阅读说明：本技术 一种防水卷材用pvdf复合tpo耐晒抗老化复合膜及制备方法 (A kind of the waterproof roll sun-proof anti-aging composite membrane of the compound TPO of PVDF and preparation method ) 是由 易向阳 朱文勇 于 2019-08-19 设计创作，主要内容包括：本发明公开了一种防水卷材用PVDF复合TPO耐晒抗老化复合膜及制备方法,复合膜由依次设置的PVDF膜、胶水层、TPO层、粘合胶层和离型层构成,其中：所述PVDF膜的厚度为0.015～0.025mm,宽度为860mm～1920mm；所述胶水层的厚度为0.0003～0.0005mm,宽度为860mm～1920mm；所述TPO层的厚度为2～5mm,宽度为900mm～1100mm；所述粘合胶层的厚度为1～2mm,宽度为1060mm～2120mm；所述离型层的厚度为0.03～0.04mm,宽度为1060mm～2120mm。能直接用于单层屋面方面和金属屋面外露抗紫外耐晒,克服热塑性聚烯烃弹性体(TPO)片材外露抗晒寿命只有5～10年左右,使用寿命延长到25年,满足新的“市政和建筑防水通用规范”要求,维护成本大大降低。(The invention discloses a kind of waterproof roll sun-proof anti-aging composite membranes of the compound TPO of PVDF and preparation method, composite membrane is made of the pvdf membrane, glue layer, TPO that set gradually layer, bonding glue-line and release layer, wherein: the pvdf membrane with a thickness of 0.015~0.025mm, width is 860mm~1920mm；The glue layer with a thickness of 0.0003~0.0005mm, width is 860mm~1920mm；Described TPO layers with a thickness of 2~5mm, width is 900mm~1100mm；The bonding glue-line with a thickness of 1~2mm, width is 1060mm~2120mm；The release layer with a thickness of 0.03~0.04mm, width is 1060mm~2120mm.In terms of single-layer roof can be directly used in and the exposed uvioresistant of metal Roof is sun-proof, thermoplastic polyolefin elastomer (TPO) sheet material exposed anti-solarization service life is overcome there was only 5~10 years or so, service life extends to 25 years, meet new " city have stable political situation buildings waterproof general specification " to require, maintenance cost substantially reduces.)

1. a kind of waterproof roll sun-proof anti-aging composite membrane of the compound TPO of PVDF, which is characterized in that by the PVDF set gradually Film, glue layer, TPO layers, bonding glue-line and release layer are constituted, in which:

The pvdf membrane with a thickness of 0.015~0.025mm, width is 860mm~1920mm；

The glue layer with a thickness of 0.0003~0.0005mm, width is 860mm~1920mm；

Described TPO layers with a thickness of 2~5mm, width is 900mm~1100mm；

The bonding glue-line with a thickness of 1~2mm, width is 1060mm~2120mm；

The release layer with a thickness of 0.03~0.04mm, width is 1060mm~2120mm.

2. a kind of waterproof roll according to claim 1 sun-proof anti-aging composite membrane of the compound TPO of PVDF, feature exist In: the pvdf membrane is by weight ratio PVDF:LDPE:EGMA-g-PMMA: color masterbatch is 100:20~40:5~6:3~5 component system At.

3. a kind of waterproof roll according to claim 1 sun-proof anti-aging composite membrane of the compound TPO of PVDF, feature exist In: the glue layer is the polyurethane glue containing urethano and isocyanate group in strand.

4. a kind of waterproof roll according to claim 1 sun-proof anti-aging composite membrane of the compound TPO of PVDF, feature exist In: the bonding glue-line is modified butyl rubber.

5. a kind of waterproof roll according to claim 1 sun-proof anti-aging composite membrane of the compound TPO of PVDF, feature exist In: the release layer is PET release film or PE release film.

