CN101412591B - Preparation of PET and PVC composite film for decorating glass - Google Patents

Preparation of PET and PVC composite film for decorating glass Download PDF

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Publication number
CN101412591B
CN101412591B CN200810219178XA CN200810219178A CN101412591B CN 101412591 B CN101412591 B CN 101412591B CN 200810219178X A CN200810219178X A CN 200810219178XA CN 200810219178 A CN200810219178 A CN 200810219178A CN 101412591 B CN101412591 B CN 101412591B
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eva
pet
pvc
film
preparation
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CN101412591A (en
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李连春
唐舫成
汪加胜
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Jiangsu Lushan New Material Co.,Ltd.
Guangzhou Lushan New Materials Co Ltd
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Guangzhou Lushan New Materials Co Ltd
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Abstract

The invention relates to a method for preparing PET and PVC composite film for decorative glass, which is characterized by comprising the following steps: firstly mixing EVA, initiator and GMA evenly according to a 1.0%-2.0% adding dosage, grafting the mixture in double screws at 190 DEG C; after preparing a thickening master batch EVA-g-GMA, mixing the EVA and the EVA-g-GMA according to weight ratio of 90 to 10, casting the mixture on a PET film coated with an adhesion promoter; at the same time of coating the PET film, smoothly placing a PVC film from the back side of a laminating machine to the other side of a glue film to form a PET/PVC composite film; and finally unreeling the PET/PVC composite film for secondary lamination. The EVA/PET/EVA/PVC composite film prepared by the method can change positions of PET and PVC according to requirements, make full use of advantages of the PET, such as good transparency, heat resistance and mechanical performance, low PVC price, and easy printing, and can be used as the film for single-sided decorative glass. The prepared single-sided decorative glass not only has beautiful appearance, but also has good safety performance. The composite film can also be used as the film for decoration of aluminum plates, stainless steel, stones, and the like.

