the hydroxyl value of the acrylic resin is preferably 5 mgKOH / g or less, more preferably 0. The glass transition temperature of the acrylic resin is preferably in the range of −40 ° C. to 100 ° C., more preferably in the range of −20 ° C. to 60 ° C., from the viewpoints of coating film hardness and finish properties.

  The iodine value of the acrylic resin is preferably from 5 to 200, more preferably from 10 to 100, from the viewpoints of curability and finish. The iodine value represents the concentration of unsaturated groups by the number of g of iodine per 100 g of acrylic resin solid content absorbed when iodine is allowed to act on the acrylic resin.

  In the present invention, the organopolysiloxane resin is preferably a polysiloxane resin having a methyl group, an alkoxy group, a phenyl group, a hydroxyl group, an amino group, or the like.

  In this invention, the compounding quantity of organopolysiloxane resin becomes like this. Preferably it is 50-100 weight part with respect to 100 weight part of acrylic resins, More preferably, it is 60-90 weight part. When the compounding amount of the organopolysiloxane resin is out of the above range, excellent characteristics such as flame retardancy and abrasion resistance tend to decrease, which is not preferable.

  As the silane coupling agent used in the present invention, a silane coupling agent containing a vinyl group, a mercapto group, an amino group, an epoxy group, a chloro group, and an alkyl group can be used. Aminosilane can be preferably mentioned.

  These silane coupling agents can be used alone or in combination in order to obtain an adhesion imparting effect. The silane coupling agent is preferably epoxy silane or amino silane, and particularly preferably amino silane.

  Specific examples of the epoxy silane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like.

  Specific examples of aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ. -There is aminopropyltriethoxysilane.

  In this invention, as a compounding quantity of a silane coupling agent, Preferably it is 0.5-10 weight part, More preferably, it is 2-8 weight part.

  In the present invention, the silicon compound is a silicon compound used in the coating material excluding the above-mentioned organopolysiloxane resin and silane coupling agent. Preferred examples of such a silicon compound include silicone oil, modified silicone oil, and silicone RTV rubber, with modified silicone oil being more preferred.

  The modified silicone oil is preferably a reactive silicone oil, such as amino-modified, epoxy-modified, carbinol-modified, methacryl-modified, mercapto-modified, etc. Non-reactive silicone oil is methylstyryl-modified, alkyl-modified, Preferred are modified silicone oils such as higher fatty acid ester-modified.

  In addition, the structure of the modified silicone oil is such that the polysiloxane has an organic group at the side chain, the polysiloxane has an organic group at one end, the polysiloxane has an organic group at both ends, and the polysiloxane side chain. And those having organic groups at both ends are preferred.

  In this invention, the compounding quantity of a silicon compound becomes like this. Preferably it is 45-75 weight part with respect to 100 weight part of acrylic resins, More preferably, it is 50-70 weight part. When the compounding amount of the silicon compound is out of the above range, excellent characteristics such as flame retardancy and abrasion resistance tend to be lowered, which is not preferable.

  The coating material used for the flame retardant flooring of the present invention has the above-described configuration, has excellent flame retardancy and wear resistance, and has characteristics that do not generate toxic gas during combustion.

  Moreover, by applying the above-mentioned paint, the slip resistance of the floor may be difficult to slip in a dry state and may be slightly slippery in a wet state, but this is not a practically problematic level. In addition, it is possible to improve the floor slip resistance by adjusting the surface roughness after painting.

  The flame retardant flooring of the present invention can be prepared by preparing an epoxy resin composition to be a floor base material and casting it on a basement floor surface in a ship or a building. It is preferable that the floor surface used as a base | substrate is comprised with the iron plate, concrete, etc., and it is more preferable that it is especially an iron plate.

