WO1990001043A1 - A hydrophilic polymer with increased resistance to hydrophilic solvents - Google Patents

A hydrophilic polymer with increased resistance to hydrophilic solvents

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Publication number
WO1990001043A1
WO1990001043A1 PCT/CH1989/000132 CH8900132W WO9001043A1 WO 1990001043 A1 WO1990001043 A1 WO 1990001043A1 CH 8900132 W CH8900132 W CH 8900132W WO 9001043 A1 WO9001043 A1 WO 9001043A1
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WO
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Patent type
Prior art keywords
polymer
coating
according
characterized
hydrophilic
Prior art date
Application number
PCT/CH1989/000132
Other languages
German (de)
French (fr)
Inventor
Ivan Tomka
Stefan Schmidlin
Original Assignee
Ivan Tomka
Stefan Schmidlin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/047Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/14Water soluble or water swellable polymers, e.g. aqueous gels

Abstract

An aliphatic polyester with low water absorption is selected as a coating material for hydrophilic polymers like starch. The polyester can be degraded by bacteria or fungi. This polyester may, for example, be a polyhydroxycarbonic acid. It is dissolved and applied to the components, of starch, for instance, by one of the customary physical or chemical coating processes. Once the solvent has evaporated, a coating film is left on the surface. If the coating thickness is adequate, the starch thus treated can no longer dissolve or swell. Such combinations of coatings adhere poorly to one another. Improved adhesion may be achieved by various methods, e.g. by prior corona treatment of the surface for the starch and/or the addition of a solvent or swelling agent for the starch to the coating solution.

Description

Hydrophilic polymer to hydrophilic solvents increased resistance

The present invention is concerned with a hydrophilic polymer to hydrophilic solvents increased resistance, with a method for increasing the resistance of a hydrophilic polymer to hydrophilic solvents, a method for improving adhesion between a hydrophilic polymer and a hydrophobic coating and to a use of the method.

Hydrophilic polymers gain more and more importance as a so-called "engineering plastics", ie

for use as a so-called plastics. This mainly is because it is among others in the hydrophilic polymers are natural substances such as starch, gelatin, cellulose, etc., that are both cheap and on the other hand help to reduce the dependence on fossil fuels. In addition, they are useful as natural products in their processing physiologically acceptable and readily biodegradable.

In particular, the constructed on natural substances hydrophilic polymers have the disadvantage that they are on their surface due to the hydrophilicity of hydrophilic solvents such as water and solvents of similar polarity such as water, are more or less partially dissolved, resp. the surface swells.

This causes of hydrophilic polymers forth asked moldings, films, etc., for example, an insufficient resistance to water own. This is manifested in the fact that the Wassersorptionskurve of the polymers undergoes a so-called inflection point, that is, the uptake of

"Free water" in the polymer exceeds the proportion of "bound water", which just leads to the mentioned swelling. This swelling or partial dissolution of the polymers, for example by water, is such a disadvantage that the use of the above-mentioned largely produced natural-based polymers is severely limited.

It is therefore an object of the invention to provide a hydrophilic polymer, without the above mentioned drawbacks, resp. a method for increasing the resistance of hydrophilic polymer to hydrophilic Lösungsmittelnvorzuschlagen.

According to the invention the object is achieved by a polymer and a method, preferably according to at least one of the claims, in particular according to claim 1. 9

Disclosed is a hydrophilic polymer which comprises a coating of a hydrophobic material.

are proposed in particular largely hydrophilic polymers prepared based on natural ingredients such as starch, plasticized starch, gelatin, animal or vegetable proteins, cellulose, derivatives of cellulose, carbohydrates, hydrophilic polymers such as but also largely by synthesis, such as vinyl acetate, acrylic acid, polyester, and polyvinyl pyrrolidine.

In particular, it is proposed as the hydrophilic polymer plasticized starch which is prepared by supplying mechanical and / or thermal energy, wherein the preparation of the substantially homogeneous amorphous mass, ie the supply of energy to the strength, for example by means of a kneader may occur.

All polymers listed are either derived from raw materials of nature known manner, respectively. produced or produced by known methods.

All of the polymers can be prepared by at least one of the usual processing methods, such as processing for example by injection molding, extrusion etc., to moldings, sheets, tubes, etc..

The proposed hydrophilic polymers exhibit in particular to at least one of the following solvents increased resistance: - Dimethyl sulphoxide

- water, cold or hot

- Potassium hydroxide - ammonia (liquid)

- formamide

- aqueous solution of copper ethylene diamine

- 1: 1 mixture of N-Aethylenpyridiniumchlorid with dimethylsulfoxide

- pyridine

- dimethylformamide.

