CN-121973521-A - PVC sheet floor for ship fire prevention and preparation method thereof

CN121973521ACN 121973521 ACN121973521 ACN 121973521ACN-121973521-A

Abstract

The invention belongs to the field of decorative materials, and provides a ship fireproof PVC sheet floor and a preparation method thereof. According to the invention, a double flame-retardant smoke-suppressing design of the ammonium octamolybdate-silicon dioxide core-shell composite particles (the thickness of the shell layer is 30-120nm, the D50 is 0.30-1.20 mu m) and the Mg-Al-CO 3 type layered double hydroxide (the molar ratio of Mg/Al is 2.0-4.0, the interlayer spacing is 0.70-1.00 nm) is adopted, a multilayer composite structure of a high inorganic filling substrate layer (100-200 parts of magnesium hydroxide and 180-250 parts of calcium carbonate) and a nano silicon dioxide/zinc stannate modified transparent wear-resistant layer is matched, and through a precisely controlled hot-press lamination process (the lamination temperature is 135-145 ℃, the pressure is 2.7-3.3MPa and the time is 27-33 min), the problems of more than or equal to 28% of oxygen index, the smoke density grade is less than or equal to 100, the excellent wear resistance and transparent appearance are solved, the problems of narrow processing window of a high filling PVC floor, poor surface layer flame-retardant system stability and insufficient interlayer bonding toughness are solved, and the application value of a ship cabin is wide.

Inventors

XU JINAN
HE BINSHENG
Ning Youkun
ZHAO CHEN
QIU YINGWEI
DONG CHENCHAO
CHEN KAI

Assignees

浙江海利得地板有限公司
浙江海利得新材料股份有限公司

Dates

Publication Date: 20260505
Application Date: 20260206

Claims (10)

