DE1694615A1 - Thermoplastic materials based on polyvinyl chloride - Google Patents

Description

Thermoplastic materials based on polyvinyl chloride

The present invention "relates to polymeric thermoplastics . Polyvinyl chloride materials, especially polymeric thermoplastic materials Materials with chemical and physical properties, they are used in the production of films or hoses for agriculture, packaging and, in particular, sacks and make containers suitable. .

It is known that in the case of the usual compositions based on vinyl chloride polymers for the production of sacks from blown tubes, the addition of increasing amounts of plasticizers (with otherwise the same formulation) improves the cold bending strength _e

In particular, the addition of alkyl diesters leads to aliphatic Polycarboxylic acids lead to a more remarkable improvement in cold resistance.

At the same time, however, the addition of increasing amounts of plasticizers leads to an increasing decrease in tensile strength, a progressive increase in the ultimate percentage elongation and an increase in the deformation of the manufactured article

10 ö 8 1.9 / 1 β-1 0-

under constant stress (creep strain), the overall effect of adding plasticizers is therefore to improve the resistance of the sacks to mechanical stress at low temperature, which unfortunately "depends on an increase in Ve:
accompanied is _e

Increase in deformation, especially at temperatures above 10 C

It is also known that the addition of increasing amounts of Minerals with the same plasticizer content has the opposite effect, as it leads to objects that at a temperature

O *

temperature above = 10 C show increasingly less deformation, however, unfortunately, are much more fragile at lower temperatures.

On the other hand, it is extraordinary for economic reasons It is advantageous to use compositions containing a large amount of minerals, since their rice is essential below that of the polymeric material itself and that of the plasticizer.

The aim of the present invention is therefore to improve the physical-mechanical properties, in particular the resistance to brittleness at temperatures below 10 C and deformation under load at temperatures above 10 ⁰ G in thermoplastic polymeric materials based on vinyl chloride polymers, which in addition to the usual additives a 'Contain a large amount of minerals, whereby these materials are advantageously used for the production of films or hoses for agriculture, for packaging material * in general and for sacks in particular, for welded or glued containers and the like »

These and other objects are achieved by means of the polymeric thermoplastic materials based on polyvinyl chloride, which, in addition to the normal additives that are usually incorporated into such substances as stabilizers against heat, light and atmospheric influences, and ultraviolet absorbers, lubricants and dyes, are a large according to the invention Amount of minerals,

8 819/1910

preferably more than 5 parts by weight per 100 parts by weight of the polymeric material, and a plasticizer composition those from the following mixture "ordered:

a) at least one aliphatic polycarbonic acid;

Td) ister at least one of an aromatic polycarboxylic acids wherein the Aifcyl £ st '-. R of the aliphatic polycarboxylic acid in amounts of 40 Ge ^- W ,, -% or more of plasticizer mixture present isto

Surprisingly, it has been found that it is possible to obtain films or tubes (by blowing) from the polymeric materials composed according to the invention based on vinyl chloride polymers, the deformation of which “at temperatures above 10 ^° C. is significantly (“ up to 50 $) less than that similar materials that are on the market, while at the same time the flexibility (the brittleness at low temperature), even in the presence of large amounts of minerals, is kept within predetermined limits.

It is therefore surprisingly possible, the deformation under load at a temperature above +10 C and, at the same time, the Flexibility at low temperatures, which is known to that they are influenced in completely opposite ways by the same additive (either plasticizer or mineral), to improve·

In accordance with the present invention, this becomes a general improvement the properties through the simultaneous use of large ϊ · ί close to ilineralien and a suitable plasticizer together— set

PoljHfinylchloridprodukte in the sense of the present invention are so "i-roducts which are obtained by polymerization of vinyl chloride alone or with other monomers polymerizable _{therewith and contain at least 75 weight c} - ^ chemiach bound vinyl chloride, as well as the mixtures," graft polymers and I-iiüchpolyvon Vinyl chloride "

In the case of - ^ / vinyl chloride it is preferred to denote a norr-j / rle :; rol ^ ieri; iation3verfahren in aqueous suspension ei-ht-Ί-