As coating materials for the hydrophilic

Polymers, resp. in particular moldings produced therefrom, films, etc.., are those materials that exhibit low absorption of hydrophobic solvents and are suitable for film formation, ie whose molecular weight is above the limit of film formation and an at least substantially sealed

Film arise. As coating materials, inter alia, aliphatic polyester, in particular polyhydroxy own. are proposed, for example, polyhydroxycarboxylic acids, which comprises at least one hydroxycarboxylic acid of the following formula

are manufactured and / or at least one of the corresponding lactones.

To be particularly suitable, for example, polyglycolic acid, polyhydroxybutyric, Polyhydroxypropionsaure, polylactic acid or polyhydroxyvaleric are proposed or copolymers thereof or mixtures thereof. are also proposed natural fats and waxes, paraffin, zein, a hydrophobic protein, and chitin. The examples mentioned are particularly suitable is because they have on the one hand a low water vapor permeability and a low swellability and yet are biodegradable in a simple manner with play, by means of bacteria and fungi of the soil. Another advantage of the examples mentioned in the fact that they called part is. Bacterial products, ie. that they are produced by means of biotechnological methods.

Further, a method for increasing the resistance of hydrophilic polymers, resp. Proposed by produced therefrom moldings, films, etc., to hydrophilic solvents such as water in particular, by the polymer is at least partially coated with a film-forming hydrophobic material. For the coating of the hydrophilic polymer film-forming coating materials are proposed in accordance with a proposed embodiment of the inventive method, which are well soluble in a hydrophobic solvent such as chloroform or trichlorobenzene. The application of the coating on the polymer can now be achieved for example in that a cold or heated article is composed, molded from the polymer in the solution. When removing a film on the object remains, which is generated for example by evaporation of the solvent. Depending on the desired film thickness of the hydrophobic coating of the application process can be repeated several times.

but the application of the solution may also further by means of the known conventional application methods, such as, inter alia, casting, spraying, for example with a spray gun, flow coating, rolling, etc., take place. The removal of the solvent is also carried out in a known manner, for example by evaporation by means of heat or radiation. The film formation may be either give pure by precipitation of the coating material or by another molecular structure or a crosslinking reaction in the coating material enables the formation of an at least substantially sealed film-like coating, for example, under the influence of said radiation.

In case of poor solubility of the coating material, which may be particularly often the case for high molecular weight substances, it is also proposed to carry out the order on the polymer for example by means of a dispersion. Another proposed possibility is that applying the coating material in melt to the polymer. This can for example take place in that a polymer article is immersed in the melt and solidifies the coating material after removal of the article from the melt to form a film.

In particular, when coating film- or sheet-like objects from hydrophilic polymers also the application by means of co-extrusion, a per se known method of application is suitable. According to another proposed method, the coating is effected by application of the coating material in powder form. For this, all generally known application methods such as fluidized bed, electrostatic application, etc. come into question. The film formation can be effected either by simply fusing the powder or continue through Aufpolimerisation and / or crosslinking of the coating material.

The mentioned application methods are not exhaustively enumerated, as well as other methods such as electrodeposition method, application of so-called. High solids, pastes, etc. come, for the application of the coating materials in question.

It has been found that coatings having insufficient from hydrophobic materials to hydrophilic polymers in most cases to poor adhesion. the use of an adhesion promoter, it is therefore to improve the adhesion of the film-like coating further proposed which both the polymer, respectively. can be attached to its surface, as well as the coating material.

Next, at least a so-called adhesion promoter is at least the hydrophobic material and / or its solution before the application of added which the polymer during application at least partially anlδst or swells or chemically react with the polymer will be proposed. By adding the adhesion promoter, such as dimethyl sulfoxide or any other solvent or swelling agent such as a hydrophilic solvent, the hydrophilic polymer is swollen at the surface and thus enables a partial ingress of molecular chains of the hydrophobic material in the polymer or vice versa.

brought on repeated application of the coating material, for example in solution, in the hydrophilic polymer, the application of an adhesion promoter is only necessary just the first order. The information to be referred to increase the layer thickness can be carried out without the addition of an adhesion promoter. To improve adhesion, an adhesion promoter need not necessarily be used, but according to a further method proposed, this can also be achieved in that prior to coating at least the polymer, respectively. the surface of an article made of hydrophilic polymer whereby the polymer is activated physically and / or chemically substantially at its surface is exposed by means of a corona treatment of an electron and / or ion exposure. In corona treatment to increase the adhesion, there is a well-known method, for which a high voltage generator and an electrode arrangement may be used. For the intensity of the corona treatment are decisive in particular the electrode distance between the object and the electrode, the duration of treatment as well as the power of the generator. The difference from a treated to an untreated surface of the hydrophilic polymer can be obtained by spreading a powder mixture of lead oxide with

Sulfur, preferably in a ratio of about 2: be easily visualized 1, and subsequent shaking. Because the corona effect subsides after hours to days, the coating with the hydrophobic material should be done in a reasonable time. In principle can be dispensed with an adhesion promoter in the aid of the corona treatment of the polymer but also a combination of the various methods for improving the adhesion is possible.

