[go: up one dir, main page]

WO2003033571A1 - Melange colorant pour produits neutres a reticuler et a faire mousser des par moulage par injection - Google Patents

Melange colorant pour produits neutres a reticuler et a faire mousser des par moulage par injection Download PDF

Info

Publication number
WO2003033571A1
WO2003033571A1 PCT/EP2001/014964 EP0114964W WO03033571A1 WO 2003033571 A1 WO2003033571 A1 WO 2003033571A1 EP 0114964 W EP0114964 W EP 0114964W WO 03033571 A1 WO03033571 A1 WO 03033571A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture according
mixture
pigment
basic polymer
crosslinked
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2001/014964
Other languages
English (en)
Inventor
Sergio Brunetti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
API Applicazioni Plastiche Industriali SPA
Original Assignee
API Applicazioni Plastiche Industriali SPA
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 API Applicazioni Plastiche Industriali SPA filed Critical API Applicazioni Plastiche Industriali SPA
Publication of WO2003033571A1 publication Critical patent/WO2003033571A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the present invention relates to a coloring mixture for neutral products to be crosslinked and expanded by injection molding.
  • EVA injection molded manufactured articles
  • crosslinked products allows to obtain in comparison with thermoplastic materials, foamed polymers of considerable lightness and with valid physical and mechanical characteristics.
  • the process of making any manufactured article of this kind may be generally divided into two stages.
  • the known compound compositions generally comprise:
  • EVA and PE mixtures or ethylene propylene rubbers (EPR) or low and high density polyethylene, having different degrees of melt flow index (MFI) or ethylene vinyl acetate with various
  • peroxides being crosslinking agents which are activated at a predetermined temperature, such as decoumyl peroxide, bis-tert-butylperoxy propyl benzene, 2,5 bis-tert-butyl-peroxy 2,5 dimethyl exane; - coaqents. blocking the secondary reactions of peroxides optimizing the crosslinking yield such as triallylcyanurates, triallylisocyanurates, ethylene glycol dimethacrylate and trimethylolpropane-trimethacrylate;
  • - foaming agents such as azodicarbonamides of various nature which generate gas through their thermal distruction such as the industrial known types like Porofor® and Genitron®;
  • a predetermined coloration as a function of the used pigments is associated in this stage to the compound.
  • the so obtained final product is in all respects a coloured thermoplastic product adapted to be crosslinked and foamed when taken to adequate temperatures.
  • the second stage provides for transformation of the product from a coloured thermoplastic one to a final thermoset polymer.
  • the coloured compound is introduced into a press for injection of plastic material.
  • the working cycle is carried out in the range of material thermoplastic condition (normally temperatures between 85 and 120°C).
  • the molten coloured compound is injected into the mold which being heated to high temperature in the range of 150- 190°C for an adequate time, heats the polymer triggering the peroxide action, so as to start the polymer crosslinking process and transformation of the foaming agents into gas.
  • the mold is opened allowing the gases to expand suddenly the article causing its automatic ejection from the mold with a kind of little explosion.
  • the foamed article is characterized by a foamed core and a very fine and compact coloured outer surface.
  • the shape of the article follows the configuration of the mold that made said article, but has proportionally greater size as a function of the foaming agents present in the compound less the shrinkage due to the thermal contraction generated during cooling by the difference of temperature between mold and ambient.
  • the manufactured article has a compact surface with bright look and colour function of the kind and quantity of pigments present in the compound.
  • a first drawback of said method consists in that the article coloration is decided when preparing said compound. Indeed as above mentioned, the colouring agents or pigments are added when making the mixture constituting the compound. Said pigments give to the compound a fixed coloration that cannot be changed thereafter.
  • the known method generally consists in producing a colourless basic compound called neutral compound, and adding a granular colouring mixture containing the pigments diluted in a suitable carrier compatible with the neutral compound at the molding operation.
  • a first drawback of said method consists in that the used colouring mixtures alter both the mechanical characteristics and mainly the compound foaming and crosslinking features.
  • the object of the present invention is to overcome the foregoing drawbacks.
