U.S. patent number RE31,780 [Application Number 06/521,127] was granted by the patent office on 1984-12-25 for multilayer light-reflecting film.
This patent grant is currently assigned to The Mearl Corporation. Invention is credited to Scott A. Cooper, Jules Pinsky, Ramakrishna Shetty.
United States Patent |
RE31,780 |
Cooper , et al. |
December 25, 1984 |
Multilayer light-reflecting film
Abstract
Improvements in multilayer light-reflecting film are effected by
the use of thermoplastic polyester as the high refractive index
component of a system in which two or more resinous materials form
a plurality of layers.
Inventors: |
Cooper; Scott A. (Yorktown
Heights, NY), Shetty; Ramakrishna (White Plains, NY),
Pinsky; Jules (Bloomfield, CT) |
Assignee: |
The Mearl Corporation
(Ossining, NY)
|
Family
ID: |
26804693 |
Appl.
No.: |
06/521,127 |
Filed: |
August 8, 1983 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
107351 |
Dec 26, 1979 |
04310584 |
Jan 12, 1982 |
|
|
Current U.S.
Class: |
428/212;
264/1.31; 264/173.12; 264/173.16; 359/588; 428/213; 428/480;
428/483 |
Current CPC
Class: |
B32B
7/02 (20130101); G02B 5/287 (20130101); Y10T
428/2495 (20150115); Y10T 428/31786 (20150401); Y10T
428/24942 (20150115); Y10T 428/31797 (20150401) |
Current International
Class: |
B32B
7/02 (20060101); G02B 5/28 (20060101); B32B
007/02 (); B32B 027/06 (); B32B 027/36 () |
Field of
Search: |
;428/212,213,392,480,483
;264/171,173 ;350/166 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Herbert; Thomas J.
Attorney, Agent or Firm: Ostrolenk, Faber, Gerb &
Soffen
Claims
What is claimed is:
1. A transparent thermoplastic resinous laminate film of at least
10 very thin layers of substantially uniform thickness, said layers
being generally parallel, the contiguous adjacent layers being of
different transparent thermoplastic resinous materials one of which
is a .Iadd.terephthalate .Iaddend.thermoplastic polyester or
copolyester resin having a refractive index of 1.55-1.61 and the
adjacent resinous material having a refractive index which is lower
by at least about 0.03, the contiguous adjacent layers differing in
refractive index by at least about 0.03.
2. The transparent thermoplastic resinous laminate film of claim 1,
wherein said polyester or copolyester is selected from the group
consisting of poly(ethylene terephthalate), and a copolyester of
cyclohexanedimethanol and an acid comprising terephthalate
acid.
3. The transparent thermoplastic resinous laminate film of claim 1
having at least 35 layers.
4. The transparent thermoplastic resinous laminate film of claim 3
having at least about 70 layers.
5. The transparent thermoplastic resinous laminate film of claim 4
wherein said adjacent resinous material has a refractive index
which is lower by at least about 0.06.
6. The transparent thermoplastic resinous laminate film of claim 1,
wherein said polyester is polybutylene terephthalate.
7. The transparent thermoplastic resinous laminate film of claim 6,
wherein said other resinous material is polymethyl
methacrylate.
8. The transparent thermoplastic resinous laminate film of claim 1
wherein the outermost layers of said film comprise an impact
modified acrylic resin and the thickness of each of the outermost
layers is at least 5% of the total thickness of the film.
9. The transparent thermoplastic resinous laminate film of claim 8
wherein said impact modified acrylic resin is a terpolymer of
methyl methacrylate, butadiene and acrylonitrile, or methyl
methacrylate combined with an elastomer.
10. The transparent thermoplastic resinous laminate film of claim 9
wherein said polyester or copolyester resin is polybutylene
terephthlate and adjacent other resin is polymethyl
methacrylate.
11. The transparent thermoplastic resinous laminate film of claim
10 of at least 70 substantially uniformly thick layers.
Description
BACKGROUND OF THE INVENTION
The present invention relates to multilayer coextruded
light-reflecting films which have a narrow reflection band because
of light interference. When the reflection band occurs within the
range of visible wavelength, the film is iridescent. Similarly,
when the reflection band falls outside the range of visible
wavelength, the film is either ultraviolet or infrared
reflecting.