The methods described in this invention are generally suited for improving the adhesion between a substantially hydrophilic polymer and any substantially hydrophobic Beschichtungs¬material.

The method according to the invention described previously are also particularly suitable for setting the attack speed of a hydrophilic solvent to a hydrophilic polymer by the choice of layer thickness and / or the molecular weight of the hydrophobic material and the crystalline fractions and / or the chemical composition of this material. At low film thickness, respectively. at low density of the Üeberzuges due to lower molecular weight of the hydrophobic material, resp. lack of cross-linking, the attack of a hydrophilic solvent is, for example, water, faster, resp. the hydrophilic polymer is quickly dissolved partially or completely than with application of a larger film thickness, and a greater density of Üeberzuges.

All previously proposed inventive polymers and methods are not limited to hydrophilic polymers which have insufficient resistance to hydrophilic solvents, they are also to refer to polymers which have a relatively low absorption of a hydrophilic solvent. For example, a polyamide can be coated to prevent water uptake. The same is true for the hydrophobic coating which is not restricted to materials which exclude a recording or solubility in hydrophilic solvents altogether. There are for example quite usable also on thermoplastic or thermosetting polymers based coatings which have, for example, low water absorption, but not such that the protected hydrophilic polymer is damaged thereby.

The invention set forth below according to examples represent possible variants of the coating of a hydrophilic polymer with a hydrophobic material.

The examples are described with reference to the accompanying figures. They show:

Fig. 1 is a schematic diagram of a plant for the corona treatment of the surface more hydrophilic polymers,

Fig. 2 shows the electrode arrangement according to FIG. 1 in

Longitudinal cross-section, Figure 3 shows the geometry of a specimen in scale. 1: 1, which was used for carrying out the examples,

Fig. 4 shows the results of the improvement in adhesion of the test specimen in beiKoronavorbehandlung

Tabular form,

Fig. 5 shows a test arrangement for measuring the water resistance of the specimen,

Fig. 6, three sample bodies with different

Water resistance after performing the durability test, FIG. 7 is a schematic diagram of an arrangement for

Performing the adhesion tests

Fig. 8 shows the results of the adhesion improvement in

Using an adhesion promoter in table form, Fig. 9 is a heat flow diagram of polyhydroxybutyric acid used in the examples, Fig. 10 is a heat flow diagram of a coating material used in another example, and

Fig. 11 shows the results in a table of measurement of the water resistance of the coating of another example with different layer thickness.

First example:

Coating of starch with polyhydroxybutyric acid by corona treatment of the starch a) storage of the starch mold parts - resp. Starch samples:

Although the uncoated starch samples are sensitive to water, they are stored at room temperature and normal humidity. They do not change in this environment. b) cleaning of the sample: Is the strength of surface

greasy or otherwise contaminated, they must be cleaned before treatment. Essentially in the adhesion is improved. The Home Care is done with acetone or other degreasing solvent. Since the strength of the body quickly brittle under the influence of acetone, so care must be addressed. After cleaning a few minutes to wait until the acetone is completely evaporated (odor sample with the nose).

Now the starch sample can be pretreated. It must be ensured that the cleaned surface is not touched during the handling of the starch samples. Corona treatment: The apparatus used for example for the corona treatment is a laboratory facility of SOFTAL GmbH, Hamburg, Germany. The system is outlined in FIG. 1. a high voltage generator of the type 3003 is used.

A high-voltage generator 1 is connected to an electrode assembly consisting of an electrode 3 and a counter electrode 5 is connected. The counter electrode 5 is mounted on rollers and transversely with respect to the electrode 3 slidably. Between the two electrodes 3 and 5, the thickness parts are, resp. Samples 7 disposed. The electrode 3 is mounted on a protection casing 9 which can be changed by four leveling screws 11 in its height and thus also the distance between the two electrodes 3 and 5. The counter electrode 5 can be moved by an electric motor 13 with the reel spool transversely to the electrode 3 be , Further, the electrode 3 is connected to a suction unit 15 for sucking off ozone.

three parameters are varied for the treatment of strength. They are:

1. Electrode distance between the sample and the electrode,

2. Duration of corona treatment,

3. four power stages of the generator (0,1 - 0,5 kW).

The corona treatment and subsequent coating be carried out for example with the aid of Starketestkorpern or samples of FIG. 3. . The specimen in Figure 3 is to scale 1: 1 where the quoted

Mass numbers are in mm.

