EP1725593A1 - Sirop de (meth)acrylate utilise comme stabilisateur de suspension destine a des colorants - Google Patents

Sirop de (meth)acrylate utilise comme stabilisateur de suspension destine a des colorants

Info

Publication number
EP1725593A1
EP1725593A1 EP05700912A EP05700912A EP1725593A1 EP 1725593 A1 EP1725593 A1 EP 1725593A1 EP 05700912 A EP05700912 A EP 05700912A EP 05700912 A EP05700912 A EP 05700912A EP 1725593 A1 EP1725593 A1 EP 1725593A1
Authority
EP
European Patent Office
Prior art keywords
group
carbon atoms
same meanings
alkyl radical
hydrogen
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.)
Withdrawn
Application number
EP05700912A
Other languages
German (de)
English (en)
Inventor
Klaus Kabs
Frank Schäfer
Hans Lichtenstein
Bernd Klossek
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.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1725593A1 publication Critical patent/EP1725593A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
    • C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the invention relates to functional (meth) acrylate syrups or monomer-polymer systems as binders and as suspension stabilizers for colorants and colorant concentrates.
  • functional syrups are understood to mean partially polymerized mixtures of methyl methacrylate (MMA) and functionalized methacrylates.
  • MMA methyl methacrylate
  • the partial polymerization is carried out to the extent that a still pumpable monomer-polymer mixture is formed.
  • Coloring agents are available in the art for coloring plastics, which enable almost any desired coloring of the plastic molding. Plastics are mainly colored either by mass coloring in the manufacture of the plastics or in the processing of plastic powders or granulates. The coloring process is adapted to the respective plastic.
  • the colorant concentrates should have good solubility in the monomer or in prepolymers. They should also not adversely affect the course of polymerization and the demolding of the products from the glass plates of the mold.
  • the pigments should be well dispersed in the polymerization batches and, above all, the disperse state of the pigments must be sufficiently stable, i.e. H. there must be no sedimentation or re-agglomeration of the pigments.
  • the aim should be that the dispersions produced with the colorant concentrates remain stable over a period of hours to days in order to have the desired flexibility in production.
  • the colorants or pigments should be easy to process mechanically into a colorant concentrate.
  • the processing processes of the acrylic glass such as tempering, forming, stretching, etc., that occur after the polymerization is not to be negatively influenced.
  • the other mechanical properties of the colored acrylic glass, the Vicat softening temperature and the weathering behavior should not be worse than that of normal acrylic glass.
  • the partially polymerized syrup for pigment stabilization contains a polymer from the components:
  • R 2 - C - C CH 2
  • Ri is hydrogen or methyl and R 2 is a radical having a functional group from one of the following types a) to g) a) a hydroxyl group b) an NR 3 group, where R 3 and R 4 IR 4 independently of one another represent hydrogen, a linear, optionally branched alkyl radical having 1-6 carbon atoms or in which R 3 together with R, including the nitrogen and optionally together with further nitrogen or oxygen atoms, form a five- or six-membered heterocyclic system,
  • R ' 3 R' N - X - Y group where X is a linear or an optionally branched, optionally cyclic alkylene group having 2 to a total of 10 carbon atoms, Y is oxygen or a radical -NR 5 - and R ' 3 and R ' 4 have the same meanings as R 3 and R 4 and R 5 represents hydrogen or an alkyl radical having 1 to 6 carbon atoms or
  • X "and Y" have the same meanings as X and Y, n is zero or one and R ⁇ is hydrogen or an alkyl radical having 1 to 6 carbon atoms,
  • the syrup according to the invention can be processed and dispersed very well together with all pigments known per se.
  • the colorants used to prepare the colorants are also suitable for coloring the polymers, ie. H. both inorganic and organic dyes or pigments or nanoparticles. They can be taken from the prior art based on the plastics to be colored (see Vieweg-Esser, Kunststoff-Handbuch, Volume IX, 'Polymethacrylate', C. Hansen Verlag 1975).
  • pigments are e.g. B. carbon blacks, iron oxide, titanium dioxide, phthalocyanine blue and green dioxazine and quinacridone-like pigments.
  • the concentration of the colorants in the syrup according to the invention is generally 10-70% by weight, preferably 30-60% by weight and particularly preferably 40-50% by weight, based on the mass of the syrup.
  • the colorants are incorporated into the syrup according to the invention by means of the customary processes which are known in the prior art.
  • the proportion of the master batch in the total batch is generally between 0.05 and 10% by weight, preferably between 0. 1 and 5 wt .-% and particularly preferably between 0.5 and 3 wt .-%.
  • the introduction into the precursors used for the polymerization of the acrylic or methacrylic resins according to the prior art, such as syrups, prepolymers and / or monomers and monomer mixtures, can be carried out in the customary manner, for example by stirring.
  • the subsequent processing steps for example the filling of the syrup into the shaping polymerization chambers and the subsequent polymerization step can then be carried out analogously to the prior art method, likewise the subsequent demolding of the finished polymer plates.
  • Acrylic resins are generally made up entirely or in large part of esters of acrylic and methacrylic acid, in particular methyl methacrylate (MMA) as monomers, if appropriate in addition to MMA, from other copolymerizable monomers.
  • MMA methyl methacrylate
  • the matrix polymers based on methyl methacrylate can, for. B. still contain proportions of 0 to about 45 wt .-% of other comonomers.