  Since the floor base material of the flame retardant flooring of the present invention can be cast and molded on the basement floor surface, there is no boundary surface like a flooring laid by tiling or the like, and moisture penetrates through the gap. There is no risk of rusting the iron plate that is the floor base. Moreover, a flooring material can be accurately and uniformly formed on a floor surface having a water draining gradient or the like.

  In the present invention, the thickness of the floor base material is preferably 2 to 10 mm, more preferably 4 to 6 mm. If the thickness of the floor base material is less than the above, uneven absorption may be insufficient, and if it exceeds the above range, the cost becomes high, which is not preferable.

  The floor base material of the flame-retardant flooring of the present invention has a work life of 1 to 2 hours and is excellent in workability. Moreover, after casting, it can be dried and cured by natural drying at room temperature for about 24 hours.

  The flame-retardant flooring of the present invention is one in which the above-mentioned paint is applied to the surface of the floor base material after the floor base material is molded and cured. The method for applying the paint is not particularly limited, and can be preferably applied by a method such as airless spray application or brush application, and more preferably applied by airless spray application.

  In this invention, the thickness of the coating material apply | coated to a floor base material becomes like this. Preferably it is 10-100 micrometers, More preferably, it is 20-40 micrometers. If the thickness of the coating is less than the above, the effect of improving the wear resistance tends to decrease, and if it exceeds the above range, the flexibility tends to be somewhat lacking, which is not preferable.

  The flame retardant flooring of the present invention has excellent flame retardancy because the floor base material is composed of a modified epoxy resin, a phosphorus flame retardant, aluminum hydroxide and a curing agent, and generates a toxic gas during combustion. There is nothing to do. In addition, the paint applied to the floor base material surface is made of acrylic resin, silicon compound, organopolysiloxane resin and silane coupling agent, so it does not generate toxic gas during combustion and has excellent wear resistance. It has characteristics.

Therefore, when the flame retardant flooring of the present invention is evaluated by ASTM-E-662-1979 (no frame, heated for 15 minutes), the amount of generation of toxic gases such as hydrogen chloride gas, chlorine gas, and cyan gas is generated during combustion. , Preferably 0 g / m ³ . Furthermore, it is flame retardant having self-digestibility and has excellent wear resistance. For this reason, the flame-retardant flooring of this invention is useful as a flooring of a ship or a building.

  Hereinafter, the flame-retardant flooring of the present invention will be specifically described with reference to examples. Items common to the examples and comparative examples are as follows.

[Production of evaluation base material]
As an epoxy resin composition constituting the floor base material, 84% by weight of urethane-modified epoxy resin (Adeka Resin EPU-11 manufactured by Asahi Denka Kogyo Co., Ltd.) and 16 side-chain modified epoxy resin (Araldite XB-4122 manufactured by Ciba Geigy Japan) are used. % By weight, based on 100 parts by weight of these modified epoxy resins, 23 parts by weight of a polyphosphate flame retardant (Sumisafe P manufactured by Sumitomo Chemical Co., Ltd.) and 91% of aluminum hydroxide (Hijilite H-42 manufactured by Showa Denko KK) 34 parts by weight of an aliphatic modified polyamine (Adeka Hardener EH-220 manufactured by Asahi Denka Kogyo Co., Ltd.) was blended and adjusted in parts by weight and a curing agent.

  The resulting epoxy resin composition was cast on a Teflon (registered trademark) coated formwork and face plate to a thickness of 6 mm, and allowed to dry naturally at room temperature for 24 hours to be cured. 48 hours after cure. Thereafter, the formwork and the face plate were peeled off to obtain the tile-like floor base material of the present invention.

[Flammability test]
Based on JIS-Z2391, it evaluated by the horizontal and vertical combustion test by a 50w test flame.

[Combustion gas test]
According to ASTM-E-662-1979, the generation amount [g / m ³ ] of hydrogen chloride gas (HCl), chlorine gas (Cl ₂ ), and hydrogen cyanide gas (HCN) is determined depending on the conditions of heating for 15 minutes without a flame. It was measured.

