new process for producing an extrusion laminated film without any chemical primer - non anchor coating extrusion laminating process.
Linear low density polyethylene (LLDPE)
Widely used in various packaging and extrusion lamination applications.
Low density polyethylene is usually molten during extrusion lamination
Extrusion and lamination on the adhesive surface of the substrate, which is pre-
Coated with a chemical primer to promote the adhesion between the base film and low density polyethylene (
Anchor coating treatment).
An example of this process is shown in the figure. 1.
Anchor coating treatment creates many problems, such as when a chemical primer is dried by evaporation of an organic solvent, the organic solvent harmful to humans is scattered into the air, thus causing environmental hazards in and around the workplace adds an additional step in the process of increasing production costs.
Various surface treatment methods for melting poly-
Olefin nets and substrate films were prepared using methods such as Corona, ozone, plasma, etc.
Well known (1-7). Briggs et al. (8)
The results show that the ozone treatment of moltenPE web introduces a large amount of oxidation of PE and increases the adhesion to aluminum foil. Inagaki (9)
Describes the hydrogen atom of non-fatty polyamide (PA6)
, Is mainly extracted from aliphaticcarbons by electron and oxygen atoms to form-C-O-
Treatment Group by oxygen plasma.
However, these surface treatment methods do not promote adhesive properties and anchor coating treatment.
In many applications, the bonding properties of the laminate at the boiling temperature of the water are particularly important.
In this paper, we propose a new extrusion process (
Extrusion lamination process)
Used to produce laminated film without any chemical primer.
The process includes ozone treatment of molten low density polyethylene mesh and Corona treatment of PA film.
LLDPE laminated film prepared using this method has similar properties as low density polyethylene laminated film.
FT-studied the bonding mechanism of this new technology
Extraction methods for IR, ESCA, and reactive PA.
The experimental low density polyethylene used in this study is Sumikathane L716-H (
Melt flow rate: 7g/10min at 190 [TIME]degrees]C)
Produced by Sumitomo Chemical. , Ltd.
Two-way stretch nylon film (ONy)
This study is EmblemON-RT (thickness: 15 [[micro]meter])
Produced by Unitika Co. , Ltd.
The anchor coating agent is titabond t-120/T-300 system(Polyurethane system)
Produced by Japanese soda company. , Ltd.
The chemicals used are 2,2, 2-
Trifluoride ethanol (TFE)
, Trifluoride (TFAA)andn-
Heptaane is the analytical grade produced by Wako Pure Chemical Industry Co. , Ltd. We used the co-
Extrusion press produced by Sumitomo Heavy Industry Co. , Ltd.
There are two extrusion presses (
Screw diameter: 65mm, L/D: 32).
The laminating machine is equipped with an ozone shower device (NewSolvex -
1 manufactured by Softal Japan Limited)
And the corona unit (
P1100 system produced by pillar Co. , Ltd).
The temperature of the resin is 280-315[degrees]
C into a molten Net (
Width: 500mm, thickness: 30-70[[micro]meter]).
Line speed is 80-
100 m/min, air container area (
Ozone content: 15-40 g/[m. sup. 3])
Is blown on the surface of the ololten web.
Then, the molten network is laminated through-line (
Density of Corona treatment: 0-103W/[m. sup. 2]/min).
Schematic diagram of non-anchor coating extrusion lamination process model flow as shown in Fig. 2.
Under stirring conditions, unreacted nylon 6 was extracted at room temperature with tfe.
After drying under vacuum, residues of ONy/LDPE laminated film were analyzed with ESCA and FT-IR.
Study on the energy spectrum of electronic scalabmk-
II manufactured by FI surface science Systems Co. , Ltd. The X-
X-ray source is MgK [Alpha](1254 eV).
The indoor pressure of the splitter is 7 x [10. sup. -7]Pa. The take-
The departure angle of photoelectric is 75 [degrees].