The multilayer films and methods by which they can be produced are
known in the art. In this connection, the reader's attention is
directed to the following U.S. patents which are hereby
incorporated by reference: U.S. Pat. Nos. 3,328,003; 3,442,755;
3,448,183; 3,479,425; 3,480,502; 3,487,505; 3,511,903; 3,549,405;
3,555,128; 3,565,985; 3,576,707; 3,642,612; 3,711,176; 3,759,647;
3,773,882; and 3,801,429.
The multilayer films are composed of a plurality of generally
parallel layers of transparent thermoplastic resinous material in
which the contiguous adjacent layers are of diverse resinous
material whose index of refraction differs by at least about 0.03.
The film contains at least 10 layers and more usually at least 35
layers and, preferably, at least about 70 layers.
The individual layers of the film are very thin, usually in the
range of about 30 to 500 nm, preferably about 50-400 nm, which
causes constructive interference in light waves reflected from the
many interfaces. Depending on the layer thickness and the
refractive index of the polymers, one dominant wavelength band is
reflected and the remaining light is transmitted through the film.
The reflected wavelength is proportional to the sum of the optical
thicknesses of a pair of layers. The reflected wavelength can be
calculated by the formula ##EQU1## In this formula, .lambda. is the
reflected wavelength, M is the order of reflection, t is the layer
thickness, n is the refractive index, and 1 and 2 indicate the
polymer of the first layer and the polymer of the second layer,
respectively. The quantity nt is the optical thickness of a layer.
For first order reflection, i.e. when M is 1, visible light is
reflected when the sum of optical thicknesses falls between about
200 and 350 nm. When the sum is lower than about 200, the
reflection is in the ultraviolet region of spectrum and when the
sum is greater than about 350 nm, the reflection is in the infrared
region.
The quantity of the reflected light (reflectance) and the color
intensity depend on the difference between the two refractive
indexes, on the ratio of optical thicknesses of the layers, on the
number of layers and on the uniformity of the thicknesses. If the
refractive indexes are the same, there is no reflection at all from
the interfaces between the layers. In the multilayer films, the
refractive indexes of contiguous adjacent layers differ by at least
0.03 and preferably by at least 0.06 or more. For first order
reflections, reflectance is highest when the optical thicknesses of
the layers are equal although suitably high reflectances can be
achieved when the ratio of the two optical thicknesses falls
between 5:95 and 95:5. Distinctly colored reflections are obtained
with as few as 10 layers; however, for maximum color intensity it
is desired to have between 35 and 1000 or even more layers. High
color intensity is associated with a reflection band which is
reltively narrow and which has high reflectance at its peak. It
should be recognized that although the term "color intensity" has
been used here for convenience, the same considerations apply to
the invisible reflection in the ultraviolet and infrared
ranges.
The multilayer films can be made by a chill roll casting technique
using a conventional single manifold flat film die in combination
with a feedblock which collects the melts from each of two or more
extruders and arranges them into the desired layer pattern.
Feedblocks are described in the aforementioned U.S. Pat. Nos.
3,565,985 and 3,773,882. The feedblocks can be used to form
alternating layers of either two components (i.e. ABAB . . . );
three components (e.g. ABCABCA . . . or ACBCACBC . . . ); or more.
The very narrow multilayer stream flows through a single manifold
flat film die where the layers are simultaneously spread to the
width of the die and thinned to the final die exit thickness. The
number of layers and their thickness distribution can be changed in
inserting a different feedport module. Usually, the outermost layer
or layers on each side of the sheet are thicker than the other
layers. This thicker skin may consist of one of the components
which makes up the optical core; may be a different polymer which
is utilized to impart desirable mechanical, heat sealing, or other
properties; or may be a combination of these.
The high refractive index component used heretofore in commercial
production has been polystyrene (refractive index 1.60). Other high
index resins which are optically suitable but which have
disadvantages in terms of cost or difficulty of extrusion in the
multilayer process are polycarbonate (1.59), vinylidene chloride
(85%)-vinyl chloride (15%) copolymer (1.61), and
polydichlorostyrene (1.62). Polystyrene in combination with such
lower refractive index polymers as poly(methyl methacrylate),
polypropylene, and ethylene vinyl acetate, all of which are close
to 1.50 in refractive index, produces iridescent films of desirable
optical properties which, however, reveal deficiencies in certain
mechanical properties. For example, the adhesion between individual
layers of the multilayer structure may be insufficient, and the
film may suffer from internal delamination or separation of layers
during use. The iridescent film is often adhered to paper or board
for its decorative effect, and is then used for greeting cards,
cartons, and the like. Delamination of the film is unsightly and
may even lead to separation of the glued joints of carton. In
addition, the solvent resistance and heat stability of such films
are not as great as desired for widespread utilization.
Accordingly, it is the object of this invention to provide new and
improved multilayer light-reflecting films which exhibit increased
resistance to delamination, improved solvent resistance and/or
improved heat stability. This and other objects of the invention
will become apparent to those skilled in this art from the
following detailed description.
SUMMARY OF THE INVENTION
This invention relates to an improved multilayer light-reflecting
film and more particularly to a transparent thermoplastic resinous
film of at least 10 generally parallel layers in which the
contiguous adjacent layers are of diverse transparent thermoplastic
resinous material differing in refractive index by at least about
0.03 and at least one of the resinous materials being a
thermoplastic polyester or copolyester resin.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
It has now been found that the objectives of this invention are
realized by employing as the high refractive index component a
transparent thermoplastic polyester or copolyester resin which is
characterized by a refractive index of about 1.55 to about 1.61.
Examples of usable thermoplastic polyester resins include
poly(ethylene terephthalate) (PET) which is made by reacting either
terephthalic acid or dimethyl terephthalate with ethylene glycol;
polybutylene terephthalate (PBT) which is made by the catalyzed
condensation of 1,4-butanediol with either terephthalic acid or
dimethyl terephthalate; and the various thermoplastic copolyesters
which are synthesized using more than one glycol and/or more than
one dibasic acid. PETG copolyester, for example, is a glycol
modified PET made from ethylene glycol and cyclohexanedimethanol
(CHDM) and terephthalic acid; PCTA copolyester is an acid modified
copolyester of CHDM with terephthalic and isophthalic acids.
Iridescent films of high color intensity and greatly improved
properties are obtained by using the thermoplastic polyester resins
as the high refractive index resins in conjunction with
thermoplastic resins of a lower refractive index. A list of typical
resins falling in the latter category is given in Table 1 and it
will be appreciated that in making suitable combinations, a
refractive index difference of at least about 0.03, preferably at
least about 0.06, is maintained.
TABLE 1 ______________________________________ Approximate Polymer
name: Refractive Index ______________________________________ FEP
(fluorinated ethylene-propylene 1.34 copolymer
Polytetrafluoroethylene 1.35 Polyvinylidenefluoride 1.42
Polychlorotrifluoroethylene 1.42 Polybutyl acrylate 1.46 Polyvinyl
acetate 1.47 Ethyl cellulose 1.47 Polyformaldehyde 1.48
Polyisobutyl methacrylate 1.48 Polybutyl methacrylate 1.48
Polymethyl acrylate 1.48 Polypropyl methacrylate 1.48 Polyethyl
methacrylate 1.48 Polymethyl methacrylate 1.49 Cellulose acetate
1.49 Cellulose propionate 1.49 Cellulose acetate-butyrate 1.49
Cellulose nitrate 1.49 Polyvinyl butyral 1.49 Polypropylene 1.49
Ethylene vinyl acetate 1.50 Low density polyethylene (branched)
1.51 Polyisobutylene 1.51 Ionomer 1.51 Natural rubber 1.52 Perbunan
1.52 Polybutadiene 1.52 Nylon (condensation copolymer of hexa- 1.53
methylene-diamine and adipic acid Polyvinyl chloroacetate 1.54
Polyethylene (high density linear) 1.54 Polyvinylchloride 1.54 A
copolymer of 85 parts by weight methyl 1.54 methacrylate and 33
parts by weight styrene ______________________________________
A preferred combination in accordance with this invention involves
the use of polybutylene terephthalate (PBT) as the thermoplastic
polyester and poly(methyl methacrylate) (PMMA) as the low
refractive index material. To prepare the film, the polyester was
fed to the feedblock from one extruder and the PMMA was fed from a
second extruder to form a 0.8 mil (20 .mu.m) thick film consisting
of 115 optical layers and two polyester skin layers. Each skin
layer was about 10% of the thickness of the total film. The
polyester optical layers were each about 0.2 .mu.m in optical
thickness, the PMMA optical layers each about 0.1 .mu.m. A
112-centimeter die was used to produce a 90-centimeter wide film of
uniform overall thickness. The film was brightly iridescent, and
was prevailing green and red when seen by reflection at
perpendicular incidence.
