DE2215121A1 - Process for the manufacture of composite sheet material - Google Patents

Description

Hamburg 50 - Koenigstrasse 28 2215121

W.25215 / 72 12 / Sch

Z Λ 3ι 72

Cosden Oil & Chemical Company Big Spring, Texas (V.St.A.)

Process for the manufacture of composite Railway material.

The invention relates, and in particular, to the manufacture of multi-layer or multi-layer sheet material on the extrusion of polystyrene sheet material, which has a thin protective layer made of ABS polymer, Vinylidene fluoride polymer or acrylic acid ester polymer.

Extrusion processes for the production of multilayer web material are known. However, so far use known methods essentially exclusively a certain type of containment technique in which a Flow of thermoplastic material, typically the volumetrically smaller flow, complete, i.e. equiaxed surrounded by a second stream of such material before the entire composite stream passes through an ejector nozzle or ejection mold passes through it. Alternatively, the enclosure can be effected in the cavity of an ejection mold · In both types of process, what is obtained is in the form of a web Product characterized by an inner layer made of a kind of thermoplastic material, which is between

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two outer layers is arranged or enclosed by these, which consist of a second thermoplastic material.

Heretofore, in the area of ejecting multiple thermoplastic resin layers simultaneously, "little success has been achieved, with one possible exception, when a layer is merely to be placed on top of another layer. In most attempts a number of ejection forms have been used, by" which two separate webs of different material were first formed by ejection. Then the layers were arranged on top of one another and then passed through a further ejection mold or through a narrowed opening. Other attempts have used complex ejection molds in which individual molten streams of thermoplastic material are stacked in the mold cavity just prior to passage through the die lips or die lips.

The possible exception mentioned above relates to US Pat. No. 3,476,627, in which a method is disclosed in which two streams of molten thermoplastic resin are combined in a conduit upstream of a discharge nozzle are such that they have a sharply defined * connection plane to have. The composite stream is then passed through an ejection mold in such a way that the connection plane runs parallel to the main flow direction dos Harzes, which it assumes in the design of the web material · The above disclosure relates primarily to the simultaneous ejection of multilayer polyvinyl butyral resin. However, this reference generally relates to a method of simultaneous ejection multiple layers of a multi-layer sheet material made of different thermoplastic resins which have similar processing characteristics and which adhere to one another. Furthermore, this known method is limited by the requirement that the volume of a given

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Resin component at least $ 25 of the total resin content amounts to.

In contrast, the present invention relates to the manufacture of multilayer sheet material from two materials that have different processing characteristics which are to a high degree incompatible with one another and which have so far not led to any success in any attempt have, by means of simultaneous ejection of several layers and by means of conventional layer formation processes, one strong to maintain adhesive bond between the layers. · Previous attempts to eject such materials at the same time or Ejecting them together resulted in multilayered products in which the individual layers were very easily separated from each other could be peeled off, and similar attempts to combine materials of this type into laminated bodies by ejection a molten layer of one polymer onto a preformed sheet of second polymer resulted in similar results unsatisfactory results. The invention further relates to multilayer web material which consists mainly of a cheap material, i.e. polystyrene, and only a very thin layer or "veneer" made of a second, more expensive polymeric material, which has highly desirable surface characteristics, i.e. ABS polymer, vinylidene fluoride polymer, and acrylic acids s t erpo lyiaer

It is therefore a primary purpose of the invention to provide a method of making multilayer web material of two or more usually incompatible polymeric materials by means of a single ejection process.

Another purpose of the invention is to provide a method of manufacturing multilayer Web material, the main thickness of which consists of cheap polymeric material, and which has a relatively thin surface layer made of more expensive polymeric material that exhibits highly desirable surface characteristics.

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A particular purpose of the invention is to produce a multilayer sheet material which consists mainly of polystyrene and which has a protective surface layer made of ABS polymer, vinylidene fluoride polymer or acrylic acid ester polymer.

