DE2256110A1 - PACKING MATERIAL - Google Patents

Description

PATENT LAWYERS 9 9 R R 1 1 Π

DIPL. ING. WALTER MEISSNER DIPL. ING. HERBERT TISCHER DIPL. ING. PETER E. MEISSNER MDNCHEN DIPL. ING. H. JOACHIM PRESTING

BERLIN

1 BERLIN 33 (GRUNEWALD), NOV 12, 1972 HERBERTSTRASSE 22

'/ Ha.

47-1122

JAPAN SYNTHETIC RUBBER COMPANY LIMITED,

1, Kyobashi 1-chome, Chuo-ku, Tokyo, Japan

packing material

The invention relates to a novel packaging material. In particular The invention relates to a packaging material with desired quality features, including very good transparency, Permeability for gases, tear resistance and slip resistance.

After an extensive search for a plastic film or sheet with excellent packaging properties, now found that a resinous mass composed of a polybutadiene composed mainly of units in the 1,2-configuration is formed, or consists of such a polybutadiene mixed with a film or sheet-forming thermoplastic resin, Films or sheets provide highly desirable quality characteristics. The present invention is based on this discovery.

The main object of this invention is therefore to provide a packaging material in the form of a plastic film or sheet, which is characterized in that such an article is made in a conventional manner from a resinous mass composed of 100 to 5% by weight of a polybutadiene a bandage structure of not less than 70 % units of the 1,2-configuration and a crystallinity of not less than 10% and 0 to 95% by weight

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Another thermoplastic resin is _y capable of film or sheet formation.

The amount of units in 1,2 configuration in the polybuta- # serve with a bandage structure mainly of units of the 1,2-configuration (here for the sake of simplicity as 1,2-polybutadiene referred to), which were used in experiments to practice the invention, according to the infrared absorption analysis of Morero (Horero et al .: Chim. e Ind. (Milano), 41, 758 (1959). The crystallinity was established by the Method of density measurement from the formula

I _ X _| 1 - X
^d " ^d cr ^d am

calculated, where d: density of the sample measured at 20 ° C

d _cr : density of the crystalline region

d _am : density of the amorphous region X: crystallinity in percent

The value of d _{cr used} was that of the crystalline 1,2-polybutadiene, which was calculated by Natta from X-ray experiments to be 0.963 (G. Natta: J. Polymer Sci., 20, 251 (1956)). The value of d used was 0.894 or the density of the 1,2-polybutadiene obtained by the synthetic method proposed in US Pat. No. 3,498,963 (corresponding to British Pat. No. 1,158,296) and which was found to be completely amorphous by X-ray analysis .

1,2-polybutadlene useful in practicing the invention contains no less than 70 #, preferably no less than 85 #, units of the 1,2-configuration in the dressing structure and has a crystallinity of no less than 10 %, preferably between 10% and 5096. It can be made, for example, according to the teachings of U.S. Patents 3,498,963 and 3,522,332 (corresponding to British Patents 1,158,296 and 1,189,257, respectively). It is impossible with 1,2-polybutadiene, which has units in the 1,2-configuration and a crystallinity outside the above-specified ranges, to achieve the advantageous

To obtain effects of the present invention.

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Thermoplastic resins which can be used in admixture with 1,2-polybutadiene in accordance with this invention are any resin that can form plastic films or sheets. Typical examples include polyolefins such as polyethylene (low, medium and high pressure grades), polypropylene and polybutene-1, polystyrene, acrylonitrile-styrene-butadiene copolymer resin (ABS resin and ethylene-vinyl acetate copolymer. The advantages of the invention are particularly pronounced when 1,2-polybutadiene is used alone or in a mixture with polyolefins. The mixtures should not be less than 5% by weight, preferably not less than 10 % by weight of 1,2-polybutadiene contain.

Such a thermoplastic resin can be mixed with 1,2-polybutadiene be mixed in the usual way; there are no restrictions on the mixing method to be used.

