WO1998014326A1 - Composition polymere - Google Patents

Composition polymere Download PDF

Info

Publication number
WO1998014326A1
WO1998014326A1 PCT/FI1997/000594 FI9700594W WO9814326A1 WO 1998014326 A1 WO1998014326 A1 WO 1998014326A1 FI 9700594 W FI9700594 W FI 9700594W WO 9814326 A1 WO9814326 A1 WO 9814326A1
Authority
WO
WIPO (PCT)
Prior art keywords
rosin
wax
polymer
waxes
polymer composition
Prior art date
Application number
PCT/FI1997/000594
Other languages
English (en)
Inventor
Hannu Karhuketo
Original Assignee
Upm-Kymmene Oyj
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
Application filed by Upm-Kymmene Oyj filed Critical Upm-Kymmene Oyj
Publication of WO1998014326A1 publication Critical patent/WO1998014326A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
    • B32B37/0015—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid warp or curl
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28—Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/30—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper

Definitions

  • This invention relates to a polymer composition and in particular to a polyester composition suitable for extrusion coating and lamination of paper and paperboard.
  • the invention relates also to processes for the preparation of the polymer compositions of this kind and to articles prepared by the method.
  • the invention concerns a composition formed of a polymer or polymer blend constituting the basic structures and an additive mixed therewith in low amount.
  • the polymer composition comprises at least one polyester and at least one additive selected from the group consisting of waxes, oils and rosins.
  • the polymer is especially one which is capable of attaining a relatively high level of crystallinity, for example at least 30 %, especially 50 to 90 %.
  • Such polymers may be produced biologically or synthetically.
  • Suitable biologically produced polymers typically include at least one biologiclly or synthetically produced polyhydroxyalkanoate (PHA) having units of the following formula (I):
  • C m H n contains especially at least 2 carbon atoms in the straight polymer chain.
  • C m H n contains 2 to 5 carbon atoms in the polymer chain and the remainder, if any, in a side chain joined to the carbon of the carbon chain.
  • m is 3 or 4
  • the molecular weight of the polymer is for example over 50O00, especially over 100O00, up to e.g. 2 x 10 6 .
  • Polyhydroxyalkanoate can be a fermentation product in a manner known per se, and associated manufacturing methods are disclosed for instance in the publications EP-A-69497, US-4101533, EP-A-144017 and EP-A-0392687.
  • the PHA may be synthetic, and chemical processes for its preparation are published in the literature.
  • the invention is applicable also to synthetic polymers, especially to those where units in the polymer chain are joined to each other through a hetero atom next to the carboxylic carbon, such as polyesters and polyamides.
  • synthetic polymers are polycapro- lactone, polylactides and such polyesters that are esterification products between dicarboxylic acids or their derivatives and diols.
  • the polymer is preferably a biodegradable polyester, especially a polyhydroxyalkanoate of the kind where the units have at least two carbon atoms in the straight polymer chain and preferably a side group of at least one carbon atom joined to this chain.
  • a biodegradable polyester especially a polyhydroxyalkanoate of the kind where the units have at least two carbon atoms in the straight polymer chain and preferably a side group of at least one carbon atom joined to this chain.
  • the additive is a wax, an oil or a rosin.
  • Rosins are preferably selected from the group consisting of rosin and rosin derivatives, terpene phe- nolics and pure phenolic resins; and more particularly from the group consisting of natural and modified rosins, such as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerised rosin, polymerised rosin, glycerol and pentaerythritol esters of natural and modified rosins, such as the glycerol ester of pale wood rosin, the glycerol ester of polymerised rosin, the pentaerythritol ester of hydrogen- ated rosin, the phenolic-modified pentaerythritol ester of polymerised rosin, the pentaerythritol ester of hydrogenated rosin, the phenolic-modified pen
  • the above-mentioned natural rosins and their derivatives obtained by modification are of plant origin, and their raw material, usually rosin of coniferous trees (colophony) is a renewable natural resource.
  • Waxes are preferably selected from the group consisting of 12-hydroxy- stearamide wax, hydrogenated castor oil, oxidised synthetic waxes, polyethylene oxide having a weight-average molecular weight above 1000, camauba wax, AKD wax, bee wax, spermaceti, lanolin, shellac wax, candelilla wax, bayberry wax, sugar cane wax, ouricury wax, Douglas-Fir Bark wax, castor wax, rice-bran wax, jojoba wax, Japan wax, montan wax, peat waxes, ozokerite and ceresin waxes, petroleum waxes, particularly paraffin waxes, polyethylene waxes, polymethylene waxes, chemically modified hydrocarbon waxes and substituted amide waxes.
  • Waxes are usually esters of long-chain aliphatic carboxylic acids with long-chain monoalcohols, such as bee wax, but they also include substances of other chemical structure having certain physical behaviour, especially viscosity and melting properties.
  • plasticisers may be present in or with the polymer there may be other materials present.
  • one or more plasticisers may be present.
  • the ratio of plasticiser to polymer depends on the intended use of the composition. The range 2 to 30 phr w/w (parts per hundred resin parts) includes most of the likely uses.
  • plasticisers for these polymers are suitable and any plasticisers which are found to plasticise these polymers subsequent to this invention would be suitable for use herein. Examples of such plasticisers are:
  • esters of polybasic acids such as phthalates, isophthalates, citrates, fumarates, glutamate, phosphates or phosphites.
  • the esterified radicals may be for example C r C 12 alkyl, aryl, or aralkyl. Particular examples are dioctyl-, dibeptyl- and dirindecyl-phthalates and dialkylalkylene oxide glutamate (Plasthall 7050);
  • high boiling esters of diols and polyols especially esters of glycols, polyglycols and glycerol.
  • the acid derived radicals of the ester typically contains 2 to 10 carbon atoms. Examples are triacetin, diacetin and glyceryl dibenzoate; (c) aromatic sulphonamides such as paratoluene sulphon- amide.
  • a particularly preferred plasticiser is a doubly esterified hydroxy- carboxylic acid having at least 3 ester groups in its molecule.
  • Doubly esterified means that at least some of the hydroxy groups of the hy- droxycarboxylic acid are esterified with a carboxylic acid and at least some of the carboxy groups thereof are esterified with an alcohol or phenol.
  • Preferably at least the hydroxycarboxylic acid from which the ester is derived is aliphatic or cycloaliphatic. Its backbone structure (that is, apart from carboxy groups) preferably contains 2 to 6 carbon atoms. It contains preferably 2 to 4 carboxy groups and 1 to 3 hydroxy groups; and preferably the number of carboxy groups exceeds the number of hydroxy groups.
  • An example of such a plasticiser is Estaflex (acetyltri-n-butyl citrate).
  • nucleating agent is often preferable in the polymer composition.
  • conventional nucleating agents include boron nitride (EP-A-0291024), ammo- nium chloride (WO-A-9119759) and DZB/ZnSt (EP-A-0400855).
  • the amount of nucleating agent, if present, will generally be less than or equal to one part per hundred resin parts (phr) if only because of the wasted cost of adding excess nucleating agent.
  • the lower limit of nucleating agent present is effectively 0 phr, which is to say that its presence is optional.
  • the nucleant is preferably present in amounts in the range from 0.1 to 2 phr.
  • the polymer composition can be used in any of the other methods for forming articles, particularly extruded films.
  • the polymer composition may contain any other of the additives commonly used in polymer processing, for example, pigment, particulate or fibrous or platy filler or reinforcer.
  • the polymer composition can also comprise other extrudable polymers blended with the basic polymer, but in this case the amount of the basic polymer of the total amount of all polymers should be at lest 50 wt-%, preferably at least 75 wt-% in this blend.
  • Examples of articles made by such methods include coated products such as paper and/or paperboard. These types of materials can be used for example for packaging applications.
  • the formulations may also be suitable for extruding film andfor coating different films, fibres and non-woven fabrics.
  • a process for the preparation of coated articles which comprises preparing a polymer composition as previously defined and extrusion coating the polymer on to a substrate which can be a paper, pa- per board, or a film of some suitable material, especially such a film that in the process conditions of extrusion coating has different shrinking properties with respect to the basic material of the polymer coating (polymer or blend of polymers) between the extrusion temperature and end temperature (usually room or storage temperature).