BATH

1B34615

tenes homopolymer to be used, the molecular weight calculated from the viscosity in cyclohexanone at 0.40 wt, -% / v * at 25 ⁰ C, a viscosity value of 0.30 to 0.75 equivalent, and its Seilchengrösse 150-50 microns lies"

The substances that can be used as liineralieri according to the present invention can be selected from a variety of products whose i.-atur and Eigenech ^! f that are well known to your person skilled in the art, select ₀

A preferred group of substances includes calcix amcarbonate, Calcium silicate, diatomaceous earth, quartz, silica, toner ie and the like, in amounts from 5 to -50 and preferably about 20 GrewiCiJ.t3tei.leh per 100 parts by weight of the vinyl chloride polymer be used «'- - - ■.

particularly suitable for the present invention proved Calziumcarbcnat, insbesondere- in the form of particles, ^x _'# ettsäuren soaps and the like are coated with mineral waxes. and have such a particle size distribution that at least 50 fo a diameter less than 5 microns and at least 80 fo a diameter less than 15 microns »

According to the present invention, the allyl esters can be aliphatic polycarboxylic acid used as components of the "plasticizer composition can be chosen from a large series of compounds.

Particularly suitable are the alkyl esters of lemon, isomalein, Adipic, sebacic, azelaic acid and the like.

A particularly preferred group of these compounds includes Alkyl esters of adipic acid having the following general formula

GOOR «-. .-

COOR "
in which R 'and R "are the same or different from one another and

BAD ORIGINAL ' \

Represent radicals with a linear or branched hydrocarbon chain, and which contains 4 to 13 carbon atoms.

These alkyl esters of aliphatic polycarboxylic acids are used alone or used in the mixture in amounts of 40 to 95 wt .-%, based on 100 parts by weight of the plasticizer mixture.

The esters of an aromatic bicarboxylic acid used as components of the plasticizer mixture according to the present invention can be selected from a large number of connections will.

A preferred group of these "compounds stiffen the esters of Phthalic acids, which are characterized by the following general formulas:

> s. S COOR ¹ ·· ¹¹¹¹ ROOC

COOR ¹ " ¹ ^ Sj ^^ * CO-O- (R). - 0-OC

in which R ^'11 and R ¹¹ ' ^{1 are the} same or different from one another and represent a radical with a linear or branched hydrocarbon chain and which has 4 to 13 and preferably 6 to TO carbon atoms, or represent an aryl or alkylaryl radical, on the other hand R denotes a hydrocarbon radical with a straight or branched chain and 2 to 8 carbon atoms. {

These esters alone or in a mixture are according to the present Invention in amounts of 5 to 60 parts by weight based on 100 Parts by weight of the plasticizer mixture used.

The following examples serve to illustrate the invention *

example 1

100 parts by weight of a commercially available polyvinyl chloride, the

t Ö 9 β 1 9/1 9 1 O

-β- 1B94615

known under the name SICROH 548 J ¹ M (trademark of Societa Edison, Milan) were 5 minutes with the following

at room temperature
solid additives en / mixed;

- 20 parts by weight of CaCO, the product type that is sold under the name Omya BSH by GMYA S ₀ A ₀ *

- 5 parts by weight of dibasic lead phosphite _e

- 0.5 parts by weight stearic acid ₀

The thus obtained G-up erniacfr was heated to 60 ⁰ C, then a Weichm was icherzusammensetzung containing the following ingredients - ewroii.tsteilen OB 'in quantities of 35 to 60. P added: - - ■. -

- Dioctyl phthalate, daa on the. Market is known as SICuL 150 (.. ■ trademark of Societa Edison, Milan) ₀ . .

- Butylbenzylphtiialat, known on the market as SICOL 160 (trademark of Societa Edison, Milan) _{or similar}

- Diisodecyl phthalate, known in the market as SICGL 134- is (trademark of Societa. Edison, i'iailand) ..

- Dioctyl adipate known in the market as SICOL 250 (trademark of Societa Edison, Kailand) ' _e

For simplicity, these compounds are plasticizers "means," in \ the text below by the following abbreviations

Dioctyl phthalate as - DOP

Butyl benzyl phthalate as BBP

Diisodecyl phthalate as' DIDP

Dioctyl adipate as DOA

The G-emiscn thus obtained was heated and under Hühren to 90 ⁰ C "maintained at this temperature with continuous stirring for 10 minutes ·

The obtained (dry) ^ emic v / urae -and cooled to 40 C ⁼ withdrawn from the mixer

Q 9 8 I 9/1 9 1st G.