6. a kind of preparation of Claims 1 to 5 described in any item waterproof rolls sun-proof anti-aging composite membrane of the compound TPO of PVDF Method, it is characterised in that: the pvdf membrane raw material is by being put into diameter for raw material PVDF, LDPE, EGMA-g-PMMA and color masterbatchIt is prepared by the parallel double-screw pelletizer that draw ratio is 40:1.

7. a kind of waterproof roll according to claim 6 preparation method of the sun-proof anti-aging composite membrane of the compound TPO of PVDF, It is characterized by: the preparation step of the EGMA-g-PMMA is as follows:

Using PMMA as monomer, 4,4 '-azos (4- cyanopentanoic acid) are initiator, and thioacetic acid is chain-transferring agent, passes through free radical Telomerisation has synthesized PMMA-COOH oligomer, using the PMMA-COOH oligomer as assembling unit, make its with it is linear Epoxy group on polymer EGMA (ethylene-methyl methacrylate glycidyl ester copolymer) main chain is on PVDF and the interface LDPE Ring-opening reaction, in-situ preparation EGMA-g-PMMA graft polymers occurs.

The present invention relates to architectural waterproof material field, in particular to a kind of waterproof roll is sun-proof anti-ageing with the compound TPO of PVDF Change composite membrane and preparation method.

In waterproofing industry, thermoplastic polyolefin-like (TPO) waterproof roll is one kind using polyvinyl resin as base-material, using elder generation Into flaked thermoplastic's rubber based elastic waterproof material made of polymerization technique and special formulation, not plasticizer-containing in ingredient is not deposited Become fragile in the migration of plasticizer, have that tensile strength is big, wear is good, easy processing, can weld, is easy for construction, recycling completely, it is green Colour circle is protected.

TPO material thermoplastic elastomer (TPE), a part of molecule segment of polymer crystallize, and another part segment keeps submissive Property, so that material has the segment of rigidity and elasticity simultaneously, the physical crosslinking structure with thermoplastic elastomer (TPE).Molecular backbone is C~C key, side group C~H key, C~H bond energy protect C~C main chain ability limited.

The substrate of TPO is PE, and ultraviolet light is the principal element for causing PE aging, and its energy is in attack high score Sub- chemical structure leads to most have power in scission of link, chain rupture etc. " photic chemical degradation " effect.According to quantum light theory, 290~ Energy possessed by the ultraviolet light of 400nm range is higher than energy required for various chemical bond ruptures on TPO chain, and extreme ultraviolet light The presence of (200~00nm of wavelength) can also be such that the photooxidation resistance of material becomes apparent.So although TPO has certain resist Ultraviolet ability, anti-ultraviolet ageing ability is limited, exposed weather-proof generally at 5~10 years or so even if increasing ultraviolet-resistant aid, according to New " city have stable political situation buildings waterproof general specification " requires: the roof waterproof time limit is more than 25 years, it is clear that as exposed anti-solarization material, TPO cannot reach exposed and require more than 25 years.

In order to overcome the above-mentioned deficiencies of the prior art, it is sun-proof with the compound TPO of PVDF that the present invention provides a kind of waterproof rolls Anti-aging composite membrane and preparation method.

In order to achieve the above objectives, the technical solution adopted by the present invention to solve the technical problems is: a kind of waterproof roll use The sun-proof anti-aging composite membrane of the compound TPO of PVDF, by the pvdf membrane, glue layer, TPO that set gradually layer, bonding glue-line and release layer It constitutes, in which:

The pvdf membrane with a thickness of 0.015~0.025mm, width is 860mm~1920mm；

The glue layer with a thickness of 0.0003~0.0005mm, width is 860mm~1920mm；

Described TPO layers with a thickness of 2~5mm, width is 900mm~1100mm；

The bonding glue-line with a thickness of 1~2mm, width is 1060mm~2120mm；

The release layer with a thickness of 0.03~0.04mm, width is 1060mm~2120mm.

Preferably, the pvdf membrane is by weight ratio PVDF:LDPE:EGMA-g-PMMA: color masterbatch be 100:20~40:5~ The component of 6:3~5 is made.