With the foregoing in mind, according to the invention, there is provided a method of making composite Sheet material made of polystyrene, which has a relatively thin protective layer made of ABS polymer, vinylidene fluoride polymer or acrylic acid ester polymer. The method includes joining or merging a molten one Stream of polystyrene and a molten stream of ABS polymer, vinylidene fluoride polymer or acrylic acid ester polymer in a discharge line of an ejection mold, corresponding to a single layer of molten material the cross-section of the conduit, the flow being a relatively sharply defined intermediate surface or boundary surface between the polystyrene and the second polymer. After that, this stratified stream is passed through a web-shaped Out of material ejecting form, the form lips or nozzle lips generally with the aforementioned intermediate surface or interface are aligned. Firm adherence between the polystyrene and that of any of the three above Said materials existing protective layer or second layer is achieved in that at the connection point of the two polymer streams, the melt viscosity of the ABS polymer, vinylidene fluoride polymer or acrylic acid ester polymers is relatively close to the melt viscosity of the polystyrene, and advantageously close to is identical to that. In this process, the relative proportion of the material used for the protective layer is preferably less than about 20 volume # based on total polymeric material. Important operating parameters include the temperature at which each polymeric material emerges from the ejection mold and also the temperature the ejection form.

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The invention is explained below with reference to the drawing, for example.

S ¹ Ig. 1 shows schematically an apparatus for

Manufacture of multilayer sheet or pile material using the method according to FIG the invention. · ■ ·· '/ *; ■'

Pig. Figure 2 is a cross-sectional view taken along line 2-2 of Pig. 1. -

Pig. 3 is a sectional plan view; the ejection shape and the inlet line of the device according to Pig. 1.
Pig. Figure 4 is a cross-sectional view taken along line 4-4

the pig. 2.

In accordance with the invention it has been found that a multilayer sheet or polycarbonate material consists of two polymeric Materials can be produced previously using conventional ejection techniques or by post ejection applied layering techniques could only be combined with great difficulty. In particular, the Bahnoder Polienmaterial (below for the sake of simplicity Called sheet material) according to the invention from a layer of polystyrene, which has a thickness that is substantially the desired thickness of the final composite Corresponds to the web material. There is a relatively thin outer layer on one or both sides of the polystyrene layer made of ABS polymer, vinylidene fluoride polymer or acrylic acid ester polymer glued. In this way, a composite sheet material is created which has the desired has economic characteristics of polystyrene and at the same time the iio undesirable surface properties the ABS polymer, vinylidene fluoride polymer or acrylic acid ester polymer owns. Such material, which through a chemically resistant surface layer Made of ABS polymer, it is used for the manufacture of linings for refrigerator doors, butter jars and very suitable for containers for greasy or oily foods

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suitable. The material with a protective layer of vinylidene fluoride polymer is characterized by a excellent resistance to weathering and to chemical attack, and also by a high resistance to Abrasion · The protective material made of acrylic acid ester polymer is characterized by good resistance to Weathering and high impermeability to oxygen and water vapor, making these materials special useful for making containers for food packaging and building products are

An important feature of the invention is that it has been found that a substantially uniform and relatively thin layer of ABS polymer, vinylidenefluoride polymer and acrylic acid ester polymer (hereinafter for simplicity half called "protective material") with the main layer or sub-layer of polystyrene in one single ejection process can be safely combined. Although similar ejection methods are known, such as by As set out in the above-referenced U.S. Patent, the known methods relate to the ejection of chemical similar or at least compatible resin materials, whereas the method according to the invention is chemically and physically dissimilar resins have been used successfully. In particular, it has been found that polystyrene and one of the three protective materials can be ejected together to produce a multi-layer sheet material, which shows strong adhesion between the protective material used and the polystyrene, if the protective material concerned is selected so that it has a melt viscosity that corresponds to the melt viscosity of the chosen polystyrene is relatively close, or if instead the chosen protective material has a melt viscosity has, for example, adjusted to a V / ert by increasing the temperature of the polymer sufficiently which is close to the V / ert of the melt viscosity of the polystyrene. Although it is not possible to set exact limits

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In terms of the degree of similarity required between the relevant melt viscosities of the polymeric materials, and although there may be some degree of unpredictability between particular polymers falling into any broad characterization, generally satisfactory results are obtained in accordance with the invention if the melt viscosity of the protective material in question is within the range of about 50% 1 & 150 % of the melt viscosity of the polystyrene; these relative values are only important under the actual joint ejection conditions, since in most cases the protective material in question, its melt viscosity deviates from the melt viscosity of the polystyrene under standard test conditions to a greater extent so that the deviation is outside the specified range, the melt viscosity can be changed under the processing conditions so that the melt viscosity of the Sch Utilization material can be adjusted so that its value is close to the value of the melt viscosity of the polystyrene.

