RU2039661C1 - Decorating laminate material - Google Patents

Abstract

FIELD: decorating laminate material production. SUBSTANCE: laminate material has main layer of thermoplastic resin, fibre reinforced layer of thermoreactive resin and binding layer of thermoplastic resin with melting temperature below melting temperature of main thermoplastic resin. It also has intermediate layer of laminate material, decorating and protecting layers. In the case, one side of intermediate layer is saturated with main thermoplastic resin and its other side with thermoplastic resin of binding layer, between them there is laminate material interlayer not saturated with thermoplastic resins. As interlayer they use textile materials in the form of fabrics, rugs, strips, stockinet sheets or paper of glass, organic or mineral fibres. Decorating layer is also made of laminate materials, based on glass or organic fibres. It is made of two interlayers: first one is saturated with thermoplastic resin of binding layer and second one is saturated with resin of protective layer. Main layer is made of structural thermoplasts with lowered inflammability: self-extinguishing polycarbonate, polysulfone, etc. Protective layer is made of transparent water-resistant thermoplasts also with lowered inflammability and smoke formation: polyvinylidenefluoride, other melting fluoroplastic. Decorating laminate material has following ratio of layers (by thickness), mm: main thermoplastic layer 0.01 2.0; fibre reinforced thermoreactive layer 0.03 1.0; interlayer 0.025 0.2; binding layer 0.02 0.2; decorating layer 0.05 0.7; protective layer 0.04 0.3. EFFECT: decorating laminate material is used in production of laminate decorating layer with lowered inflammability and smoke formation. 2 cl, 1 tbl

Description

 The invention relates to polymer layered materials for decorative purposes and can be used for the manufacture of interior passenger transport in the aviation, automotive, shipbuilding and other industries.

Known sheet polymeric materials for decorative purposes such as polystyrene and polyvinyl chloride plastics [1]
These materials have good decorative properties, but low strength (σ _in. , 4-7 kgf / mm ² ) and significant smoke emission. Currently, they do not comply with the airworthiness standards of civil aircraft.

The sheet decorative decorative paper-layered plastic DBSP [2], which has a higher strength (σ _century , 12-14 kgf / mm ² ) and meets the uniform airworthiness standards for combustibility and smoke formation, is also widely known. However, this material is produced with a thickness of at least 1.6 mm, which does not allow it to be used for the manufacture of thin (0.2-0.5 mm) skins of three-layer honeycomb panels, which are currently used as the main structural element of the interior of modern passenger aircraft.

 Also known is the phenolic fiberglass sheet KAST-VS [3] which is widely used for the manufacture of skin of three-layer honeycomb panels in aircraft cabins. This material has high strength properties, meets the standards of airworthiness for combustibility and smoke formation, but does not have decorative properties. In this case, for decorative decoration, a polyvinyl chloride film of the PDOAZ-25 brand (TU 400-1-114-77) is used, glued onto the finished panels manually with toxic polyurethane adhesives VK-11 and VK-45.

 Thus, such skins have a significant smoke emission and cannot be used on modern passenger aircraft.

 The closest known technical solutions is a layered material, which contains a layer of thermoplastic resin, a layer of thermosetting resin, fiber reinforced resin and an intermediate layer of thermoplastic having a melting point lower than the melting temperature of the main thermoplastic layer. The intermediate layer is designed for bonding the main and cured thermosetting layer [4] This material has high strength, stiffness, impact resistance and can be processed into products of single curvature by vacuum molding. It is intended for the manufacture of various structural parts of water pipes, fan blades, corrugated panels and other products.

 However, this material does not have decorative properties and belongs to the category of fire hazardous materials, since it is based on combustible and highly fuming thermoplastics polyethylene, polypropylene, polyamide, etc. The increased fire hazard and lack of decorative properties make it difficult to use this material for the manufacture of interior parts for passenger aircraft, river, sea, rail transport and other objects.

 The aim of the invention is to reduce flammability and smoke.