To evaluate this polyester/PMMA film for resistance to
delamination, one surface of the film was restrained either by
backing with adhesive coated tape or by adhesive lamination to
rigid paperboard. Pressure sensitive tape was applied to the other
surface of the film. The film withstood many pulls on the tape
without any sign of delamination, even when the tape was applied at
the edge of the film. The test was made still more severe by wiping
the exposed side with a solvent, such as toluene, which promotes
delamination in other types of iridescent film, e.g. polystyrene
(PS)/propylene-ethylene copolymer (PP) and PS/ethylene vinyl
acetate (EVA). The polyester/PMMA film withstood the tape test
without any sign of delamination.
Other prior art films similarly failed in these delamination tests.
For example, the brightly iridescent film consisting of PS/PMMA was
so brittle that it fractured under the conditions of the test.
Iridescent films consisting of PS/PP and PS/EVA delaminated readily
under the same test conditions.
A number of other properties are also superior to those of
previously known films. These include excellent mar resistance,
temperature resistance, and solvent resistance. The latter is most
important for film which is brought in contact with adhesives,
printing inks, or lacquers containing organic solvents.
To test the solvent resistance of the film, each of a number of
solvents was applied to the surface of individual samples by means
of a soaked cotton swab. The solvent was permitted to air dry. The
PBT/PMMA iridescent film underwent no change on treatment with
aliphatic or aromatic hydrocarbons or their mixtures, alcohols,
aliphatic esters such as ethyl acetate and butyl acetate, or
ketones such as acetone and methyl isobutyl ketone. The previously
known commercial films of PS/PMMA, PS/PP, and PS/EVA, evaluated by
the same technique, suffered crazing, loss of gloss, change of
color, or loss of color when exposed to several of these solvents,
including heptane, toluene, and various commercial mixed
hydrocarbon solvents, as well as butyl acetate and methyl isobutyl
ketone.
Temperature stability of the polyester film was similarly superior
to that of previously known films. Samples were placed in
air-circulating ovens for 30 minutes at various temperatures. The
temperature of first change was noted, with the following results:
Polyester film PBT/PMMA, 220.degree. C.; prior art films PS/PMMA,
150.degree. C.; PS/PP, 130.degree. C.; PS/EVA, 120.degree. C.
Improved temperature stability is very important for applications
in which the films is to be laminated or adhered to another surface
by a technique which requires elevated temperature.
It was mentioned previously that the skin layer is thicker than the
optical layers. Each skin layer should have a thickness of at least
about 5% of the total thickness of the film, and may be as great as
about 40% of the total film thickness. A variant of the film
utilizes a third extruder to provide on each surface an outer skin
of thermoplastic impact-modified acrylic resin. This skin layer may
supplant the usual skin layer which consists of one of the optical
components, or may be added on top of it. Each impact acrylic layer
should be in thickness at least about 5% of the total thickness of
the film; the sum of each impact acrylic layer and the adjacent
optical resin skin layer, if any, may be as great as about 40% of
the total film thickness or even greater.
Impact acrylic imparts improved winding characteristics and
resistance to blocking, and provides a surface which is very
receptive to adhesives, printing inks, and hot stamping foils. Such
film in addition has improved resistance to ultraviolet light.
The impact-modified acrylic resin may be a copolymer, e.g. methyl
methacrylate polymerized with another monomer such as methyl
acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, styrene,
or butadiene; a terpolymer or multi-polymer made from three or more
of such monomers; or a blend of methyl methacrylate with elastomer,
vinyl, or other modifiers. Commercial impact acrylics are available
as Lucite T-1000 (DuPont) and Plexiglas DR (Rohm & Haas).