1. The marine fireproof PVC sheet floor is characterized by comprising a base material layer and a transparent wear-resistant layer, wherein: The substrate layer consists of, by mass, 20-40 parts of di-2-ethylhexyl terephthalate, 2-5 parts of total heat-stable system consisting of calcium stearate and zinc stearate, 100-200 parts of magnesium hydroxide, 180-250 parts of calcium carbonate, 8-15 parts of Mg-Al-CO 3 type layered double hydroxide, wherein the molar ratio of Mg to Al in the Mg-Al-CO 3 type layered double hydroxide is 2.0-4.0, the interlayer spacing is 0.70-1.00nm, the thickness of a shell layer of the ammonium octamolybdate-silica core-shell composite particle is 30-120nm, the particle D50 is 0.30-1.20 mu m, and the mass fraction of silica in the core-shell composite particle is 15-60wt%; The transparent wear-resistant layer comprises, by mass, 100 parts of polyvinyl chloride resin, 10-30 parts of di-2-ethylhexyl terephthalate, 1-4 parts of a heat stabilization system consisting of calcium stearate and zinc stearate, 0.20-1.00 parts of silicon dioxide and 0.05-0.50 part of zinc stannate hydroxide.
2. The marine fire resistant PVC sheet flooring according to claim 1, wherein the ammonium octamolybdate-silica core-shell composite particles are prepared by: A1. The preparation of raw materials comprises the steps of adding ammonium octamolybdate into deionized water for dissolution, adding absolute ethyl alcohol into the obtained solution, adding ammonium hydroxide solution to enable the pH value of a system to be 8.5-10.5, and adding 3-aminopropyl triethoxysilane; A2. pre-reacting, namely stirring for 0.5-1.5h at 20-40 ℃; A3. Coating sol-gel, namely dripping tetraethoxysilane in 0.5-2.0h at 20-40 ℃ and continuously reacting for 1-6h to obtain slurry containing core-shell particles; A4. Performing post-treatment, namely performing solid-liquid separation on the slurry, washing for 1-3 times by adopting a mixed solution of ethanol and deionized water according to a mass ratio of 1:1, and drying for 4-12 hours at 60-110 ℃ to obtain the ammonium octamolybdate-silicon dioxide core-shell composite particles; The structural parameters of the ammonium octamolybdate-silicon dioxide core-shell composite particles are that the shell thickness is 30-120nm, the particle D50 is 0.30-1.20 mu m, the mass fraction of silicon dioxide in the core-shell composite particles is 15-60wt%, the moisture content after drying is 0.05-0.50wt%, the shell thickness is the average shell thickness measured by a transmission electron microscope, the particle D50 is the volume distribution median particle diameter measured by a laser particle size analyzer, and the moisture content is the mass fraction measured by a Karl Fischer moisture measurement method.
3. The marine fire resistant PVC sheet flooring according to claim 1, wherein the Mg-Al-CO 3 layered double hydroxide is prepared by: B1. The preparation of raw materials comprises the steps of dissolving magnesium nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water to obtain a metal salt mixed solution, wherein the molar ratio of Mg to Al in the metal salt mixed solution is 2.0-4.0, and the total concentration of metal ions is 0.50-2.00mol/L; B2. Adding the metal salt mixed solution obtained in the step B1 into the alkaline carbonate solution at 60-80 ℃ to keep the pH value of the system at 9.0-11.0; B3. aging at 60-80deg.C for 4-8 hr; B4. Post-treatment, namely washing the mixture with deionized water until the pH value of the filtrate is 7.0-8.0 after solid-liquid separation, and drying the mixture for 8-12 hours at 60-80 ℃ to obtain the Mg-Al-CO 3 type layered double hydroxide; The structural parameter of the Mg-Al-CO 3 type layered double hydroxide is that the interlayer spacing is 0.70-1.00nm, the moisture content after drying is 0.10-1.00wt%, the interlayer spacing is 003 crystal face spacing measured by X-ray diffraction, and the moisture content is mass fraction measured by a Karl Fischer moisture measurement method.
4. The marine fire-resistant PVC sheet flooring according to claim 1, wherein the mass ratio of calcium stearate to zinc stearate in the heat stabilizing system is 0.5-2.0.
5. The marine fire-resistant PVC sheet flooring according to claim 1, further comprising a silane coupling agent selected from at least one of 3-aminopropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane and vinyl trimethoxysilane, the silane coupling agent being used in an amount of 0.05 to 0.50 parts by mass based on 100 parts by mass of the polyvinyl chloride resin in the substrate layer.
6. The marine fire-resistant PVC sheet flooring according to claim 1, wherein a transition layer consisting of polyvinyl chloride resin, ammonium octamolybdate-silica core-shell composite particles and di-2-ethylhexyl terephthalate is provided between the base material layer and the transparent wear layer, the transition layer having a thickness of 20 to 200 μm, the ammonium octamolybdate-silica core-shell composite particles being used in an amount of 2 to 15 parts by mass, the di-2-ethylhexyl terephthalate being used in an amount of 15 to 35 parts by mass, based on 100 parts by mass of the polyvinyl chloride resin in the transition layer; The average primary particle size of the silicon dioxide raw material used in the transparent wear-resistant layer is 5-50nm, the average primary particle size is measured by a transmission electron microscope, the tin content of the zinc stannate hydroxide in the transparent wear-resistant layer is 40-45wt%, and the tin content is mass fraction calculated by element Sn.
7. A method of producing a fire-resistant PVC sheet flooring for ships according to any one of claims 1 to 6, comprising the steps of: s1, preparing a substrate layer, namely weighing raw materials according to the substrate layer formula of claim 1, mixing the raw materials in high-speed mixing equipment to enable the temperature of the raw materials to reach 110-125 ℃ to obtain a substrate layer dry blend; S2, plasticizing and sheeting the substrate layer, namely plasticizing the substrate layer dry mixed material in banburying equipment at 155-175 ℃ for 1-4min, and then carrying out calendaring molding to obtain a substrate layer sheet; s3, proportioning and tabletting the transparent wear-resistant layer, namely weighing raw materials according to the formula of the transparent wear-resistant layer in claim 1, mixing the raw materials in high-speed mixing equipment to obtain a dry wear-resistant layer mixture, plasticizing the dry wear-resistant layer mixture in banburying equipment at a plasticizing temperature of 155-175 ℃ for 1-4min, and then carrying out calendaring molding to obtain a transparent wear-resistant layer sheet; S4, lamination, namely carrying out hot press lamination on the substrate layer sheet and the transparent wear-resistant layer sheet, wherein the lamination temperature is 135-145 ℃, the lamination pressure is 2.7-3.3MPa, and the lamination time is 27-33min, so that the ship fireproof PVC sheet floor is obtained.
8. The preparation method according to claim 7, wherein the mixing time of the high-speed mixing in the step S1 is 5-15min, the roll temperature of the calendaring in the step S2 is 150-175 ℃, and the mixing of the dry mixed materials of the wear-resistant layer in the step S3 enables the material temperature to reach 95-115 ℃.
9. The method according to claim 7, wherein a silane coupling agent is added to the base material layer dry mix in step S1, the silane coupling agent being used in an amount of 0.05 to 0.50 parts by mass based on 100 parts by mass of the polyvinyl chloride resin in the base material layer.
10. The method according to claim 7, wherein the magnesium hydroxide and the calcium carbonate are subjected to a drying treatment before step S1, and the moisture content after drying is 0.05 to 0.50wt%, the moisture content being a mass fraction measured by karl fischer moisture measurement.