- 7 - 1684B15

The dry mixture was then processed in a cylinder grinder, wherein the temperature of the cylinder during a period of time was valid from Hinuteft at 150 0 «, - *.

The raw strip thus obtained was converted into a conventional liche granulation mill given "■

To the mechanical properties of the polyaerenmateri obtained as you can judge better, "Flatten" were with - different Dimensions, shapes and dimensions manufactured on which the OeStImJ-IUHg of the mechanical properties, was made ο

The procedures were chosen so that the obtained - "'" erte,. Since they were obtained from "isotropic" material, they were comparable with one another - it is known to the skilled person that films which orientate themselves differently during the conversion stage may vary in mechanical properties and depending on show clearly different practical behavior in their orientation * ^1. ...:, - '-_..- "

For this purpose the was prepared as described above Granulate again in a suitable cylinder mixer at 150 0 Machined for 5 minutes to obtain a strip of polymeric material from which the "plate" could be made, their type and finishing method of the mechanical to be determined Properties depended on ■ ". '".

a) Plates for the preparation of samples on which tensile measurements (ASTM D-412) and measurements to determine the cold bending temperature (ASTM P-1043) were carried out. 75 g of the polymeric composition of the type described above were placed in a square mold, which in subjected to a vertical plate press at a temperature of 150 ⁰ C for 3 minutes under a pressure of 75 Atü wurdej it was because until cooled to 'room temperature. The plate obtained in this way had a thickness of 1.5 mm,

ϊ>) Plates for measuring the "Shore" Α hardness (ASTM D-I706) 40 g of the above polymeric composition were placed in a graduated mold, which was placed in a vertical platen press at a temperature of 150 ° C. for 4 minutes

■■■■■. . ' 1093 19/1910

Pressure of 75 AtU was subjected, -which to room temperature was cooled * The plate was 3 mm thick «,

c) flattening the .Herstellung of samples on which the determination of the mate rial deformation · unt he cons tant e r load (Krie ch strain) was carried out "(internal method of the. broom friction in ASTM D-674) o

180 g of the above polymer composition were given in a square shape, which is initially a 'Heating for 2 minutes to 150G and still reads in a vertical Plate press at 150 C for 4 minutes a pressure of 125 Atü was subjected; a slow cooling followed Room temperature to avoid the occurrence of deformations or stresses in the polymer material as a result of sudden temperature to.avoid.turabfalls »The plate was 1.5 mm thick.

&) ■ Plates for the production of robes on which tear strength measurements were made » (ASTM D-689) ■"

5g of ^u emiüehes described above were placed in a quadrati specific form which was unterworfeil in a vertical platen press at a temperature of I50 C 3 Hinuten a pressure of 75 Atü; then it was cooled to room temperature. The plate was 0 ^ 2 mm thick

In Table I are the mechanical properties of the polymer composition indicated, which was prepared as indicated above, with one of the components of the ^ eichmrchergemiseh.es has been omitted:

Table I.

Components

PVC, parts by weight Il DOP, Il BBP, ti DIDP, tr DOA, (GaOO ₃ ) Surcharge

1 OO 5 100Θ 5 100 LTv 100 5 - b 12, 12, 5 12, 5 1 2, 5 ■ - 5 12, 12, 1 2, 12, - b .12, 1 2, 12, 12, . - 2 O 20th 20th 20th

VO 9 8 1 9/1 3 1 0

Mechanical properties

I-Iodu-1, kg / mm breaking load, kg / cm elongation, ^ "Shore" A "hardness creep elongation ( <& = 0.6 kg / mnr)

1.65 1.70 1.60 1.75 2.25 ' 2.30 2.20 2.4 240 230 235 ' 235 • 91 91 89 93 / mm ² ) 13.3 13.7 12.8 12.4 + 23 ° 0 5800 6800 7OOO 5700 +10 ⁰ C 3100; 3300 3400 2500 O ⁰ O 1800 1900 2000 1000

Tear strength, "g / mm" at +23

It Il ti

Cold resistance (cold bending _?
temperature) at 9500 kg / cm, C -1 - 1.0 - 14.0 - 10.0 - 1.0

= Change in deformation under constant load over time (10 days)

From the figures given in Table I it can be seen that with the same mineral additive (OaCO ^) in the plasticizer composition, the V / eglassen τοπ DOP, BBP or, DIDP practically no negative influence on the tensile strength properties and also not on the cold bending temperature “Omitting DOA, on the other hand, causes a noticeable decrease in tensile strength at 0 C and. obviously also the cold bending temperature «

This shows the importance of the presence of DOA in the '"eic lime-rather gladly i, j ch for achieving a good tear strength at low temperature and thus for reducing the possibility "" raking the sack at low temperature, both as a result of bumps from travelers,

Example 2

The vor.otenorj'je Jeisfjiel was repeated with the difference daso one Wc ichm ^ cnorsysteme used in which the DOA and DOP ^{l '1} erjge gradually from 0 to 25 parts by weight, based on polyvinyl chloride, has been increased "

The results obtained here are shown in the following Table II reproduced «,

109819/1910

Components

PVC, 'parts by weight DOP, ",
■ BBP, "

DQA, "
σ set amount (CaCO ")

CD ^

- * Mechanical properties »

CD - '^:;"

_ ± module j kg / mm *

ψ breaking load, kg / mm ο elongation, fo

Shore "A" hardness. ,

Creep strain {d = 0.6 kg / mm Ir *.

ο ^{c &} heat resistance ,, g / mm at +23 G

H ti .H + 1O ⁰ O Ii it it o ° C>'"'» -1Q ⁰ C

Tabel II 5 100 5 100 5 100 20th Ij 100 100 5 100 5 12, 5 25th 5 12, 5 12.5 12, 5 5 12, 5 12, 5 12, 5 12.5 12, 5 12p 12, 5 12, 12, 5 12.5 12, 12, 12, 12, - 12.5 25th 12, 20th 2U 20th 20th 20th

Cold resistance (at 9500 kg / cm ^) ⁰ C

1.65 1.10 0.65 1.75 1.10 '0.65 2.25 1.90 1.55, 2.40 1.90 1.50 240 280 330; 235 280 330 91 81 73 93 8.1 72 15.3 21.5 31.6 12,; 4 21.5 31.5 5800 9000 19000 5700 9000 9400 3100 6000 780Ü 2800 6000 7500 1800 3600 4500 1800 3600 '53OO 1000 2100 3500 1000 2100 5000 -11.0 -26 -35 -V5 -26 -41, c

A comparison of the figures given in Table II shows that "when adding from 0 to 25 parts by weight of DOP" and DOA with the other components remaining the same, the mechanical and creep properties at room temperature are subject to practically the same fluctuations; however, 1O ⁰ C "an increase in the DGA Henge improved at a I'enip3ratur below about + rasehencisrweise lie üeissfestlgkeitseigenschaften ₀

Example 3

As in Example 1, three polymer compositions were prepared based on 100 parts of polyvinyl chloride . _For the normal additives using "a" calibration system from 45> 5 view "- * .- = DCP and 54.5% by weight - * ->. DGA, 3e.d0.ch different amounts of I-iineralzu3chla _f ; (CaCO-) were added.

The results in terms of mechanical properties are indicated in the following table III,

- - ■! Table III

Components ι creep strength, g / mra at A? G t (a) W- Cc) PVC ₉ parts by weight II Il It +23 ⁰ C 100 100 100 DCP " Il ti f! +10 ⁰ C 20th 20th 20th DOA, - " 0 ° S 24 24 24 Surcharge (CaCO ₃ ) "' 0 20th 40 Hechantsehe properties Module, kg / mm ^ 1 1.1 1.2 Breaking load, kg / mm '" 1.90 1.75 1.60 De-umn-, ρ ;, _ .. 300 280 250 Shore "A" hardness. 80 83 84 24 19th 17th 8000 9000 8000 6500 65ΟΌ 4000 4300 ^ -4300 1800

Cold resistance (cold bending tempera

tur), C.

