Efficient flame-retardant film and production process thereof

Abstract

The invention provides an efficient flame-retardant film and a production process thereof, and relates to the technical field of flame-retardant films. An efficient flame-retardant film comprises a surface layer, a core layer and an inner layer. The surface layer is prepared from the following raw materials in parts by mass: 10 to 40 parts of copolymerized PP, 7 to 36 parts of a flame retardant, 0.4 to 1.5 parts of an anti-UV agent, 0.01 to 0.1 part of an anti-aging agent, 0.5 to 3 parts of an anti-sticking agent and 0.2 to 3 parts of titanium dioxide master batch. The flame-retardant film provided by the invention has excellent flame retardance.

Description

Technical Field

[0001] The present invention relates to the technical field of flame retardant films, and in particular to a highly efficient flame retardant film and its production process. Background Art

[0002] A flame retardant film is a thin film material with fireproof performance and is widely used in multiple fields such as construction, transportation, electronics, new energy, etc. In case of a fire, the flame retardant film can effectively isolate the flame and the fire source, reduce heat transfer, lower the surface temperature of the material, and delay the further degradation process. Its main function is to protect materials and personnel safety by inhibiting and delaying the combustion of plastics. Traditional halogen-based flame retardants may release toxic gases during combustion, while halogen-free flame retardant additives reduce smoke emissions and are more environmentally friendly. Summary of the Invention

[0003] Based on the technical problems existing in the background art, the present invention proposes a highly efficient flame retardant film and its production process.

[0004] A highly efficient flame retardant film proposed by the present invention includes a surface layer, a core layer, and a inner layer.

[0005] Preferably, the surface layer comprises the following raw materials in parts by mass: 10 - 40 parts of copolymerized PP, 7 - 36 parts of flame retardant, 0.4 - 1.5 parts of anti-UV agent, 0.01 - 0.1 part of anti-aging agent, 0.5 - 3 parts of anti-sticking agent, 0.2 - 3 parts of titanium white masterbatch.

[0006] Preferably, the thickness of the surface layer is 1.0 - 1.5 μm.

[0007] Preferably, the core layer comprises the following raw materials in parts by mass: 150 - 200 parts of PP, 100 - 180 parts of flame retardant, 6 - 10 parts of anti-UV agent, 0.1 - 1 part of anti-aging agent, 3 - 16 parts of titanium white masterbatch.

[0008] Preferably, the thickness of the core layer is 26 - 28 μm.

[0009] Preferably, the inner layer comprises the following raw materials in parts by mass: 10 - 40 parts of PP, 5 - 35 parts of flame retardant, 0.4 - 1.5 parts of anti-UV agent, 0.01 - 0.1 part of anti-aging agent, 0.5 - 3 parts of anti-sticking agent, 0.2 - 3 parts of titanium white masterbatch.

[0010] Preferably, the thickness of the inner layer is 1.0 - 1.5 μm.

[0011] More preferably, the flame retardant includes modified attapulgite, hydroxide, polycarbosilane, POE.

[0012] More preferably, the preparation method of the flame retardant comprises the following steps:

[0013] S1. Disperse the modified attapulgite clay in solvent A and perform ultrasonic treatment to obtain mixed solution A; add mixed solution A to the hydroxide, mix evenly, and then dry to obtain mixture A;

[0014] S2. Disperse the polycarbosilane in solvent B and stir evenly to obtain mixed solution B; add mixed solution B to mixture A, mix evenly, and then dry to obtain mixture B;

[0015] S3. Disperse γ-methacryloxypropyltrimethoxysilane in solvent C and stir evenly to obtain mixed solution C; add mixed solution C to mixture B, mix evenly, and then dry to obtain mixture C;

[0016] S4. Mix POE and mixture C evenly to obtain the flame retardant.

[0017] More preferably, in S1, solvent A is selected from one or more of ethanol and water.

[0018] More preferably, in S1, the preparation of the modified attapulgite clay includes the following steps: subject the attapulgite clay to high-temperature treatment, disperse it in a methanol solution, add graphene, perform solvothermal reaction, wash and dry to obtain the modified attapulgite clay.

[0019] More preferably, the high-temperature treatment includes calcining at 400 - 550 °C for 2 - 3 h.

[0020] More preferably, the solvothermal reaction includes reacting at 130 - 150 °C for 8 - 12 h.

[0021] More preferably, the mass ratio of the attapulgite clay to graphene is (5 - 10):1.

[0022] More preferably, in S1, the hydroxide includes one or more of magnesium hydroxide and aluminum hydroxide.