 The goal is achieved in that the layered material containing a thermoplastic resin base layer and a fiber reinforced thermosetting resin layer using a thermoplastic resin layer with a melting point below the melting temperature of the thermoplastic core further comprises a layer of fibrous material impregnated on one side with a thermoplastic base layer, and on the other hand, thermoplastic with a melting point lower than the melting temperature of the main thermoplastic layer, decorative and protective layers with the following ratio of material layers by thickness, mm: Main thermoplastic layer 0.01-2.0 Fiber-reinforced thermosetting layer 0.03-1.0 Layer of fibrous material (intermediate layer) 0.025-0 , 2 A layer of thermoplastic resin with a melting point lower than the melting temperature of the main thermoplastic layer (adhesive layer) 0.02-0.2 Decorative layer 0.05-0.7 Protective layer 0.04-0.3 As an intermediate layer using fabrics, paper and other fibrous materials from glass, mineral or organic fibers .

 The decorative layer is also made of fibrous material based on glass or organic fibers. It consists of two layers: the 1st layer is impregnated with a thermoplastic resin bonding layer; The 2nd layer is impregnated with a thermoplastic protective layer.

 For the protective layer, waterproof transparent thermoplastics with reduced flammability of polyvinylidene fluoride, fluoroplast 32, etc. are used.

 For the main layer, structural thermoplastics are used: self-extinguishing polycarbonate, polysulfone, etc.

Decorative laminate is made as follows. They impregnate fibrous material, for example, CBM fabric from high-strength aramid fiber, with a 15% solution in acetone of the reaction product of ED-20 epoxy resin and polyisocyanate taken in a 1: 1 ratio. The treated fabric is dried until solvent is removed. Then collect the bag, layer by layer alternating a film of self-extinguishing polycarbonate and treated tissue CBM. An intermediate layer of fiberglass E2-62 is laid on the top layer of a polycarbonate film. The assembled package is placed in a press heated ^to 200 ° C, held for 30 minutes under a pressure of 5-15 kgf / cm ^2, and cooled to room temperature.

Then, a 0.04 mm thick polyethylene film is laid on the obtained laminated preform from the side of E2-62 fiberglass fabric, covered with Agat decorative lavsan fabric, and an F-2M protective film of polyvinylidene fluoride is laid on a decorative fabric. Again, put the bag in a press heated to 170 ^about C, incubated for 10-15 minutes under a pressure of 5-15 kg / cm ² and cooled to room temperature.

 The ratio of the layers of decorative material in thickness can vary widely depending on the purpose.

 When performing the examples, the following materials were used.

 1. A film of self-extinguishing polycarbonate (PC) TU 6-19-151-271-86.

2. The film of polysulfone (PSN) TU 6-19-151-285-88
3. Film F-2M TU 6-05-041-615-82
4. Film from polyamide-12 (PA-12) TU 1-596-38-86
5. Film from polyethylene (PE) GOST 10354-82
6. Ftoroplast-32 (F-32) TU 6-05-05-161-84
7. Ftoroplast-42 (F-42) GOST 25428-82
8. Fiberglass T-15P-76 TU 6-11-491-79
9. Fiberglass T10-80 GOST 19170-73
10. Fiberglass E2-62 GOST 19907-83
11. Fiberglass E1-25 GOST 19907-83
12. Carbon tape ELUR 0.08P TU 6-06-N 119-85
13. Fiberglass EZ-100 GOST 19907-83
14. Fiberglass EZ-200 GOST 19907-83
15. Phenylone paper TU OP13-7310005-18-83
16. Lavsan fabric "Agate" TO 17/62 RSFSR 958-87 to GOST 14938-79
17. Resin ED-20 GOST 10587-84
18. Polyisocyanate TU 6-84-585-75
19. Phenolic resin SF 341A GOST 18694-80
20. Melamine-formaldehyde resin MS-P100-S TU 6-05-1867-79
21. Fabric SVM TU 17 RSFSR 62-9575-80
Example 1. The CBM fabric of high strength aramid fiber is treated with a 15% solution of ED-20 resin and polyisocyanate in acetone taken in a 1: 1 ratio. They are dried in air until the solvent is removed. Then collect the bag, layer-by-layer laying on a metal strip with a separation layer a film of self-extinguishing polycarbonate 0.05 mm thick, a layer of treated CBM fabric, a film of self-extinguishing polycarbonate (PC), an intermediate layer of fiberglass E2-62. The package is closed with a second metal gasket separating layer is placed in a press heated ^to 200 ° C, is kept under a pressure of 15 kg / cm ^2, and cooled to room temperature.

On the resulting laminate preform is placed an adhesive layer of a PE film (mp. 107 ° ^C) 0.04 mm thick, it is placed a decorative fabric mylar "agate" 0.2 mm thick multi-color print pattern that is impregnated with a solution of F-32 ethyl acetate.

The assembled stack is placed between two metal strips with separation layers, laying in a press heated to ¹³⁰ ° C, compressed under a pressure of 5 kg / cm ^2, and cooled to room temperature.

The ratio of the layers of the obtained material is as follows, mm: Main thermoplastic layer 0.05 Fiber-reinforced thermosetting layer 0.16 Intermediate layer 0.06 Adhesive layer 0.04 Decorative layer 0.2 Protective layer 0.05
Material properties are given in the table.

PRI me R 2. One layer of fiberglass E1-25 is treated with a 10% solution of resin ED-20 in acetone and dried in air until the solvent is removed. Collect package stacking layers on a metal gasket with a separating layer materials in the following sequence: SPE (m.p. 215 ^{° C.)} The film layer, a layer treated fiberglass E1-25; PSN film layer; E1-25 raw fiberglass layer. The assembled package is placed in a press and compressed at 260 ^C under a pressure of 10 kg / cm ² for 15 min. Then, the resulting laminated preform is cooled to room temperature. Powder F-32 (T _pl. 105 ^о С) is applied in an even layer to the workpiece from the raw E1-25 fiberglass fabric, E2-62 fiberglass with a printed pattern is laid on it and closed with a transparent colorless PC film 0.04 mm thick. The package is laid between two metal gaskets with a separation layer, placed in a press heated to 170 ^° C and held under pressure of 15 kg / cm ^{2 for} 10 minutes. Then cooled to room temperature.

The ratio of the layers of the obtained material is the following, mm: Main thermoplastic layer 0.01 Fiber-reinforced thermosetting layer 0.03 Intermediate layer 0.025 Adhesive layer 0.02 Decorative layer 0.06 Protective layer 0.04
Material properties are given in the table.

PRI me R 3. One layer of fiberglass T10-80 is treated with a 10% solution of phenolic resin SF-341A, dried in air until the solvent is removed. In the metal gasket with a separating layer is applied uniformly powder F-42 _(mp. 160 ° ^C), it is placed on fiberglass cloth T10-80 treated with phenolic resin glass cloth to be uniformly applied powder F-42 and covered with fiberglass T15P-76. The package is covered with the second metal pad separating layer preform is placed in a press and compressed at ¹⁸⁰ ° C under a pressure of 10 kg / cm ² for 30 minutes, then cooled to room temperature. A PE film is placed on the obtained preform of the laminated material from the T15P-76 fiberglass fabric, covered with decorative phenylone paper, and F-32 powder is applied on the surface of the paper with an even layer. The assembled stack is placed between two metal strips with separation layers, laying in a press and compressed under a pressure of 5 kg / cm ² at 130 ^{° C} for 10 min. The material is cooled to room temperature.

The ratio of the layers of the obtained material is the following, mm: Main thermoplastic layer 0.15 Fiber-reinforced thermosetting layer 0.3 Intermediate layer 0.2 Bonding layer 0.12 Decorative layer 0.05 Protective layer 0.04
Material properties are given in the table.

PRI me R 4. 5 layers of carbon tape ELUR 0.08P treated in a 5% solution of polysulfone in methylene chloride. Air dried for at least 30 min, then in an oven at 80 ° ^C for 20 minutes. On a metal gasket with a separation layer is laid, layer by layer alternating, a PSN film 0.04 mm thick and a treated carbon tape. On the upper layer of the PSN film, lay the EZ-100 fiberglass. The package is covered with the second metal pad with a separating layer in the lay press and compressed at 270 ^C under a pressure of 10 kg / cm ² for 30 minutes. Then cooled to room temperature. A 0.05 mm thick PA-12 film is placed on the obtained laminate preform from the fiberglass fabric, an EZ-200 fiberglass with a printed pattern is placed on it, and closed with a 0.1 mm thick F-2M protective film. The package was placed between two metal strips with a separating layer in the lay press and compressed under a pressure of 5 kg / cm ² at ¹⁸⁰ ° C for 20 min. Then cooled to room temperature. The ratio of the layers of the obtained material is the following, mm: Main thermoplastic layer 0.04 Fiber-reinforced thermosetting layer 0.085 Intermediate layer 0.1 Bonding layer 0.05 Decorative layer 0.1 Protective layer 0.1
Material properties are given in the table.

EXAMPLE EXAMPLE 5 One layer of fiberglass TZT-78 treated with 10% solution of melamine formaldehyde resin P100-MS-S, air dried 60 minutes, then in an oven at ¹²⁰ ° C for 20 minutes. Collect the bag, laying on a metal strip with a separation layer of 20 layers of PC film, put one layer of treated TZT-78 fiberglass on the top layer of the PC film, lay 20 layers of PC film on it again, put 0.1 mm thick phenylon paper on the top layer of the film . The package is covered with the second metal pad separating layer is placed in a press and compressed ^at 210 C under a pressure of 10 kg / cm ² for 30 minutes, then cooled to room temperature. Two layers of polyethylene film 0.1 mm thick are laid on the obtained blank from the side of phenylone paper, covered with TP-0.7 fiberglass from roving with embossed weave and powder f-32 is applied to the fiberglass surface with an even layer. The package was placed between the metallic spacers with a separating layer in the lay press and compressed at 130 ^C under a pressure of 5 kg / cm ² for 40 minutes.

 Then cooled to room temperature.

The ratio of the material layers is as follows, mm: Main thermoplastic layer 2.0 Fiber-reinforced thermosetting layer 1.0 Intermediate layer 0.1 Bonding layer 0.2 Decorative layer 0.7 Protective layer 0.3
The properties are shown in the table.

Thus, the introduction into the layered material of the decorative and protective layers, as well as the intermediate layer containing in the middle a layer not impregnated with resins, allows to obtain a material with good decorative properties. Fireproof material properties are provided by a combination of combustible and non-combustible components. Without the introduction of an intermediate layer by directly connecting the layered preform to the decorative layer through the bonding layer, it is not possible to obtain a material with good decorative properties. This is because the color of the laminate blank has a strong influence on the decorative properties. When using a blank based on CBM fabric having a brown color, the printed pattern of the decorative layer acquires a dirty tan. If the preform is used based on carbon fibers, the material becomes almost black. Even fiberglass fabrics that are white in the initial state, after processing with thermosetting resins, acquire a yellowish or other shade, which significantly changes the color of the decorative layer, especially with pastel gray-blue tones of the printed pattern. The combination of thermoplastics with glass and other fabrics without first impregnating the latter with solutions of thermosetting resins impairs the rigidity and interlayer strength of the material. In addition, pre-impregnation of the reinforcing fabrics reduces the manufacturing layered preform temperature in some cases at 20-40 ^{° C,} as there is no need for deep impregnation thermoplastic melt fibers. The connection of the main thermoplastic layer with a fiber reinforced thermosetting layer occurs during the pressing process due to the good adhesive interaction of the thermoplastic melt and the thermosetting resin.

 From the table it follows that the proposed material has significantly less combustibility and smoke formation compared with the known and has good decorative properties. In addition, the replacement of the PDOAZ-25 brand PVC film, which is currently the main material for the interior decoration of passenger airplanes, with decorative fabrics made of glass or organic fibers, can reduce the complexity of manufacturing interior parts, reduce the toxicity of the process and increase the production culture. It should also be noted that when the PDOAZ-25 film is glued to the interior panels manually, defects of non-sticking, swelling, bubbles, and peeling of the film often occur. Therefore, the molding of the decorative layer to plastic provides a smooth, even surface with excellent decorative qualities.

Claims (1)

1. A DECORATIVE LAYERED MATERIAL containing a base layer of thermoplastic resin and a fiber reinforced layer of thermosetting resin using a layer of thermoplastic resin with a melting point lower than the melting temperature of the main thermoplastic layer, characterized in that it further comprises a layer of fibrous material impregnated on the one hand, thermoplastics of the base layer, and on the other hand, thermoplastics with a melting point lower than the melting temperature of the main thermoplastic layer, deco ativnost and protective layers with the following ratio of layer thickness, mm:
Main thermoplastic layer 0.01 2.0
Fiber-reinforced thermosetting layer 0.03 1.0
Layer of fibrous material 0.025 0.2
Layer of thermoplastic resin with a melting point n
lower than the melting temperature of the main thermoplastic
layer 0.02 0.2
Decorative layer 0.05 0.7
Protective layer 0.04 0.3
2. The material according to claim 1, characterized in that the protective layer is made of a polymer with reduced flammability and moisture permeability.

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