Ratio of existing oxygen or nitrogen to carbon atoms (O/C or N/C)
Determined by the product of the relative sensitivity to [from the peak intensity region]O. sub. 1S]or [N. sub. 1S]and thatfor [C. sub. 1S]. The [Delta](O/C)
Decided by Eq 1. [Delta](O/C)= [(O/C). sub. a]-[(O/C). sub. 0](1)Here (O/C)
A is the measured value of 30 minutes after treatment ,[(O/C). sub. o]
No-measured value. treatment. The FT-IR [
Table data omitted from Table 1]
The FT/IR 7300 system produced by JASCO was used in this study, including ATR-
Unit 500M of attenuation total reflection (ATR)measurement.
Evaluate the adhesive properties of the laminated film from the peel strength.
15mm wide laminated film stripped at a pulse speed of 200/min with self-strain
Type tensile testing machine produced by Dongyang precision machine company. , Ltd.
Results and discussion 1)
Adhesion properties of films produced by non-anchor coating extrusion lamination process (NACELP).
Peel strength of 4 kinds of ONy/hdpe (15/60 [[micro]meter])
Laminated film is shown in Table 1.
Peel strength of laminated films produced with NACELP (
Combination of Corona treatment on the Ony-based membrane and ozone treatment on the low density polyethylene network)
Compared with the other two processed films and the one that has not been processed, its value is very high.
Dependence of Corona treatment density on peel strength as shown in the figure3.
Peel strength of ONy substrate film from ozone-
With the increase of the density of discharge treatment, the low density polyethylene mesh after treatment increases.
When the discharge treatment density is about 60 W/[m. sup. 2]
/Min, the peel strength is about 600g/15mm.
On the other hand, the peel strength of the ONy substrate film of the untreated dlp network only increases slightly with the increase of the density of the corona treatment.
Peel strength of ONy substrate film from ozone-
Treated low density polyethylene mesh (15/70 [[micro]meter])
After boiling in hot water for 30 minutes, as shown in Table 2.
The peel strength did not decrease after boiling treatment.
However, the peel strength of the laminated film produced using the usual laminating process of the anchor coating agent decreased from 880g/15mm to 180g/15mm after boiling treatment.
Laminated films produced with NACELP have better adhesive properties after boiling than laminated films produced with the usual anchor coating process.
When the low density polyethylene network is extruded and laminated to other base materials, such as ethylene-
Polyester, glass paper, etc.
Using NACELP, good adhesion performance was also obtained.
[Effect of Corona treatment[C. sub. 1S]]
Measurement by corona of the spectra of the films of the ONy substrate treated and not treated by the corona as shown in Fig. 4.
The intensity is somewhat different. [C. sub. 1s]]
Solar Corona spectrum
In the higher binding energy region, the treated membrane and the untreated membrane (287 [approximately]291 eV).
The data show that the intensity will increase after the corona treatment of the ONy sub-layer film. Inagaki et al. (10)
Shows many oxidation functional bases (-C-O-, [greater than]C = O, and -C(= O)-O-)
It may be formed through the treatment of the corona.
So we adoptedDelta](O/C)
To fix the number of these oxidation function groups.
Data of (O/C)
The density of Corona treatment is plotted in the figure5. The value of [Delta](O/C)
As the density of the corona treatment increases.
The peel strength of the ONy/LDPE film produced by Nacelp increases with [increase]Delta](O/C)[
Diagram omitted in figure 6].
Therefore, this extrusion lamination process is important to form an oxidized functional mass produced by the ronatreatment on the laminated film.
Effect of ozone treatment [[C. sub. 1S]]
Measurement of the spectrum of 290 [extruded low density polyethylene mesh with polyethylenedegrees]
Figure C shows both ozone treated and untreated7.
Intensity][C. sub. 1S]]
Spectrum of high binding energy region (286[approximately]289 eV)
Increase after ozone treatment of molten polyethylene [LDPE)web.
This result indicates that many oxidation functional groups may also be formed by ozone treatment.
It has been proved that trifluoride [TFAA)
Selectively reacts with oh-based in the gas phase (11). An ozone-
The treated LDPEfilm was treated with TFAA in the gas phase and studied by ESCA.
Fluorine atoms were detected in the ESCA spectrum.
Therefore, we estimate the oh-
Low density polyethylene film treated with TFAA reaction, some of the functional groups formed by ozone treatment are oh-based. The ozone-
The treated film of low density polyethylene and the particles of low density polyethylene are dissolved
Heptaane, extracted samples with FT-IR (shown inFig. 8).
Luongoet al identified the peaks of various carbonyl bases. previously (12).
Oxygen addition function group (-CHO, -C(=O)-OH, -C(= O)-O-, and -C (= O)-OO)
Detected in ozone
A low density polyethylene film similar to the data of Luongo et al was processed. 4)
Interaction between functional groups generated on theCorona
Treated ONy and ozone
As mentioned above, the treated low density polyethylene film on the interface, the surface of the treated ONy substrate film with the Corona and the surface of the treated low density polyethylene mesh with ozone form an oxidation functional group
In NACELP, these surfaces are in contact with the interface (ONy/LDPE)
When pressed under high temperature conditions (T = 280 = 320 [degrees]C).
When polar solvent (ex. ethanol)
Injected into the interface of the adhesive layer, the low density polyethylene film can be stripped from the ony-based film, and the peel strength reduces the original value by 90%.
The same phenomenon was observed in laminated films produced using traditional laminating processes with anchor coatings.
These results show that on the surface of ONy and low density polyethylene films, the bonding properties of hydrogen bonds composed of oxidized functional groups appear.
Remove the ONy substrate film of the ONy/dlp laminated film by 2,2, 2,2-
Trifluoride ethanol (TFE)
, Where ONy has a high solubility.
The surface of residual low density polyethylene film was analyzed by ESCA and FT-IR.
The surface of low density polyethylene film with peel strength of 670g/15mm has [N/C]value of 0.
025 determined by ESCA (Table 3). The FT-IR(ATR)
Figure 1 shows the spectrum of the surface of this low density polyethylene. 9.
Absorption of 1640 [cm. sup. -1]
Assigned to amide-I([Upsilon]C = O)
The one in 1550 [cm. sup. -1]to amide-II ([Delta]N-H)
According to Do and others. (13).
We believe that the reaction of nylon 6 with LDPEcannot is dissolved by TFE.
The low density polyethylene film surface after removing the ONy layer consists of untreated low density polyethylene, nylon 6 with TFE, and only [competitive]N/C]
Values, these results show that the interfaces of nylon 6 and LDPElayer formed hydrogen bonds and bonded bonds during NACELP. 5)
Model of adhesive mechanism schematic model of NACELP adhesive mechanism as shown in figure10.
Through the discharge treatment on the ONy substrate film and the ozone treatment of the molten low-density polyethylene network, hydrogen bonds and bonded bonds with oxygen functional groups are formed. CONCLUSIONS 1)
A new process of extrusion laminated film without any chemical primer was developed.
We found that good adhesive properties can be obtained by ozone treatment of molten polyethylene (LDPE)
Activation processing of Web and asubstrate movies. 2)
The peeling strength between the ONy substrate film and the LDPEfilm produced using this non-anchor coating extrusion lamination process shows that the film is higher than the traditional lamination process using the anchor coating agent3)
We present a bonding mechanism model for this process.
Hydrogen and bonded bonds through the oxidation functional group are responsible for enhanced adhesion.
This process has the potential to perform high-speed and low-temperature processing in extrusion lamination.
The author hopes to thank Dr.
Masahiro Kakugo of Sumitomo Chemical, Ltd.
Thank you for your support. Y.
Nogawa of Sumitomo Chemical,Ltd. , for [
Table data omitted in Table 3]
Measured by electronic energy spectrum, sir. Y.
Mr. Gao Dao andT.
Cheung Chau of Sumitomo Chemical, Ltd.
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