Description

PVC sheet floor for ship fire prevention and preparation method thereof Technical Field The invention relates to the field of floor materials for ships, in particular to a fireproof PVC sheet floor for ships and a preparation method thereof. Background The safety of the internal cabin environment of a ship as a core carrier for ocean transportation and ocean engineering is directly related to the life safety of crews and the reliability of ship operation. As an important component in the ship, the ship cabin floor not only needs to bear high-strength personnel activities and equipment operation loads, but also needs to maintain stable performance for a long time in complex marine environments such as high humidity, salt spray corrosion, temperature fluctuation and the like. Particularly in the sudden accidents such as fire disaster and the like, the flame retardant performance and the low smoke and low toxicity characteristics of the floor material become key defense lines for life safety. Polyvinyl chloride (PVC) sheet flooring plays an important role in ship cabin decoration due to its good workability, chemical resistance, slip resistance and economy. However, with the continuous rise of fire safety standards for ships by the International Maritime Organization (IMO), higher demands are being placed on the flame retardant performance, smoke density control, durability and appearance quality of PVC floors. The existing PVC floor meets the technical challenges of narrow processing window, poor uniformity of appearance of transparent wear-resistant layers, insufficient bonding strength among layers of a multilayer structure and the like while meeting the high flame-retardant low-smoke performance, and is difficult to comprehensively balance fireproof safety and service performance, so that the development of the ship fireproof PVC sheet floor with excellent flame-retardant smoke-suppression performance, good processing adaptability and long-term service stability has important significance. Currently, flame retardant modification of PVC floors for ships is mainly realized by adding inorganic flame retardant fillers. However, the prior art still suffers from the disadvantage of having a flame retardant smoke suppressant design for multi-layer PVC flooring, first, high inorganic flame retardant fill resulting in narrow processing window and loss of transparency. When the filler amount of magnesium hydroxide, calcium carbonate and the like reaches more than 100-200 parts, although the flame retardant property is improved, the melt fluidity of the PVC matrix is reduced, the calendaring temperature window is reduced, the defects of uneven plasticization, rough surface and the like are easily generated, and meanwhile, the light transmittance and the appearance uniformity of the transparent wear-resistant layer are damaged. For example, china patent with publication number CN109021447A discloses a high wear-resistant flame-retardant PVC floor and a preparation method thereof, but the defects of high processing temperature sensitivity and large haze of a transparent layer exist. Second, the high hardness requirement of the wear resistant skin contradicts the compatible stability of the low smoke flame retardant system. Fillers such as magnesium hydroxide can improve hardness and scratch resistance, but have poor compatibility with the traditional smoke suppressant, are easy to agglomerate or phase separate, and lead to the attenuation of flame retardant smoke suppressant effects. Third, the interlayer adhesion toughness of the multilayer structure is insufficient. The interface bonding force between the substrate layer and the transparent wear-resistant layer is weak, delamination, foaming and other failures easily occur in the use process, and meanwhile, acid gas released by the inorganic flame-retardant filler in the combustion process can corrode the interface between layers, so that the bonding strength and the long-term stability of the flame-retardant smoke-suppressing function are weakened. Disclosure of Invention The invention aims to provide a ship fireproof PVC sheet floor and a preparation method thereof, which solve the problems that the existing multilayer PVC floor is difficult to consider the transparent uniformity of a calendaring processing window and appearance, the compatible stability of a high-hardness scratch-resistant and low-smoke flame-retardant system of a wear-resistant surface layer and the pain point of natural coupling contradiction between the interlayer bonding toughness of a multilayer structure and the long-term effectiveness of an acid absorption barrier/smoke suppression function under the high inorganic flame-retardant/smoke suppression filling condition. According to the invention, a double flame-retardant smoke suppression design thought of the ammonium octamolybdate-silica core-shell composite particles and Mg-Al-CO 3 type layered double hydroxide is adopted, the interfacial