Description

A kind of preparation method who is used for the PET and the PVC composite package of ambetti
Technical field
The present invention relates to the Chemicals manufacture field, particularly a kind of preparation method who is applied to the PET and the PVC composite package of ambetti.
Background technology
The structure of common single face chilled glass is glass/glued membrane/PVC or PP, and wherein glued membrane is used the EVA glued membrane usually, on PVC or PP the printing various patterns, through hot pressing with three's composite molding.This method has more shortcoming, and one, the common easy flavescence of EVA glued membrane, influence attractive in appearance; Two, PVC or PP thermotolerance are relatively poor, and the phenomenon that when multiple glazing hot pressing simultaneously, sticks together between PVC or PP paper and other glass produces waste product; Three, for the good occasion of decorating film reflecting effect, this structure can't realize; It is on glass to want elder generation that the EVA glued membrane is put in when four, preparing, and puts decorating film again, complicated operation.
In order to deal with problems one, there is producer to attempt preparation anti-yellowing property EVA glued membrane preferably, but relatively poor with the bonding force of PVC/PP; In order to deal with problems two, there is the people once to do barrier film manufacture order surface strengthening glass with PET, but troublesome poeration; In order to prepare reflecting effect ambetti preferably, there is the people once to make the decoration notacoria with the PET that prints, not only cost is higher, and the PET elongation at break is lower, and safe effect is relatively poor.
Summary of the invention
The objective of the invention is to overcome above-mentioned various deficiencies of the prior art, put forward the preparation method that a kind of supply is used for the PET and the PVC composite package of ambetti, self-adhesion not under this composite package coated face normal temperature; Prepared single face chilled glass not only transmittance is good; Non-yellowing, bonding with PVC, PET, and can select bonding plane according to demand; When requiring reflecting effect better, selecting PET is bonding plane, and selecting PVC under other occasion is bonding plane.
In order to achieve the above object; The present invention adopts following technical scheme to solve, and the preparation method of its composite decoration glued membrane is: EVA, initiator, GMA are mixed 190 ℃ of following grafting in twin screw by the 1.0%-2.0% addition earlier; After tackify masterbatch EVA-g-GMA prepared; By 90: 10 weight ratios with EVA and EVA-g-GMA blend and curtain coating on the PET film that scribbles adhesion promotor, PET film gummed is put into the PVC film from the rear side that drenches the film machine opposite side of glued membrane simultaneously reposefully; Form the PET/PVC composite package, the PET/PVC composite package is unreeled carry out secondary pouring film at last.
Above-mentioned preparation method, described PET and PVC composite package are four-layer structure: EVA/PET/EVA/PVC or EVA/PVC/EVA/PET.
Above-mentioned preparation method, described pet sheet face is coated with one deck adhesion promotor.
Above-mentioned preparation method, described adhesion promotor can be chosen any one kind of them or several kinds from following reagent: rosin, X 050, organic silicon rigidity-increasing stick, acrylate.
Above-mentioned preparation method, the EVA glued membrane that is coated on PET or PVC surface is the mixture of EVA 90 weight parts and EVA-g-GMA10 weight part formation.
Above-mentioned preparation method, said EVA-g-GMA are the EVA graft glycidyl methacrylate.
Above-mentioned preparation method, used EVA VA content is 20-40%, and melting index is 5-30%, and preferred VA content is 20-30%, and melting index is 5-20g/10min.
Above-mentioned preparation method, the EVA-g-GMA preparation is carried out in twin screw extruder, and temperature of reaction is 160-210 ℃.
Above-mentioned preparation method, the used initiator of said EVA graft glycidyl methacrylate is 2,5-dimethyl--(peroxo--2; The 5-di-t-butyl) hexane, Di Cumyl Peroxide 99,1; Wherein a kind of of 1-two (t-butylperoxy) 3,3,5-trimethyl-cyclohexane; Consumption is 0.02-0.1%, is preferably 0.02%-0.08%.
Above-mentioned preparation method, the amount of the used GMA of said EVA graft glycidyl methacrylate is 0.8-2.0%, is preferably 1.0%-2.0%.
The composite decoration glued membrane that the present invention processes through above-mentioned preparation method, coated face be self-adhesion not at normal temperatures, and prepared single face chilled glass is to decorate and security a kind of the collection, and the ambetti of good application prospect is arranged.It not only can protect the person and property safety, but also keeps the attractive in appearance transparent of glass, can select the pattern of decorating film simultaneously according to hobby, has application surface very widely.Be widely used at refrigerator and various appliance panel, wardrobe door, indoor various compartments in recent years.And can select bonding plane according to demand, when requiring reflecting effect better, selecting PET is bonding plane, and selecting PVC under other occasion is bonding plane.
Embodiment
Embodiment 1
The preparation of composite decoration glued membrane:
With a kind of VA content is 28%; Melting index is the EVA (model: EVAFLEX260) of 6.0g/10min; 0.02 part of Di Cumyl Peroxide 99 (DCP); SY-Monomer G (GMA) cooperates for 1.0 parts together, and the mixture that is obtained through 190 ℃ of twin screw extruder extruding pelletizations, is prepared into tackify masterbatch (EVA-g-GMA).
EVA-g-GMA prepare the back by 90: 10 (weight ratio) with EVA (EVAFLEX260) and EVA-g-GMA blend and curtain coating (adhesion promotor employing rosin) on the PET film that scribbles adhesion promotor; PET film gummed is simultaneously put into the opposite side of glued membrane with the PVC film from the rear side that drenches the film machine reposefully, forms the PET/EVA/PVC composite package; At last the PET/EVA/PVC composite package is unreeled, and the PVC face is carried out secondary pouring film.
EVA Choice of Resin VA content is 20-40%, and melting index is 5-30g/10min; More preferably VA content is 20-30%, and melting index is 5-20g/10min.VA content is high more, and toughness is good more, and the transparency is good more, but mechanical property is poor more; Melting index is related to the thickness of intermediate coat behind degassing performance and the lamination.MI is big more, and processing characteristics is good more; But in screw rod the residence time short more, graft effect is poor more; Degassing performance is better, but the reduction of the viscosity of the intermediate coat that obtains, thereby make the intermediate coat behind the lamination ooze out from the edge section, the thickness of intermediate coat reduces, and the impact resistance of glass descends.
Initiator is selected the higher kind of efficiency of initiation, as 2, and the two isovaleronitriles of 2 '-azo, 2,2 '-Diisopropyl azodicarboxylate, 2-tertiary butyl azo-2-cyanogen-pentane, 2-tertiary butyl azo-isobutyronitrile.Superoxide can be from following selection: 2, and 5-dimethyl--(peroxo--2,5-di-t-butyl) hexane, Di Cumyl Peroxide 99, Lucidol, 1,1-two (t-butylperoxy) 3,3,5-trimethyl-cyclohexane, cyclohexanone peroxide, methylethyl ketone peroxide.Preferably: 2,5-dimethyl--(peroxo--2,5-di-t-butyl) hexane, Di Cumyl Peroxide 99,1,1-two (t-butylperoxy) 3,3,5-trimethyl-cyclohexane.Content is preferably 0.02-0.1%, and more preferably 0.02%-0.08%.Content is few more, and the radical of generation is few more, and graft effect is poor more; Content is big more, and graft effect is big more, but may produce gel, and influence is produced.
The content of GMA is preferably 0.8-2.0%, and more preferably 1.0%-2.0%.Content is more little, and it is just more little that radical collides the monomer probability that it grafting is successful, influences graft effect; Content is big more, and graft effect is good more, but the degree of GMA autohemagglutination is big more.
The preparation of single face chilled glass:
With composite decoration glued membrane surface with glue (PVC face) and glass gluing, will cement all around with scotch tape, obtain molectron.Prepare 2 molectrons; Fold by glass/compound cutan/glass/compound cutan and to put into rubber bag; The degassing is 5 minutes under 0.1Mpa vacuum tightness, under keeping this degassing phase, it is moved in the baking oven, rises to 110 ℃ from room temperature and keeps 30 minutes down; Make glass and composite decoration glued membrane bonding, be prepared into the single face chilled glass.
Embodiment 2
Except (model: (model: EVAFLEX220) other all prepare composite decoration glued membrane and single face chilled glass by embodiment 1 same method EVAFLEX260) to change EVA into the EVA among the embodiment 1.
Embodiment 3
Other all prepare composite decoration glued membrane and single face chilled glass by embodiment 1 same method except the DCP among the embodiment 1 being changed to BPO (Lucidol).
Embodiment 4
Except the masterbatch preparation temperature among the embodiment 1 is changed into 170 ℃ by 190 ℃, other all prepare composite decoration glued membrane and single face chilled glass by embodiment 1 same method.
Embodiment 5
Change the PET face into except secondary among the embodiment 1 is drenched face, and will change into outside the PET face with the glass gluing face, other all prepare composite decoration glued membrane and single face chilled glass by embodiment 1 same method.
The single face chilled glass and the bounding force test sample that are obtained embodiment 1-5 carry out following experiment, and its result is shown in table 1.
1) detection of bonding strength
The single face chilled glass that is prepared into is cut into wide 2.5cm, and long 10cm's is rectangular as sample.Carry out 180 ° with a tension testing machine then and peel off experiment.Speed is 50cm/min.
2) prolonged preservation property
To decorate composite package 40 ℃ of held of temperature 40 days, then according to measuring the stripping strength that this decorates composite package with the same method of above-mentioned bonding strength testing experiment.
3) aging resistance
Prepare laminated glass appearance (glass/EVA glued membrane/glass) with the EVA glued membrane and carry out xenon lamp aging experiment 3000h, the variation of test yellowness index.
Whether stick together when 4) producing situation and outward appearance
Table 1 (performance of single face chilled glass)
The EVA/PET/EVA/PVC composite package that the inventive method provides can change the position of PET and PVC as required, and it is good and the PVC price is low, be prone to the advantage of printing to make full use of the transparency, thermotolerance, the mechanical property of PET, can be used as the single face ambetti and uses film.Not only outward appearance is beautiful for prepared single face ambetti, and has good safety performance; Above-mentioned composite package also can be used as decorations such as aluminium sheet, stainless steel, stone material and uses film.Its preparation method and principle are identical, and performance is similar, do not enumerate one by one at this.