[0023] More preferably, the mass ratio of magnesium hydroxide to aluminum hydroxide is (1 - 3):(1 - 3).

[0024] More preferably, in S2, solvent B is selected from one or more of methanol and toluene.

[0025] More preferably, in S3, solvent C is selected from one or more of ethanol and acetone.

[0026] More preferably, in S3, the mass ratio of γ-methacryloxypropyltrimethoxysilane to mixture B is (0.5 - 2):100.

[0027] More preferably, the mass ratio of the modified attapulgite clay, hydroxide, polycarbosilane, and POE is (1 - 5):100:(5 - 10):(15 - 20).

[0028] More preferably, the ethylene content in the copolymerized PP is 1 - 4%.

[0029] More preferably, the melt index of the copolymerized PP at 230°C and 2.16 kg is 4 - 16 g / 10 min.

[0030] More preferably, the melt index of the PP at 230°C and 2.16 kg is 1.5 - 2.0 g / 10 min.

[0031] More preferably, the anti-UV agent is selected from one or more of UV-242, UV-284, and UV-531.

[0032] More preferably, the anti-aging agent is selected from one or more of antioxidant 1098 and antioxidant 1010.

[0033] More preferably, the anti-sticking agent is selected from one or more of silica, talc, zeolite, limestone, erucamide, and oleamide.

[0034] More preferably, the content of titanium dioxide in the titanium dioxide masterbatch is 50 - 60%.

[0035] The present invention also provides a production process for a highly efficient flame-retardant film, comprising the following steps:

[0036] S1. Mix the raw materials of the surface layer, core layer, and inner layer evenly and co-extrude to obtain a melt;

[0037] S2. Subject the melt to casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain a highly efficient flame-retardant film.

[0038] Preferably, in S1, the extrusion temperature is 230 - 250°C.

[0039] Preferably, in S2, the longitudinal stretching ratio is 4.5 - 5.5.

[0040] Preferably, in S2, the transverse stretching ratio is 9 - 10.

[0041] The beneficial effects of the present invention are as follows:

[0042] The high-efficiency flame-retardant film of the present invention comprises a surface layer, a core layer and an inner layer. The surface layer comprises copolymerized PP, a flame retardant, an anti-UV agent, an anti-aging agent, an anti-sticking agent and a titanium white masterbatch; the core layer comprises PP, a flame retardant, an anti-UV agent, an anti-aging agent and a titanium white masterbatch; the inner layer comprises PP, a flame retardant, an anti-UV agent, an anti-aging agent, an anti-sticking agent and a titanium white masterbatch; the raw materials of each layer act synergistically, and the prepared flame-retardant film not only has excellent flame-retardant performance, but also has certain wear resistance.

[0043] By controlling the thickness of the surface layer to 1.0-1.5μm, the thickness of the core layer to 26-28μm, and the thickness of the inner layer to 1.0-1.5μm, the thickness of the flame retardant film is about 30μm, which can be widely used in surface coating of building materials, decorative materials, floor tiles, surface coating of electronic products, etc.

[0044] The flame retardant film prepared by the present invention is a halogen-free flame retardant film. The "halogen" of the halogen-free flame retardant film refers to the halogen elements in the periodic table (including F, Cl, Br, I, At, Ts). The halogen-free flame retardant film can form a carbonized layer when burning to prevent heat transfer and oxygen contact, thereby achieving a flame retardant effect; since it does not contain halogen elements, no harmful gases will be released during combustion, which complies with international environmental regulations and is friendly to the environment and human health. The flame retardant includes modified attapulgite, hydroxide, polycarbosilane, and POE. The raw materials act synergistically. By controlling the raw material ratio and its preparation process, the flame retardant obtained has good compatibility with the resin, so that the flame retardant film has excellent flame retardant properties and has certain toughness. The halogen-free flame retardant film has a small amount of smoke, a small density, and a low cost when burning. At the same time, it also produces less toxic and corrosive gases. The halogen-free flame retardant film prepared by the present invention has a thickness of about 30μm and a density of about 0.92g / cm 3 , and has VTM-0 grade flame retardant effect.

[0045] In the present invention, titanium white masterbatch is added to the surface layer, the core layer and the inner layer. The titanium white masterbatch is similar to the resin particles, has good dispersibility, is more evenly mixed, and ensures stable product color.

[0046] The present invention adds anti-sticking agents to the surface layer and the inner layer, and by selecting anti-sticking agents of different components for synergistic effect, on the one hand, it helps to make the surface of the film present a concave-convex structure, and when the film layers are in contact with each other, it is easier to peel off; on the other hand, the addition of organic anti-sticking agents has little effect on the transparency of the film, and also has a slip-increasing function, so that the film has a lower friction coefficient and will not cause scratches on the surface of the film, while maintaining a high gloss; the present invention uses anti-sticking agents of different components in a mixed manner, so that the slip-increasing effect of the organic anti-sticking agent and the anti-sticking performance of the inorganic anti-sticking agent can be utilized, while reducing their respective negative effects, playing an opening role while also playing a certain slipping role. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 Schematic structural diagram of the high-efficiency flame-retardant film proposed by the present invention, 1 - surface layer, 2 - core layer, 3 - inner layer. Specific implementation mode

[0048] The technical solution of the present invention will be described in detail through specific embodiments.

[0049] The materials, reagents, etc. used in the following examples can be obtained from commercial sources without special instructions.

[0050] Example 1

[0051] A high-efficiency flame-retardant film, including a surface layer, a core layer, and an inner layer;

[0052] The surface layer includes the following raw materials in parts by mass: 25 parts of copolymerized PP, 20 parts of flame retardant, 0.5 part of UV-resistant agent, 0.05 part of anti-aging agent, 2 parts of anti-sticking agent, and 0.5 part of titanium white masterbatch. The thickness of the surface layer is 1.0 μm. The melt index of the copolymerized PP at 230 °C and 2.16 kg is 4.5 g / 10 min.

[0053] The core layer includes the following raw materials in parts by mass: 185 parts of PP, 160 parts of flame retardant, 7 parts of UV-resistant agent, 0.5 part of anti-aging agent, and 10 parts of titanium white masterbatch. The thickness of the core layer is 28 μm.

[0054] The inner layer includes the following raw materials in parts by mass: 25 parts of PP, 20 parts of flame retardant, 0.5 part of UV-resistant agent, 0.05 part of anti-aging agent, 2.5 parts of anti-sticking agent, and 0.5 part of titanium white masterbatch. The thickness of the inner layer is 1.0 μm.

[0055] The UV-resistant agent is UV-531; the anti-aging agent is antioxidant 1098; the anti-sticking agent is composed of silica, limestone, erucic acid amide, and oleic acid amide in a mass ratio of 1:1:1:1.

[0056] The preparation method of the flame retardant includes the following steps:

[0057] S1. After treating attapulgite clay at 450 °C for 2 h, it is dispersed in a methanol solution, graphene is added, and a solvothermal reaction is carried out at 140 °C for 10 h, followed by washing and drying to obtain modified attapulgite clay, where the mass ratio of attapulgite clay to graphene is 5:1; the modified attapulgite clay is dispersed in ethanol and ultrasonicated to obtain a mixed solution A; magnesium hydroxide and aluminum hydroxide are mixed in a mass ratio of 1:3 to obtain a hydroxide, and the mixed solution A is added to the hydroxide, and after mixing evenly, it is dried to obtain a mixture A;

[0058] S2. Polycarbosilane is dispersed in toluene and stirred evenly to obtain a mixed solution B; the mixed solution B is added to the mixture A, and after mixing evenly, it is dried to obtain a mixture B;

[0059] S3. Disperse γ-methacryloyloxypropyltrimethoxysilane in ethanol, stir evenly to obtain a mixed solution C; add the mixed solution C to the mixture B, after mixing evenly, dry to obtain a mixture C; wherein, the mass ratio of γ-methacryloyloxypropyltrimethoxysilane to the mixture B is 1:100;

[0060] S4. Mix POE and the mixture C evenly to obtain a flame retardant;

[0061] Among them, the mass ratio of the modified attapulgite clay, hydroxide, polycarbosilane, and POE is 3:100:5:15.

[0062] A production process of a highly efficient flame retardant film includes the following steps:

[0063] S1. Mix the raw materials of the surface layer, core layer, and inner layer evenly respectively and co-extrude to obtain a melt, and the extrusion temperature is 240 °C;

[0064] S2. Subject the melt to film casting, longitudinal stretching, transverse stretching, winding, and slitting to obtain the film. The stretching ratio of the longitudinal stretching is 4.5, and the stretching ratio of the transverse stretching is 9.5.

[0065] After testing, the flame retardant grade of the highly efficient flame retardant film prepared in this example reaches the VTM-0 grade, the friction coefficient is 0.15, and its wear amount is 1.23% tested according to GB / T 1689-2014.