-26

-25

-24

1098 1 97 1310

! 694615

From those listed above. It can be seen from the figures that with the same type and the same tightness of the plasticizer used, an increase in the mineral additive leads to a deterioration in the tensile strength at temperatures of and below + 1O ^{0 G} as well as a reduction in constant load deformation.

Taking into account the strong changes in the tensile strength value at ⁰ ° C when increased from 20 to 40 parts of the aggregate, it is preferred ■ - except in special cases - 20 "Gevichtsteile MineralZuschlagj based _a uf not to exceed 100 parts by weight of polymer material ,,

> - ■■■: ■■■■ -ν-

Example 4

Using the procedure of Example 1, two polymer compositions were prepared with different plasticizer compositions and different mineral additives. Composition • a) was typical of PVC bags of good general quality; Togetherness. Settlement b) corresponded to the conditions _{0 explained above}

The results in terms of mechanical properties dor both materials on panels with a thickness of 1.5 mm (and of 0.2 mm when measuring the tensile strength) are summarized in the following "Table IV:

Table IV

Components tfichtsteile PVC, Ge. Il DOP, Il BBP, Il DOA, CaCO ₃

(a) Cb) 100 100 26th 20th 10 - 24th 40 2 C

BATH 1 0 9S 19/1910

Mechanical properties

Module, kg / mm

Load at break, kg / mm elongation ;, for Shore "A" hardness

Creep resistance (ο = 0.6 kg / mm · - ■ Heissfestigkelt at H-23 ° G

"+ 1O ⁰ G ti it 0 ° C ■

Cold bending temperature, ⁰ G

In the following table Y the numbers are given which relate to the mechanical properties of films which were obtained by blow extrusion (thickness: 0.2 mm) from two materials designated in Table IV as a ) and b),

0.9 1.1 1.5 1.75 240 280 79 83 23 19th 7000 9ÜC-0 4000 6500 2000 4300 - 25th - 25th

19/1910

Table V Mechanical properties

module
ASTM D 882

Breaking load ASTM D 882

ASTM D oG2

Longitudinal direction kg / mm

Cross direction, kg / mm

Longitudinal direction, kg / mm

Transverse direction longitudinal direction

Cross direction longitudinal direction.

Creep elongation ^ = 0.4 kg / mm

(became, as above

described, measured) transverse direction

Tear strength at + 23 ° C ASTM D 689 ■ a) b) 9.9-1.1 1 ο 3-1 ο

1. -1.2 1.8. - 2

1.7-1.9

260-300

Longitudinal direction

g / mm SUOG

at +10 'cross direction bOüO Longitudinal direction

2500

at O ⁰ O transverse direction

g / mm. 3500

1.1-1.3

2 ₀ 2-2 "4th

280-320

3OO-34U 320-360 13 10

15th

Transverse direction

g / mm 10 ₀ UuO 10,000

Longitudinal direction _:.

g / mm '5000 7000

8000 4000

500J

Finally, two rows of sacks were made starting from the blown hoses made from the polymer materials a) and b)

These sacks were filled with 50 kg of ammonia sulphate and conditioned at O ⁰ O for 2 weeks. They were then subjected to ball-and-socket tests, with the impact occurring laterally on the larger side

BATH ORIGINAL

1 O9819 / 1910

Tabel VI 1 X 82 a) χ 82 50 1 H) 50 χ 82 00- 5.0 160 χ 82 160 50 o ^G. 0 °. OO 0 ° 60 too 0 ° 60 20th

Materials Sack size - cm drop height - cm test temperature - breakage - i °

■ Eye tables IV, T and ¥ 1 -is ' to "" recognize, - that by a) reduction of the additional quantities,
) yaraainderuii ^ · the; .W

c) DOA arrangement. ■ χει "W ^ i ehinj. Ehe rgemi 8 ch

at the same time the deformation under constant load so \ t? o1i1 of the-'material as well as the 3rtc.lces produced from it> the breaking load and tear strength at low temperatures are caused, although-these.properties are opposite » ----- ■ -. -.

Tatseähjclieh was improved Diniensionsbestäadigkeit at temperatures over 10 ⁰ C because the "creep" was reduced; CX c- · I was early the behavior at temperatures below 10 G air; Desteu, -

109819/1910

- 16 Example 5

Example no. 2 was repeated with the difference that one Used dioctyl azelate instead of dioctyl adipate. The amount of dioctyl azelate and dioctyl phthalate gradually increased from 0 to 25 parts by weight based on 100 parts by weight of the polyvinyl '. Chloride increased.

The results thus obtained are recorded in Table VII below.

1 0.9 81 9/191 Ö

Components

PVc, parts by weight DOP, "BBP,"

, DIDP, »* DOAz," Input amount (CaCO-)

Mechanical properties 2

Module, kg / m breaking load, kg / mm 'elongation, % Shore «A" hardness creep strain (

0.6 kg / mm) λ!

Tear strength, g / mm bijg + Resistance to "" +

η
η

₊ 10 ° C

o ° c

- 10 ° C

2 ν o,

Cold resistance (at 9500 kg / cm) C

Table VII 100 100 100 100 100 100 12.5 25th 12.5 12.5 12.5 - 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 - 12.5 25th 12.5 ' 20th 20th 20th 20th 20th 20th 1.15 - 0.70 1.75 1.15 0.70 1.70 1.95 1.60 2.40 1.95 1.55 2, 30 290 345 235 290 345 250 82 74 93. 82 73 92 22.6 32.7 12.4 22.6 22.7 1 * 4% 9500 9500 5700 9500 10,000 6000 6300 8200 2800 6300 7900 3250 3900 4900 1800 3900 5600 2000 2200 3700 1000 2200 5300 1050 -25 -34 -1.5 -27 -42.0 -10.0

* DOAz - dioctyl azelate

From the comparison of the data in Table VII, it can be seen that if one uses dea? other constituents, the amount of the two gradually increased from 0 to 25 parts by weight, the mechanical and creep properties undergo practically the same changes at room temperature, while, on the other hand, at a temperature below +10 C the quantitative increase in DOAz surprisingly improves the tensile strength properties .

109819/1910

Claims (10)

Claims 1 «Thermoplastic vinyl chloride compounds, suitable for Production of foils, characterized in that they are mineral- contain additives together with a plasticizer mixture of the following ingredients? a) "at least one ester of an aliphatic polycarboxylic acid, namely an alkyl ester of isomalein, citric, adipic, sebacic or azelaic acid, the alkyl radicals being the same or different from one another and having straight or branched chains with 4 to 13 carbon atoms, and the alkyl ester in Amounts of at least 40 Q & w * -% or more, based on the softener composition, are present, and b) at least one ester of an aromatic polycarboxylic acid, namely an alkyl, aryl or alkylarylphthalic acid ester or Glycoldiphtalat, where the alkyl radicals are identical to one another or are different and straight or branched chains with 4 to 13, preferably 6 to 10 carbon atoms, the The aryl radical is preferably a phenyl radical, the alkylaryl radical is preferably a benzyl radical and the glycol radical is diphtalate has a straight or branched chain of 2 to 8 carbon atoms , and where de ^ L, mineral additives in amounts of 5 to 50 parts by weight, based on 100 parts by weight of polyvinyl chloride. 2. Thermoplastic compositions according to claim 1, characterized in that that the mineral additive consists of one or more substances, namely calcium carbonate, calcium silicate, kieselguhr, Quartz, silica or aluminum oxide. 3. Thermoplastic compositions according to claim 2, characterized in that that the calcium carbonate is in the form of small particles with such a size distribution that 50% less than 5 microns in diameter and at least 80% less than 15 microns in diameter, where these particles are preferably coated with mineral wax, fatty acids, or soaps. 109810/1910 if. Thermoplastic compositions according to claims 1, 2 or 3, characterized in that the ester designated as (a) is dioctyl adiphate and the ester designated as (b) is dioctyl phthalate wherein the amount of the ester (a) is about 54% by weight of the plasticizer amounts to. "... 5 · Films and tubular films consisting of the thermoplastic compositions according to claims 1-4. . Consisting of sacks or welded or glued containers from the thermoplastic masks according to claims 1 -4, FUri Montecatini Edison S.p.A. Lawyer 10 9 8 13/1910