The selected times, power levels and the electrode spacings are shown in Fig. 4 in which results concerning improving adhesion are tabulated with corona treatment. d) Procedure for corona treatment: This is

described below with reference to Figures 1 and 2. 1. The starch samples 7 are glued purified with double sided tape on the counter electrode 5, an aluminum plate which is the ground. This bond. is used for fixing as well as for maintaining the parallelism to the electrode 3. Thus, a definite distance d between the sample 7 and electrode 3 is ensured. 2. The electrode spacing is accurately set, as shown in Fig. 2. Fig. 2, the electrode arrangement shows in longitudinal cross section. Between the electrode 3 and the counter electrode 5 to the latter, the starch samples 7 are arranged. Below the electrode 3 a so-called. Dielectric 8 is applied to this. As the distance d is the distance between the dielectric 8 and the sample 7 is now referred to. 3. The ozone extraction 15 is turned on.

4. The motor 13 for the transverse movement of the aluminum plate 5 with the sample 7 thereon is set in motion. (It is also possible not to move the sample and to vary the treatment time. In this way the following point 5 is omitted)

the generator 5. Immediately turned on at maximum power and passing off after pull through of the sample 7 under the electrode 3 again. 6. The sample 7 is without touching the surface, set aside for subsequent coating. Because the corona effect subsides after a few hours or days, the sample should be coated in a reasonable time. e) Coating: The coating solution is

from between 1% to 15% of polyhydroxy butyric acid, dissolved in chloroform. For the measurement of adhesion improvement with the corona treatment according to the table in Fig. 4, a 5% Polyhydroxybuttersäurelösung is used. The molecular weight of polyhydroxybutyric in this example is about 410 * 000th

The polyhydroxy butyric acid used in the present example is characterized in more detail in the attached heat flow diagram in Fig. 9. Fig. 9 illustrates a heat flow diagram of the PHB-preparation used in Examples 1 and 2. The photograph was taken from a commercial heat flow meter (DSC = differential scanning calorimetry) from Perkin Elmer.

This PHB has at about 5 ° C an endothermic

Glass transition 30, at about 52 ° C, an exothermic Rekristallisationsumwandlung 31 and at about 176 ° C, a melting endothermic conversion on. The required amount of heat at the glass transition 30 is substantially smaller than in the

Melting conversion 32, which it can be seen that it is in this PHB preparation to a highly crystalline polymer.

With respect to polyhydroxybutyric but also molecular weights of about 300,000 a few million can be used up. With other used Beschichtungsmateriallen smaller molecular weights, for example, 50,000 are possible. It is essential, in particular the film forming limit of the coating material used.

In the present example, an immersion apparatus is used to coat the samples. The test specimens are immersed at a rate of, for example, about 7 cm / sec in the coating solution and pulled out again. The residence time of the specimen in the solution can be arbitrarily selected by switching a dipping mechanism used, for example '. In the present example, the corona-pretreated samples are only rapidly immersed and then immediately withdrawn from the solution. Drying: If a plurality of dipping operations is necessary, should be maintained between dips in each case, to the formed film is dried.

The drying, ie the Wegdampfen of the solvent is carried out, for example, in air at room temperature. To obtain a highly water-resistant layer, the sample is coated, for example, three times with a 5% Polyhydroxybuttersäurelösung. After each dipping process at least 10 minutes to be maintained until the film is dry. Testing the water resistance. In order to check the water resistance of the coating on the starch surface, the subsequent test with respect to Figures 5 and 6 is proposed.

small rings 17 are placed on the dried starch body. 7 Into the interior of the ring aqueous iodine-potassium iodide solution-filled. Depending on the water resistance of the layer, the thickness swell if necessary, and cracks form in the layer. There, the test solution penetrates the iodine quickly, and there are formed small blue, clearly visible cracks, as shown in Fig. 6b.

Is tested for a long time, so it must be ensured that the water does not evaporate. In the case of a waterproof film, only the film surface is discolored slightly yellow by the iodine. However, it is no visible blue staining as shown in Fig. 6a.

The test body according to FIG. 6c shows poor water resistance, respectively. a significant turning blue. If the samples have passed the water test, for example after 48 hours of continuous, so there are no visible blue discoloration, the samples are tested for the adhesion of the layer. Testing the adhesive strength. In order to measure the adhesive strength of the coating, the following test, with reference to Figure 7, is proposed: The test layer on the strength of a bit 7 is achieved with a sharp knife from the untreated starch surface. This makes it possible that a clamp 25 can be attached to the peeled part of the layer 23rd

The specimen 7 is clamped in a holder 21st To the terminal 25 can now a tank 29 connected via a wire 27, are attached. In this container 29, weights can fill. These serve the adhesion of the layer 23 placed with the

to correlate weight. The adhesive strength is exceeded when the weight force acting on the terminal 25 to the layer, resulting in that the layer peels off without further addition weight and without external influence.