The two-component iridescent films display excellent resistance to
delamination, and good iridescent color regardless of which
component serves as the skin. Other properties may be enhanced when
one or the other component is the skin layer. With polyester/PMMA,
for example, the film is more flexible with polyester as the skin
layer, and more brittle with PMMA as the skin layer. Thus,
polyester is preferred for the skin where flexibility is desirable,
as in decorative wrappings; PMMA is preferred where the film is to
be cut into small pieces such as flakes or "glitters". The choice
depends on the particular pair of components in the optical core
and the applications for which the film is intended.
The use of a third resin as the skin layer substantially decreases
the importance of the internal sequence, since the properties are
modified by the specific skin resin. Impact acrylic as a skin may
be adjacent to either polyester or PMMA in the above example. In
other combinations, it may be desirable to choose a particular
sequence in order to assure maximum adhesion between the skin layer
and the multilayer optical core.
In order to further illustrate the present invention, various
examples are set forth below and it will be appreciated that these
examples are not intended to limit the invention. Unless otherwise
stated, all temperatures are in degrees Centigrade and all parts
and percentages are by weight throughout the specification and
claims.
EXAMPLE 1
Alternating Layers of Polyester and Poly(methyl methacrylate)
(PMMA)
Polybutylene terephthalate thermoplastic polyester was fed to the
feedblock from one extruder and PMMA from a second extruder to form
a 0.75 mil (19 .mu.m) thick film consisting of 115 optical layers
and 2 polyester skin layers. Each skin layer was about 20% of the
thickness of the total film. The polyester optical layers were each
about 0.15 .mu.m in optical thickness, the PMMA layers about 0.07
.mu.m. The film was brightly iridescent, and was prevailingly blue
and green when seen by reflection at perpendicular incidence. The
film displayed excellent resistance to delamination as well as
superior solvent resistance and temperature stability.
EXAMPLE 2
Polyester/PMMA multilayer structure with additional skin layers
containing impact modified acrylic copolymer
A multilayer structure similar to that of Example 1 was prepared,
except that a second skin layer was added to each surface by means
of a third extruder. This outer skin layer consisted of a mixture
of equal parts of two resins, (1) PMMA and (2) an impact-modified
acrylic resin, namely, Lucite T-1000 (DuPont) a polymethyl
methacrylate modified with elastomer. This film was superior to
that of Example 1 in that its winding and antiblocking properties
were superior, and it was more suitable for printing and hot
stamping.
EXAMPLES 3-15
Various thermoplastic polyester polymers and copolymers were
utilized in conjunction with a number of polymers of lower
refractive index, sometimes in two-component structures, sometimes
in structures utilizing additional components for skin layers, as
shown in the following tabulation. All examples yielded intensely
iridescent films with improved heat stability and, .[.expecially.].
.Iadd.especially .Iaddend.where PMMA was the low index polymer,
improved resistance to delamination.
______________________________________ High Index Low Index Skin
Layer Example Polymer Polymer Polymer(s)
______________________________________ 3 PBT EVA PBT 4 PBT EVA PMMA
and impact modified polymethyl methacrylate 5 PBT PP PBT 6 PBT PP
PP 7 PBT PP PMMA and impact modified polymethyl methacrylate 8 PBT
Ionomer PBT 9 PBT Ionomer Impact modified copolymer of methyl
methacrylate and butyl acrylate 10 PETG PMMA PETG 11 PETG PMMA PMMA
and impact modified polymethyl methacrylate 12 PET PMMA PET 13 PET
PMMA Modified acrylic terpolymer of methyl methacrylate, butadiene,
and acrylonitrile 14 PCTA PMMA PCTA 15 PCTA PMMA PMMA and impact
modified polymethyl methacrylate
______________________________________
Various changes and modifications can be made in the present
invention without departing from the spirit and scope thereof. For
example, while the invention has been described with reference to
cast film, flat film type of film production, iridescent films can
also be made by the tubular process (blown film). Accordingly, the
various embodiments disclosed herein were for the purpose of
illustration only and where not intended to limit the
invention.
* * * * *