  • esters of methacrylic acid or acrylic acid such as. B. the acrylic acid methyl ester, acrylic acid butyl ester, ⁇ -chloroacrylic acid methyl ester, methacrylic acid ethyl ester; further (optionally substituted) amides of acrylic or methacrylic acid, such as acrylamide and methacrylamide, methylol methacrylamide and acrylamide.
  • amides of acrylic or methacrylic acid such as acrylamide and methacrylamide, methylol methacrylamide and acrylamide.
  • acrylonitrile, styrene and derivatives the same such as ⁇ -methylstyrene
  • vinyl esters of carboxylic acids such as vinyl acetate and the like. ä.
  • crosslinking monomers such as ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, triglycol dimethacrylate, trimethylolpropane trimethacrylate or allyl compounds, such as, for. B. allyl methacrylate, triallyl cyanurate or trially isocyanurate.
  • Impact modifiers can also be used.
  • the polymerization can be carried out in a manner known per se, using the experience of technology (cf. H. Rauch-Puntigam and Th. Völker in "Acryl- und Methacrylitatien", Springer-Verlag 1967 and J. Brandrup - EH Immergut, Polymer Handbook, 2nd Edition, Wiley-Interscience (1975), the basic features of which have already been described in DE-PS 639 095.
  • Peroxide or azo compounds for example, can be used in the usual amounts as initiators for the radical polymerization of the monomers (such as the acrylic monomers, styrene and derivatives, esters of vinyl compounds).
  • the known regulators and / or retarders in the known concentrations are suitable for controlling the molecular weight. May be mentioned for.
  • the degree of polymerization and thus the molecular weight of the resin molecules formed can be adjusted, as is known, by the initiator concentration and / or the regulator concentration. So you will usually use 0.01 to 1.0 wt .-% of initiator in the polymerization of acrylic resins.
  • regulator and / or retarder is generally between 0.01 and 0.5% by weight, preferably between 0.05 and 0.2% by weight.
  • M w molecular weights of the matrix polymers are in the range from 2 10 5 to 5 0 6 .
  • the Vicat softening temperature (according to DIN 53460, method B) is usually> 100 ° C.
  • the polymerization batches may also contain the auxiliaries known per se, such as UV absorbers, plasticizers, light and thermal stabilizers, antioxidants, flame retardants, etc.
  • the syrup can also be produced in close proximity to the polymerization processes of the prior art (see above “preparation of the polymers”).
  • the polymerization is generally triggered by free radical formers, preferably by peroxide or azo compounds in the usual amounts (usually between 0.02 and 0.1% by weight, based on the monomers).
  • free radical formers preferably by peroxide or azo compounds in the usual amounts (usually between 0.02 and 0.1% by weight, based on the monomers).
  • the known redox systems, accelerators, etc. can also be used with advantage (cf. H. Rauch-Puntigam "Acrylic and Methacrylic Compounds", Springer Verlag 1967).
  • the known regulators and / or retarders are also suitable for controlling the molecular weight here. eg sulfur regulator in the concentrations known per se
  • the addition of regulator is generally between 0.01 and 0.5% by weight, preferably between 0.05 and 0.2% by weight.
  • the syrup is produced, for example, according to the following regulation:
  • MMA plus additives are required per batch.
  • the mixture contains MMA, 5% 2-hydroxyethyl methacrylate, 1% 2-dimethylaminoethyl methacrylate and 0.04% initiator 2,2'-azobis (2,4 dimethylvaleronitrile).
  • half of the solution is placed in the cooking container.
  • the second half remains in the feed tank.
  • the cooking process is started in automatic mode.
  • the solution is heated to 73 ° C. At this temperature, the inflow of the second half of the Solution from the inlet tank between 18 l / min. and 30 I / min. The temperature should not exceed 93 ° C.
  • the coolant is drained.
  • the polymer content is 10 - 30% depending on the cooling conditions.
  • the viscosity, measured in a 6 mm Ford cup is 30 - 60 seconds (according to DIN 53211).
  • Variant 1 when using the functional syrup Variant 1 of the process consists in mixing color paste and the functional syrup in a ratio of 4 to 1 and then adding this mixture in the polymerization kettle to the remaining components.
  • the second variant of the method consists in mixing the color in the form of a masterbatch together with the functional syrup according to the invention Submit boiler and add all or part of the remaining polymerization mixture and fill into the polymerization chambers.
  • the syrup according to the invention largely fulfills the technical requirements described at the outset.
  • the colorant concentrates dissolve well in the monomers or prepolymers. Their addition does not affect the course of the polymerization. They offer considerable advantages over the prior art, particularly in the demolding. For example, B. reduce or avoid the dreaded glass breakage during demolding. The relative stability of the disperse state should also be assessed positively.
  • Processing processes such as tempering, forming, stretching etc. can be carried out well.
  • the mechanical and optical properties of the colored acrylic glasses, the Vicat softening temperature and the weathering behavior are not affected compared to normal acrylic glass.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un liant soluble polymère destiné aux pigments à base de méthylméthacrylate. Ce liant est un polymère composé de méthylméthacrylate et d'au moins un autre composé radicalement polymérisable, et est utilisé sous la forme d'un sirop partiellement polymérisé.
EP05700912A 2004-03-17 2005-01-14 Sirop de (meth)acrylate utilise comme stabilisateur de suspension destine a des colorants Withdrawn EP1725593A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004015355A DE102004015355A1 (de) 2004-03-17 2004-03-17 (Meth)acrylatsirup als Suspensionsstabilisatoren für Farbmittel
PCT/EP2005/000310 WO2005097849A1 (fr) 2004-03-17 2005-01-14 Sirop de (meth)acrylate utilise comme stabilisateur de suspension destine a des colorants

Publications (1)

Publication Number Publication Date
EP1725593A1 true EP1725593A1 (fr) 2006-11-29

Family

ID=34960015

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05700912A Withdrawn EP1725593A1 (fr) 2004-03-17 2005-01-14 Sirop de (meth)acrylate utilise comme stabilisateur de suspension destine a des colorants

Country Status (7)

Country Link
US (1) US20070161744A1 (fr)
EP (1) EP1725593A1 (fr)
JP (1) JP2007529577A (fr)
CN (1) CN1926162A (fr)
CA (1) CA2557258A1 (fr)
DE (1) DE102004015355A1 (fr)
WO (1) WO2005097849A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101421348B (zh) * 2006-04-14 2011-09-07 普立万公司 液体色母料

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421889A (en) * 1975-08-08 1983-12-20 Hoechst Aktiengesellschaft Aqueous dispersion paints and process for making the same
JPS58206621A (ja) * 1982-05-27 1983-12-01 Mitsui Toatsu Chem Inc メチルメタクリレ−トシラツプ組成物
DE3323951A1 (de) * 1983-07-02 1985-01-03 Röhm GmbH, 6100 Darmstadt Acrylatharze als bindemittel fuer farbmittelkonzentrate
DE3821116B4 (de) * 1988-06-23 2006-07-13 Röhm GmbH & Co. KG Verfahren zur Herstellung von eingefärbten Polyacrylatplatten
DE68925636T2 (de) * 1989-06-27 1996-07-18 Mitsubishi Rayon Co Hochtransparente, schlagfeste Methacrylharz-Gussplatte und Verfahren zu ihrer Herstellung
DE4102345A1 (de) * 1991-01-26 1992-07-30 Basf Ag Formkoerper auf basis von fasern
WO1996030434A2 (fr) * 1995-03-24 1996-10-03 John Gould Nouveaux concentres d'additifs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005097849A1 *

Also Published As

Publication number Publication date
JP2007529577A (ja) 2007-10-25
DE102004015355A1 (de) 2005-10-06
CA2557258A1 (fr) 2005-10-20
WO2005097849A1 (fr) 2005-10-20
US20070161744A1 (en) 2007-07-12
CN1926162A (zh) 2007-03-07

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