Claims (9)

1. preparation method who is applied to the PET and the PVC composite package of ambetti; It is characterized in that: earlier EVA, initiator, GMA are mixed by the 1.0%-2.0% addition; 190 ℃ of following grafting in twin screw, after tackify masterbatch EVA-g-GMA prepared, by 90: 10 weight ratios with EVA and EVA-g-GMA blend and curtain coating on the PET film that scribbles adhesion promotor; PET film gummed simultaneously; The PVC film is put into the opposite side of glued membrane reposefully from the rear side that drenches the film machine, form the PET/PVC composite package, at last the PET/PVC composite package is unreeled and carry out secondary and drench film.
2. preparation method according to claim 1 is characterized in that: described PET and PVC composite package are four-layer structure: EVA/PET/EVA/PVC or EVA/PVC/EVA/PET.
3. preparation method according to claim 1 is characterized in that: described pet sheet face is coated with one deck adhesion promotor.
4. preparation method according to claim 3 is characterized in that: described adhesion promotor is chosen any one kind of them or several kinds from following reagent: rosin, X 050, organic silicon rigidity-increasing stick, acrylate.
5. preparation method according to claim 1 is characterized in that: the EVA glued membrane that is coated on PET or PVC surface is the mixture of EVA 90 weight parts and EVA-g-GMA10 weight part formation.
6. preparation method according to claim 5 is characterized in that: said EVA-g-GMA is the EVA graft glycidyl methacrylate.
7. preparation method according to claim 1 is characterized in that: used EVA VA content is 20-40%, and melting index is 5-30%, and preferred VA content is 20-30%, and melting index is 5-20g/10min.
8. preparation method according to claim 6 is characterized in that: the used initiator of said EVA graft glycidyl methacrylate is 2,5-dimethyl--(peroxo--2; The 5-di-t-butyl) hexane, Di Cumyl Peroxide 99,1; Wherein a kind of of 1-two (t-butylperoxy) 3,3,5-trimethyl-cyclohexane; Consumption is 0.02-0.1%, is preferably 0.02%-0.08%.
9. preparation method according to claim 6 is characterized in that: the amount of the used GMA of said EVA graft glycidyl methacrylate is 0.8-2.0%, is preferably 1.0%-2.0%.
CN200810219178XA 2008-11-18 2008-11-18 Preparation of PET and PVC composite film for decorating glass Active CN101412591B (en)

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CN101412591B true CN101412591B (en) 2012-03-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086955A (en) * 2014-06-27 2014-10-08 绿宝电缆(集团)有限公司 Oil-resistant and temperature-resistant PET cable sheath material with low cost

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GB0915687D0 (en) 2009-09-08 2009-10-07 Dupont Teijin Films Us Ltd Polyester films
GB2488787A (en) 2011-03-07 2012-09-12 Dupont Teijin Films Us Ltd Stabilised polyester films
GB201310837D0 (en) 2013-06-18 2013-07-31 Dupont Teijin Films Us Ltd Polyester film -IV
GB201317551D0 (en) 2013-10-03 2013-11-20 Dupont Teijin Films Us Ltd Co-extruded polyester films
CN105482548B (en) * 2015-12-28 2019-01-04 广东天元汇邦新材料股份有限公司 A kind of environment-friendly PVC decorating film and preparation method thereof
BR112019001676A2 (en) 2016-07-29 2019-05-14 3M Innovative Properties Company multilayer films and adhesive tapes
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CN109628003A (en) * 2018-08-08 2019-04-16 常州斯威克光伏新材料有限公司 A kind of molding furniture PVC compoiste adhering film and preparation method thereof
CN114121342B (en) * 2021-11-29 2024-02-09 安徽电气集团股份有限公司 Torsion-resistant flexible cable for wind power generation

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CN1157946A (en) * 1996-02-01 1997-08-27 陈慎僖 Manufacturing method for combination of laser full-picture film with glass and product
CN1654201A (en) * 2005-01-19 2005-08-17 王欣南 PET-PVC composite reinforced glass slab
WO2006064117A1 (en) * 2004-12-16 2006-06-22 Arkema France Adhesive composition based on ethylene copolymers, useful for extrusion-coating and extrusion-lamination on a variety of supports

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1157946A (en) * 1996-02-01 1997-08-27 陈慎僖 Manufacturing method for combination of laser full-picture film with glass and product
WO2006064117A1 (en) * 2004-12-16 2006-06-22 Arkema France Adhesive composition based on ethylene copolymers, useful for extrusion-coating and extrusion-lamination on a variety of supports
CN1654201A (en) * 2005-01-19 2005-08-17 王欣南 PET-PVC composite reinforced glass slab

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086955A (en) * 2014-06-27 2014-10-08 绿宝电缆(集团)有限公司 Oil-resistant and temperature-resistant PET cable sheath material with low cost
CN104086955B (en) * 2014-06-27 2015-12-30 绿宝电缆(集团)有限公司 A kind of low cost oil resistant heatproof PET cable jacket material

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Effective date of registration: 20201105

Address after: 510530 No. 22 Pubei Road, Yunpu Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province, 1 building, 2 building, 3 building and 4 Building

Patentee after: GUANGZHOU LUSHAN NEW MATERIALS Co.,Ltd.

Patentee after: Jiangsu Lushan New Material Co.,Ltd.

Address before: 303, room 2, building 22, 510530 Pu Po Road North, Guangzhou, Whampoa, Guangdong

Patentee before: GUANGZHOU LUSHAN NEW MATERIALS Co.,Ltd.