Preferably, the glue layer is the polyurethane glue containing urethano and isocyanate group in strand.

Preferably, the bonding glue-line is modified butyl rubber.

Preferably, the release layer is PET release film or PE release film.

A kind of preparation method of the waterproof roll sun-proof anti-aging composite membrane of the compound TPO of PVDF, the pvdf membrane raw material by Raw material PVDF, LDPE, EGMA-g-PMMA and color masterbatch are put into diameterDraw ratio is the parallel double-screw of 40:1 Pelletizer preparation.

Preferably, the preparation step of the EGMA-g-PMMA is as follows:

Using PMMA as monomer, 4,4 '-azos (4- cyanopentanoic acid) are initiator, and thioacetic acid is chain-transferring agent, by certainly PMMA-COOH oligomer has been synthesized by base telomerisation, using the PMMA-COOH oligomer as assembling unit, make its with Epoxy group on line polymer EGMA (ethylene-methyl methacrylate glycidyl ester copolymer) main chain is in PVDF and LDPE circle Ring-opening reaction, in-situ preparation EGMA-g-PMMA graft polymers occur on face.

Due to the application of the above technical scheme, the present invention have compared with prior art it is following the utility model has the advantages that

1. by the Kynoar of high-intensitive, submissive thermoplastic polyolefin elastomer (TPO) sheet material and anti-ultraviolet ageing (PVDF) film is compound by compounding machine, and in terms of capable of being directly used in single-layer roof and the exposed uvioresistant of metal Roof is sun-proof, overcomes Thermoplastic polyolefin elastomer (TPO) sheet material exposed anti-solarization service life only has 5~10 years or so, and service life extends to 25 years, full Foot new " city have stable political situation buildings waterproof general specification " requires, and maintenance cost substantially reduces；

2. the sun-proof film of uvioresistant made of Kynoar (PVDF) composite thermoplastic polyolefin elastomer (TPO) sheet material is done At sheet material effectively reduce room temperature because its Kynoar (PVDF) has it to reflect its sun light action, play energy conservation Environmental-protection function is green product；

3. the sun-proof film of uvioresistant made of Kynoar (PVDF) composite thermoplastic polyolefin elastomer (TPO) sheet material is done At sheet surface self-cleaning it is good, not glue grieshoch, appearance looks elegant.Meet the clean aesthetic in city；

4. the innovation of the invention consists in that manufacture Kynoar (PVDF) film using multilayer blown film by the way of, because blow-up And stretching, having the function of biaxial tension, isotropism enhancing, product mechanical property increases, overcome curtain coating extrusion molding tensionless winkler foundation, The characteristics of poor mechanical property of product；

5. the innovation of the invention consists in that manufacture Kynoar (PVDF) film raw material use blending and modifying method, By material lifetime time limit requirement, fluorine content in PVDF is adjusted；

6. the innovation of the invention consists in that bonding vinylidene (PVDF) film and thermoplastic polyolefin elastomer (TPO) sheet material Glue use ageing-resistant flexible polyurethane glue, glue is free of double bond, and ageing-resistant performance is good, and modified glue toughness increases Add；

7. the present invention uses special overlapping mode, the PVDF efficiently solved is unable to overlap edge hardly possible because that cannot heat Topic；

8. by compound, by the high intensity of thermoplastic polyolefin elastomer (TPO) sheet material and Kynoar (PVDF) Anti- solarization is ageing-resistant to be effectively combined, and two kinds of material properties are complementary to one another, and extend the usage scenario of two kinds of materials；

9. Kynoar (PVDF) composite thermoplastic polyolefin elastomer (TPO) sheet material has high intensity, vertical, horizontal is drawn Stretch Qiang Du≤70Mpa.

Fig. 1 is the structural schematic diagram of the present embodiment；

In figure: 1, pvdf membrane；2, glue layer；3, TPO layers；4, glue-line is bonded；5, release layer.

Specific embodiment

Combined with specific embodiments below, the contents of the present invention are described in further detail:

One embodiment of the invention provides a kind of Kynoar (PVDF) film composite thermoplastic polyolefin elastomer (TPO) piece The sun-proof waterproof sheet of uvioresistant made of material is five-layer structure:

First layer is pvdf membrane 1, and with a thickness of 0.015~0.025mm, width 860mm~1920mm, width ratio TPO is short 200mm.Width is short be PVDF material itself can not sweat soldering, both sides, which are given, stays 100mm to overlap hem width degree, mutual with TPO material Hot melt is so the width of PVDF is less than TPO width 200mm, and the outer layer with width 100mm is PVDF, and internal layer TPO composite membrane is done Overlap edge.PVDF thickness is in 0.015~0.020mm, and TPO thickness is in 2~5mm；

The second layer is glue layer 2, same to take because retaining with a thickness of 0.005~0.010mm, width 860mm~1920mm Edge fit, the short 200mm of width ratio TPO；

Third layer is thermoplastic polyolefin elastomer (TPO) sheet material, with a thickness of 2~5mm, width 1060mm~2120mm；

4th layer is bonding glue-line 4, and bonding glue-line 4 can be the gluey material that modified butyl rubber etc. has bond properties Material, with a thickness of 1~2mm, width 1060mm~2120mm；

Layer 5 is release layer 5, and the material of release layer 5 can be PET release film or PE release film, main to play isolation work With with a thickness of 0.035~0.04mm, width 1060mm~2120mm.

First layer pvdf membrane 1 of the present invention is granulated, with methyl methacrylate (PMMA) with parallel double-screw pelletizer is modified For monomer, 4,4 '-azos (4- cyanopentanoic acid) (ACVA) are initiator, and thioacetic acid (TGA) is chain-transferring agent, pass through free radical Telomerisation has synthesized PMMA-COOH oligomer, and the feed ratio by adjusting monomer, initiator and chain-transferring agent three, It has been prepared that molecular weight is controllable, the PMMA-COOH oligomer of the relatively narrow molecular weight 2000~8000 of molecular weight distribution；

Again using PMMA-COOH oligomer as assembling unit, make itself and line polymer EGMA (ethylene-methyl methacrylate Glycidyl ester copolymer) on PVDF and the interface LDPE ring-opening reaction, in-situ preparation EGMA- occur for the epoxy group on main chain G-PMMA graft polymers.EGMA-g-PMMA can effectively improve the phase between PVDF and LDPE as PVDF and LDPE compatilizer Capacitive reduces the interfacial tension between blend components, enhances the caking property between interface, greatlys improve PVDF/LDPE blending The mechanical property of object.

By weight Kynoar (PVDF): low density polyethylene (LDPE) (LDPE): expanding material EGMA-g-PMMA: color masterbatch= 100:20~40:5~6:3~5, uses diameterDraw ratio (L/D)=40:1 parallel double-screw pelletizer, changes Property be granulated, be constructed to the PVDF modified materials of blown film.

PVDF (Kynoar), molecular formula-(CH2-CF2) n-, because of C-F bond energy 489KJ/mol, structure determines performance, PVDF fluorine element is due to maximum, the atomic radius very little with electronegativity and the C-F bond distance formed is short, bond energy is big, F atom and fluorine-containing Group is difficult to interrupt main chain to main chain design features, the UV energy such as shield, and forms uvioresistant irradiation, gasproof It waits, radiation resistance, the performance characteristics such as resist chemical, stain resistant, waterproof.As thermoplastic polyolefin-like (TPO) waterproof roll Protection materials, PVDF (Kynoar) outer layer protection can be such that the exposed anti-solarization of thermoplastic polyolefin-like (TPO) waterproof roll uses, It is more than 25 years that the roof waterproof time limit, which can be extended,.

With three layers of upper inflation film manufacturing machines blowing monochromatizing or double-colored pvdf membrane 1, double-colored pvdf membrane 1, such as tunica albuginea, black film, black and white film, Blue-black film, green tunica albuginea etc., with LDPE content is adjusted, to adjust PVDF fluorinated volume, to accomplish the anti-solarization film of different years.

The second layer of the present invention is glue layer 2, using polyurethane glue, because containing urethano and isocyanate group in strand Glue, due to contain highly polar isocyanates and carbamate groups, have very high reactivity, being capable of room temperature curing. The backbone flexibility of polyurethane is fine, its biggest characteristic is that tolerance impact endurance test shock and flexural fatigue, peel strength is very high, especially resistance to Cryogenic property is extremely excellent, and glue is free of double bond, and ageing-resistant performance is good, and modified glue toughness increases.

Third layer of the present invention is TPO layer 3, thermoplastic polyolefin elastomer (TPO) sheet material overall thickness 2mm~5mm, with polymerization Type TPO resin is basic raw material, passes through the preparation TPO waterproof roll PP Pipe Compound such as addition fire retardant, lubricant and other auxiliary agents.

Of the invention the 4th layer is bonding glue-line 4, and bonding glue-line 4 can be modified butyl rubber etc. with bond properties Colloidal material.

Layer 5 is release layer 5, and 5 material of release layer can be PET release film or PE release film, mainly play buffer action.

The prior art is compared, and the present embodiment has the advantages that

1. by the Kynoar of high-intensitive, submissive thermoplastic polyolefin elastomer (TPO) sheet material and anti-ultraviolet ageing (PVDF) film is compound by compounding machine, and in terms of capable of being directly used in single-layer roof and the exposed uvioresistant of metal Roof is sun-proof, overcomes Thermoplastic polyolefin elastomer (TPO) sheet material exposed anti-solarization service life only has 5~10 years or so, and service life extends to 25 years, full Foot new " city have stable political situation buildings waterproof general specification " requires, and maintenance cost substantially reduces；

2. the sun-proof film of uvioresistant made of Kynoar (PVDF) composite thermoplastic polyolefin elastomer (TPO) sheet material is done At sheet material effectively reduce room temperature because its Kynoar (PVDF) has it to reflect its sun light action, play energy conservation Environmental-protection function is green product；

3. the sun-proof film of uvioresistant made of Kynoar (PVDF) composite thermoplastic polyolefin elastomer (TPO) sheet material is done At sheet surface self-cleaning it is good, not glue grieshoch, appearance looks elegant.Meet the clean aesthetic in city；

4. the innovation of the invention consists in that manufacture Kynoar (PVDF) film using multilayer blown film by the way of, because blow-up And stretching, having the function of biaxial tension, isotropism enhancing, product mechanical property increases, overcome curtain coating extrusion molding tensionless winkler foundation, The characteristics of poor mechanical property of product；

5. the innovation of the invention consists in that manufacture Kynoar (PVDF) film raw material use blending and modifying method, By material lifetime time limit requirement, fluorine content in PVDF is adjusted；

6. the innovation of the invention consists in that bonding vinylidene (PVDF) film and thermoplastic polyolefin elastomer (TPO) sheet material Glue use ageing-resistant flexible polyurethane glue, glue is free of double bond, and ageing-resistant performance is good, and modified glue toughness increases Add；

7. the present invention uses special overlapping mode, the PVDF efficiently solved is unable to overlap edge hardly possible because that cannot heat Topic；

8. by compound, by the high intensity of thermoplastic polyolefin elastomer (TPO) sheet material and Kynoar (PVDF) Anti- solarization is ageing-resistant to be effectively combined, and two kinds of material properties are complementary to one another, and extend the usage scenario of two kinds of materials；

9. Kynoar (PVDF) composite thermoplastic polyolefin elastomer (TPO) sheet material has high intensity, vertical, horizontal is drawn Stretch Qiang Du≤70Mpa.

The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand the contents of the present invention and be implemented, and it is not intended to limit the scope of the present invention, it is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the scope of protection of the present invention.