[0066] Example 2

[0067] A highly efficient flame retardant film includes a surface layer, a core layer, and an inner layer;

[0068] The surface layer includes the following raw materials in parts by mass: 10 parts of copolymerized PP, 7 parts of flame retardant, 0.4 part of anti-UV agent, 0.02 part of anti-aging agent, 0.5 part of anti-sticking agent, and 0.2 part of titanium white masterbatch. The thickness of the surface layer is 1.0 μm. The melt index of the copolymerized PP at 230 °C and 2.16 kg is 4.5 g / 10 min.

[0069] The core layer includes the following raw materials in parts by mass: 150 parts of PP, 120 parts of flame retardant, 6 parts of anti-UV agent, 0.3 part of anti-aging agent, and 5 parts of titanium white masterbatch. The thickness of the core layer is 28 μm.

[0070] The inner layer includes the following raw materials in parts by mass: 10 parts of PP, 7 parts of flame retardant, 0.4 part of anti-UV agent, 0.02 part of anti-aging agent, 0.5 part of anti-sticking agent, and 0.2 part of titanium white masterbatch. The thickness of the inner layer is 1.0 μm.

[0071] The anti-UV agent, anti-aging agent, and flame retardant are the same as those in Example 1.

[0072] The anti - sticking agent is composed of talc, erucamide, and oleamide in a mass ratio of 1:0.5:1.

[0073] The production process of the high - efficiency flame - retardant film is the same as that of Example 1.

[0074] After testing, the flame - retardant grade of the high - efficiency flame - retardant film prepared in this example reaches VTM - 0, the coefficient of friction is 0.18, and its wear amount is 1.75% tested in accordance with GB / T 1689 - 2014.

[0075] Example 3

[0076] A high - efficiency flame - retardant film, including a surface layer, a core layer, and a lining layer;

[0077] The surface layer includes the following raw materials in parts by mass: 40 parts of copolymerized PP, 36 parts of flame - retardant, 1.5 parts of anti - UV agent, 0.05 part of anti - aging agent, 3 parts of anti - sticking agent, and 2 parts of titanium white masterbatch. The thickness of the surface layer is 1.5μm. The melt index of the copolymerized PP at 230°C and 2.16 kg is 4.5 g / 10 min.

[0078] The core layer includes the following raw materials in parts by mass: 200 parts of PP, 180 parts of flame - retardant, 8 parts of anti - UV agent, 1 part of anti - aging agent, and 15 parts of titanium white masterbatch. The thickness of the core layer is 27μm.

[0079] The lining layer includes the following raw materials in parts by mass: 40 parts of PP, 35 parts of flame - retardant, 1.5 parts of anti - UV agent, 0.05 part of anti - aging agent, 3 parts of anti - sticking agent, and 2 parts of titanium white masterbatch. The thickness of the lining layer is 1.5μm.

[0080] The anti - UV agent, anti - aging agent, and anti - sticking agent are the same as those in Example 1.

[0081] The preparation method of the flame - retardant is only different from that of Example 1 in that the mass ratio of modified attapulgite clay, hydroxide, polycarbosilane, and POE is 5:100:6:18.

[0082] The production process of the high - efficiency flame - retardant film is the same as that of Example 1.

[0083] After testing, the flame - retardant grade of the high - efficiency flame - retardant film prepared in this example reaches VTM - 0, the coefficient of friction is 0.14, and its wear amount is 1.08% tested in accordance with GB / T 1689 - 2014.

[0084] Example 4

[0085] A high - efficiency flame - retardant film, including a surface layer, a core layer, and a lining layer;

[0086] The surface layer comprises the following raw materials in parts by mass: 35 parts of copolymerized PP, 20 parts of flame retardant, 1 part of UV-resistant agent, 0.05 part of anti-aging agent, 2 parts of anti-sticking agent, and 1 part of titanium white masterbatch. The thickness of the surface layer is 1.5 μm. The melt index of the copolymerized PP at 230 °C and 2.16 kg is 4.5 g / 10 min.

[0087] The core layer comprises the following raw materials in parts by mass: 180 parts of PP, 150 parts of flame retardant, 7 parts of UV-resistant agent, 0.5 part of anti-aging agent, and 8 parts of titanium white masterbatch. The thickness of the core layer is 27 μm.

[0088] The inner layer comprises the following raw materials in parts by mass: 35 parts of PP, 20 parts of flame retardant, 1 part of UV-resistant agent, 0.05 part of anti-aging agent, 2 parts of anti-sticking agent, and 1 part of titanium white masterbatch. The thickness of the inner layer is 1.5 μm.

[0089] The UV-resistant agent, anti-aging agent, anti-sticking agent, and flame retardant are the same as those in Example 1.