A film or sheet can be formed using any of the usual techniques, such as a blow molding, T-injection molding or calendering process.

The film or sheet made up of the 1,2-polybutadiene alone or from a resinous mass containing 5 wt .- 6 or more 1,2-polybutadiene contains, are formed according to the invention, are excellent in terms of mechanical properties, such as tensile strength, Impact resistance and surface slip resistance. In addition, they have low haze and high overall light transmission or are extremely transparent. In addition to other features, there is a high permeability for oxygen and carbon dioxide before. The high gas permeability is beneficial for the food industry «, because when packing meat the film or leaf prevents discoloration of the contents, and when packing vegetables or fruits are packed, he keeps them fresh. The high tensile strength is combined with a high tear strength and resistance to stitches and bumps so that the film or sheet is useful for wrapping crustaceans such as crabs and lobster to make. Advantage of this invention is that the film or sheet has high transparency and flexibility can be obtained without plasticizers. In addition, the oriented film or sheet formed in accordance with the present invention is proportionate shrinkable at low temperatures and can be used for shrinkage

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packaging can be applied. It is also possible if you from the tendency of 1,2-polybutadlene, upon exposure to a crosslink to succumb, prefers to irradiate the film or sheet with ultraviolet radiation so that it is within can be cured in a short period of time to such an extent that a minor blow can easily break it can break. Thus, the degree of photolysis can be increased by using an ultraviolet absorber of a suitable one if necessary Type can be regulated in an appropriate amount, and the problem of plastic waste pollution can accordingly be solved will.

It is natural in practicing the invention possible to use a stabilizer, a reinforcing agent, lubricant and other conventional additives.

The present invention is defined by the following non-limiting ones Examples explained.

example 1

A polybutadiene 95% of units of 1,2-configuration and having a crystallinity of 25% and an intrinsic viscosity (Jj ^]) of 1.43 (determined at 3O ⁰ C in toluene) which was placed in a Filmblasvorrichtung, and by an injection mold at 135 ⁰ C, an inflated film (i. Orig.inflation film) was formed. In the same way, both a mixture of the polybutadiene and commercial high-pressure polyethylene in a mixing ratio of 1: 1 (weight ratio) and, as a control, polyethylene alone were blown into films. As samples for the tests for total light transmittance and haze films were made of 0.185 cm thick of the same materials using a forming and deck press at 110 ⁰ C.

Various properties of these films and sheets were determined. The results are shown in Table 1.

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Test size Comparison
example 47-1122 1,2-polybuta
serve _Ä ^ _X x - 5 - High pressure
polyethylene 2256110 o, oo9o Table 1 Film thickness (cm) o, oo57 Example of
invention 168 Tensile strength ^Ä ^
(Machine direction) 146 1,2-polybuta-
service / high
pressure p olyathy-
len mixture (kg / cm ² ) o, o115 58o Strain * '
(Machine direction) 250 146 I05 Elmendorf tear resistance
Iran + ■ arC ^ 75 54o iveii / ftc /
(kg / cm) Gas permeability coefficient
efficient:
(x 1o ° cc.cm / cm sec.cm Hg) * ⁵ ^ 128 5.66 at 20 ° CO ₂ 1.63 , ■ 28.42 \ _f \ j ^ » 6.00 13, o3 at 40 ° CO ₂ 5.4o 2.41 7o, 26 co ₂ 17.73 1o, oo over 7o ° ! "riktionswinkel * ⁴ ^ 7 ° 9.7 ^ 11.32 Impact resistance * ⁵ ^
(kg / cm) 5.51 29.51 o, 185 Thickness ^{- 6} ^ (cm) o, 185 19.5 ° 7o, 6 Overall translucent
speed * 7) (^) 29 10.03 ' 1o Turbidity * ⁷ ^ (#) • 65 o, 185 55.2 37

Notes: 3e1) Samples made with a ψ $ dumbbell cutter

according to

according to JIS Kö ^ cvl; .% eprä ^ t _{: J} j //, aren, were under tension on an "Instron-type device

tt '

.., -. ij.oj j '..: ■

309821/0317

according to JIS Z1702

measured using a Seikaken type Gaspermeabilitätstester at a measuring temperature of 20 ⁰ C.

measured with a Toyo Seiki ■ TSS friction iron tester.

according to ASTM-DI709.

* '' 'using a form on a cover press

110 ⁰ C were molded 0.185 cm thick films as test samples. Measured with Tokyo Denshoku's integrating spherical light transmission tester.

Example 2

A polybutadiene containing 90 % units of 1,2 configuration and having a crystallinity of 25 % and 1.61 (determined in toluene at 30 ° C.) and polystyrene (hereinafter referred to as PS) were in a ratio mixed 1: 1 and evenly · melted together on a roller mill; with a cover press, a film was formed at 110 ⁰ C. In a similar way, an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), ABS resin and polypropylene (hereinafter referred to as PP) were mixed with the polybutadiene and films were produced from the mixtures on a cover press. For comparison, sheets of PS, EVA, ABS resin and PP alone were molded in the same manner. The samples thus obtained were subjected to the property tests. The results are shown in Table 2 .

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Tabel 2 strain
k1) Friction
angle
k2) Test sample Mixed
(Weight)
behaves
nis Tensile strength
speed x1)
kg / cm * j 690 over 70 ° 1,2-polybutadiene _ 172.2 720 Il (Comparative example) EVA - 199.7 750 M. (Example) 1,2-poly
butadiene / EVA 50/50 209.4 140 . 26.5 ° (Comparative example) PP - 353.0 240 over 70 ° (Example) 1,2-poly
butadiene / PP 50/50 184.0 10 27.5 ° (Comparative example) PS - 55.9 20th over 70 ° (Example) 1,2-poly
butadiene / PS 50/50 59.2 10 24.3 ° (Comparative example)
SECTION 14.9 350 over 70 ° (Example) 1,2-poly
butadiene / ABS 80/20 74.2
ί

Notes: x1) _Films were made with a ^ 2 dumbbell cutter

embossed according to JIS K6301; the test specimens thus obtained were tested for tension with a tester from Instron type with a train speed of 500 mm / min, tested.

* 2)

measured with Toyo Seiki's TSS friction angle · · tester.

Example 3

Tests were carried out with 1,2-polybutadienes with different crystallinities. Using 1,2-polybutadienes with crystallinities of zero (amorphous, comparative example), 14.96 and 30% , films were formed on a cover press and tested for tensile strength, right-angle tear strength and friction angle. The results are shown in Table 3.

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Tabel

Test sample

1,2-bond crystal! - tensile strength- elongation (^ -permeability * ² ^ 9o ° * ³ ^ slip resistance

Tear «4)

nity (5 «) keit type) (kg / cm ^)

speed
(kg / cm)

Amorphous 1,2-polybutadiene 86, ο

2oo

152OO

over 7o *

U) O U5 OO

crystalline 1,2-polybutadiene

88.7 92 _t o

30th

9o

229

75o 56 ο

83 oo 62oo

37
93

Notes: * 1) _{measured in the} same way as described in example 2

* 2)

according to ASTM-D14-34

Samples embossed with a B-type cutter according to JIS K63o1 were tested.

measured in the same manner as in Example 2

to to

cn

Example 4

Two kinds of polybutadiene containing 68 % (comparative example) and 90 % units in 1,2-configuration, respectively, were tested in the same manner as described in Example 2; the results shown in Table 4 were obtained. .

Table 4

test salary on * 68.0 Crystal «· W. train Elongation 9o2 »2) Tear Frik sample l, 2-one line firm «11 firm functional to run <*) speed Hl)
(kg / cm ^z ) (%) speed angle 1.61 (kg / cm) ■ 3) 139.3 54.3 II, 2-Po 90.2 25th 2.20 580 over 70 ° lybuta
serve 42.7 24.8 Il 19th 210 η

Notes: »1)

gladly in the same way as in Bei

game 2 described »

'measured in the same way as the example 3f

■ 3)

measured in the same manner as in Example 2.

Example 5

Mixtures of 1,2-polybutadiene units, 90% in 1,2-conf iguration contained and a crystallinity of 25% and of 1.30 (determined in toluene at 30 ⁰ C) exhibited, and high-pressure polyethylene in mixture Ever duty ratios of 20:80 , 50:50 and 80:20 (by weight) were produced in the same way as described in Example 2 and processed into films by means of a cover press. For comparison purposes, 1,2-polybutadiene was replaced by high-proportion cis-1,4-polybutadiene (Japan Synthetic Rubber's JSR BRO1) and mixed with polyethylene in similar proportions. The ones from the mixes

10- «

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produced films were also tested. Table 5 shows the results.

Table 5

train
firm
ability "
(kg / cm ² ) Deh
tion
(%) 0 ₂ -per
meabi-
lity
*1) -ü2)
Total-
light-
by-
lazy-
speed
(X) * 2)
Tru
exercise
{*) optimal
tempera
ture to
Warmver
seal ( ⁰ CT
«3) Polyethylene (PE) 130 500 2.26 56.0 25.8 115-125 tf, 2-polybutadiene
(1,2-BR) 152 590 9.88 87.5 2.8 85-95 Cis polybutadiene
(Cis-BR) 1 760 * 4) 89.0 10.0 - PE / 1,2-BR = 80:20 121 530 3.10 52.5 41.3 105-115 "50:50 123 550 4.80 66.4 18.5 about 100 "20:80 127 630 7.77 79.0 11.0 approx. 90 PE / Cis-BR = 80:20 75 50 3.67 56.0 50.8 approx. 120 "50:50 37 90 9.74 64.0 39.3 approx. 120 • 20:80 4th 370 43.8 69.0 25.1 -

Notes: «1) _{measured in the} same way as in example 1

described; Unit χ 10 "" ¹⁰ cc.cm/cm ² sec.cmHg.

Measuring temperature: 25.5 C.

measured in the same manner as described in Example 1, except that the films 1 mm thick.

two strips, each 1 cm wide, of each test film were placed on top of one another and shared heat sealed by a heat seal tester of the Nippon Rika Kogyo. The optimal Temperatures became from the shape of each heat-sealed product and from the stress at break the heat seal determines the heat seal

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recovery time was 2 seconds and the pressure 2 kg / cm,

Cis-BR alone failed because of difficulties not be tested in the manufacture of its test specimens ·.

Example 6

A blown film was formed from the same 1,2-polybutadiene that was used in Example 2 and then ^{subjected to a weathering test at 40 °} C. using a weatherometer. Films made from various commercial thermoplastic resins were also tested for comparison purposes. The results are shown in Table 6. It can be seen from the table that 1,2-polybutadiene has photocrosslinking property. The exposed 1,2-polybutadiene film was easily broken into pieces by light impacts.

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Table 6

225Sl 1O

Test size 3 Example d
invention Comparative example .09 EVA 42 Polypropylene ( _IL j. 5 1,2 poly
butadiene Polyethy
len .35 44 09 52 Thickness (mm) 1o 54 52 .20 16 15th 296 1155 "" 3o 166 195 .22 320 31 1077 O hour 205 189 .40 278 59 1082 Weathering tests:
(by means of weathering
apparatus measured) 3 177. 197 298 1050 Tensile strength O hours 5 136 194 326 1093 1o 180 197 238 1054 15th 217 198 440 125 3o 570 320 590 115 O hour 515 290 495 115 3 465 290 510 115 .2 Strain(#) 8th 270 295 510 125 .8th 1o 15th 285 400 115 .3 15th 15th 255 0. 95 3o 0.09 0 0. 96 49.8 0 0. 96 1 97.5 0 - - Toluene un-
soluble (% 99.8 - 0. ^ - 100 0 0. 96 100 0

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Table 6 (continued)

1 sim ilar example Polyvinyl
chloride nylon Poly-;
ester - Poly-
carbonate • 5 75 54 50 , 100 51 9 325 722 1866 100 790 6th 317 926 1776 693 • 314 619 1750 701 4th 311 492 1791 754 4th 336 494 1758 769 369 703 1755 " 734 270 305 100 120 285 325 .95 110 265 265 95 110 253 265 105 115 275 170 95 115 270 300 95 110 61 - 100 86. 68 100 100 78. 67. 99.5 100 72. - 100 66. - 63. 64. 100 44. Poly
styrene 50 530 593 549 '501 357 340 25th 35 25th .3 20th .4 X5 8th 15th 0 8th 0 0 0 0, 0. 0. .06 .08 05 44 20th

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-Ii--

Example 7

A film with a thickness of 20 μm was formed from polybutadiene which had 92 % 1,2-addition units, a crystallinity of 23 % and Fo] of 1.30 (determined in toluene at 30 ^° C.). Meat was wrapped with the polybutadiene film and ^{stored in a refrigerator at 0} ° C .; no change in the color of the meat was observed after one week of storage.

For comparison, meat stained with a polyvinylidene chloride film of 20 / u thickness was wrapped and stored in the same refrigerator within 2 days. in the In the case of meat that was not wrapped, discoloration occurred within a day.

Example 8

There was formed a film of 50 / u thick of polybutadiene containing 90% 1,2-addition units, a crystallinity of 25% and Mj of 1.61 (determined in toluene at 30 ⁰ C) was obtained. Three bags of 25 cm × 22 cm in size were prepared by folding the polybutadiene films of 50 cm × 22 cm in size. In each bag was packed 600 g of ABS resin pellets, the three rims of each bag sealed two seconds at 80 ⁰ C and 2 kg / cm ^ Drucfa IEISS. For a comparison, contained three bags, the ABS resin pellets obtained in the same manner as described above, hot except that a polyethylene film of 50 used / u thickness, and the film 2 seconds at 105 ⁰ C and 2 kg / cm pressure was sealed. These bags were dropped from a height of 2 m onto concrete at 25 ° C. and the appearance of the bags was observed.

There was no change in the three bags of polybutadiene film

noted, however, a heat-sealed part came on one Bag out of polyethylene film.

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Claims (7)

Claims 1J packaging material which is formed from a resinous composition comprising (A) 100 - 5 wt .- # polybutadiene having an association structure of not less than 70% 1,2-addition units and a crystallinity of not less than 10% and (B ) Contains 0-95% by weight of at least one thermoplastic resin capable of film or sheet formation. 2. Packaging material according to claim 1, characterized in that that the material is formed from polybutadiene alone. 3. Packaging material according to claim 1, characterized in that the polybutadiene has units with 1,2-addition of not less than 85 % . 4. Packaging material according to claim 1, characterized marked * - net that the polybutadiene has a crystallinity between 10 and 50%. 5. Packaging material according to claim 1, characterized in that that the thermoplastic resin from the group § polyolefin, polystyrene, acrylonitrile-styrene-butadiene copolymer and Ethylene-vinyl acetate copolymer, is selected. 6. Packaging material according to claim 1, characterized in that the thermoplastic resin from the group: polyethylene, Polypropylene and polybutene-1-is selected. 7. Packaging material according to claim 1, characterized in that that the resinous mass is at least 20 wt .- ^ dee polybutadienes contains. t Dipl.-Ing. P! E. Meissner Patent attorney 309821/0317 Y *