KR100933434B1 - Polymer composition comprising a cyclic olefin copolymer - Google Patents

Abstract

Polymer compositions containing a cyclic olefin intermediate (COP) alternating arrangement PP (s-PP); Films comprising layers of such compositions and special uses thereof.

Description

Polymer composition comprising cyclic olefin copolymer {POLYMER COMPOSITION INCLUDING A CYCLIC OLEFIN COPOLYMER}

The present invention relates to a polymer composition comprising a cyclic olefin copolymer, a film comprising a layer composed of the composition and its special use.

Articles for medical use must not only meet the usual requirements such as good mechanical strength or low cost, but also, for example, the biocompatibility of the article, their ability to undergo sterilization, their flexibility, their transparency, their weldability, their impact Extremely stringent and specific requirements should be met for this special application, such as strength (including in liquid-filled containers), amount of extracting material (eg hexane) and in some cases barrier properties.

Pharmaceutical articles sold to date, such as infusions or bags for the preservation of blood bags and medicinal fluids, are based on vinyl chloride polymers, such as PVC. However, even with some advantages, this type of polymer suffers from some drawbacks, such as the need to mix high amounts of stabilizers here to improve thermal stability or high amounts of plasticizers here to obtain sufficient flexibility. Have Therefore, there is a need in the market for a medical article free of chlorinated polymers.                 

To obtain such articles, it is known to start with polyolefin-based films and weld them together (or by themselves) to make bags or bags. Solvay's patent application WO00 / 61062 describes a film containing COP (cyclic olefin polymer). However, Applicants find that welding is not very easy when using COP alone (ie, as a pure component of a film or layer), and the welds obtained have poor quality with particularly short welding times commonly used in industrial processes. Other heat sterilization, transparency and flexibility are not optimal in a single layer of multilayer structure when using pure COP. In particular, a multilayer structure comprising a pure COP layer tends to peel off after heat sterilization.

Applicant surprisingly when adding alternating polypropylene (s-PP) to the COP, it can create a medical bag or pouch that can be very easily welded and heat sterilized, leaving transparency and flexibility (after sterilization), It has a high impact strength and also shows good barrier properties (ie, against water vapor, acids and alcohols), and in the case of a multilayer structure there is no exfoliation after thermal sterilization. Other s-PPs are obtained via metallocene catalysts, which therefore show lower amounts of extracting compound and less catalyst residue than other non-metallocene PP resins.

Accordingly, the present invention relates to polymer compositions containing COP and s-PP.

The term "COP" refers to homo- or copolymers, which have side chains to reach a total of 5 to 30C. Generally, the copolymers are in the range of 2-95% by weight (preferably 10-80% by weight) for cyclic monomers and 5-98% by weight (preferably 20-90% by weight) for olefins. Cyclic monomers, C ₂ to C ₁₀ olefins. The basic cyclic monomer unit may be cyclopentene, cyclohexene, nolvornene, dicyclopentadiene, tetracyclododecene or methyltetracyclododecene.

Linear side chain:

R1, R2 (= CxHy + 1, x, y = 0,1,2, ...)

Or cyclics such as dicyclopentadiene, which is the actual norbornene with the actual cyclopentadiene side chain:

Preferred are norbornene having consequently:

Olefin is advantageously ethylene. COP is preferably a homo- or copolymer of norbornene with or without side chains; It is homopolymer of nolvornene (with or without side chains, but preferably with cyclopentadiene as side chain, i.e. dicyclopentadiene is preferred) or with norbornene (with or without side chain) and ethylene Copolymers are more preferred. In the latter case, the ethylene content is advantageously 30 to 95% by weight (preferably 40 to 80% by weight), and the norbornene content is advantageously 5 to 70% by weight (preferably 20 to 60% by weight). .

The s-PP according to the invention is up to 30% C ₂ -C ₈ hybrid monomers, preferably copolymers or homopolymers of ethylene and propylene. It is preferred for polyolefins with controlled crystallinity as described in WO00 / 061062. This is a softening point below 121 ° C. (measured according to ASTM standard D1525) after treatment under at least suitable conditions (which is described in WO00 / 061062 and incorporated herein by reference) even when the resin manufacturer announces high values. (Or "Bikat point") is preferable. Therefore, it is preferable that the s-PP according to the present invention exhibits salient features that can easily reduce their crystallinity during processing thereof. It is advantageous in the content of the present invention that the use of suitable treatment conditions, as far as possible, to provide reduced crystallineity to these s-PP resins increases the transparency and flexibility of the overall structure.

The polydispersity of S-pp according to the invention is advantageously 8 or less and preferably 4 or less. This feature indicates a low dispersion of molecular weight, which increases the separation between the melting point range and the softening point range and thus can effectively have more action on crystallinity during processing.

Moreover, the melt flow index of s-PP used is advantageously 10 g / 10 min, preferably 6 g / 10 min or less (the homopolymer of propylene polymer and butene under 190 ° C./2.16 kg conditions for ethylene polymer and butene copolymer). Measured according to ASTM standard D1238 under conditions of 230 ° C./2.16 kg).

In the compositions according to the invention the s-PP is generally present in an amount of 1% or more, in particular 10% or more (weight compared to the total weight of the mixture), and the COP content of the mixture is generally 70% or More, in particular 80% or more. Generally s-PP is present in an amount of 30% or less, in particular 20% or less, and COP is present in an amount of 99% or less, in particular 90% or less.

The composition according to the invention may contain other thermoplastic polymers in addition to s-PP and COP resins. These other polymers are advantageously chosen from polyolefins or hydrocarbons which are not supercrystalline or amorphous in the form of:                 

An olefin copolymer composed of at least two C ₂ to C ₁₀ alkenes containing at least 60% by weight of ethylene and / or propylene and / or butene but not containing at least 90% by weight of the same hybrid monomer.

Ethylene and / or propylene and / or butenes and C ₅ to C ₁₀ olefins [e.g., ethylene and 1 in amounts to have linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE) or ultra low density polyethylene (VLDPE) -Copolymers of octene] and one or more other hybrids of 10-40% by weight, preferably selected from carboxylic acid or ester groups, for example vinyl acetate, methyl, ethyl or butyl acrylate and methyl methacrylate or carbon monoxide Olefin copolymers containing monomers.

Elastomeric polymers with blocks of styrene and olefins (for example styrene-butadiene-styrene, styrene-ethylene-butylene-styrene or copolymers of styrene-ethylene-propylene-styrene type, etc.).

High branched homopolymers (eg low density polyethylene (LDPE) or medium density polyethylene (MDPE)).

Hydrogenated hydrocarbons such as paraffin or paraffin oil.

Advantageously the composition according to the invention optionally comprises styrene-ethylene-butylene-styrene (SEB) comprising styrene-ethylene-butylene (SEB) styrene, optionally comprising styrene-ethylene-propylene (SEP) It additionally contains at least one resin chosen between ethylene-propylene-styrene (SEPS) and ethylene-1-octene copolymers (preferably prepared by the metallocene process). SEBS and / or SEPS are preferred because they can be made into permanent and peelable seals (at low temperatures) with films and because they improve impact strength. The total concentration of these resins is generally 1% or more (weight to the total composition), preferably 10% or more. It is generally 29% or less, preferably 20%.

The composition according to the present invention can be easily processed into a desired kind from flat (film or sheet) to three-dimensional (container), and can be processed in a single layer structure or in a multi-layer structure.

One of the preferred configurations of the present invention relates to a film containing at least one base layer comprising the composition described above.

The term "film" is generally used to denote a thin, flat structure or tubular structure (in the case of a partial film) having a thickness of 1000 μm or less, preferably 500 μm or less, in particular 250 μm or less. will be. In practice a thickness of 100 μm or more, in particular 150 μm or more, is suitable.

The film according to the invention generally has at least one other layer in addition to the base layer containing the composition mainly composed of s-PP and COP. Since the COP is sensitive to grease at particularly low amounts, such as when contacting or manipulating it, the film according to the invention preferably contains at least one outer layer which does not contain COP, in particular containing two such outer layers. It is preferable. In this case these layers are located on each side of the base layer. The additional layer preferably contains at least 30% of metallocene technical PP (alternatively or identically arranged homopolymers or copolymers with ethylene, for example). The choice of PP resins obtained through metallocene catalyst technology improves the purity of the overall structure (extraction and catalyst residue content). According to a preferred configuration of the present invention, the film has a layer containing s-PP and / or i-PP prepared by metallocene technology on at least one side of the base layer for the same reason as described above, and SEBS having SEBS, SEB, It contains at least one resin selected between SEPS, SEPS with SEP and ethylene-1-octene copolymers prepared by metallocene technology. The total concentration of these resins is generally at or below 70%.

In order to further improve the sealing force of the film according to the invention, s-PP and / or i-PP produced by metallocene technology; At least one resin selected from SEBS, SEBS with SEB, SEPS with SEP and ethylene-1-octene copolymers prepared by metallocene technology; At least one supercrystalline or non-amorphous selected between ethylene-vinylacetate (EVA), ethylene-methyl acrylate (EMA), ethylene-ethylacrylate (EEA) or ethylene-butyl acrylate (EMA) polymer It is advantageous to contain at least one outer layer (sealing layer) containing the polyolefin. Only those which exhibit a content of at least 10% of the hybrid monomers in the finally mentioned copolymers are naturally considered to be additional constituents. These copolymers are generally at or above 0.1% (weight of the total composition) and preferably at least 1%. This is generally at or below 15%, preferably at most 10% and most preferably at most 7%. Preferably, a mixture of EVA and EMA in the total amount of at least 1% or especially at least 5% yields good results. This can make a weldment having a very reproducible tensile strength, which is very useful for making items with peelable seals such as multi-sealed bags or pouches comprising a permanent outer seal and at least one peelable seal.

In addition to the above-mentioned layers, it is advantageous to include a layer in pieces as an inner layer of the above-mentioned film from an economical point of view.

The film according to the present invention is embossed in a known manner to prevent blocking (that is, it can be done in an inclined shape).

The film according to the invention may additionally contain a barrier layer containing resins such as EVOH, PA ...

Preferred structures of the film according to the invention are the following layers:

1. Between s-PP and / or i-PP with SEBS, SEBS with SEB, SEPS with SEB, SEPS with SEP and ethylene-1-octene copolymer with metallocene technology with at least 60% metallocene technology A (outer layer) containing 0-40% of at least one resin selected from

2. s-PP / COP mixture consisting of at least 70% COP and at least 1% s-PP and SEBS, SEBS with SEB, SEPS with SEP and ethylene-1- made by metallocene technology Layer B (base layer) containing 0-29% of at least one resin selected between octene copolymers

3. at least 50% s-PP and / or i-PP made of metallocene technology; At least one resin of 0-49% selected between SEBS, SEBS with SEB, SEPS with SEP and ethylene-1-octene copolymer made from metallocene technology; Layer C (sealing layer) containing at least 1% EVA and EMA mixture

And a piece layer between layers A and B1.

Optionally this preferred film may contain an additional layer (B ′) between layers B and C, which layer comprises at least 30% by weight of s-PP and / or i-PP and SEBS made of metallocene technology. And at least one resin of 0-70% selected between SEBS with SEB, SEPS with SEB and ethylene-1-octene copolymer made with metallocene technology.

The film according to the invention is very easy to weld and therefore can be used very conveniently for making bags. Accordingly, the present invention relates to a bag made of the film described above. Preferably the bag is a multi-seal bag comprising at least one permanent outer seal and at least one peelable seal. Permanent seals are those that cannot be easily peeled off by hand and generally represent a seal that exhibits a tensile strength of at least 2000 N / m (according to ASTM / ISO F88) or in particular at least 3000 N / m. Peelable seals are easily peelable by hand. In general, it is a seal showing a tensile strength of 2000 N / m or less. The optimum temperature, pressure and welding time ranges can be very easily determined by one of ordinary skill in the art using several tests to obtain permanent and peelable seals each having a given structure. In general, permanent and peelable seals can be achieved using hot gas or hot appliance welding, with the latter being preferred.

Films and bags according to the present invention can be used in any application where their flexibility, sealability, transparency, ability to disinfect and barrier properties are important. The pharmaceutical sector is such a field of use. The bag according to the invention is particularly suitable for containing pharmaceutical fluids such as actual dosing, infusion, nutrition. The film according to the invention can be welded to the bag to store the acid and alcohol used for cleaning or purifying some medical devices due to its good barrier to alcohol and acid. One use that yields very good results is the storage of acetic acid in bags of double yarn, storage of concentrated solutions of acetic acid (up to 50% by weight) and others, containing water. The two yarns are separated by a peelable seal, which is destroyed immediately before use to obtain an acetic acid solution at a reasonable concentration. The bag according to the invention has a much longer shelf life than that according to the prior art, ie hardly evaporation takes place.

Finally, the polymer composition according to the invention may be advantageous for use in injection molded articles. In most of the application parts of the films and bags described above, the latter is often used to connect some kind of device (such as a perfusion or dialysis device) and to make such a connection, which is often used with tubes or similar connecting parts. It is manufactured by injection molding. In order to have a complete system of identical polymer components and to achieve the advantages listed above, it is advantageous that these injection molded articles comprise the same polymer composition as described above.

In the following example:

-i-PP is ATOFINA's EOD 9421 class (MFI of 5 according to ASTM D1238).

G1657급이다.-SEBS is SHELL's KRATON

It is class G1657.

EVA and EMA are ULOF218 and 16MA03 grades from ATOFINA (about 3 MFIs and about 18% VA or MA),

8007급이다(30의 MFI(ISO 1133, 260℃, 2.16㎏)).-COP is TIAS TOPAS

Class 8007 (30 MFI (ISO 1133, 260 ° C, 2.16 kg)).

Haze and transparency (= total luminous transmittance) are measured according to ASTM D1003-00.

The film is made using flat dies and feed blocks by co-extrusion, each layer having its own independent single screw extruder (60 and 45 mm in diameter and 25D barrel length). The temperature fixed to the die, supply block and adapter is about 220 ° C.

The bags are made of these films by hot appliance welding under the following conditions: temperature = 142 ° C., pressure = 6 bar, time = 1.3 seconds.

Comparative Example 1:

Co-extrude a multilayer film having peelable seal properties comprising the following layers:

Layer A (outer layer): mixture of i-PP (90 wt.%) And SEBS (10 wt.%)

Layer B1: i-PP (100 wt.%)

Layer B2: mixture made of i-PP (75% by weight) and SEBS (25% by weight)

Layer C (sealing layer): a mixture made of i-PP copolymer (75 wt%), SEBS (22 wt%), EVA (2 wt%) and EMA (1 wt%)

The total thickness of the film is 200 μm with a layer B1 of 40 μm. Its haze is 4% and its transparency is 96%.

Comparative Example 2:

Same as Comparative Example 1 except making layer B1 COP (100% by weight). The total thickness of the film is 200 μm in total with layer B1 of 40 μm. Its haze is 5% and its transparency is 95.5%.

Example 3: Films According to the Invention

Same as Comparative Example 1 except that Layer B1 was prepared from a mixture of COP (85 wt.%) And s-PP (15 wt.%).

The total thickness of the film is 200 μm in total with layer B1 of 40 μm. Its haze is 6.2% and its transparency is 95%.

Steam Sterilization and Dropping Tests

10 bags are made of the films of Comparative Examples 2 and 3 respectively, filled with 3 liters of water, and each series of 5 is steam-sterilized (121 ° C./250° F., 30 minutes). The bag made from Comparative Example 2 after steam-sterilization shows peeling. The bag according to the present invention (Example 3) does not exhibit peeling. In the drop-test of two sterilized or unsterilized samples, the bag made according to the present invention remained in the drop-test carried out on a flat floor at a height of 2 meters, indicating that the bag made of Comparative Example 2 did not remain in the test.

Acetate storage:

A bag made from the film according to Comparative Example 1 and a bag made from the film according to Example 3 were charged with 50 ml of an aqueous solution of various percentages of acetic acid (0.24, 48, 74, 96%). The total surface area of all veins is 150 cm 2. The bags are stored at 23 ° C. and 40 ° C. for 135 days. The results (average of two samples) are shown in Table 1.

Table 1: Weight loss of grams of water and acetic acid mixtures at 23 ° C and 40 ° C after 135 days of storage

23 ℃ 23 ℃ 40 ℃ 40 ℃ % HAc Comparative Example 1 Example 3 Comparative Example 1 Example 3 0 -0,298 -0,244  -3,66 -2,851 0 -0,302 -0,317  -3,772 -3,333 24 -0,26 -0,208  -3,521 -2,49 24 -0,281 -0,235  -3,521 -2,965 48 -0,263 -0,168  -4,136 -2,296 48 -0,265 -0,198  -4,143 -2,54 74 -0,271 -0,098  -5,075 -1,614 74 -0,289 -0,116  -5,292 -1,91 96 -0,402  0,114  -9,862 -0,188 96 -0,46  0,146 -10,327 -0,171

Where% HAc = weight percent of acetic acid in the solution

As can be seen from the results in Table 1, the bags / films / compositions prepared according to the present invention show significantly lower weight loss. Therefore, there is little leaching of acetic acid and almost no smell.

Mechanical property:

The film according to Comparative Example 2 exhibits a strain at about 50% breakage, the other film in Example 3 exhibits a strain at 150% break and shows a decrease in elastic modulus of 70 MPa as compared to the film according to Comparative Example 2. This indicates that the bags / films / compositions prepared according to the invention are more flexible than conventional ones.

Claims (16)

A polymer composition comprising 70 to 99% by weight of a cyclic olefin polymer (COP) and 1 to 30% by weight of alternating polypropylene (s-PP). The polymer composition of claim 1, wherein the COP is a homopolymer or copolymer of norbornene with or without side chains. The styrene-ethylene-butadiene-styrene (SEBS), styrene-ethylene-butadiene-styrene (SEBS) with styrene-ethylene-butadiene (SEB), styrene-ethylene-propylene-styrene (SEPS), styrene A polymer composition additionally containing at least one resin selected between styrene-ethylene-propylene-styrene (SEPS) with ethylene-propylene (SEP) and an ethylene-1-octene copolymer made by metallocene technology. A film containing at least one base layer containing the polymer composition according to claim 1, 2 or 3. 5. The styrene-based resin according to claim 4, wherein on at least one side of the base layer, alternate polypropylenes produced by metallocene technology and / or styrenes having styrene-ethylene-butadiene-styrene and styrene-ethylene-butadiene At least one selected between ethylene-butadiene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-propylene-styrene with styrene-ethylene-propylene and ethylene-1-octene copolymers made with metallocene technology A film comprising a layer containing a resin. The method of claim 4, further comprising: at least one outer layer containing s-PP and / or i-PP made by metallocene technology; Styrene-ethylene-butadiene-styrene, styrene-ethylene-butadiene-styrene with styrene-ethylene-butadiene, styrene-ethylene-propylene-styrene, styrene-ethylene-propylene-styrene and metallocene technology with styrene-ethylene-propylene At least one resin selected from among ethylene-1-octene copolymers prepared with; A film containing at least one resin selected between ethylene vinyl acetate and ethylene methyl acrylate. The method of claim 4 wherein the next layer: 1) styrene-ethylene-butadiene-styrene, styrene-ethylene with s-PP and / or i-PP and styrene-ethylene-butadiene-styrene, styrene-ethylene-butadiene, produced by at least 60% by weight of metallocene technology; At least one resin of 0-40% by weight selected from -propylene-styrene, styrene-ethylene-propylene-styrene with styrene-ethylene-propylene and ethylene-1-octene copolymers made by metallocene technology Floor A (outer floor) 2) s-PP / COP mixture consisting of at least 70% by weight of COP and at least 1% by weight of s-PP, styrene-ethylene-butadiene-styrene, styrene-ethylene-butadiene-styrene with styrene-ethylene-butadiene, 0-29% by weight of at least one resin selected between styrene-ethylene-propylene-styrene, styrene-ethylene-propylene-styrene with styrene-ethylene-propylene and ethylene-1-octene copolymers made by metallocene technology Layer B (base layer) containing 3) at least 50% by weight of s-PP and / or i-PP prepared by metallocene technology; Styrene-ethylene-butadiene-styrene, styrene-ethylene-butadiene-styrene with styrene-ethylene-butadiene, styrene-ethylene-propylene-styrene, styrene-ethylene-propylene-styrene with styrene-ethylene-propylene, and metallocene Layer C (sealing layer) comprising 0-49 wt% of at least one resin selected between the ethylene-1-octene copolymers prepared by the technique, and a mixture of at least 1 wt% of ethylene vinyl acetate and ethylene methyl acrylate And a film composed of a piece layer between layers A and B. Bag produced by welding the film according to claim 4. The multi-silicone white bag of claim 8, comprising at least one permanent outer seal and at least one peelable seal. An injection molded article comprising the polymer composition according to claim 1, 2 or 3. Bag produced by welding the film according to claim 5. 12. The multi-threaded white bag of claim 11, comprising at least one permanent outer seal and at least one peelable seal. Bag produced by welding the film according to claim 6. The multi-silicone white bag of claim 13, comprising at least one permanent outer seal and at least one peelable seal. Bag produced by welding the film according to claim 7. The multi-silicone white bag of claim 15, comprising at least one permanent outer seal and at least one peelable seal.