[0090] The production process of the high-efficiency flame-retardant film is the same as that in Example 1.

[0091] After testing, the flame-retardant grade of the high-efficiency flame-retardant film prepared in this example reaches the VTM-0 grade, the friction coefficient is 0.15, and its wear amount is 1.25% tested according to GB / T 1689-2014.

[0092] Comparative Example 1

[0093] The difference between Comparative Example 1 and Example 1 is that the flame retardant is a commercially available flame retardant (ZM W-QYHM-MX-4 from Zhongmei Magnesium Industry), and the anti-sticking agent is composed of silica and limestone in a mass ratio of 1:1.

[0094] After testing, the flame-retardant grade of the flame-retardant film prepared in Comparative Example 1 reaches the VTM-1 grade, the friction coefficient is 0.25, and its wear amount is 2.42% tested according to GB / T 1689-2014.

[0095] In summary, the flame-retardant film provided by the present invention has excellent flame-retardant performance and wear resistance.

[0096] The above is only the preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, shall be covered by the protection scope of the present invention.

Claims

1. A high-efficiency flame-retardant film, characterized in that: It includes a surface layer, a core layer and an inner layer; the surface layer includes the following raw materials in parts by weight: 10-40 parts of copolymer PP, 7-36 parts of flame retardant, 0.4-1.5 parts of anti-UV agent, 0.01-0.1 parts of anti-aging agent, 0.5-3 parts of anti-sticking agent and 0.2-3 parts of titanium dioxide masterbatch.

2. The high-efficiency flame-retardant film according to claim 1, characterized in that: The core layer comprises the following raw materials in parts by weight: 150-200 parts of PP, 100-180 parts of flame retardant, 6-10 parts of anti-UV agent, 0.1-1 part of anti-aging agent, and 3-16 parts of titanium dioxide masterbatch.

3. The high-efficiency flame-retardant film according to claim 1, characterized in that: The inner layer comprises the following raw materials in parts by weight: 10-40 parts of PP, 5-35 parts of flame retardant, 0.4-1.5 parts of anti-UV agent, 0.01-0.1 parts of anti-aging agent, 0.5-3 parts of anti-sticking agent, and 0.2-3 parts of titanium dioxide masterbatch.

4. The high-efficiency flame-retardant film according to claim 1, characterized in that: The method for preparing the flame retardant comprises the following steps: S1, dispersing modified attapulgite clay in solvent A, and subjecting to ultrasonic treatment to obtain a mixed solution A; adding the mixed solution A to the hydroxide, mixing evenly, and drying to obtain a mixture A; S2, dispersing polycarbosilane in solvent B, stirring evenly to obtain a mixed solution B; adding the mixed solution B to the mixture A, mixing evenly, and drying to obtain a mixture B; S3, dispersing γ-methacryloxypropyltrimethoxysilane in solvent C, stirring evenly to obtain a mixed solution C; adding the mixed solution C to mixture B, mixing evenly, and drying to obtain a mixture C; S4. Evenly mix POE and mixture C to obtain a flame retardant.

5. The high-efficiency flame-retardant film according to claim 4, characterized in that: In the above S1, the preparation of modified attapulgite clay comprises the following steps: after high temperature treatment of attapulgite clay, dispersing it in a methanol solution, adding graphene, solvent thermal reaction, washing and drying, to obtain modified attapulgite clay.

6. The high-efficiency flame-retardant film according to claim 4, characterized in that: In the S1, the hydroxide includes one or more of magnesium hydroxide and aluminum hydroxide.

7. The high-efficiency flame-retardant film according to claim 4, characterized in that: The mass ratio of the modified attapulgite clay, hydroxide, polycarbosilane and POE is (1-5):100:(5-10):(15-20).

8. The high-efficiency flame-retardant film according to claim 1, characterized in that: The melt index of the copolymer PP at 230°C and 2.16kg is 4-16g / 10min; the anti-UV agent is selected from one or more of UV-242, UV-284, and UV-531; the anti-aging agent is selected from one or more of antioxidant 1098 and antioxidant 1010; the anti-sticking agent is selected from one or more of silica, talc, zeolite, limestone, erucamide, and oleamide.

9. A production process of a high-efficiency flame-retardant film according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1, mixing the raw materials of the surface layer, the core layer and the inner layer respectively and extruding them together to obtain a melt; S2, the melt is cast into sheets, longitudinally stretched, transversely stretched, rolled up and slit to obtain a high-efficiency flame-retardant film.

10. The production process according to claim 9, characterized in that: In the S1, the extrusion temperature is 230-250°C.

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