If the adhesion improvement treatment is successful, a weight difference between treated and untreated sample must be measurable. The

Results of adhesion tests are given in the table in Fig. 4. It is noted to be that all coatings are the same and the layer application was made within each nearly equal time intervals after the corona treatment. The table of FIG. 4 it is evident that with a corona treatment, the adhesive strength of the hydrophobic polymer, such as starch, can be greatly increased.

Second example:

Coating of starch with polyhydroxybutyric using dimethyl sulfoxide as an adhesion promoter, the starch samples for this example is equal to be treated and with point b) of the preceding example.

Points c) and d) be omitted, ie, the corona treatment may be omitted. These two

Points are replaced by the following point i). i) pre-treating the starch with an adhesion enhancement solution: dimethylsulfoxide or shortly called DMSO, is regarded as a swelling and a solvent for the starch. Is one of an ordinary 1% to 15% Polyhydroxybuttersäurelδsung example, from 0.1% to 10% DMSO added and coated to the surface strength so that, one achieves strong adhesion improvement. In the present example, the sample with 0.5%, 1% and 3% DMSO is coated in a 3% polyhydroxy butyric acid-chloroform solution. For the Polyhydroxybuttersäurelösung another suitable solvent, such as trichlorobenzene instead of chloroform can be used.

Likewise, other starch solvents can, for example pyridine are used as a bonding agent, instead of DMSO. A possible parameter here represents the time during which the sample in DMSO-Polyhydroxybuttersäurelösung remains before it is withdrawn. In the present example, immersion times are chosen from 1 and 30 sec. In this case, only a part of the sample is coated. After this first coating, the sample is dried for 24 hours. Thereafter, at point f) can be moved on the previous example, ie further coating using adhesion promoter-free solution. In the present example, a layer is extracted twice each applied to the sample.

Exact details and the results of the water and peel strength tests can be found in the table in Fig. 8. As can be seen from this table, a significant increase in adhesion strength between the treated and untreated starch moldings can be observed. The water resistance lasts at least 24 hours without visible change of the surface to. Third example:

Adjusting the resistance of strength against water through the choice of the layer thickness of the coating

In this example a copolymer of polyhydroxybutyric acid (PHB) with polyhydroxyvaleric acid (PHV) used in the ratio of 4 to 1 as a new coating material. As carrier material in turn serves strength - the same material as in Examples 1 and 2. FIG.

The heat flow diagram of FIG. 10, which was created in analogy to Fig. 9, the copolymer PHB / PHV characterized. At about 3 ° C is an endothermic glass transition 35, at about 74 ° C, an exothermic recrystallization is 36 and at about 125 ° C, a melting endothermic conversion visible. It is now to be noted that the glass transition 35 relative to the melt 37 conversion is not as small as in Fig. 9, indicating lower crystallinity of the copolymer with respect to pure PHB. A consequence of this is, for example, a slightly improved solubility of the coating material in chloroform.

In the present example it is investigated what influence having the layer thickness of the coating material on the water resistance of the coated thickness. This is examined to determine in this example that the strength tends to beschich one hand, once, twice or three times is immersed in the coating solution and on the other hand, three different concentrations of the coating material are chosen in the coating solution.

To better understand the influence of

Layer thickness on the water resistance will be omitted carried out in Examples 1 and 2 measures to improve adhesion of the coating on the starch. The non-corona treated Stärkeprüfkδrper be one, two or three times immersed in the dipping solution, which strength a l%, 3% or 5% PHB / PHV solution in chloroform represents. Subsequently, the coated test specimens, as mentioned in the previous examples, dried, resp. the solvent is evaporated. The now dry coated test specimens are subjected to the water test described in Example. 1 The results of the different water tests are summarized in the table in Fig. 11. In this case, it is clearly seen that the water resistance increases with increasing layer thickness of the coating. The layer thickness is influenced on the one hand by the number of dipping steps of the starch in the diver solution and on the other hand, by the concentration of coating material in the dipping solution. This example clearly shows that access of water to the support material with increasing Lδsungskonzentration and an increasing number of dipping steps is more hindered, hence the water resistance of the starch, resp. attack speed of the water can be individually adjusted to the thickness.

The three presently selected Examples 1 to 3 are carried out with moldings of any other hydrophilic polymer as starch in the same manner. As coating materials come together with the example used polyhydroxybutyric respectively. the copolymers essentially all aliphatic polyesters, such as in particular those based on polyhydroxy carboxylic acids in question. The solvents used,

Adhesion promoters, application conditions, etc. can be varied in the x-arbitrary manner and changed.

In particular, in the corona treatment is further to cause the system shown in Fig. 1 is a laboratory unit, which is particularly suitable for the corona treatment of test specimens. In the corona treatment of non-planar objects such as hollow bodies, the electrode assembly must of course be chosen differently. In the case of hollow bodies, for example, is not, as shown, a selected plate-shaped electrode, but an insertable into the hollow body point or rod-shaped electrode. Newcomers headings:

- J. Branddrup, Polymer Handbook, J. Wiley & Sons,

2. ed., NY

- Donovan JW (1979), Biopolymers 18: 263

- J. Hansmann, surface treatment methods

Improve adhesion. Paper and Kunstst.-proce.,

4 u. 7, 1981

- E. Husemann and E. Siefert, Makrom. Chemistry. 128

288 (1969)

- B. Vergnes, JP Villemaire, Rheological behavior of low moisture molten maize starch, Rheol. acta: 570-576 (1987)

- Winnacker, Kuchler, Chemical Technology, 4th Edition, Carl Hanser Verlag., 1986

- The theory and practice of corona treatment for

Improving Adhesion, TAPPI, Vol. 65, No. 8, 1982

Claims

claims:
1. Hydrophilic polymer to hydrophilic solvents increased resistance, characterized by a coating of a hydrophobic material.
2. The hydrophilic polymer, preferably according to at least one of the claims, essentially consisting of at least one of the following materials: - starch
- plasticized starch
- gelatin
- an animal or vegetable protein
- a derivative of a protein
- cellulose
- a derivative of cellulose
- a carbohydrate
- vinyl acetate
- acrylic acid polymer
- polyvinylpyrrolidone.
3. The hydrophilic polymer, preferably according to at least one of the claims, such as according to one of claims 1 or 2, consisting essentially of plasticized starch which is prepared by supplying mechanical and / or thermal energy.
4. The hydrophilic polymer, preferably according to at least one of the claims, such as claim 1, 2 or 3, with increased resistance to at least one of the following solvents:
- dimethyl sulfoxide
- Water
- hot water
- potash
- ammonia
- chloral hydrate
- formamide
- aqueous solution of copper ethylene diamine
- essentially a 1: 1 mixture of N-Aethylenpyridiniumchlorid and dimethylsulfoxide
- pyridine
- dimethylformamide.
5. The hydrophilic polymer, preferably according to at least one of the claims, such as according to one of claims 1 to 4, essentially comprising a coating consisting of at least one aliphatic polyester.
6. The hydrophilic polymer, preferably according to at least one of the claims, such as according to one of claims 1 to 5, characterized in that the coating comprises at least one Polyhydroxycarbonsaure.
7. The hydrophilic polymer, preferably according to at least one of the claims, such as according to one of claims to 1 to 6, characterized in that the coating comprises at least one polyhydroxy carboxylic acid, prepared from at least one hydroxycarboxylic acid of the following formula:
and / or made from at least one corresponding lactone.
8. The hydrophilic polymer, preferably according to at least one of the claims, such as according to one of claims 1 to 7, essentially comprising a coating of at least one of the following materials: - polyglycolic
- polyhydroxybutyric
- polylactic acid
- polylactic acid
- polyhydroxyvaleric
and / or a copolymer thereof.
9. The hydrophilic polymer, preferably according to at least one of the claims, such as according to one of claims 1 to 5, characterized in that the coating comprises at least one of the following substances:
- zein, a hydrophobic protein
- chitin
- natural fats and / or waxes
- paraffin
10. A method for increasing the resistance of a hydrophilic polymer to hydrophilic Lösungsmittein, characterized in that the polymer is at least partially coated by a film-forming hydrophobic material.
11. A method, preferably according to at least one of the claims, such as claim 10, characterized in that the hydrophobic material in a
Solvent which dissolves only the hydrophobic material is substantially, but not the material to be coated, is brought into solution and then either by immersion of the polymer in the solution, or by spraying, or by
is applied casting, or by flooding, or by rolling to the polymer, and then, to form, after removal of the solvent, an at least substantially sealed film-like coating.
12. A hydrophilic polymer, preferably according to at least one of the claims, such as claim 11, characterized in that the hydrophobic material is dissolved in chloroform and / or trichlorobenzene.
13. A method, preferably according to at least one of the claims, such as claim 10, characterized in that the hydrophobic material is applied in dispersed form to the polymer.
14. A method, preferably according to at least one of the claims, as will be extruded onto the polymer according to claim 10, characterized in that the hydrophobic material is brought in the melt or that the coating of the polymer is carried out by co-extrusion of polymer and hydrophobic material.
15. A method, preferably according to at least one of the claims, such as claim 10, characterized in that the hydrophobic material, placed in powder form, is applied by means of vortex internally or electrostatically to the polymer and then the film formation under the influence of heat and / or radiation he follows.
16. A method, preferably according to at least one of the claims, such as according to one of claims 10 to 15, characterized in that to improve adhesion between the polymer coating and a bonding agent is used.
17. A method, preferably according to at least one of the claims, such as according to one of claims 10 to
16, characterized in that a bonding agent is for improving the adhesion of the film-like coating is at least the hydrophobic material and / or its solution before the coating is added, wherein the polymer at least partially dissolves or swells or which reacts chemically with the polymer.
18. A method, preferably according to at least one of the claims, such as according to one of claims 16 or
17, characterized in that is used as an adhesion promoter dimethylsulfoxide.
19. A method, preferably according to at least one of the claims, such as according to one of claims 10 to
15, characterized in that at least the polymer by means of a corona treatment, an electron and / or ion exposure is subjected to improve adhesion of the film-like coating before application of the coating, whereby the polymer is activated physically and / or chemically substantially on its surface.
20. The method according to any one of claims 16 to 18 and according to claim 19th
21. A method for improving adhesion between a hydrophilic polymer and a hydrophobic coating, preferably at least one of claims 16 to 20th
22. Use of the method, preferably according to at least one of claims 10 to 21, for setting the attack speed of a hydrophilic solvent, a hydrophilic polymer by choice of the layer thickness and / or the molecular weight of the hydrophobic material.
PCT/CH1989/000132 1988-07-20 1989-07-13 A hydrophilic polymer with increased resistance to hydrophilic solvents WO1990001043A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CH2779/88-6 1988-07-20
CH277988 1988-07-20

Publications (1)

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WO1990001043A1 true true WO1990001043A1 (en) 1990-02-08

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PCT/CH1989/000132 WO1990001043A1 (en) 1988-07-20 1989-07-13 A hydrophilic polymer with increased resistance to hydrophilic solvents

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EP (1) EP0378646A1 (en)
CN (1) CN1039604A (en)
ES (1) ES2022769A6 (en)
WO (1) WO1990001043A1 (en)

Cited By (19)

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WO1992010539A1 (en) * 1990-12-05 1992-06-25 Henkel Kommanditgesellschaft Auf Aktien Starch-based materials and/or moulded parts modified by synthetic polymer compounds and process for producing the same
WO1993014911A1 (en) * 1992-01-30 1993-08-05 Warner-Lambert Company Biodegradable shaped article with a resistant coating and means for exposing the core, and a process for making said article
DE4237535A1 (en) * 1992-11-06 1994-05-11 Tomka Ivan Biodegradable polymer blend
US5320669A (en) * 1992-12-14 1994-06-14 Iowa State University Research Foundation, Inc. Cereal grain-based biodegradable thermoplastic compositions
WO1994013734A1 (en) * 1992-12-04 1994-06-23 Franz Haas Waffelmaschinen Industrie-Gesellschaft Mbh Process for producing biodegradable thin-walled starch-based mouldings
US5352716A (en) * 1992-12-16 1994-10-04 Ecostar International, L.P. Degradable synthetic polymeric compounds
US5512617A (en) * 1992-03-20 1996-04-30 Henkel Kommanditgesellschaft Auf Aktien Thermoplastically processable starch-based materials, shaped articles manufactured therefrom and process for producing said materials
US5635550A (en) * 1992-02-07 1997-06-03 Solvay (Societe Anonyme) Starch-based composition
US5756194A (en) * 1996-01-25 1998-05-26 The United States Of America, As Represented By The Secretary Of Agriculture Enhanced water resistance of starch-based materials
US5854345A (en) * 1996-05-24 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US5861216A (en) * 1996-06-28 1999-01-19 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer laminates
US6025417A (en) * 1996-02-28 2000-02-15 Biotechnology Research & Development Corp. Biodegradable polyester compositions with natural polymers and articles thereof
US6054510A (en) * 1996-02-28 2000-04-25 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable formed article
FR2791603A1 (en) * 1999-04-01 2000-10-06 Ard Sa Water-resistant biodegradable composite material useful for making containers comprises a core of thermoplastic starch and a shell of a biodegradable polymer having a low melting point and a high viscosity
EP0495950B2 (en) 1990-08-09 2002-04-03 NOVAMONT S.p.A. A laminated film with a starchy matrix and low permeability and methods for its production
US6558760B1 (en) 1997-01-21 2003-05-06 Cryovac, Inc. Packaging film and containers made therefrom
DE10258227A1 (en) * 2002-12-09 2004-07-15 Biop Biopolymer Technologies Ag Biodegradable multilayer film
US6893527B1 (en) 1996-06-28 2005-05-17 William M. Doane Biodegradable polyester and natural polymer laminates
US20090179069A1 (en) * 2006-04-14 2009-07-16 Harald Schmidt Multilayer film and method for manufacturing same