  • a first object of the invention is to provide a colouring mixture for making foamed crosslinked articles allowing pigmentation of the article at the molding operation starting from a neutral compound.
  • Another object is to provide a colouring mixture that does not alter expansion and thermal shrinkage of the article when added to a neutral compound if its pigmentation features are changed. More particularly the object is to obtain that expansion and thermal shrinkage of the article are a function only of the features of the neutral compound.
  • a colouring mixture for neutral products to be crosslinked and foamed by injection molding that according to the main claim comprises: - at least a carrier consisting of at least a basic polymer; - at least a pigment; characterized by comprising also crosslinking agents or foaming agents or foaming and crosslinking agents.
  • the colouring mixture for producing crosslinked articles made by injection molding according to the present invention comprises:
  • - a carrier consisting of one or more basic polymers mixed together; and - a pigment.
  • the invention provides that the mixture comprises either crosslinking agents or crosslinking agents and foaming agents as well.
  • the crosslinking agents consist of peroxide or analogs while the foaming agents consist of azodicarbonamides or analogs.
  • the carrier consists of basic polymers such as ethylene vinyl acetates (EVA), or polyethylene (PE) and their mixtures or ethylene propylene rubber (EPR) or ethylene propylene diene terpolymer (EPDM) or a thermoplastic elastomer.
  • the pigment may be either an inorganic type or an organic type. In some cases the pigment may also be fluorescent or metalizing or pearlscent.
  • the colouring mixture comprises:
  • organic pigments 2% to 30% or inorganic pigments: 5% to 60% or their mixtures;
  • the mixture may also contain: various additives:
  • the latter should not be necessarily present in all the formulations, when included, the percentage used will be in the range of 0.1% and 10% on the total amount of the formulation components.
  • the percentage of colouring mixture on the neutral compound varies from 5 to 15% and is preferably in the range between 6 and 10%.
  • the colouring mixture in the form of granules according to the foregoing composition and the neutral compound are prepared separately.
  • Such a neutral compound of a kind known per se and obtained according to the preceding disclosure indicated as first stage may have the following formulation: - EVA 18% V.S. 2MRI 100
  • the second stage of molding the article is started. More particularly the second stage consists as already mentioned, in transforming the compound from a thermoplastic material to a thermoset final polymer.
  • the granules of neutral compound and colouring mixture properly mixed intimately, are dry introduced into a conventional injection press for plastic material. More particularly such a press comprises a punching screw injector consisting of a cylinder and a screw adapted to move the granules inside the cylinder which is heated to the desired temperature allowing the plasticization of the compound.
  • the cylinder temperature By properly controlling the cylinder temperature so as not to reach the triggering temperature which is generally in the range of 85-120°C of both the foaming agent and the crosslinking agent, it is possible to carry out the working cycle in the material thermoplastic area.
  • the molten compound is finally mixed with the pigments of the colouring mixture thus obtaining a product with homogeneous colour that can then be injected into the mold.
  • the mold is heated to a high temperature in the range of 150-190°C for an adequate time, the polymer is heated triggering the action of peroxide thus starting the polymer crosslinking process and transformation of the foaming agents into gas.
  • the stoichiometric quantity of peroxide introduced into the mixture is sufficient, it is possible to reach the total polymer crosslinking, otherwise crosslinking levels lower than 100% are obtained.
  • the crosslinkling reaction is completed until all the peroxide is consumed so as to prevent a further subsequent increase of viscosity, thus obtaining partial or total crosslinking.
  • the mold is opened thus allowing the gases to expand suddenly the article, causing its automatic ejection from the mold with a kind of little explosion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un mélange colorant pour produits neutres à réticuler et à faire mousser par moulage par injection. Ledit mélange colorant comprend un vecteur constitué d'un polymère de base et un pigment comprenant des agents réticulants.
PCT/EP2001/014964 2001-10-11 2001-12-18 Melange colorant pour produits neutres a reticuler et a faire mousser des par moulage par injection Ceased WO2003033571A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITVI2001A00210 2001-10-11
ITVI20010210 ITVI20010210A1 (it) 2001-10-11 2001-10-11 Miscela colorante per prodotti neutri reticolabili ed espandibili tramite stampaggio ad iniezione

Publications (1)

Publication Number Publication Date
WO2003033571A1 true WO2003033571A1 (fr) 2003-04-24

Family

ID=11461710

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/014964 Ceased WO2003033571A1 (fr) 2001-10-11 2001-12-18 Melange colorant pour produits neutres a reticuler et a faire mousser des par moulage par injection

Country Status (2)

Country Link
IT (1) ITVI20010210A1 (fr)
WO (1) WO2003033571A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008030732B4 (de) * 2008-06-27 2013-04-04 Ulrich Weigel Verfahren zur Herstellung von Farbkonzentratgranulatkörnern für thermoplastische Kunststoffe, Farbkonzentratgranulatkörner und deren Verwendung

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5145169A (ja) * 1974-10-16 1976-04-17 Dainichiseika Color Chem Kohatsuhohoriorefuinjushino chakushokuhoho
JPH02308831A (ja) * 1989-05-23 1990-12-21 Sanwa Kako Kk 多色模様のポリオレフィン発泡体の製造方法
WO1997048538A1 (fr) * 1996-06-21 1997-12-24 Sentinel Products Corp. Melange polymere
JP2000034361A (ja) * 1998-07-17 2000-02-02 Sanwa Kako Co Ltd 紫外線発色発泡体及びその製造方法
JP2000256470A (ja) * 1999-03-08 2000-09-19 Yazaki Corp オレフィン系発泡マスターバッチ組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5145169A (ja) * 1974-10-16 1976-04-17 Dainichiseika Color Chem Kohatsuhohoriorefuinjushino chakushokuhoho
JPH02308831A (ja) * 1989-05-23 1990-12-21 Sanwa Kako Kk 多色模様のポリオレフィン発泡体の製造方法
WO1997048538A1 (fr) * 1996-06-21 1997-12-24 Sentinel Products Corp. Melange polymere
JP2000034361A (ja) * 1998-07-17 2000-02-02 Sanwa Kako Co Ltd 紫外線発色発泡体及びその製造方法
JP2000256470A (ja) * 1999-03-08 2000-09-19 Yazaki Corp オレフィン系発泡マスターバッチ組成物

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; ADACHI, MITSUHARU ET AL: "Polyolefin foams having UV photoluminescent properties and their manufacture", XP002201843, retrieved from STN Database accession no. 132:109155 *
DATABASE WPI Section Ch Week 197622, Derwent World Patents Index; Class A17, AN 1976-41144X, XP002201845 *
DATABASE WPI Section Ch Week 199106, Derwent World Patents Index; Class A18, AN 1991-041093, XP002201844 *
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 12 3 January 2001 (2001-01-03) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008030732B4 (de) * 2008-06-27 2013-04-04 Ulrich Weigel Verfahren zur Herstellung von Farbkonzentratgranulatkörnern für thermoplastische Kunststoffe, Farbkonzentratgranulatkörner und deren Verwendung

Also Published As

Publication number Publication date
ITVI20010210A1 (it) 2003-04-11

Similar Documents

Publication Publication Date Title
EP1208954B1 (fr) Procédé de fabrication d'un article moulé
US5269991A (en) Process for obtaining mouldings with the appearance of natural stones
US6312639B1 (en) Processing aid for thermoplastic resin compositions
CN108025473B (zh) 发泡成型品的制造方法和发泡成型品
CA2417995A1 (fr) Melanges polymeres formes par pulverisation par cisaillement a l'etat solide presentant des proprietes ameliorees de fluidite
US5686515A (en) Colored polyethylene terephthalate composition and process of its manufacture
US6933344B2 (en) Thermoplastic elastomeric compositions and methods of preparing thermoplastic elastomeric compositions
US4048275A (en) Cross-linking and foaming injection molding process for ethylenic polymers
CN102712118A (zh) Pet热塑性聚合物制品，以及这种制品的制作方法
US12012496B2 (en) Method for the manufacture of a colored polymer composition
JP2512353B2 (ja) 自然石の外観をもつ成形品を得る方法及び得られた成形品
US5187202A (en) Concentrates for imparting a simulated stone effect to thermoplastic substrates
WO2003033571A1 (fr) Melange colorant pour produits neutres a reticuler et a faire mousser des par moulage par injection
JP2001294671A (ja) 着色顔料マスターバッチ及びこれを用いたブロー成形法
KR20020089353A (ko) 몰딩가능한 물질의 몰딩
WO2002016464A3 (fr) Procede de production de materiaux thermoplastiques en polyester colore comportant des operations specifiques de solidification
US4499238A (en) Thermoplastic resin products having pearl-like luster
CN102601907A (zh) 塑料印章的制备方法
US4296055A (en) Method of injection molding thermoplastic resinous products substantially free from sink marks, swirls and related blemishes
KR20180066624A (ko) Abs와 발포제를 결합한 컴파운딩 조성물로부터 제조되는 자동차 내장재
WO2002020657A1 (fr) Composes permettant de fabriquer des produits reticules d'une grande souplesse et possedant une stabilite dimensionnelle thermique elevee
WO2002020658A1 (fr) Composes utilises pour produire des produits reticules ayant un aspect de surface a fini mat, une grande souplesse ou mollesse et une stabilite dimensionnelle elevee a la chaleur
JPS588333B2 (ja) 模様入り熱可塑性合成樹脂成形品の製造方法
WO2004108384A1 (fr) Procede d'utilisation de materiaux polymeres pour former des produits en mousse façonnes
KR20000041246A (ko) 종이 또는 목재의 질감을 갖는 폴리올레핀계 수지조성물

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG US UZ VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE CH CY DE DK FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ ML MR NE SN TD TG

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

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP