DE2236789A1 - FILM-LIKE MATERIAL AND PROCESS FOR ITS MANUFACTURING - Google Patents

Description

■ 18 0 '"JJqvο 1971, Japan, Pat. Note no. 92 571/1971

Kureiia Kagaku Kogyo Kabushiki Kai aha 8, 1-chome, Nihonbashi, Horidome-ciio, öhuo-ku Tokyo, J.iPAlT

Oil-like material and process for its manufacture

The invention relates to a soft, permeable and light, sheet-like or film-like material and a method for its production. "In particular, the invention relates to a material with such physical properties that it can be used as artificial leather instead of paper or in a similar sense." this iiaterial a polyolefin-based front, about 50 - contains rrozente of inorganic material, preferably calcium sulfite, - 85 wt »

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Numerous methods are already known for producing permeable webs or foils from synthetic resin.

For example, the resin material is known to be granular to produce material that is then subjected to a sintering process »Another well-known process consists in making a mixture material from a certain To produce synthetic resin and an inorganic or organic substance, which is later removed from the mass. Another known method provides a synthetic resin to mix with a foaming agent. Extensive tests have shown that all known materials that are made by any of the known processes mentioned herein, at least one of those for the desired one The main physical properties required for the purpose are missing, e.g. flexibility, mechanical strength, permeability.

When looking at an animal hide it can be seen that it contains natural fibers that tannin to a leather fur and resin materials are converted as binding material, whereby the leather fur then artificially repeated bending and stretching loads is subjected to appropriate processing machines · This partially eliminates the tied together parts of the skin loosened to dag To whiten fur *

In papermaking, fibers are brewed using binding material to adhere to one another, wherefore

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properties similar to "are formed in skins ₀

To artificially products with leather or paper properties produce, it is known to use nonwoven products as main components and to equip them accordingly

For the production of the non-woven fabric, however, it is first necessary to produce synthetic fibers «, this production process are complicated and time-consuming

It is therefore the principal object of the invention to provide a simpler method for the manufacture of a continuous, transparent and pliant material having properties similar to natural leather or paper or the like to provide _"o

According to the invention it has been found that such a Material can be created in a very simple and convenient way by using a mixture of a polyolefin and an inorganic substance is produced, which is the main

• component contains calcium sulphite The mixture is formed in the molten state into a skin, a sheet or a similar product, which is then subjected to uniaxial or multiaxial stretching ₀

The inorganic material may preferably range from-about 50-85 betragene Gew.Prozente of the total mixture, the calcium sulfite is preferably in the form of fine crystals with particle sizes of 1 - 100 uses Vl ©

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The olefin material has an apparent density of 0.3-1 »0, a Young's or elasticity modulus of 100-4000 kg / cm, a tensile strength, measured at least in one direction, of 50-700 kg / cm and a softening temperature, measured in accordance with Jis regulation 3 6723 (Japanese industrial standard) of less than -50 0. The term "softening temperature" is used here and in the following in the sense of a lower limit value for the temperature range in which the material is soft and pliable _e

The preform before the stretching or stretching process, which is composed of the calcium and polyolefin material, has an elongation tear strength of at least 50/5, measured according to JIS-K-6771. The material then undergoes at least one elongation subject to a length of at least 150 fo the original length in one direction "

The aforementioned molding can preferably be produced in such a way that 50-85 parts by weight of crystalline calcium sulfite hemihydrate, each of which has a rectangular shape with a short axis of 1 - 30 λΐ and a large one Axis of 5-100 yU, and 15-50 parts by weight crystalline polyethylene or polypropylene are mixed together. The mixture then undergoes a stretch in the flat subject to the extent mentioned. This stretching becomes the intimate bond condition binds the sulfite and the Polyolefin crystals forced to separate from the front ;, whereby cavities are formed »

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Instead of the aforementioned stretching, the mixture can auoh Bending or twisting stresses are subjected to 'easily a similar separation at the interfaces to trigger "

The mixed molding produced in the process according to the invention is used, is characterized in that it has a more than 20 ° higher "softening temperature" T-, according to the Measurement specifications according to JIS K-6723 in comparison with the corresponding value of the molded article, that of torsional deformation has been subjected to more than 90 degrees “After a twofold twist the value of T- is less than -50 Ο «This one not to be expected from the start Property is extremely remarkable.

As an example it should be mentioned that high-density polyethylene has a specific gravity of about ¹ 0.93-0.98, while that of calcium sulfite hemihydrate is generally about 2.45-2.55 ". The same value for a polyethylene material containing 50-85 percent by weight of the hemihydrate in a molded state in the above-mentioned shape is 1.4-1.9o

In common technical experience, a crystalline, high molecular composition, as molded, such as high density polyethylene, generally exhibits increased crystallization after being subjected to elongation so that it has an increased density. iu'u lij b it is therefore remarkable that a molding made from a polyolefin compound shows a specific gravity of ^{/ r} l - 1/4 deo original after it has been

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has been subjected to a certain stretching process

The change in the apparent density of a briquette ouch a polyethylene-calcium sulfite gemisoh depending on the extent of stretching or elongation is in the following Table I shown.

Table I.

Change in the apparent density of formations from a polyethylene-potassium sulfite mixture) with an increase in the Streok factor

before the Stretch factor 4x 6x PE / CaSO, Stretching 2x Weight $ apparent density, g / cm

50/50 1.43 40/60 1.50 30/70 1.61 20/80 Io86

0.63

0.74 0.64 0.66 0.65 0.55 0.57 (0.6) ⁺

+ Stretching 3x>

Annotation:

Calcium sulfite was made in E'orm of fine rectangular prisms » shaped crystals are used, which have a short axial length of 5 - 10 / U and a larger axial length of 30 - 40 / U exhibited. The polyethylene used was a material produced in a low-pressure process with a melt index of 0.3.

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'fabeile I clearly shows.! that the density value noticeably decreases. Execution of the stretching pre-cooking decreases ₀ However, it does not change so much with a change in the composition ratio and the number of stretching processes ο

The sulfite crystals of the mixture according to the invention are not deformed or crushed even during the LOrmungsvorganges subjected, In the invention Stretching or stretching takes the degree of orientation of the polyethylene crystals and the degree of grain zuo At this stage of the process, the sulfite crystals lead Shifts in relation to the polyethylene crystals and thereby promote the formation of evenly distributed Cavities which lead to a noticeable reduction in density, as the experiments on which the invention is based have shown to have"

The stretching process and the conditions to be complied with can correspond to usual processes of this kind «)

Preferably, however, the conditions of the stretching process are chosen so that certain tensions in the "to be treated Material generated and exerted on the material to such an extent that during the stretching process * ganges a cross-association occurs, among such The preferred stretching conditions selected are the polyethylene-calcium sulfite composition subject to alignment, and the grain of the polyethylene may be noticeable be emphasized, especially so that the firmness of the

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The final product is improved _e stretching may be carried out under an appropriately selected temperature v / ground, wherein the range is from about room temperature to about at most 13O ⁰ O.

At a temperature below room temperature temperature no sufficient extent can be obtained at stretch "at a temperature above about 150 ⁰ C temperature, the polyethylene can soften, so that the desired voltage conditions can not be realized _e

For the molding used in the process according to the invention, which contains polyolefin and a specially selected inorganic substance, preferably finely crystalline calcium sulfite, the inorganic substance must have such special properties that allow an evasive and simple separation of the two substances at the boundary areas if the molding is mechanical Is subjected to tension. The common, commercially available simple calcium sulfite cannot be used for this purpose _e

The most suitable one calcium seems to be the fine in the form of cubes or fine rectangular nlfittenartiger or prism-like body has, each a short axial length 1-30 ax and a larger axial length of 5 - / has lüO u "This sulphite is calcium sulphite-hydrated and bustoht made of miiiiiiii ^ large, cubic or rectangular-slat-shaped ^; ^ on Kin ::, ölkriül; ..! ll (jiio liil the well-known indiuj IvS. rush Hi ¹ ι · ί? Ι, οΙ.Ί uiij: υ-

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BATH ORIGINAL

method, or the like can for example by reaction gaseous sulfur dioxide with hydrated lime or acidic alkali metal sulphite with slaked lime or calcium chloride this sulfite not 'be prepared The sulfite / experienced with the known industrial' produced is a fine crystalline powder with grain sizes of less than one η or has the Form of rather large polycrystals o Noticeably developed single crystals are practically impossible to obtain with these known methods. . ·

For the production of sulphite in accordance with the above requirements for use in the process according to the invention, a production process is particularly recommended in which acidic alkali metal or ammonium sulphite is caused to react with calcium carbonate. Although it is extremely desirable that the individual sulphite crystal be pure and as pure as possible has a smooth surface, in order to achieve a better separation of the sulfite hemihydrate crystal in the sense of the above description, a mixture with other inorganic substances can also be used for mixing with the polyolefin _{or the like}

These inorganic additives can have other shapes and dimensions than those specified above «) For this Purpose, based on the g total amount of the mixture, up to about 30 percent by weight of regular calcium sulfite, gypsum, calcium carbonate, iron oxide, zinc oxide, kieselguhr, Quartz sand, regular sand, talc and / or the like

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BATH ORIGINAL

be added, the specially selected crystalline calcium sulfite hemihydrate forms the main component of the mixture and has sizes from 1 - 100 xx .

A polymer or copolymer is preferably used as the polyolefin used, which has ethylene and / or polypropylene as the main component, which has a better crystalline did and has a melt index of less than 10 »

Olefins can be used as the copolymer components such as ethylene, propylene, uuten, pentene and the like, halogenated Olefins such as vinyl fluoride, chlorofluoroethylene, tetrachlorethylene and the like and / or unsaturated Compounds that are copolymerizable with ethylene, such as vinyl acetate, alkyl (meta) aorylate and the like «

The sheet, or sheet, or fur products associated with the Processes according to the invention are produced have sufficient flexibility and permeability themselves noticeably low temperatures, such as -50 C and less, and are comparable to leather and paper. Such film products can be printed and / or colored with oily or aqueous inks or dyes. aside from that They can be glued by means of aqueous, oily or curable adhesives, so that they can be used for numerous purposes instead of conventional leather and paper are suitable.

It must still be emphasized that this is for the purposes of the invention

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Process "usable calcium sulfite in large quantities as By-product is available when reducing combustion gases desulphurisation of environmental pollution, »That is why the invention can also be used with the To make desulphurisation of combustion gases economical; So far, the by-products occurring, namely calcium sulfite, could not be used in any economic way Used extensively, especially when large quantities are involved. Because 'calcium sulfite by oxidation turns into gypsum at high temperatures, which is useful for humans is harmless, and the products according to the invention are extremely difficult to burn, the invention provides also in this respect noticeable progress

The accompanying drawing illustrates the relationship between the composition ratio of polyethylene-calcium sulfitin an unstretched pell and the apparent density *

A commercially available product under the name "Hyzex" with a density of. 0.95 g / ml used The calcium sulfite was in the form of prismatic crystals with a particle size of 5 - 4-0 yes and a density of 2.52 g / ml *

example 1

Several compilations, which are shown in the following Table II and calcium sulfite hemihydrate with a specific gravity of 2.52 in the form of a prismatic J'.r.i ijt.'j.'11'j with shorter axial dimensions of 5 - 10 / u and or axial measurement from 20-4Ou and commercially available

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- 12 ORIGINAL BATHROOM x-

Containing polyethylene with a melt index of 0.3 were in each case thoroughly kneaded. For this purpose, the compositions were passed through a calender, the rollers of which were kept at a surface temperature of 150-160 °, the processing time being 3 minutes. 5 mm Diokee These skins were cut separately into sizes of 10 cm × 10 cm. Three such sections of each group were further treated in a stack on a press which had mold plates coated with chrome by pressing at a temperature of 180-190 ⁰ O and a load of 100 kg / cm over 5 minutes, a pressed sheet was found by 1 mm in thickness · This pressed sheet was cut into sizes of 5 cm χ 10 cm and then subjected to uniaxial stretching in heated air of 100 - subjected to 12O ⁰ G "The The stretching factor is given for each test in Table II »

Regardless of the stretch factor, the apparent density was less than 1.0 g / cm and all film products were permeable "

For comparison, commercially available calcium sulfite hemihydrate or calcium sulfite was used which was obtained by bubbling Joliwefeldioxid-G-as in milk of lime and finer crystals with grain sizes below 5 Ά aufwiese In combination with polyethylene could not pressed sheets in a bath of heated air be stretched that had less than 130 C »

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The composition, the prismatic calcium sulfite crystals Contains within the meaning of the invention, a uniform separation in the interface area between the two Polymer constituents and the sulphite constituents are subjected to «The separation is carried out throughout the area of the pressed sheet, and evenly everywhere, determined The material can therefore be a stretching process in be subjected to a heated state "-

In contrast, in the case of the reference or control samples Ir ₀ 5-1, 5-2, 5-3 and 5-4 listed in Table II below, extremely uneven stretching was found. The external tensions were concentrated at individual points in the stretching area. For this reason, the control samples were destroyed before they reached a 1.5-fold elongation due to the stretching. The desired permeable films could not be realized in this way.

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Table II

CO CD CD

Compositions of polyethylene / calcium sulphite hemihydrate Mixtures and relationship between toughness or tensile strength and elongation and apparent density of the variously elongated Duster

Ivluster P Ξ / ¹
• ΚΤτ ·
~ Weight isSO ₃ .1 / 2 H ₉ O Stretch factor
(x times) Strength ¹ 'Auslän- ^ Young-Hodui' Spec.Gew.
kg / cm ^ gung kg / cm ^ g / cm * 73
32
18th 2800
1920
2760 1.43
0.74
0.64 T ^ temperature (4)
⁰ G - 1-1
1-2
1-3 50/50 unstretched
4th
6th 121
493
450 174
30th
26th 2000
1620
1950 O VD LA
LA VD VD
OOO
HOO 20.4
less than -80 2 - 2
2 -3 40/60 unstretched
4th
6th 113
380
310 255
18th
10 1800
1390
1970 1.61
0.55
0.57 13.0
-80
Il 3- 1
3-2
3-3 30/70 unstretched
4th
6th 92
270
240 121
116
63 1100
500
1000 1.86
0.76
OooO -4.0
-80
Il 4-1
4-2
4-3 20/80 unstretched
2
3 61
73
85 -39.0 ^
-80 -JT
Il iCcmxroll-Pü /
^{: <Γβ} wx. GaSO-. 1/2 H ₂ O Stretch factor
(xnal) destroyed (not
Il
Il
ti stretchable) 5-1 50/50
40/60
3 0/7 C
20/30 1.5
Il
Il
Il

(1) rni - olyäxhylen ("Hysex ¹ ', Diente 0.95 g / cm", melt index 0.3)

(2) calcium sulfite, the finer by bubbling sulfur dioxide gas in milk of lime in the form of hemihydrate _M Zrisxalle mix Tsilchen-u-Rössen less is 5 / u prepared as

Q (3) Measurement of strength and elongation was carried out in accordance with JIS-K 6723/1969 at a winding speed. 200 mm / min at the seam temperature on a "Tenshiron" tension tester, which is manufactured and sold by Toyo Ssiki K. Ii _{0,! I'okyo.} (4; For an explanation of T ^ see above.

Example 2 '.

A composition of calcium sulfite semi-hydrate in the form of spherical crystals with a true specific gravity of 2.49 and commercially available polypropylene with an O melt index of o. _? 5 - see sample 6-1 in Table III below, was ^{rolled into a film on a calender with a roller surface temperature of 180-19O 0} O. This 3PoIie was then air-cooled and diaxially stretched on a tenter machine in an air bath that at 130 - _β was heated 150 ⁰ G - this resulted, I β uniformly distributed interface between the separations. MIl and the matrix material. "Stretched 3PeIl produced in this way showed an apparent density of 0.5 g / cm" The values for strength, elongation and "softening temperature" T ^ (lower limit of the temperature range ^ in which the material is pliable) are given for this 3Polie in the following table 3 ⁴ _o

Table III

Strength, elongation and lowest temperature limit, up to the softness and flexibility - exists, for a calendered and biaxially stretched film of a polypropylene / calcium sulfite hemihydrate composition

Mu r.3ter - 1 PP / 0aS0iol / 2 H ₀ O more biaxial O-
kg / cm ' ¹ ' Longer ο Ij? Young Mr D. Stretch (1) " "·· / Modulo Ue w ο / 0 factor Firm 7 °
(D ⁰ C kg / cm lengthways, crossways speed 123 6th 30/70 4- 4- 220 less than 3000 fold fold ger - as -80

(1) '// erte igoi-ieoaen in the longitudinal direction of the pattern j the strength of the unstretched film was 138 kg / cm, - die.aus-läii .-: ung 123 / oo

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BATH ORIGINAL

223678S

Example 3

The pattern 3-1 (PE / Oa3O ₃ .l / 2H ₂ O = 30/70 wt. ^). According to the above-mentioned Example 1 and given below in Table IV under 7-2, a bending treatment of 90 bends was successively subjected, starting at one end and progressing through the middle part to the other end of the pattern. This resulted in the mechanical separation the polyethylene and oil-sulfite constituents ", in comparison sample 7-1 was made from polyethylene alone without filler material. Tension loads were only exerted on this comparison sample from the outside".

The samples stressed in this way were measured with reference to the temperature T " _t, which forms the lower limit for the snugness and softness." The result is given in Table IV below.

Tabel template 4th M. Temperature T- 3 ⁰ O
64 ° a template
TJ-p Just slide off
Polyethylene
Pattern 3-1 7-1
7-2 Before Naoh
Bending steps example - I ⁰ O
. - 4 ⁰ O

This example relates to the production of oaloium sulfite for use in the invention, combustion exhaust gas, the

come from a power plant equipped with steam boilers

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which are heated with heavy oil are treated with an aqueous sodium sulphite solution. 5200 g of the aqueous solution, which also contained ₀ % acid soda sulphite, 14% 7% sodium sulphite and 3% sodium sulphate, were introduced into a reaction vessel , which was equipped with a stirrer and made to react by adding 200 g of Galoium carbonate at 80 0 for ninety minutes. The calcium carbonate had previously been sieved with a 200-mesh sieve. '

The calcium sulfite occurring as a reaction product was Immediately put in a filter unit for a possible Avoid oxidation, and was filtered in the unit, and the filtered material washed with clean water The calcium sulfite thus obtained showed under the microscope the shape of prismatic crystals with substantially uniform Dimensions. The shorter axial length was 5 - 10 / u, the larger axial length 30 - 40 / u.

When immersed in methyl red benzene solution, the crystals turned red and showed solid acidity with a Acid number of + 3.3- + 4.8 “3you were determined by contact with p-Dimethylaminazobenzene not colored

Example 5

The calcium sulfite obtained in the previous example 4, that is a true 3-specific3 weight of 2.52, measured with Toluene, was thoroughly commercialized with low pressure Polyethylene with a melt index of 0.3 mixed,

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This composition was roughly on a roller mixer Kneaded for 10 minutes, the surface temperature of the calender rolls being 150-160 G, and into sheets of about 0.5 thickness now rolled out.

These slides were bottomed to sections 10 cm × 10 cm. Three such cut sheets were treated in a pile on a press, the chrome-plated mold plates having, and indeed for 5 minutes at a temperature of 18O ⁰ G and a load of 100 kg / cm. The pressed sheet was cut into sizes of 2 cm × 10 cm and then subjected to uniaxial stretching in air heated to 100-120 G. The experiment was repeated under various conditions which are given in Table V. The stretching factor is also given in Table V for each test.

Irrespective of the stretching factor, there was an obvious one Density less than 1.0 g / cm j all film products were permeable. The strength was excellent. The products could float on water.

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Table V

Pattern elongation factor strength elongation
PE / OaSO ^ (xraal) kg / cm. ■ $ "g / ml

unstretched - "- . - ■. 1.-43 50/50. 4th 480-550 24-35 Oe-74 VD 600-650 8-30 Oo 64 unstretched 150-200 150-250 1.50 40/60 4th 350-400 15-40 Oo 66 6th 300-350 20-30 0o65 unstretched 80-120 50-170 Io61 30/70 4th 250-300 15-21 . O «55 6th 200-270 8-15 ■ 0.59 20/80 - unstretched
3 60-100
100-130 ■ 20-70
10-20. Io86
0o6

The specified foil strengths of the exemplary embodiments do not constitute a fundamental limitation of the invention

- PATENT CLAIMS

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Claims (1)

PATENT CLAIMS o Permeable, film-like material with a content of 50 - 85 percent by weight of an inorganic substance, which mainly consists of calcium sulfite crystals with a Particle size from 1 to 100 microns, and from 15 to 50 percent by weight polyolefin, the material being a apparent specific gravity of 0.3 - 1.0 p / cm, a Young's modulus of 100 - 4000 kg / cm, a tensile strength of 50 - 700 kg / cm ^ and a lower limit of Exhibiting softness and pliability of less than -50 0 2β method of making a permeable sheet-like Material, characterized in that a mixture of 50-85 percent by weight of an inorganic Substance whose main component is calcium sulfite crystals with particle sizes of 1 - 100 u, and 15 - 50 percent by weight of polyolefin and the mixture is calendered to a film and that the film at least in one direction to at least 1.5 times its original length is stretched. 209885/1256