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CN103061128A (en) * 2012-12-07 2013-04-24 淄博兰雁集团有限责任公司 Producing method of environment-friendly composite sizing agent

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DE2910374A1 (en) * 1979-03-16 1980-09-18 Hoechst Ag Flowable mixtures of hydrophilic polymers contg. insoluble cpds. - for adhesives, wallpaper pastes, in building industry, and dyestuffs and inks
US4372311A (en) * 1980-09-12 1983-02-08 Union Carbide Corporation Disposable articles coated with degradable water insoluble polymers

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Cited By (25)

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Publication number Priority date Publication date Assignee Title
EP0495950B2 (en) 1990-08-09 2002-04-03 NOVAMONT S.p.A. A laminated film with a starchy matrix and low permeability and methods for its production
US5439953A (en) * 1990-12-05 1995-08-08 Henkel Kommanditgesellschaft Auf Aktien Starch-based materials and/or molded parts modified by synthetic polymer compounds and process for producing the same
WO1992010539A1 (en) * 1990-12-05 1992-06-25 Henkel Kommanditgesellschaft Auf Aktien Starch-based materials and/or moulded parts modified by synthetic polymer compounds and process for producing the same
WO1993014911A1 (en) * 1992-01-30 1993-08-05 Warner-Lambert Company Biodegradable shaped article with a resistant coating and means for exposing the core, and a process for making said article
US5635550A (en) * 1992-02-07 1997-06-03 Solvay (Societe Anonyme) Starch-based composition
US5512617A (en) * 1992-03-20 1996-04-30 Henkel Kommanditgesellschaft Auf Aktien Thermoplastically processable starch-based materials, shaped articles manufactured therefrom and process for producing said materials
DE4237535A1 (en) * 1992-11-06 1994-05-11 Tomka Ivan Biodegradable polymer blend
DE4237535C2 (en) * 1992-11-06 2000-05-25 Biotec Biolog Naturverpack A biodegradable polymer blend, a method and a film
WO1994013734A1 (en) * 1992-12-04 1994-06-23 Franz Haas Waffelmaschinen Industrie-Gesellschaft Mbh Process for producing biodegradable thin-walled starch-based mouldings
US5576049A (en) * 1992-12-04 1996-11-19 Franz Haas Waffelmaschinen Industriegesellschaft M.B.H. Process of manufacturing rottable thin-walled starch-based shaped elements
US5320669A (en) * 1992-12-14 1994-06-14 Iowa State University Research Foundation, Inc. Cereal grain-based biodegradable thermoplastic compositions
US5352716A (en) * 1992-12-16 1994-10-04 Ecostar International, L.P. Degradable synthetic polymeric compounds
US5756194A (en) * 1996-01-25 1998-05-26 The United States Of America, As Represented By The Secretary Of Agriculture Enhanced water resistance of starch-based materials
US6054510A (en) * 1996-02-28 2000-04-25 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable formed article
US6025417A (en) * 1996-02-28 2000-02-15 Biotechnology Research & Development Corp. Biodegradable polyester compositions with natural polymers and articles thereof
US5854345A (en) * 1996-05-24 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US6040063A (en) * 1996-06-28 2000-03-21 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer laminates
US6893527B1 (en) 1996-06-28 2005-05-17 William M. Doane Biodegradable polyester and natural polymer laminates
US5861216A (en) * 1996-06-28 1999-01-19 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer laminates
US6558760B1 (en) 1997-01-21 2003-05-06 Cryovac, Inc. Packaging film and containers made therefrom
FR2791603A1 (en) * 1999-04-01 2000-10-06 Ard Sa Water-resistant biodegradable composite material useful for making containers comprises a core of thermoplastic starch and a shell of a biodegradable polymer having a low melting point and a high viscosity
DE10258227A1 (en) * 2002-12-09 2004-07-15 Biop Biopolymer Technologies Ag Biodegradable multilayer film
EP2399738A1 (en) 2002-12-09 2011-12-28 BIOP Biopolymer Technologies AG Biodegradable multi-layer film
US20090179069A1 (en) * 2006-04-14 2009-07-16 Harald Schmidt Multilayer film and method for manufacturing same
US8715816B2 (en) * 2006-04-14 2014-05-06 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Multilayer film and method for manufacturing same

Also Published As

Publication number Publication date Type
CN1039604A (en) 1990-02-14 application
EP0378646A1 (en) 1990-07-25 application
ES2022769A6 (en) 1991-12-01 application

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