[Hardness test]
Shore hardness A was measured according to JIS-K 6301.

[Abrasion resistance test]
In accordance with JIS-K7204, a wear test using a wear wheel was performed under conditions of a load of 1 kg and a wear frequency of 1000 times.

[Impact resistance test]
In accordance with JIS-K6902, the occurrence of cracks, cracks and dents in the flame retardant flooring was visually evaluated.

[Heat resistance test]
After heating at a temperature of 100 ° C. for 8 hours, the surface state, swelling and discoloration were visually observed.

[Solvent resistance test]
In accordance with JIS-K6902, the surface state after 6 hours of MEK and toluene in the flame retardant flooring was observed, and the occurrence of cracks and cracks was visually evaluated.

[Slip resistance test]
In accordance with ASTM-E-303-74 “Measurement Method of Surface Friction Characteristics Using British Pendulum Sliding Resistance Tester”, the sliding resistance of flame retardant flooring in the DRY and WET states was evaluated under conditions without WAX. .

Example 1
A paint having a mixing ratio of 100 parts by weight of acrylic resin, 70 parts by weight of organopolysiloxane resin, 60 parts by weight of silicon compound, and 5 parts by weight of silane coupling agent was prepared. The obtained paint was applied to the floor base material of the present invention by airless spraying and dried and cured at a temperature of 60 ° C. for 20 minutes to obtain a flame retardant floor material.

The obtained flame retardant flooring had a weight of 8.4 kg / m ² and a paint thickness of 10 μm.

  The evaluation results of the obtained flame-retardant flooring are shown in Table 1. The results of the heat resistance test showed no abnormalities, the results of the impact resistance test showed no cracks, cracks or dents, and the results of the solvent resistance test showed that both MEK and toluene were in the surface state. There was no abnormality, and neither swelling nor discoloration was observed.

Comparative Example 1
A flame retardant flooring was evaluated in the same manner as in Example 1 except that a urethane-based coating was used as the coating and applied to the floor base material of the present invention.

The obtained flame retardant flooring had a weight of 8.4 kg / m ² and a paint thickness of 200 μm.

  The evaluation results of the obtained flame-retardant flooring are shown in Table 1. The results of the heat resistance test showed no abnormalities, the results of the impact resistance test showed no cracks, cracks or dents, and the results of the solvent resistance test showed that both MEK and toluene were in the surface state. There was no abnormality, and neither swelling nor discoloration was observed.

Comparative Example 2
As the floor base material, a PVC resin tile having a thickness of 2 mm and a latex composition (including an adhesive) for unevenness adjustment having a thickness of 3 mm were used.

The weight of the obtained flame-retardant flooring was 10.4 kg / m ² .

  The evaluation results of the obtained flame-retardant flooring are shown in Table 1. The results of the heat resistance test showed no abnormalities, the results of the impact resistance test showed no cracks, cracks or dents, and the results of the solvent resistance test showed that both MEK and toluene were in the surface state. There was no abnormality, and neither swelling nor discoloration was observed.

  The flame-retardant flooring of the present invention (Example 1) maintains self-extinguishing flame retardancy, generates no toxic gas at the time of combustion, and has a conventional abrasion resistance (Comparative Example 1). ).

Claims (2)

  A floor base material composed of a resin composition containing 8 to 25 parts by weight of a phosphorus-based flame retardant, 75 to 100 parts by weight of aluminum hydroxide, and 25 to 90 parts by weight of a curing agent with respect to 100 parts by weight of a modified epoxy resin. A flame retardant flooring coated with a paint comprising acrylic resin, silicon compound, organopolysiloxane resin and silane coupling agent. The said coating material consists of 55-85 weight part of organopolysiloxane resin, 45-75 weight part of silicon compounds, and 0.5-10 weight part of silane coupling agents with respect to 100 weight part of acrylic resins. Flame retardant flooring.