Abstract

Composition polymère qui est appliquée sur la partie supérieure d'un substrat approprié par revêtement par extrusion, stratification ou d'autres procédés et qui forme au moins une couche dudit revêtement. Ladite composition contient au moins une paraffine, une huile ou une colophane en tant qu'adjuvant. La présente invention permet d'empêcher l'enroulage du substrat recouvert et le craquelage du revêtement après le revêtement par extrusion.
PCT/FI1997/000594 1996-10-01 1997-10-01 Composition polymere WO1998014326A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI963935A FI963935A (fi) 1996-10-01 1996-10-01 Polymeerikoostumus
FI963935 1996-10-01

Publications (1)

Publication Number Publication Date
WO1998014326A1 true WO1998014326A1 (fr) 1998-04-09

Family

ID=8546784

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1997/000594 WO1998014326A1 (fr) 1996-10-01 1997-10-01 Composition polymere

Country Status (2)

Country Link
FI (1) FI963935A (fr)
WO (1) WO1998014326A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6727298B2 (en) 2000-03-08 2004-04-27 Basf Aktiengesellschaft Method for reducing the permeability of films or coatings to water vapor
WO2023153277A1 (fr) * 2022-02-08 2023-08-17 株式会社カネカ Corps stratifié biodégradable, son procédé de production et corps moulé