To show the relationship between relative melt viscosity and the adhesion of ABS polymer and polystyrene, Comparative results are shown in Table I below for two representative sheet materials ejected together specified ·

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Table I.

Melt viscosity values

CD OD t-LO

polymer

1. A3.S - Dow Chemical Co.-

Polystyrene

π ~ „.ς -> ^ Oil S. - Ma Corp. • • Chenie al Co Division of C2 Inp.-ct 32 5D Warner yrcl Pellet rbon c. · Λ co Follow Borg

Cosien Oil & Cher.ical Co. Impact 82pD Pellets

Melt flow rate, Brabender rotary

measured by extrusion torque (10 min.)

• elastometer (A.S.T.M. meter / gram

D-1258-63T), condition G.

(Gms./10 minutes) liability

2.20

420

Well

2.0-3.0

570

0.50

780

bad

2.0-3.0

370

In order to show the relationship between the relative melt viscosity and the adhesion of vinylidene fluoride polymer and polystyrene in laminates, data is given in Table II below for a representative coextruded sheet material, the abbreviation "PVI ¹ " being used for the protective material.

to

■ 5

φ
-ρ
U
φ

CQ
-P

: α5
-P
• Η

CQ O

IQ
• Η

to

γΗ

CQ

I F!

. 4 = I.

Φ Fl f4, Ω Φ Φ CtS 04 * U O Φ

CQ

4>
• Η
Φ

μ ο bQ-H • Η CQ

■ Η 43

Ü5

faO 'F!

_r c1 FüQ CO O · to _r q <ή φ

Η O) Φ

pq .p 2

H + ¹ HFl O) ΝΦβ H 03 O φ 03 +3 0 Φ CO

Λ 0 1'J O (DH 03 bO

)O

Ir CO \ KNCM CQ v-

I U

HO

ClJ

O ··

• Η ·

0

Φ

ι ο h>

• 2 bottles -MH

O O KN

ω ω

CM

G)

H P

O W

P ^ h

P ^ ο

HO

KN

r »

ΚΛ I

O CM

ο η

LfN

CM

O H OO

Fl O 43 43

Φ · Η Ο Φ

rd S til rl

ω φ Pi H

ο, ei Yi φ

O O H ^

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Contributes to the relationship between relative melt viscosity and adhesion of acrylic material and polystyrene material To show layered structures are given in Table III below for representative results ejected web-like materials.

bfl

Φ ι pi 0 ¹ Xi fH C5 pj • 43 r | • Η U ω Φ CQ fH Φ U pi 43 bO ρ 0 φ Fh φ φ S) P! Φ V-
«^^ 43 CQ 0 pi CQ Φ "ο Φ CQ O ω φ Φ P. PJ ^> n : ctJ CD 0 0 43 fH O Φ CD O • Η FQ ω H CQ P- oo \ O K \ M. 43 I. OJ CQ • Η CQ V- H • Η Φ PJ * I. H [> O P. H N M) • Η • H • Η CQ CH Φ Φ • H 0 PJ Ü3 H , Cj • Η 43 • Φ O J; , Q ω .0 HH CD O W. φ hD cq pj • Η- ^ H Ti «Η Φ N H Φ #> 0 Xi & O CQ (X) I.

-P-H

• H: cd B 0

«Λ

O OJ

r

I. ιο CQ I. o3 I. P. CQ I. CQ ω fH I. 08 I. P. CQ OJ CD IA 4 ³ Cj • Η Φ LTN 43 fH CtJ H H H • OJ ω fH CiJ M. r> H H • OJ Φ φ M. ω O ■ Η O CO H Φ (I) φ fH O • Η O OO H 43 ■ Η ?H O O H 43 H O k O O H ω c '3 +3 Φ CQ c $ Ph CQ 4-3 43 Φ φ Φ ■ Ρ PJ H O Ph Φ CQ PS H O Ph H S. H CQ Φ CD CD H 0 V- Φ CD «J t * 3 Ph ι * ' ^r cJ O ί>: ν ~ O Ρ < fH :O H ω • Η fH : ο CO • 0 CQ • Η 0 fH O O ο 0 H O I. 0 Γί H Φ Ph O Φ • O Φ 0 Cj rj H I. O • φ O H ν P * OJ O Ph El IrH

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The fact that one of the three protective materials (ABS polymer, vinylidene fluoride polymer, acrylic acid ester polymer) and polystyrene has a strongly adhesive multilayer Web material that can be obtained as described and pointed out above is actually surprising to others polymeric materials that are usually incompatible with polystyrene such as polyolefins not with polystyrene can be ejected to obtain a satisfactorily adhered multilayer product independently of possibly close values of the melt viscosity of the two polymers.

As a further important feature it has been found that the ejection process according to the invention can be carried out for the production of multilayer web material which has extremely thin surface layers of one of the above three protective materials, the surface layers being on the order of 1 mil or less in comparison See the total thickness of the sheet material, for example 10 to 12 mils. This is achieved by providing relative feed rates of the polystyrene and one of the three protective materials such that the volume of the protective material generally does not exceed about 25 % of the total resin feed and preferably less than about 20 ° /> the Gesarotharzzufuhr is. Relative feed rates for the respectively used "protective material of less than about 15% are typically preferred even more. This is in direct contrast to del?-Known technique disclosed in the ability to work only above a minimum resin content for any given resin component of at least 25 vol _e% is.

The principles of the invention are generally applicable to the manufacture of either multilayer polymeric film material (less than 10 mils in thickness) or to the manufacture of sheet material (10 millimeters in thickness). Jeüocli FolioTsmaterial has not much popularity on PoIysty ^ olbacis ^, ονοηυο.η according to the

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Difficulties encountered in adapting this material for use in blown film machines or blown film machines which are commonly used in the manufacture of film products in conjunction with ejection equipment. Accordingly, generally speaking, it is possible to make a composite sheet of a polystyrene layer 4 or 5 mils thick, or even 1 mil thick, with a surface layer of one of the three aforementioned protective materials 1 mil or thinner in thickness. In practical terms, the products of most interest are multilayer sheet materials from 10 mils to about 10 mm (3/8 inch) thick with a surface layer of one of the three aforementioned protective materials, for example 1/4 or 1/2 mil to several mil. accordingly, it is to be understood that the volumetric feed rates or supply amounts are for the protective material is often very small, for example less than 1%, when thicker sheeting is desired, and that likewise amounts above 20% or 25% are also contemplated when very thin film is produced.

A device is shown schematically in FIG. 1 and denoted by the reference numeral 10. This device is particularly suitable for carrying out the method according to the invention. The device 10 includes a first ejector 11 for ejecting molten polystyrene, and connected thereto a discharge line 12. A second ejector 14 with a discharge line 15 can deliver a smaller flow of molten material made of one of the three protective materials mentioned. The line 15 ends at the line 12 at a point upstream of the mold 17 which forms the web material and which is in working connection with the line 12 and receives the flow from it. The strip material 19 is formed on the forinlippon or nozzle lips 18 and then by means of polished rollers 21, 22 and 23 from the forii 1? γ ^ ρχ ·; e leads.

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Prop. Fig. 2 is a sectional view of the delivery conduits 15 and 15, the ejection mold 17 and the chill roller assembly 21; 22 and 23. In Fig. 2, the cutting of the lines 12 and 15 and the shape of the polystyrene resin 31 and of one of the three protective materials mentioned existing resin 32 when combined in conduit 12 to form a stratified stream which is an interface nverb connection level 25 has. The layer formation on the The point where the two resins come together is supported by a metal plate 34 in the line 12 near the point is arranged, on which the line 15 into the line 12 entry. In a similar manner, the passage of the layered resin stream into a mold manifold line 27 is at one Limiting rod or orifice plate rod 28 and finally through the lips 18 through to the chrome rollers or chill rolls shown. It should be noted that the individual Resin material layers their layer shape and layer arrangement maintained despite the very small amount of protective material, so that an end product is formed is, which is a substantially uniform surface layer of one of the three protective materials Has.

Figure 3 is a top plan view of conduit 12 and ejector die 17 around the pattern of lateral flow of the molten polymeric material as it enters and passes through ejection mold I7. 4 shows more clearly the preferred shape of the plate 34 disposed in the conduit 12.

In order to produce multilayer sheet material or sheet material with satisfactory adhesion between the layers, it is necessary during the expulsion.certain Observe procedural limitations. While it is of course desirable to have relatively steady flow of Polystyrene and the protective material concerned by the ■ / device to get through and any turbulence

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in the device, these limitations or restrictions are very typical of most ejection processes using high viscosity synthetic resins. More important limitations (although not entirely unrelated to the foregoing) reside in the ejection temperatures for the polystyrene and the particular protective material used, as well as the temperature maintained in the ejection mold. The expulsion of the polystyrene from the ejector 11 into the conduit 12 should be carried out at a temperature of about 205 to 260 ° C (400 to 500 ° F), whereas the ABS polymer from the ejector 14 should be carried out at a temperature of about 220 to about 288 ° C (430 to 550 ° F) should be delivered. The acrylic ester polymer should be dispensed from the ejector at a temperature of about 232 ° C to about 300 ° C (450 to 570 ° I ¹ ), while the vinylidene fluoride polymer should be dispensed in the temperature range dispensed for the expulsion of the polystyrene. The role of the latter temperature ranges can be seen in view of the foregoing relative to the desired melt viscosity of the three protective materials at the time of joint ejection. However, these ranges are not intended to represent absolute limitations of the invention, but merely indicate the middle ranges in which the melt viscosity of the three protective materials can be brought to a value close to the V / ert of the melt viscosity of polystyrene, so that strong adhesion between the layers in the ejected web material is created. It will be understood that the invention encompasses the use of the three protective materials when the materials are ejected at still higher temperatures to produce satisfactory adhesion to the polystyrene layer when ejected together.

As stated, the temperature also represents an important one Process variable, but not from the standpoint of Adhesion of the layers to one another as seen. Instead of this

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this parameter affects the surface characteristics, e.g. gloss, etc., of the ejected web material. The temperature should be kept relatively constant during ejection, with typical values for ABS polymer and polystyrene co-ejecting in the range between about 205 and 288 ° C (400 and 550 ° F). The best surface gloss is achieved at temperatures above about 260 ° C (500 ° F). Typical values for common discharge of vinylidene fluoride and polystyrene lie in the range of about 218 to about 273 ° G (425 to 525 ° F), excellent surface gloss at temperatures above 232 ⁰ C (450 ° P) is obtained. For discharging Acrylsäureesterpolymer polystyrene and the corresponding values are about 215 to 260 ° C (420 to 5OO ⁰ F), excellent surface gloss is achieved at temperatures above 232 ° 0 (450 ° F).

When polystyrene and ABS polymer are ejected together , the conditions maintained at the chill roll device also affect the surface properties of the end product. The preparation of smooth web material usually requires the use of highly polished rollers ₉ d "h _e chrome-plated rolls, typically three rollers are used, each having a diameter of about 304 mm (12 inches) and is carried out so that the inside circulate cooling water can. However, when ABS polymer is coextruded as the surface layer with polystyrene, it has been found that a temperature which is slightly higher than the normal upper surface temperature, for example 60 to 79.5 ° 0 (140 to 175 ° P), and also a lower than normal top roller pressure, for example a pressure high enough to overcome the upward spring stress on the rollers, are required to achieve optimal surface characteristics, especially gloss. If an Ac: cy! Material with polystyrene

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co-ejected as the surface layer, it has been found that roller temperatures of about 66 ° C (150 F), and roller pressures approximately large to overcome upward spring tension on the rollers, are capable of producing acceptable surface characteristics, in particular Shine. When discharged with the polystyrene vinylidene fluoride polymer together as a surface layer has been found, however, that a temperature that is slightly higher than the normal rolling temperature, for example about 71 to 77 ° C (160 to 170 ⁰ F) for the upper roller 77 to 82 ° C (170 to 180 ° F) for the middle roll and 60 to 71 ° C (140 to 160 ° F) for the bottom roll, and lower than normal top roll pressure, such as nearly sufficient up pressure to overcome spring tension acting on the rollers, are necessary in order to achieve optimal surface properties, especially gloss.

Other process variables of lesser concern include the pressures under which the polystyrene and protective materials are separately expelled prior to being brought together. These pressures are of minor importance

and are typically in the range of about 52 kg / cm and

211 kg / cm ² (between 750 and 3OOO psi) for the * polystyrene

2 current, and in a similar way between about 35 kg / cm

and 211 kg / cm (between 500 and 300 psi) for the flow of one of the three protective materials. Of course, the pressure downstream of the point where the streams are brought together is the same in both streams.

The term polystyrene as used herein includes homopolymers of styrene and copolymers of Styrene with other polymerizable and polymerized clay Monomers. The latter category includes impact polystyrenes, the graft copolymers of styrene on conjugated Diene backbone compounds such as folybutsdiene, butadienstr / rolnri Schpolymerisate, Eutadienacrylnitr.i] rrlschpolyrnerisat e,

2 0 SP U ** / η 9 9 /,

natural rubber, etc. This category also includes normal copolymers of styrene with others known common monomers.

Similarly, the term ABS polymer is to be interpreted in its broadest sense to include the now characterize well-known class of graft copolymers, the acrylonitrile monomers, butadiene monomers and styrene monomers. All kinds of ABS products is available in stores. Suitable ABS resins for use in the method according to the invention, on the basis of the molecular weight, the melt index and / or the Melt viscosities given for a given resin can be selected by one skilled in the art.

In the same way, the terms vinylidene fluoride polymer are to be interpreted in a broad sense in order to Vinylidene fluoride homopolymers and copolymers of vinylidene fluoride with small amounts of other compatible copolymerizable To include vinyl monomers. A variety of vinylidene fluoride products are commercially available. Suitable vinylidene fluoride resins for use in the method according to the invention can be conveniently selected by those skilled in the art are derived from the data for molecular weight, melt index and / or melt viscosity for any one given resin.

In addition, it is to be understood that the term acrylic acid ester polymer refers to a broad class of polymers Materials referred to on the basis of acrylic acid esters and / or methacrylic acid esters. The lower alkyl esters represent the preferred class of materials. The intended definition includes homopolymers of acrylic acid esters and methacrylic acid esters as well as intermediate polymers of these with small amounts of compatible co-polymerizable Monomers, most commonly other acrylic monomers, e.g. acrylic acid, methacrylic acid, acrylonitrile, Acrylamide, etc. as well as styrene family monomers. The definition also includes mixtures and / or grafts

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of acrylic ester polymers with additional modifying polymers such as rubbery impact modifiers. An important class of such blended polymers includes acrylic ester homopolymers or acrylic ester intermediate polymers, mixed with graft copolymers of acrylic ester, and optionally other monomers on a rubbery backbone polymer. See, for example, the United States patents 3 261 887, 3 354 238 and 3 4-75 516.

A variety of acrylate ester polymers are commercially available. An example of the multi-blend acrylic polymers, mentioned above are the acrylic polymers from American Cyanamid sold under the trade name XT multi-polymers are brought onto the market. Suitable Acrylic resins for use in the method according to the invention can be conveniently selected from among those skilled in the art Molecular weight, melt index and / or melt viscosity data for any given resin.

It should be noted that multilayer sheet material is made under the principles of the present invention which has a layer of ABS polymer, vinylidene fluoride polymer on both sides of the polystyrene layer and / or acrylic ester polymers. Such implementation requires only various minor modifications in the equipment used to carry out the procedure. It is the same it should be understood that in place of the ejection shapes shown in the drawing, various other types of ejection shapes such as an end feed form.

The invention is illustrated below by way of examples explained in more detail.

example 1

A main resin stream made of impact polystyrene (Cosden Oil & Chemical Co. 825D Pellets) is made from a two-stage ventilated ejector with a diameter of 114.3 (4- 1/2 inches) with an auger and pressure ratio

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emitted at 4: 1. A single stage ejector approximately 32 mm (1.25 inches) in diameter, also with a screw providing a pressure ratio of 4: 1, is arranged as shown in Figures 1 and 2 and provides a second stream of ABS resin ( Dow Chemical. Co. - White 230) with a melt flow rate or amount, as measured by ASTM D-1238-63T ejection plastometer, of 2.20 grams per 10 minutes at a Brabender torque of 420 meter-grams (10 minutes). The polystyrene is ejected at a temperature of 227 ° C (440 ° F) and a feed rate of about 308 kg / h (680 lbs. Qe hour). The ABS side stream is removed from the above-mentioned discharge means at a temperature of about 262.5 ° C (505 ° 3 ¹⁾ "and h in a supply amount of approximately 13" 6 kg / (30 lbs per hour) leave.

The two Hara flows are then combined in a discharge line of the ejection device for the polystyrene using a baffle or guide plate with a design as shown in FIG. There is a single layered two-component flow with a horizontal connecting or boundary plane between the polystyrene and the ABS polymer. The bicomponent stream is directed to a centrally fed sheet forming die which opens to an ejector slot 94 cm (37 inches) wide with the lips set about 59 mils apart. The mean temperature of the mold is about 250 ⁰ C (480 ° P).

When leaving the Iform lips, the ejected one arrives Train through a row of three polished chrome-plated cooling whales each 305 mni (12 inches) in diameter, of which the upper roller to about 60 ° C, the middle V.'al ze to about 71 ° C and the lower roller to about 40.5 ° C is held. The YJ al ζ pressures on the upper roller uixl of the lower roll are at a gap stiffening of

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Maintained 52 mils at about 1.4 kg / cm (20 psi). The polishing rollers and the subsequent rubber rollers are with operated at a speed about 8 # higher to bring the ejected web to a final thickness of 55 mu to stretch.

Examination of the final sheet product shows a substantially uniform layer of ABS polymer about 2½ mils thick firmly adhered to the impact polystyrene base layer. This thickness corresponds pretty closely to the relative feed rates for the both resins, i.e. about 4.4 #.

Example 2

A main resin stream of impact polystyrene (Cosden Oil & Chemical Co. 825D Pellets) is ejected from an ejector according to Example 1. In Example 1, a second stream is ejected from an ejector according to Example 1. This second stream consists of polyvinylidene fluoride resin (KF Polymer - 1100 Pellet - Kureha Chemical Industry Co., Ltd.), having a high molecular weight, high crystallinity and a Brabender torque of 300 meter-grams (10 minutes). The polystyrene is ejected at a temperature of 227 ° C and with a feed rate of about 308 kg / h. The polyvinylidene fluoride resin sidestream is ejected from said ejector at a temperature of about 232 ° C (450 ° F) and at a feed rate of about 3.6 kg / h (8 lbs per hour).

The two resin streams are then combined in the discharge line of the ejector used for the polystyrene using a guide plate arrangement according to FIG. 2. A single Zv / eicotnponent layer flow is entered with a horizontal connection. ^ - or boundary bone between the polystyrene and the polyvinylidene fluoride resin. The Zv / eikomponentenstrom v / ies to a central powered, sheet-like material forming AuostoJ? forin

2G9843 / 0994

which opens to an ejection slot 101 cm (40 inches) wide with the lips set about 20 mils apart. The mean temperature of the ejection mold is around 274 ° C (520 ° W),

After leaving the lips, the ejected web passes through a series of polished chrome-plated chill rolls of the same diameter as in Example 1, of which the upper roll is at a temperature of 7 ° C and the middle roll is at a temperature of 79> 5 ° G the lower roller is kept at a temperature of 65.5 ° 0 . The roller

2

top and bottom pressures are maintained at 1.6 kg / cm and 1.25 kg / cm (23 and 18 psi), respectively, with a gap setting of 18 mil. The polishing rollers and subsequent rubber rollers are driven at a speed 14 # higher, to stretch the ejected web to a final thickness of 19 mils.

Examination of the final sheet product shows a substantially uniform layer of polyvinylidene fluoride resin about 0.225 mil in thickness which is securely adhered to the base layer of impact polystyrene. This thickness corresponds pretty closely to the relative feed rates or feed rates for the two resins, ie about 1.2 %.

Example 3

A main resin stream of impact polystyrene (Cosden Oil & Chemical Co. 825D Pellets) is emitted from an ejector Ejected according to Example 1. A second stream of acrylate ester polymer (Röhm & Haas Co. - Type VM Plexiglas (Polymer based on methyl methacrylate), melt flow rate, measured by A.S.T.M. D-1238-63T, Condition G a 2.35 grams / 10 minutes, Brabender torque = 580 meter-grams (10 minutes) is also ejected from an ejector according to Example 1. The polystyrene will be at a temperature of about 244 ° C (470 ° F) and in at a rate of about 308 kg / h (680 lbs per hour). The acrylic ester oil atom is at one temperature ejected from the said ejector device at a temperature of 260 ° C,

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at an amount of about 13.6 kg / h (30 lbs each Hour),

The two resin streams are then in the delivery line -der. ejecting means for ejecting the polystyrene combined using a guide plate assembly according to Pig. 2. The result is a single two-component layer flow with a horizontal connecting or boundary plane between the polystyrene and the acrylic material. Of the Two-component flow is fed to a centrally fed, web-like material forming ejection mold, which opens in an ejection slot as wide as in Example 1 with the nozzle lips set at about 59 mils. the mean temperature of the ejection mold is around 2115 ° C (420 ° F).

After exiting the nozzle lips, the ejected web passes through a series of three polished chrome-plated chill rolls of the same diameter as in Example 1, of which the top roll is set to about 52 ° C, the middle roll to about 65.5 ° C and the bottom roll is kept at about 49 ° C.

The top and bottom roller pressures are maintained at about 1.6 kg / cm (22 psi) with a gap setting of 53 mils. The buffing rollers and subsequent rubber rollers are driven at approximately 8 % higher speed around the ejected web stretch to a final thickness of 55 mils.

Examination of the final sheet material exhibited a substantially uniform layer of acrylic polymer thick et v / a 2.5 mil, which ensures adhered to the base layer of impact polystyrene. This thickness corresponds pretty closely to the relative feed rates for the two resins, ie 4.4 % acrylic material.

According to the invention , a method is provided for jointly ejecting multilayer sheet material made of polystyrene and ABS polymer, vinylidene fluoride polymer or acrylic ester polymer, in which at least one layer of one of the three last-mentioned materials is attached to the base

209843/0994

The polystyrene layer securely adheres. Furthermore, the method according to the invention enables production of multilayered 3? olien- or sheet material made of polystyrene with very thin surface layers of one of the three mentioned materials, the surface layer can be thinner than 1 mil

209843/0994

Claims (11)

Claims j process for the manufacture of composite BahnÖIaberial, with two streams of Harzraaterial underneath Formation of a sharply defined intermediate or boundary surface in an ejection form can be combined and ejected, characterized in that a layer of polystyrene and at least one further layer of ABS polymer, vinylidene fluoride polymer or acrylic ester polymer molten stream of polystyrene and a molten stream of ABS polymer, vinylidene fluoride polymer, or acrylic ester polymer brought together in a conduit to form a single bed stream of molten material with the Line cross-section corresponding cross-section and with a relatively sharply defined intermediate or boundary surface between the polymeric materials to form the stratified stream of molten material through a web-shaped material Forming ejection form is guided, the lips of which generally zvri.sch.en with the intermediate or boundary surface both polymeric materials are aligned, and that an ABS polymer, vinyln'dene fluoride polymer or acrylic ester polymer is used with an iron melt viscosity or odor an adjusted melt viscosity, that of the melt viscosity of polystyrene comes very close. 2. The method according to claim 1, characterized in that a relative proportion of ABS polycer, Vinylidenfluoridpo lymer or Acrylenterpolyrcer of less than about 20 £>, based on the total polymeric flaterials, ver'.iei / Lei. will. 3 · The method according to claim Λ or 2, characterized [-clronr-. draws that to form the v.'c-nir'rr ^ enn cinon ana er or. al :: the polystyrene layer an AcrylfeEterpolyiner vcvv.'ondot i.-rr-l .. 209843/0994
CQpy 4. The method according to claim 1 or 2, characterized in that for forming the at least one other than a vinylidene fluoride polymer is used in the polystyrene layer. 5. The method according to claim 1 or 2, characterized in that that an ABS polymer is used to form the at least one layer other than the polystyrene layer. 6. The method of claim 5 »characterized in that the molten stream of ABS polymer is ejected at a temperature of about 221 ° C to about 288 ° G (430 to 550 ° F), and that the molten stream of polystyrene at a Temperature of about 205 to about 260 ° G (400 to 500 ° F) is emitted, 7 · The method according to claim 3 »characterized in that that the molten stream of acrylic ester polymer is at a temperature of about 232 to about 299 ° C (450 to 570 ° F) is ejected., and that the molten stream of polystyrene at a temperature of about 205 to about 260 ° G is expelled. 8. The method according to claim 4, characterized in that that the molten stream of vinylidene fluoride polymer is ejected at a temperature of about 205 to about 260 ° 0 and that the molten stream of polystyrene is ejected at a temperature of about 205 to about 260 ° C ' will. ■. 9. The method according to claim 6, characterized in that that the ejection mold is at a temperature of about 205 to maintained at about 288 ° G (400 to 550 ° F). 10. The method according to claim 7 »characterized in that that the ejection mold is maintained at a temperature of about 215 to about 260 ° C (420 to 500 ° F). 11. The method according to claim 8, characterized in that the ejection mold at a temperature of about 218.5 maintained to about 273 ° C (425 to 525 ° F). 209843/0994 COPY L e r s e i t e