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1222665A (en) * 1968-04-29 1971-02-17 Milprint Inc Extrusion-coating of ethylene-vinyl acetate coatings
US5169889A (en) * 1992-01-27 1992-12-08 National Starch And Chemical Investment Holding Corporation Poly hydroxybutyrate/hydroxyvalerate based hot melt adhesive
WO1995015260A1 (fr) * 1993-11-30 1995-06-08 Zeneca Limited Film biodegradable
EP0699800A2 (fr) * 1994-08-31 1996-03-06 National Starch and Chemical Investment Holding Corporation Enductions thermofusibles pour papier et carton

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1222665A (en) * 1968-04-29 1971-02-17 Milprint Inc Extrusion-coating of ethylene-vinyl acetate coatings
US5169889A (en) * 1992-01-27 1992-12-08 National Starch And Chemical Investment Holding Corporation Poly hydroxybutyrate/hydroxyvalerate based hot melt adhesive
WO1995015260A1 (fr) * 1993-11-30 1995-06-08 Zeneca Limited Film biodegradable
EP0699800A2 (fr) * 1994-08-31 1996-03-06 National Starch and Chemical Investment Holding Corporation Enductions thermofusibles pour papier et carton

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FILE WPI, Derwent Accession No. 93-327462, LIOU C: "Transfer Printing Paper Prepn.-Comprises Coating Three Film Layers on Art paper and 20-50 kg/cm Pressure at 130-150 Deg. C for 7-151 Sec/ to Transfer Printing to Cloth"; & TW,A,208 056 (21-06-93), DW9341. *
FILE WPI, Derwent Accession No. 94-114861, TOPPAN PRINTING CO LTD: "Biodegradable Paper Container - Comprises Paper Laminate with Biodegradable Plastic Layer"; & JP,A,06 064 111 (08-03-94), DW9414. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6727298B2 (en) 2000-03-08 2004-04-27 Basf Aktiengesellschaft Method for reducing the permeability of films or coatings to water vapor
WO2023153277A1 (fr) * 2022-02-08 2023-08-17 株式会社カネカ Corps stratifié biodégradable, son procédé de production et corps moulé

Also Published As

Publication number Publication date
FI963935A (fi) 1998-04-02
FI963935A0 (fi) 1996-10-01

Similar Documents

Publication Publication Date Title
US7094840B2 (en) Compositions comprising low molecular weight polyhydroxyalkanoates and methods employing same
AU683466B2 (en) Polyester composition
US5863991A (en) Biodegradable polymers, the preparation thereof and the use thereof for the production of biodegradable moldings
US5817721A (en) Biodegradable polymers, the preparation thereof and the use thereof for producing biodegradable moldings
EP0675913B1 (fr) Resines thermoplastiques biodegradables et procede pour leur preparation
US6046248A (en) Biodegradable polymers, the preparation thereof and the use thereof for producing biodegradable moldings
TWI378969B (en) Polyester compositions for calendering
US6111058A (en) Biodegradable polyesteramide and a process of preparing
EP1694750B1 (fr) Procede de calandrage de polyesters
US20050137304A1 (en) Process for calendering of polyesters
US20100330315A1 (en) Projet hot melt compostable
WO1996025446A1 (fr) Polymeres biodegradables, leur procede de fabrication et leur emploi dans la fabrication de pieces moulees biodegradables
HU222853B1 (hu) Biológiailag lebontható polimerek, eljárás előállításukra és felhasználásuk biológiailag lebontható formatestek előállítására
US6111006A (en) Process for preparing films and coatings
CA1047690A (fr) Methode pour la fabrication des copolyesters et melanges adhesifs appliques a chaud, a base de copolyesters
EP1497352B1 (fr) Copolymeres blocs amorphes cristallins
CN113631657A (zh) 聚羟基烷酸酯系树脂组合物、其成型体及膜或片
EP0998381A1 (fr) Revetements polyhydroxyalcanoate
EP0746585B1 (fr) Procede de preparation de films et de revetements
WO1998014326A1 (fr) Composition polymere
KR101850514B1 (ko) 3d 프린터 필라멘트용 생분해성 수지 조성물 및 그를 이용한 유연성 및 내충격성이 우수한 3d 프린터용 필라멘트
KR100255116B1 (ko) 생분해성 고분자의 제조방법
KR101831854B1 (ko) 내가수분해성 및 생분해성이 우수한 코폴리에스테르 수지 조성물
US5760170A (en) Polyester composition
JPH0718167A (ja) 可塑剤及びポリエステル系樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998516265

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase