CN1436204A - Magnetic or magnetisable bonding agent composition - Google Patents

Magnetic or magnetisable bonding agent composition Download PDF

Info

Publication number
CN1436204A
CN1436204A CN01811259A CN01811259A CN1436204A CN 1436204 A CN1436204 A CN 1436204A CN 01811259 A CN01811259 A CN 01811259A CN 01811259 A CN01811259 A CN 01811259A CN 1436204 A CN1436204 A CN 1436204A
Authority
CN
China
Prior art keywords
magnetic
vinylbenzene
monomer
adhesive composition
reaction
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.)
Pending
Application number
CN01811259A
Other languages
Chinese (zh)
Inventor
B·雷塞
U·希斯
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.)
Emtec Magnetics GmbH
Original Assignee
Emtec Magnetics GmbH
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 Emtec Magnetics GmbH filed Critical Emtec Magnetics GmbH
Publication of CN1436204A publication Critical patent/CN1436204A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
    • G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
    • G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
    • G11B5/7023—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent containing polyesters, polyethers, silicones, polyvinyl resins, polyacrylresins or epoxy resins
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • 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
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
    • C09D155/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Magnetic Record Carriers (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a bonding agent composition containing at least one block copolymer which can be produced by means of radical polymerisation, at least two blocks of different monomer compositions, and at least one magnetic or magnetisable pigment. The invention also relates to a method for producing such a bonding agent composition and the use thereof.

Description

Magnetic or magnetisable bonding agent composition
The present invention relates to make and have a segmented copolymer that at least two monomers are formed different blocks by Raolical polymerizable a kind of comprising at least, adhesive composition with at least a magnetic or magnetisable pigment is used to method for preparing this adhesive composition and uses thereof.
Comprise polymkeric substance or two or more mixture of polymers as binding agent and comprise in addition and at least aly be dispersed in magnetic in the adhesive composition or the adhesive composition of magnetisable pigment is usually used in production magnetic or magnetizable layer, for example be used to produce magnetisable coating, but in particular for producing magnetic recording medium.These magnetic recording mediums are widely used in and are forming the especially permanent storage of data.The structure of these magnetic recording mediums generally includes non-magnetic matrix and at least onely firmly is administered on the base material and based at least a polymeric binder and at least a dispersion magnetic wherein or the magnetizable layer of magnetisable pigment.
Because the amount of information processing and storage constantly increases in the daily life, require the magnetic recording medium cocoa in very little space, to store and very high forming density and can be, i.e. standing storage and broadcast information less than mistakenly and repeatedly.Especially, therefore the stability to aging of record and the quality of playing and these magnetic recording mediums must satisfy high request.But satisfy the character that the polymeric binder in the magnetic recording medium is obviously depended in described requirement, wherein binding agent is very important to the magnetic or the magnetisable dispersing of pigments ability that are dispersed in the described binding agent with a kind of stable manner in the very long time.In order to satisfy above-mentioned requirements, attempted increasing the stability of the dispersion of magnetic paint in polymeric binder, so for example can improve magnetic behavior, the tamped density of especially residual induction, and increase magnetic paint in magnetosphere.
Usually, the decline of magnetospheric binder content is followed in the increase of pigment content.But in fact the measure of more than enumerating makes the dispersion of pigment in the dispersing method process complicate.Find that in addition the stability of dispersion is bad usually.In addition, required snappiness of magnetic recording medium and elasticity and magnetospheric corresponding tensile strength affect adversely because of the amount of binder content descends usually.
In addition, corresponding magnetic recording medium must have very low-friction coefficient and high-wearing feature and erasibility, especially when they directly contact with the mechanism that is used to read the data that are stored on the recording medium or information.In addition, even described mechanical property at extreme weather conditions, for example also should guarantee under high temperature and high atmospheric moisture.But known many prior art binding agents can not satisfy these requirements at present.In many cases, the wetting and dispersion of pigment affects adversely, especially for the magnetic paint that segments very much.Any aggregate that sintering produces disperses insufficient in the dispersing method process or can not suitably prevent reassociating of granules of pigments.This can cause the magnetic behavior of recording medium bad.
For fear of above-mentioned shortcoming, the past often adds a spot of lower molecular weight dispersion agent dispersion to help dispersing method.But these lower molecular weight dispersion agents have shortcoming.Therefore, they ooze out easily, promptly for example at disadvantageous weather condition, as appearing on the surface of magnetic recording medium under high atmospheric moisture and the temperature, cause in record or playback equipment with all parts of contact with tape on, especially overhead deposition.In addition, friction increases because of these settlings, and this magnetic recording medium can read or stop up during apparatus for writing passing through as a result.
When another problem appears at polymeric binder branch sperromagnetism or magnetisable pigment, show as binding agent or binder mixtures and dispersion wherein magnetic or the compatibility problem between the magnetisable pigment.Because these pigment generally have water-wetted surface, the consistency of binding agent can for example improve by introduce the hydrophilic-structure composition in binding agent.But this can cause the hydrophilic nmature increase of magnetic recording layer to make magnetosphere at moisture, and especially the existence of the moisture relevant with high temperature is expanded down, and some lower-molecular-weight component can ooze out as a result.
In the past, many polycondensates or addition polymer are as the polymkeric substance of the binding agent that can divide sperromagnetism or magnetisable pigment.Also constantly attempt using the binding agent of making and using with the form of random copolymers subsequently by Raolical polymerizable.
The use of addition polymer or polycondensate might influence the chemistry and the physicals of used binding agent basically, because addition polymerization or polycondensation can bring the block structure of corresponding binding agent in suitable reaction.But the shortcoming of these binding agents is that along with the control that increases material property, necessary employing is more complicated, and generally multistep is synthetic.Especially often reacting under the situation of the addition polymer for preparing by isocyanic ester and to the respective compound of isocyanate-reactive, the processing of toxicity isocyanic ester can be used as shortcoming and proposes.In addition, these polymkeric substance generally have the high polymolecularity of bad control.
On the contrary, prepare random copolymers by Raolical polymerizable and simplified this method basically.But products therefrom is difficult to control its physics or chemical property, and can not establish these performances with ad hoc fashion usually.
For example, US-A5,695,884 have described a kind of thermoplastic polyurethane with at least one sulfonate groups.Sulfonate groups is introduced urethane by the polyester polyol that contains sulfonate, comprises sulfonate groups so again as the sulfosalicylic phthalate derivative.The shortcoming of this step is to need many reactions steps just can obtain final polymeric binder.
DE-A 40 39 749 relates to and a kind ofly has the urea groups of no OH and have the branched polyurethanes of molecular weight 30 000-200 000 at the end of the chain.But described binding agent does not have block structure, is difficult to control its performance and obviously complicated the synthesizing of same needs.
The currently known methods that is used for free polymer readical preparation therefore can not the Composition Control polymerization degree, block length distribution, polymolecularity and block structure.Therefore, valuable performance, as dissemination, flowing property or physical strength be not exclusively realization just, if any.Therefore the known binding agent that can make by Raolical polymerizable needs to add in addition the lower molecular weight dispersion agent cause above-mentioned unfavorable performance, or add have as ion or other polarity fixed group and can with the monomer of the interactional functional group of surface of pigments.But this is not the gratifying approach that addresses the above problem.On the one hand, these monomeric being introduced in the known binding agent of making by Raolical polymerizable with polar group can only be controlled by halves; On the other hand, can only obtain having fixed group usually to regulate the interactional monomer of binding agent and surface of pigments ideally difficultly.
Therefore, need a kind of adhesive composition that does not have the above-mentioned shortcoming of prior art.
An object of the present invention is to provide adhesive composition, it comprises can plain mode makes by Raolical polymerizable but has excellent dissemination, the binding agent of excellent physical and mechanical property and suitable long-term character.
The inventor has been found that by containing at least a segmented copolymer that can make by Raolical polymerizable and the adhesive composition of magnetic or magnetisable pigment can realize this purpose.
Therefore the present invention relates to a kind of adhesive composition, and it comprises at least and can make and have segmented copolymer and at least a magnetic or the magnetisable pigment that at least two monomers are formed different blocks by Raolical polymerizable.
In the present invention, adhesive composition is meant a kind of mixture, and it comprises at least aly can make and have the segmented copolymer that at least two monomers are formed different blocks by Raolical polymerizable, and comprises at least a magnetic or magnetisable pigment in addition.
In the present invention, segmented copolymer is meant a kind of at least two polymkeric substance that are characterised in that the polymer blocks that different monomers is formed that have.In the present invention, the different monomers composition is meant that at least two zones of segmented copolymer have at least two and have the blocks that different monomers is formed.In the present invention, the transition between two blocks might be a successive, promptly can have the monomeric zone of the formation block with random or rule ordering between two kinds of blocks.But also can predict in the present invention, the transition between two blocks is discontinuous basically.Basically discontinuous transition is meant that the length of zone of transition is shorter than at least one block of being separated by zone of transition basically.In an embodiment preferred of the present invention, the chain length of this zone of transition is lower than by 1/10 of the block length of at least one block of zone of transition separation, preferably is lower than 1/20.
In the present invention, different monomer compositions are meant that the monomer that constitutes corresponding block is at least one characteristic, and for example at their mutual keyed jointing, their conformation or formation go up different.Be preferred for segmented copolymer of the present invention and have at least two monomer whoses compositions different block on monomer constitutes at least.
In a preferred embodiment, it is about 5 that the polymolecularity that can be used for segmented copolymer of the present invention is lower than, and for example is lower than about 4 or be lower than about 3.
The molecular weight that can be used for segmented copolymer of the present invention is usually at least about 1 000, but preferably higher, and for example 2 000,4 000,8 000 or 10 000.According to the required mechanical property of the product that can utilize this novel binders composition to make, molecular weight surpasses 20 000, for example surpasses 40 000, surpasses 60 000 or surpass 80 000 segmented copolymer and can be used for the present invention.Can advantageously use molecular weight to surpass 100 000 segmented copolymer.
In this article, molecular weight is meant the M that can obtain under the following conditions by GPC wValue:
Eluent: THF, standard substance: polystyrene, Waters system, UV detector, Waters410, RI detector: Waters 481, pump: 510; Post: crosslinked polystyrene (useful range: 500-100 000 g/mol), from PSS (Mainz).
The preparation that can be used for the segmented copolymer of adhesive composition of the present invention is undertaken by Raolical polymerizable.According to required block number, preparation can be used for the method for the segmented copolymer of novel binders composition and carries out at least two steps.But can adopt even more step, depend on required block number.For example, if preparation has the segmented copolymer of four kinds of blocks, need four steps usually with the preparation corresponding polymer.This is equally applicable to greater or lesser block number.Required number of steps is identical with the block number that obtains in segmented copolymer usually.
In a preferred embodiment of the invention, segmented copolymer is by may further comprise the steps (i) at least and method is (ii) made:
(i) under condition of free radical, the reaction mixture reaction that will comprise following material obtains reaction product (A):
-at least a monomer (a) that can radical polymerization,
-at least a radical initiator and
-structural formula (I) compound
Figure A0181125900091
R wherein 1-R 4Be hydrogen in each case independently of each other, distinguish alkyl group unsubstituted or that replace, group of naphthene base or aromatic alkyl group, or aromatic hydrocarbon radical unsubstituted or that replace, prerequisite is at least two radicals R 1-R 4Be aromatic hydrocarbon radical unsubstituted or that replace, or R 1And R 2Or R 3And R 4Be in couples in each case have 6-18 carbon atom replacement or unsubstituted aromatic hydrocarbon and have between carbon atom and heteroatoms and with structural formula I in the two key conjugated multikeys of C-C functional group and
(ii) the reaction product (A) that will in step (i), obtain under condition of free radical with at least a can radically homo or monomer (b) reaction of copolyreaction, obtain reaction product (B).
In the step (i) of aforesaid method, the monomer that all can free radical reaction can be used as monomer (a).
For example, can radically homo or copolyreaction and comprise hydrophilic radical, carboxyl for example, the compound of sulfo group or phosphate group can be used as monomer (a).In this case, monomer (a) is can radically homo or the hydrophilic monomer of copolyreaction, and promptly water solubility is higher than cinnamic monomer.
Certainly also can use the mixture of different hydrophilic monomers as monomer of the present invention (a).
But in another embodiment of the present invention, also can use be can Raolical polymerizable and water solubility and vinylbenzene quite or even lower monomer.
In addition, at least a hydrophilic monomer and the monomeric mixture of at least a hydrophobic can be according to the aforesaid method polymerizations.Particularly, below can mention and be monomer (a):
Monoene belongs to unsaturated C 3-to C 10-monocarboxylic acid or C 4-to C 8The C of-dicarboxylic acid 1-to C 20-alkyl and hydroxyalkyl acrylate, methyl methacrylate for example, Jia Jibingxisuanyizhi, propyl methacrylate (all isomer), butyl methacrylate (all isomer), methacrylic acid 2-ethylhexyl, IBOMA, methyl acrylate, ethyl propenoate, propyl acrylate (all isomer), butyl acrylate (all isomer), 2-EHA, isobornyl acrylate, vinylformic acid benzyl ester, phenyl acrylate, stearyl acrylate base ester, ethyl maleate, hydroxyethyl acrylate, the vinylformic acid hydroxypropyl ester, the hydroxyl acrylic butyl ester and with 2-50 mol ethylene oxide, propylene oxide, the alkoxylate C of oxybutylene or its mixture reaction 1-to C 18(methyl) acrylate of-alcohol; The methacrylic acid benzyl ester, phenyl methacrylate, methacrylic acid stearyl, methacrylonitrile, vinylbenzene, alpha-methyl styrene, vinyl cyanide, functionalized methacrylic ester; Acrylate and vinylbenzene, be selected from glycidyl methacrylate, methacrylic acid 2-hydroxyethyl ester, hydroxypropyl methacrylate (all isomer), hydroxymethyl butyl acrylate (all isomer), the cyclohexyl methyl acrylate, the cyclohexyl acrylate, hexyl methacrylate and ethylhexyl acrylate are (in each case, all isomer), methacrylic acid diethylamino ethyl ester, the triglycol methacrylic ester, itaconic anhydride, methylene-succinic acid, glycidyl acrylate, methacrylic acid 2-hydroxyethyl ester, vinylformic acid diethylamino ethyl ester, the triglycol acrylate, Methacrylamide, N-tert-butyl Methacrylamide, N-n-butyl methyl acrylamide, the N-methylol methacrylamide, the N-hydroxyethyl methacrylamide, N-tert-butyl acrylamide, N-butyl acrylamide, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, vinyl benzoic acid (all isomer), diethylamino vinylbenzene (all isomer), Alpha-Methyl vinyl benzoic acid (all isomer), diethylamino-alpha-methyl styrene (all isomer), the p-vinyl toluene, the p-vinylbenzenesulfonic acid, methacrylic acid trimethoxy-silylpropyl ester, methacrylic acid triethoxysilylpropyltetrasulfide ester, methacrylic acid three butoxy silyl propyl diesters, methacrylic acid diethoxymethyl silyl propyl diester, methacrylic acid dibutoxy methyl-silicane base propyl diester, methacrylic acid diisopropoxy methyl-silicane base propyl diester, dimethylaminoethyl acrylate methyl oxygen base silyl propyl diester, methacrylic acid diethoxy silyl propyl diester, methacrylic acid dibutoxy silyl propyl diester, methacrylic acid diisopropoxy silyl propyl diester, vinylformic acid trimethoxy-silylpropyl ester, vinylformic acid triethoxysilylpropyltetrasulfide ester, vinylformic acid three butoxy silyl propyl diesters, dimethoxy-methyl silyl propyl acrylate, vinylformic acid diethoxymethyl silyl propyl diester, vinylformic acid dibutoxy methyl-silicane base propyl diester, vinylformic acid diisopropoxy methyl-silicane base propyl diester, vinylformic acid dimethoxy silyl propyl diester, vinylformic acid diethoxy silyl propyl diester, vinylformic acid dibutoxy silyl propyl diester, vinylformic acid diisopropoxy silyl propyl diester, vinyl-acetic ester and vinyl butyrate, vinylchlorid, vinyl fluoride, bromine ethene, vinyl alcohol, C 1-to C 18The vinyl ether of-alcohol, alkoxylate C 1-to C 18The vinyl ether and the polyoxyalkylene of-alcohol, as polyoxyethylene, the vinyl ether of polyoxytrimethylene or polyoxybutylene, monoene belong to unsaturated C 3-to C 10-monocarboxylic acid, its an alkali metal salt and/or ammonium salt, vinylformic acid for example, methacrylic acid, dimethacrylate, ethylacrylic acid, allyl acetic acid or vinylacetic acid, and monoene belongs to unsaturated C 4-to C 8-dicarboxylic acid, its monoesters, acid anhydrides, an alkali metal salt and/or ammonium salt, toxilic acid for example, fumaric acid, methylene-succinic acid, methylfumaric acid, methylene radical propanedioic acid, citraconic acid, maleic anhydride, itaconic anhydride or Methylpropanedioic acid acid anhydride; And the monoene that comprises sulfo group belongs to unsaturated monomer or its salt, for example its basic metal or ammonium salt, as allyl sulphonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), methallylsulfonic acid, vinyl sulfonic acid, vinylformic acid 3-sulfo group propyl ester or methacrylic acid 3-sulfo group propyl ester, and the monoene that comprises phosphonyl group belongs to unsaturated monomer or its salt, and for example its basic metal or ammonium salt are as vinyl phosphonate, allyl group phosphonic acids or acrylamido ethyl propane phosphonic acid, and monoene belongs to unsaturated C 3-to C 10-monocarboxylic acid or C 4-to C 8The acid amides that the acid amides of-dicarboxylic acid and N-replace, acrylamide for example, the N-alkyl acrylamide or the N that in alkyl group, have 1-18 carbon atom respectively, N-dialkyl group acrylamide is as the N Methacrylamide, N, the N-DMAA, N-tert-butyl acrylamide or N-octadecyl acrylamide, N-monomethyl hexyl maleinamide, the single decyl maleinamide of N-, diethylamino propyl methyl acid amides or acrylamido oxyacetic acid; And (methyl) acrylic acid alkyl aminoalkyl ester, vinylformic acid dimethyl aminoethyl ester for example, dimethylaminoethyl acrylate methyl base amino-ethyl ester, vinylformic acid ethylamino ethyl ester, methacrylic acid diethylamino ethyl ester, vinylformic acid dimethylaminopropyl ester or dimethylaminoethyl acrylate methyl base aminopropyl ester; And vinyl ester, as vinyl formate, vinyl-acetic ester or propionate, these materials also can exist with hydrolysed form after polyreaction; And the N-vinyl compound, N-vinyl pyrrolidone for example, the N-caprolactam, the N-vinyl formamide.N-vinyl-N-methylformamide, 1-vinyl imidazole or 1-vinyl-glyoxal ethyline; And C 1-to C 18The vinyl ether of-alcohol, alkoxylate C 1-to C 18The vinyl ether and the polyoxyalkylene of-alcohol, as polyoxyethylene, the vinyl ether of polyoxytrimethylene or polyoxybutylene, the vinylbenzene or derivatives thereof, as alpha-methyl styrene, indenes, Dicyclopentadiene (DCPD), the monomer that has amino or imino group is as dimethylaminoethyl acrylate methyl base amino-ethyl ester, vinylformic acid diethylamino ethyl ester, diethylamino propyl methyl acid amides or allyl amine, the monomer that has quaternary ammonium group, for example exist for by with alkaline amino-functional with acid, as spirit of salt, sulfuric acid, nitric acid, formic acid or acetic acidreaction and the salt that obtains, or for season form (example of suitable season agent is the sulfuric acid dimethyl esters, the sulfuric acid diethyl ester, methyl chloride, ethyl chloride and benzyl chloride), as vinylformic acid dimethyl aminoethyl ester hydrochloride, diallyldimethylammonium chloride, vinylformic acid dimethyl aminoethyl METH chlorine, dimethyl aminoethyl aminopropyl-Methacrylamide methoxy vitriol, vinyl pyridine salt or 1-vinyl imidazole quinoline salt; The wherein monomer that after polyreaction and hydrolysis subsequently, discharges of amino group and/or ammonium group, for example N-vinyl formamide or N-vinyl acetamide and two or more above-mentioned monomeric mixtures.
In preferred embodiments, vinylbenzene or one or more above-mentioned styrene derivativess, acrylic or methacrylic acid, C 1-C 4-alkyl or hydroxyl-C 1-C 4-alkyl acrylate or methacrylic ester, vinyl-acetic ester, two or more mixture of one of above-mentioned vinyl ether or its, that replace or unsubstituted vinyl pyrrolidone, or its two or more mixture or this first monomer (a ') with at least a can radically homo or the mixture of other monomer (a) of copolyreaction as first monomer (a).
According to the present invention, structural formula compound (I) is used for preparation feedback product (A)
Figure A0181125900121
R wherein 1-R 4Has above-mentioned implication.In the present invention, heteroatoms is meant the atom that is different from carbon and can forms multikey (two keys or triple bond) with carbon atom.
In an embodiment preferred of the present invention, 1,1,1-dinaphthyl ethene, 4,4-vinylidene two (N, N '-xylidine), 4,4-vinylidene two-(amino-benzene), cis-stilbene, trans-stilbene, the α-Ben Jibingxisuan methyl ester, α-phenyl methyl methyl acrylate, α-phenyl vinyl cyanide, two or more mixture of α-phenyl methyl vinyl cyanide or its is as having compound in structural formula I.In another embodiment preferred of the present invention, 1 is as having compound in structural formula I.
Suitable in addition compound in structural formula I is by the substituting group of electrophilic or metastatic electron on one or two aromatic hydrocarbon radical, as tert-butyl, the diphenylethlene of the replacement that benzyl or CN group replace, or alkoxyl group diphenylethlene, as methoxyl group-, oxyethyl group-or uncle-butoxy diphenylethlene and similar sulfo-or aminocompound.
The step of aforesaid method (i) is carried out in the presence of at least a radical initiator.Preferably, initiator should dissolve in solvent for use or solvable at the monomer that is used for polyreaction at least.But in general, can use all to be usually used in the azo and/or the peralcohol of radical chain polymerization reaction.
The 10th page of 17-34 of the WO 98/01478 that suitable initiator for example is described in is capable, incorporates it into the application as a reference fully at this.
In an embodiment preferred of the step (i) of aforesaid method, add relatively large radical initiator, the amount of radical initiator in reaction mixture 0.5-50 preferably wherein, more preferably 1-20% weight is in each case based on the total amount of monomer (a) and initiator.The ratio of preferred initiator and structural formula I compound is 3: 1-1: 3, more preferably 2: 1-1: 2, especially 1.5: 1-1: 1.5.
When preparation adhesive composition of the present invention, above-mentioned reaction according to step (i) can be carried out in aqueous environment or under essentially no water condition.
If the described aqueous phase that is reflected at according to step (i) carries out, the term water in this article refers to the phase that comprises 10-100% weight water.If the water-content of water is lower than 10%, in the present invention preferably, this water comprises water and one or more water-miscible solvents, as THF, and methyl alcohol, ethanol, propyl alcohol, butanols, acetone, the mixture of methyl ethyl ketone or analogue.But also can as aromatic solvent, for example carry out reaction under the existence of the mixture of toluene at Shui Heshui unmixability solvent according to step (i).
Above reaction according to step (i) can for example be carried out in the presence of alkali.Can use organic or inorganic, preferred lower molecular weight alkali.The example of suitable alkali is NaOH, KOH, and ammonia, diethanolamine, single-, two-and triethylamine, dimethylethanolamine and or its two or more mixture.Good result can be for example using ammonia, two-or obtain during two or more mixture of three ethanol or its.
But also can in organic solvent or under the situation that does not have solvent, for example in melt, carry out reaction according to step (i).If mention a kind ofly in organic solvent or the reaction under the situation that does not have solvent in the present invention, this is meant and a kind ofly is being lower than 10, preferably is lower than 5 or be lower than the reaction that the existence of 1% weight water takes place down.In another embodiment of the present invention, with at least a its preparation in step (i) in organic solvent or the segmented copolymer that under the situation that does not have solvent, carries out be used for the novel binders composition, the water-content of this reaction mixture is lower than 0.5, for example is lower than 0.3 or be lower than 0.1% weight.In another embodiment of the present invention, being reflected under the anhydrous condition of step (i) carried out, and promptly water-content is lower than 0.001% weight.These water-contents can for example obtain by using the commercially available solvent that is commonly used for organic solvent in Raolical polymerizable.
Suitable solvent among the present invention is all polarity and non-polar organic solvents in principle, and wherein corresponding and preferred resulting polymers may at high temperature be soluble.Suitable solvent is, for example, and C 3-to C 10-alkane, hexanaphthene, perhydronaphthalene, acetone, methyl ethyl ketone, diisobutyl ketone, tetrahydrofuran (THF) ， diox, benzene, toluene, glycol is as ethylene glycol and triglycol, some of them or all end groups are rolled into a ball by end capped glycol ethers, as the glycol monomethyl methyl ether, ethyl acetate, methyl alcohol or ethanol or have the homologue (if desired as solubility promoter) of the alkanol of the highest 18 carbon atoms or its two or more mixture.
In general reaction according to step (i) is being carried out on the room temperature and under monomeric decomposition temperature, and selected temperature range is preferably 50-150 ℃, and more preferably 70-120 ℃, especially 80-110 ℃.
, carry out under about 20 crust of for example about 1.5-100 or about 2-in general at 1-300 according to the reaction of step (i).
Although the molecular weight distribution M that uses polystyrene to measure by gel permeation chromatography to molecular weight distribution at all without limits, as standard substance w/ M n≤ 4, preferred≤3, more preferably≤2, especially≤1.5 and under special circumstances also≤1.3 reaction product can obtain in the basis reaction of (i).The molecular weight of reaction product (A) can be controlled in the grace period by selecting monomer (a) and the ratio of compound (I) with radical initiator.Especially, the content of compound (I) decision molecular weight and feasible, the amount of compound (I) is big more, and the gained molecular weight is low more.
The reaction product that obtains in the reaction according to step (i) is for example directly further handled with preparation and is included in segmented copolymer in the novel binders composition.But also can at first temporarily store in the present invention, and further do not handle until after a while according to the reaction product of step (i).In another is handled, be defined as the big initiator of step further reaction (ii) below being used as according to the reaction product of step (i).
Following steps (ii) in, with the reaction product of step (i) with can radically homo another monomer of copolyreaction or with two or more these monomeric mixture reaction.In according to step this reaction (ii), the reaction product of step (i) therefore with at least a can freely select can radically homo or copolyreaction and the monomer (b) that on the above at least a performance that early defines, is different from the used monomer of step (i) (a) react.If two or more monomeric mixtures are used for the reaction according to step (i), other monomer (b) can be used for step (ii), but just in time can adopt the mixture of two or more monomers (b).What all were crucial in this article is, the monomer that is used for step (i) be used for step monomeric difference (ii) and be, the block that obtains in the reaction according to step (i) is being different from the block that obtains in (ii) in step at least a above-mentioned performance.
In principle, explaining the suitable monomer (b) of doing of the mentioned monomer of monomer (a).
According to carrying out under the normal condition of Raolical polymerizable being used on the step reaction principle (ii), also can in solvent or under the situation that does not have solvent, carry out at aqueous phase according to the reaction of step (i).
In described method, step (i) and (ii) cocoa on room and time, carry out independently of each other, step (i) is at first carried out, and follows by step (ii).Step (i) and (ii) also can be only in a reaction vessel order carry out, promptly at first at least a monomer (a) is carried out partially or completely Raolical polymerizable according to required purposes or desired properties in the presence of the compound of structural formula (I), and add at least a monomer (b) subsequently and carry out Raolical polymerizable equally.
But the present invention also can will comprise the monomer mixture of at least a monomer (a) and at least a monomer (b) from bringing into use and reaction in the presence of compound (I).
Suppose, compound (I) at first with one or more monomers (a) reactions, on specific molecular weight, react with monomer (b) in addition then by its reaction product that forms (A).
According to reactions steps, the present invention can prepare functionalized polymkeric substance in end group group, block, many blocks or gradient copolymer, star polymkeric substance, graft copolymer or branched copolymers.
Can also with the polymkeric substance (B) that obtains in (ii) in step another reactions steps (iii) with other monomer (c) reaction, wherein monomer (c) can for example be selected from above-mentioned enumerating equally.The reaction carrying out as above to step (i) and description (ii).Therefore this novel method can be used many steps of the material property restriction that only is subjected to reaction conditions and resulting polymers basically and use the monomer of any required respective number to carry out.
According to the requisite number of block in the segmented copolymer, step reaction product and polymkeric substance (B) (ii) can (iii) be used for the polymkeric substance of novel binders composition with other monomer (c) or with the mixture reaction of two or more other monomers (c) in another reactions steps with preparation.The mixture of monomer (c) or two or more monomers (c) can for example be selected from above-mentioned the enumerating of monomer (a).Reaction is according to above step (i) and (ii) described carrying out.Utilize this reactions steps, can prepare and have the block of any requisite number basically, for example 5,10,20,50 or the segmented copolymer of 100 kind of block.
In this article, all block whether have different monomers form or do not obtain wherein two or more different monomers with particular order in conjunction with or random multiple block order unimportant.Importantly, at least two blocks have the different monomer composition of above definition.
In the method for preparation example as the segmented copolymer that is used for the novel binders composition, step (iii) in
(iii) the reaction product (B) that obtains in (ii) in step can be therefore under the condition of free radical at least a can radically homo or the reaction down of the monomer (c) of copolyreaction, this reaction repeats several times with identical or different monomers (c) if desired in proper order.
Can be in a simple manner, by using the structural formula I compound that can obtain easily that segmented copolymer is provided, this multipolymer has for example fixed group block, as based on (methyl) vinylformic acid, allyl sulphonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), methallylsulfonic acid, vinyl sulfonic acid, the block of vinylformic acid 3-sulfo group propyl ester or methacrylic acid 3-sulfo group propyl ester, described block has the length of at least one monomeric unit, and in addition, preferably have the hydrophobic polymer block, as based on vi-ny l aromatic monomers, vinylbenzene as vinylbenzene or replacement, with the non-aromatic vinyl compound,, also can use according to compound in structural formula I to have the hydrophobic and the segmented copolymer of fixed group block subsequently to provide as vinyl-acetic ester.
In the present invention, the fixed group block is meant the block with the surface interaction of a kind of attractive mode and pigment.
Find that also those monomers with electron rich ethylenical unsaturated double bonds can carry out radically homo or copolyreaction by described method.The example of these compounds is vinyl ether, vinyl ester, for example vinyl-acetic ester, or above-mentioned N-vinyl compound.
In described method, monomer can for example needn't be followed specific hydrophilic and hydrophobic monomer sequence basically with any required sequential co-polymerization.
In addition, for example, can prepare the polymkeric substance that can be used for the novel binders composition with following structure: poly-((methyl) vinylformic acid-random block-(methyl) acrylate-b-(vinylbenzene-random block-(methyl) acrylate)), wherein term (methyl) acrylate is represented methacrylic acid and acrylic acid alkyl ester.
Particularly, can mention following segmented copolymer:
Poly-(vinylbenzene-b-vinylformic acid), poly-(vinylbenzene-b-methacrylic ester), poly-(vinylbenzene-b-ethyl propenoate), poly-(vinylbenzene-b methacrylic acid), poly-(vinylbenzene-b-methyl methacrylate), poly-(vinylbenzene-b-Jia Jibingxisuanyizhi), poly-(hydroxyethyl acrylate-b-methacrylic acid), poly-(N-vinyl pyrrolidone-b-methyl acrylate), poly-(N-vinyl pyrrolidone-b-ethyl propenoate), poly-(N-vinyl pyrrolidone-b-methyl methacrylate), poly-(N-vinyl pyrrolidone-b-Jia Jibingxisuanyizhi), poly-(N-vinyl pyrrolidone-b-vinylbenzene), poly-(N-vinyl pyrrolidone-b-vinyl-acetic ester), poly-(N-vinyl pyrrolidone-b-alpha-methyl styrene), poly-(N-vinyl formamide-b-methyl methacrylate), poly-(N-vinyl formamide-b-Jia Jibingxisuanyizhi), poly-(N-vinyl formamide-b-vinyl-acetic ester), poly-(N-vinyl formamide-b-methyl acrylate) and poly-(N-vinyl formamide-b-ethyl propenoate).
Below also can be used for the present invention:
Poly-(methyl methacrylate-b (vinylbenzene-random block-vinyl cyanide)), poly-(vinylformic acid n-butyl ester-b-vinylbenzene-b-vinylformic acid n-butyl ester), poly-(vinylbenzene-b-n-butyl acrylate-b-vinylbenzene), poly-(vinylbenzene-b-vinylformic acid n-butyl ester-b-vinylbenzene-b-n-butyl acrylate), poly-(methyl acrylate-b-vinylbenzene-b-methyl methacrylate-b-vinylbenzene), poly-(vinylformic acid n-butyl ester-b-vinylbenzene-b-vinylformic acid n-butyl ester-b vinylbenzene) and analogue.
Below also be suitable: poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-methyl methacrylate), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-propyl methacrylate), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-butyl methacrylate), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-Jia Jibingxisuanyizhi), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-propyl acrylate), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-methyl acrylate), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-butyl acrylate), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-ethyl propenoate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-methyl methacrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-propyl methacrylate), poly-((vinylbenzene-s-acrylamido-2-methylpropane-sulfonate sodium)-b-butyl methacrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-Jia Jibingxisuanyizhi), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-propyl acrylate), poly-((vinylbenzene-s-acrylamido-2-methyl-propane sulfonic acid sodium salt)-b-methyl acrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-butyl acrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-ethyl propenoate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-vinylbenzene); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-vinylbenzene), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-vinylbenzene), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-vinylbenzene), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-methyl methacrylate); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-methyl methacrylate), poly-((vinylbenzene-s-vinyl cyanide s-styrene sulfonic acid sodium salt)-b-methyl methacrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-methyl methacrylate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-Jia Jibingxisuanyizhi); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-Jia Jibingxisuanyizhi), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-Jia Jibingxisuanyizhi), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-p-Jia Jibingxisuanyizhi), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-propyl methyl acid esters); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-propyl methacrylate), poly-((vinylbenzene-s-vinyl cyanide s-styrene sulfonic acid sodium salt)-b-propyl methacrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-propyl methacrylate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-butyl methacrylate); Poly-((vinylbenzene-s styrene sulfonic acid sodium salt)-b-butyl methacrylate), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-butyl methacrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-butyl methacrylate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-ethyl propane sulfonic acid sodium salt)-b-methyl acrylate); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-methacrylic ester), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-methyl acrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b methyl acrylate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-ethyl propylene acid esters), poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-ethyl propenoate), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-ethyl propenoate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-ethyl propenoate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-propyl acrylate); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-propyl acrylate), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-propyl acrylate), poly-((vinylbenzene-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-propyl acrylate), poly-((vinylbenzene-s-vinyl cyanide-s-acrylamido-2-methyl propane sulfonic acid sodium salt)-b-butyl acrylate); Poly-((vinylbenzene-s-styrene sulfonic acid sodium salt)-b-butyl acrylate), poly-((vinylbenzene-s-vinyl cyanide-s-styrene sulfonic acid sodium salt)-b-butyl acrylate) and poly-((vinylbenzene-s acrylamido-2-methyl propane sulfonic acid sodium salt)-b-butyl acrylate).
Except mentioned structure, novel block copolymer also can have methacrylic acid hydroxyethyl ester and/or hydroxyethyl acrylate unit in one or more blocks, and the amount of the described monomeric unit of each block is no more than 20mol%.
The novel binders composition can comprise, for example, and only a kind of above-mentioned segmented copolymer.But in the present invention, the novel binders composition also can comprise two or more described segmented copolymers.
Except described segmented copolymer, the novel binders composition also can comprise other polymkeric substance.Other suitable polymkeric substance is, for example, and the random copolymers of making by Raolical polymerizable.For example, addition polymer or polycondensate, as polyester, polyethers, polycarbonate, polylactone, polymeric amide or urethane also are suitable for makes other polymkeric substance.
Except above-mentioned polymkeric substance, or two or more these mixture of polymers, the novel binders composition comprises the mixture of magnetic paint or two or more magnetic paints.Suitable magnetic paint is an oxygenated pigment, as γ-Fe 2O 3, γ-Fe 3O 4, CrO 2, the FeO of Co modification x(wherein x is 1.33-1.5), metallic pigment, as Fe, Co and Ni or its alloy, barium ferrite or strontium ferrite.
Other composition or compound can mix with these pigment, and this generally is conventional.Usually, these pigment are anisotropic magnetic pigment.
For example, the cobalt improved or unmodified γ-Fe of needle-like or spindle-shape 2O 3, γ-Fe 3O 4, CrO 2Or metallic pigment, as Fe, Co and Ni or its alloy are preferred.The ratio (aspect ratio) that particle size is generally 0.04-2 μ m and average longitudinal axes and average transverse axle is 2-20.In an embodiment preferred of the present invention, using particle size is that 0.07-0.8 μ m and its aspect ratio are the magnetic paints of 2-20.Metallic pigment or its alloy and and the mixture that also comprises at least a other magnetic paint except metallic pigment be especially preferred.
In addition, the novel binders composition also can comprise filler, dispersion agent and other additive, and as lubricant, carbon black or non magnetic inorganic or pigment dyestuff.
Used lubricant can be, for example, has the carboxylic acid of about 20 carbon atoms of about 10-, especially stearic acid or palmitinic acid, or the derivative of carboxylic acid, and as its salt, ester or acid amides, or its two or more mixture.
Suitable non magnetic mineral dye is, for example, and carbon black, graphite, metal, metal oxide, metal carbonate, metal sulfate, metal nitride, metallic carbide and metallic sulfide.For example can mention TiO 2(rutile or anatase octahedrite), TiO x, stannic oxide, Tungsten oxide 99.999, weisspiessglanz, ZnO, ZrO 2, SiO 2, Cr 2O 3, α-Al 2O 3, β-Al 2O 3, γ-Al 2O 3, α-Fe 2O 3, pyrrhosiderite, silicon carbide, silicon nitride, titanium carbide, magnesium oxide, boron nitride, moly-sulfide, cupric oxide, MgCO 3, CaCO 3, BaCO 3, SrCO 3, BaSO 4And silicon carbide.These compounds can be separately or are existed to mutually combine and be not limited to form and size.Compound need not to exist but available other compound carries out surface treatment with respective pure form.Also can use organic filler, as polyethylene or polypropylene.
The novel binders composition can mix with magnetic or magnetisable pigment by above-mentioned polymkeric substance and obtains.Therefore the present invention also relates to a kind of novel binders method for compositions that is used to prepare, and wherein can make and has segmented copolymer and at least a magnetic or a magnetisable colo(u)rant dispersion that at least two monomers are formed different blocks by Raolical polymerizable.
In order to prepare the novel binders composition, can make and have a segmented copolymer that at least two monomers are formed different blocks by Raolical polymerizable, therefore or the mixture of two or more these segmented copolymers can be and magnetic paint, or the mixture of two or more magnetic paints disperses together, for example become with one or more solvents and, if it is required, with filler, dispersion agent, further binding agent and other additive, as lubricant, carbon black or non magnetic inorganic or pigment dyestuff mixture together.In preferred embodiments, main ingredient in the novel binders composition, promptly especially pigment and polymeric binder are at first merged when adding a small amount of solvent and obtain paste material and thorough mixing mutually for example subsequently, and only disperse after this by mediating.Therefore, the novel binders composition can be therefore for example at diverting device, for example in tube mill or the agitating ball mill, add lubricant and may a spot of dispersion agent in, by magnetic paint and adhesive composition or used binding agent preferably other of the solution in organic solvent mediate composition and make.
If they are used to produce magnetic recording medium, this novel binders composition can be used for embodiment, is administered to and thickness is generally on the conventional rigidity or flexible parent metal of the about 200 μ m of about 0.5-.Suitable substrates is, for example, especially has the about 150 μ m of the about 4-of thickness, and the linear polyester of the about 36 μ m of for example about 5-is as the film of polyethylene terephthalate or PEN.
The present invention also relates to a kind of magnetic recording medium, the adhesive composition that it comprises the novel binders composition at least or makes by novel method.
The novel magnetic recording medium can be made in known manner.Suitably, will be at diverting device, for example in tube mill or the agitating ball mill, when adding lubricant and a spot of dispersion agent of possibility and other conventional additives, by magnetic paint and binding agent preferably the adhesive composition made of the solution in organic solvent filter, if required after mixed cross-linker, use conventional apparatus for coating, for example utilize Scraper applicator or forcing machine to be administered on the non-magnetic matrix.Coating can be carried out on one or two face of base material.
The novel binders composition can be used into multilayer, magnetic or magnetisable pigment can be identical or different in the kind and/or the amount of each layer.Also adhesion promoting layer or one or more layer that contains binding agent that does not contain magnetic or magnetisable pigment can be applied directly on the base material.Also can be a kind of layer of structure, the layer that wherein comprises magnetic or magnetisable pigment replaces with the layer that does not have magnetic or magnetisable pigment.If use a plurality of magnetic and/or nonmagnetic layer, the production of magnetic recording medium can wet bumped dry method and wetly bumps wet method and carry out by known by known.Can use known all the suitable devices of prior art.
Usually, magnetic aligning was carried out before drying on the base material at the liquid-containing binder composition.The latter was preferably under about 90 ℃ of about 50-about 10-about 200 seconds.Magnetosphere can utilize about 100 ℃ of pressure and about 25-if desired by in the process between the polishing roll of being heated, the preferred about 90 ℃ temperature of 60-and rolling and compacting on conventional equipment.Under the situation of cross-linked binder, roll before crosslinked and confirm highly beneficially, be very thermoplastic under non cross-linked state because have the polymkeric substance of OH, therefore can not be clamminess.Magnetospheric thickness is generally the about 20 μ m of about 0.1-, the about 8 μ m of preferably about 0.2-.
When producing tape, coat film is cut in the vertical the conventional width of inch specification; When the production circular record media, the desired shape punching is come out.
The application of adhesive composition in producing magnetic recording medium that the present invention also relates to the novel binders composition or make according to the present invention.
Magnetic recording medium is meant all known rigidity or flexibilities, analog or digital recording medium, for example recording or video-tape, data tape, floppy disk, magnetic card or analogue.
The present invention relates to a kind of magnetic recording medium in addition, the adhesive composition that it comprises the novel binders composition or makes according to the present invention.
In a preferred embodiment of the invention, the novel magnetic recording medium comprises ferromagnetic metal pigment or the ferromagnetic metal alloy pigment as magnetic or magnetisable pigment.In another embodiment of the present invention, adhesive composition comprises at least a other magnetic or non-magnetic pigment.
The novel magnetic recording medium can for example be used as video record band, audiotape, data tape, floppy disk, hard disk, or magnetic card.
Following examples explanation the present invention.
Embodiment
Embodiment 1
By methyl acrylate and vinylbenzene synthetic polymer reaction product
At first be taken at 125 g, 25% concentration ammonia solution in the 125 g water and be and oil bath is remained on 90 ℃.To be dissolved in 6g1 in the 125g methyl acrylate by two dropping funnels subsequently, 1-diphenylethlene and the 4.73g ammonium peroxydisulfate that is dissolved in the 22.4g water dripped in 60 minutes simultaneously.In 1 hour, drip the 4.73g ammonium peroxydisulfate that is dissolved in addition in the 22.4g water subsequently.Batch of material was kept under 90 ℃ 1 hour subsequently again.65g vinylbenzene added this batch of material and oil bath temperature is risen to 100 ℃ reach 4 hours.
Embodiment 2
By methacrylic acid and hydroxyethyl acrylate synthetic polymer reaction product
At first get 112g water and 112g 25% concentration ammonia solution and be heated to 90 ℃.Then, in 30 minutes, drip the 9.46g ammonium peroxydisulfate that is dissolved in the 45g water, and drip the 6g1 that is dissolved in the 107.5g methacrylic acid, 1-diphenylethlene fast.
The other 9.46g ammonium peroxydisulfate that is dissolved in the 45g water was dripped in 30 minutes.
After reinforced, batch of material was kept under 90 ℃ 1 hour again.Then, add 1mol hydroxyethyl acrylate and batch of material kept 5 hours down at 90 ℃ in addition.
Embodiment 3
By methyl methacrylate and hydroxyethyl acrylate synthetic polymer reaction product
At first get 360g water and remain on 90 ℃.Then, with the 10g1 that is dissolved in the 200g methyl methacrylate, 1-diphenylethlene and be dissolved in 10.3g ammonium peroxydisulfate in the 100g water dripped simultaneously in 60 minutes, and dripped the 9.2g 25% concentration ammonia solution that is dissolved in the 100g water in 90 minute.This batch of material kept under 90 ℃ 3 hours subsequently again.Then, the 25g hydroxyethyl acrylate is added the above-mentioned dispersion of 100g, then batch of material was kept 6 hours down at 90 ℃.
Embodiment 4
By methyl methacrylate, vinyl cyanide and vinylbenzene synthetic polymer reaction product
At first get 360g water and remain on 90 ℃.Then, the 10.3g ammonium peroxydisulfate that is dissolved in the 10g 1 in the 200g methyl methacrylate and be dissolved in the 100g water was dripped in 60 minutes simultaneously, and in 90 minutes, drip the 9.2g 25% concentration ammonia solution that is dissolved in the 100g water.This batch of material kept under 90 ℃ 3 hours subsequently again.
Then, 17.2g vinylbenzene and 1g vinyl cyanide are added the above-mentioned dispersion of 100g, then batch of material was kept 6 hours down at 90 ℃.
Embodiment 5
By vinylformic acid n-butyl ester and vinylbenzene synthetic polymer reaction product
At first get 360g water and oil bath is heated to 90 ℃.Drip the 11.1g1 that is dissolved in the 256g vinylformic acid n-butyl ester by three dropping funnels subsequently, the 1-diphenylethlene, and in 180 minutes, drip the 10.7g Sodium persulfate that is dissolved in the 100g water simultaneously and in 120 minutes, drip the 2.3g sodium hydroxide that is dissolved in the 100g water.Oil bath was kept under 90 ℃ 6 hours altogether.After isolating water, vinylbenzene is added remaining polymkeric substance and oil bath is descended maintenance 6 hours at 115 ℃.Then, add 169g vinylformic acid n-butyl ester and oil bath kept 6 hours down at 115 ℃.
Embodiment 6
By methyl methacrylate and vinylbenzene synthetic polymer reaction product
At first get 180g water and remain on 90 ℃.Then, simultaneously by three dropping funnels, in 60 minutes, drip and be dissolved in the 3g cis-stilbene in the 50g methyl methacrylate and be dissolved in 5g 25% concentration ammonia solution in the 50g water, and in 90 minutes, drip the 5.0g ammonium peroxydisulfate that is dissolved in the 50g water.This batch of material kept under 90 ℃ 4.5 hours subsequently again.Obtain having M.54200g/mol polymkeric substance like this with polymolecularity 2.4.
The above-mentioned polymeric dispersions of 70g is heated to 115 ℃ and be metered into 50g vinylbenzene.Batch of material was kept 6 hours down at 115 ℃ subsequently.
Embodiment 7
By methyl methacrylate and vinylbenzene synthetic polymer reaction product
At first get 180g water and remain on 90 ℃.Then, simultaneously by three dropping funnels, in 60 minutes, drip the 3g that is dissolved in the 50g methyl methacrylate trans-stilbene and be dissolved in 5g 25% concentration ammonia solution in the 50g water, and in 90 minutes, drip the 5.1g ammonium peroxydisulfate that is dissolved in the 50g water.This batch of material kept under 90 ℃ 4.5 hours subsequently again.Obtain having M like this wThe polymkeric substance of 46800g/mol and polymolecularity 2.9.
The above-mentioned polymeric dispersions of 70g is heated to 115 ℃ and be metered into 50g vinylbenzene.Batch of material was kept 6 hours down at 115 ℃ subsequently.
Obtain having M wThe polymkeric substance of 168000 g/mol and polymolecularity 4.2.
Embodiment 8
By methyl methacrylate synthetic polymer reaction product
At first get 180g water and remain on 90 ℃.Then, simultaneously by three dropping funnels, in 60 minutes, drip the 5g 4 that is dissolved in the 100g methyl methacrylate, 4-vinylidene two (N, accelerine), with the 4.6g 25% concentration ammonia solution that is dissolved in the 100g water, and in 90 minutes, drip the 5.1g ammonium peroxydisulfate that is dissolved in the 100g water.
This batch of material kept under 90 ℃ 4 hours again.Obtain having M wThe polymkeric substance of 2150g/mol and polymolecularity 1.2.
Embodiment 9
By methyl methacrylate synthetic polymer reaction product
At first get 360g water and remain on 90 ℃.Then, in 60 minutes, will be dissolved in the 200g methyl methacrylate the 10g 1 and in be dissolved in the 10.3g ammonium peroxydisulfate of 100g water, and the 9.2g 25% concentration ammonia solution that will be dissolved in 90 minutes in the 100g water drips simultaneously.Batch of material kept under 90 ℃ 3 hours subsequently again.
Embodiment 10
For dispersion experiment, polymeric dispersions is directly used (moisture magnetic dispersion) or polymkeric substance is dry and be dissolved in (mixture) in the required solvent.
Disperse embodiment
Embodiment 1
Single belt
With 100 weight part ferromagnetic metal pigment (H c=117 kA/m; SSA=51 m 2/ g; Average grain length 170nm, average particulate diameter 25nm), 10 weight part alph-alumines (average particulate diameter 320nm), 2 weight part carbon black (BET=35m 2/ g; Primary particle size 50nm), 9 weight part new polymerss 10,9 weight parts have the commercial urethane (from Morton) of sulfonate fixed group, 2.5 weight part stearic acid, the mixture of 15 weight part tetrahydrofuran (THF)s and 15 weight part dioxs is at kneader (HKD10 type IKA high speed kneader at intermittence, from IKA-Maschinenbau, Staufen) mediated 2 hours.
The mixture of 145 weight part tetrahydrofuran (THF)s and 145 weight part dioxs is added in this kneading material in the dissolver subsequently in batches under vigorous stirring, uses agitating ball mill to disperse subsequently 9 hours.Under vigorous stirring, in dispersion, add 1 weight part butyl stearate subsequently, 5.2 the 50% weight concentration solution of the reaction product of 3 moles of inferior cresyl vulcabonds of weight part and 1 mole of trimethyl propane in tetrahydrofuran (THF) also, adds the mixture of 40 weight part tetrahydrofuran (THF)s and 40 weight part dioxs in batches.After filtration has the strainer of hole dimension 2 μ m, obtain a kind of homogeneous phase, segmentation, the applied dispersion of no throw out to settlement stability.
Dispersion is administered on the polyethylene terephthalate film with backing coating, when drying, becomes layer with thickness 3 μ m.Before drying, coated fabric through an oriented region of being made up of the coil of intensity of field 200kA/m, is orientated ferromagnetic pigments like this.After 80 ℃ of following dryings, 1/2 inch wide audiotape is handled and be cut into subsequently to film fabric at 85 ℃ with the 200kg/cm lower surface in having the steel of 6 roll gaps/steel rolling press.
Comparative Examples
Step is the commercial VC multipolymer (from Nippon Zeon) with sulfonate fixed group that new polymers 10 is replaced by equivalent weight as mentioned above.
The result who obtains in measurement provides in table.Table 1
Embodiment Comparative Examples
Time length, kneading+dispersion (h) ????2+9 ???2+13
Gloss 1 ????118 ???115
Gloss 2 ????110 ???105
Surface imperfection Do not have Do not have
RF level (dB) ????+1.8 ???+0.5
????S/N(dB) ????+1.5 ???+0.1
Wearing and tearing on video head (grade) ????1.0 ????3
Frictional coefficient, the RAF test ????0.24 ????0.26
Observed value (table 1) has following implication: gloss measurement: measure the not reflectance value at 60 ° of angles of press polish layer.
Gloss 1: not only gloss after disperse finishing
Gloss 2: at the gloss of roller platform after last 24 hour
Gloss is high more, and colo(u)rant dispersion is good more.
The RF level: frequency of radio level relative reference tape Sony RSB 01 SP in Betacam SP register (BVW 75 systems are from Sony) measures.The RF level is high more, and tape is good more.
S/N (brightness) luminance signal relative reference tape Sony RSB 01 SP in Betacam SP register (BVW 75 systems are from Sony) measures.The S/N value is high more, and tape is good more.
Frictional coefficient:
Frictional coefficient uses sample and the measuring distance 100mm of length 150mm to measure in the RAF test.After under 40 ℃ and 80% relative humidity, adjusting 15 minutes, the tape sheet is gone up the 100mm length that back and forth stretches with power 2 N and speed 20mm/s at draw point (diameter 2.5mm, 90 ° at volume angle).Frictional coefficient is being measured after 100 cycles under said temperature and the humidity condition.This value is low more, and the operating performance of mensuration is good more.
Embodiment 2
Bilayer zone
A) upper strata
With 100 weight part ferromagnetic metal pigment (H c=180kA/m; SSA=58m 2/ g; Average grain length 80nm; Average particulate diameter 25nm), 13 weight part alph-alumines (average particulate diameter 220nm), 8.2 weight part new polymers 10,3.5 weight part has the commercial urethane (from Morton) of polarity fixed group, 2 weight part stearic acid, 1 weight part tetradecanoic acid, the mixture of 15 weight part tetrahydrofuran (THF)s and 15 weight part dioxs is at kneader (HKD 10 type IKA high speed kneaders at intermittence, from IKA Maschinenbau, Staufen) the middle kneading 2 hours.
The mixture of 155 weight part tetrahydrofuran (THF)s and 155 weight part dioxs is added this kneading material in the dissolver subsequently in batches under vigorous stirring, use agitating ball mill to disperse then 10 hours.Under vigorous stirring, in dispersion, add 1 weight part butyl stearate subsequently, the 50% concentration solution of the reaction product of 3 moles of inferior cresyl vulcabonds of 4 weight parts and 1mol TriMethylolPropane(TMP) in tetrahydrofuran (THF), and add the mixture of 44 weight part tetrahydrofuran (THF)s and 44 weight part dioxs in batches.After filtering a strainer with hole dimension 2 μ m, obtain a kind of settlement stability and expection being used for the homogeneous phase on upper strata, segmentation, the applied dispersion of no throw out.
Comparative Examples 2a)
Step is that new polymers 10 is replaced by the commercial VC multipolymer (from Nippon Zeon) with sulfonate fixed group as mentioned above
B) lower floor
With 100 weight parts-ferric oxide (average grain length 118nm, average particulate diameter 28nm, SSA=60m 2/ g; From Toda), 29 weight part carbon blacks (average uncle's particle size 25nm, SSA=112m 2/ g), 13 weight part new polymerss, 10,7.5 weight parts have (Tg=70 ℃ of the commercial urethane of polarity fixed group; From Morton), 7.5 weight parts have (Tg=35 ℃ of the second commercial urethane of polarity fixed group; From Morton), 2 weight part stearic acid, the mixture of 27 weight part tetrahydrofuran (THF)s and 27 weight part dioxs was mediated 3 hours in the kneader at intermittence.The mixture of 234 weight part tetrahydrofuran (THF)s and 234 weight part dioxs is added in this kneading material in the dissolver subsequently in batches under vigorous stirring, in agitating ball mill, disperseed then 15 hours.The 50% concentration solution of reaction product in tetrahydrofuran (THF) that under vigorous stirring, in dispersion, adds 6.3 weight part 3mol inferior cresyl vulcabonds and 1mol TriMethylolPropane(TMP) subsequently.After filtration has the strainer of hole dimension 2 μ m, obtain a kind of homogeneous phase, segmentation, the applied dispersion of no throw out to settlement stability.
Comparative Examples 2b)
Step is that new polymers 10 is replaced by the commercial VC multipolymer (from Nippon Zeon) with sulfonate fixed group as mentioned above.
Using of lower floor and upper strata
Bump on the front that wetland is administered to the polyethylene terephthalate film with backing coating dispersion is wet.Before drying, coat film through an oriented region of being made up of the coil with intensity of field 200 kA/m, is orientated ferromagnetic pigments like this.After 80 ℃ of following dryings, film fabric uses has fixedly the steel of roll gap/steel rolling press under 80 ℃ and 200kg/cm and be cut into the wide video-tape of 6.35mm subsequently.
The result who obtains in measurement provides in table.Table 2
Embodiment Comparative Examples
The thickness on upper strata (μ m) ????0.26 ????0.27
The thickness of lower floor (μ m) ????1.31 ????1.32
Gloss 1 (upper strata) ????160 ????156
Gloss 2 (upper strata) ????160 ????153
Gloss 1 (lower floor) ????151 ????139
Gloss 2 (lower floor) ????149 ????137
Surface imperfection Do not have Do not have
RF level (dB) ????+1.4 ????+0.3
Wearing and tearing on video head ????1.5 ????3.5
Frictional coefficient, the RAF test ????0.13 ????0.25
Gloss, wearing and tearing and rub measurement are according to embodiment 1 described carrying out.
Frequency of radio level relative reference tape Panasonic APOG 0715-15 in DVC-MAZ device (AJ D-750 is from Panasonic) measures.
Comparison shows that of measuring result, this novel tape is because the dispersiveness of pigment in upper and lower layer better has improved output level.
In addition, good operation and abrasive nature realizes by low-down frictional coefficient in register.
Following examples illustrate the application of described binding agent in the magnetic storage medium:
Embodiment 1
Preparation has the magnetic dispersion of following composition:
Magnetic paint 100 weight parts
(needle-like contains the iron powder of cobalt; Pin length 150nm;
PH=9.5; BET surface-area: 55m 2/ g; H c:
132kA/m; Saturation magnetization: 126.6emu/g)
Inorganic carrier pigment 10 weight parts
(alph-alumine; PH=8.5; BET surface-area: 6m 2/ g;
Primary particle size: 0.3 μ m)
Carbon black 1 weight part
(primary particle size: 60nm; PH=8.0;
DBPA adsorptive value: 65cm 3/ 100g)
Binding agent 10,10 weight parts as mentioned above
Binding agent B (polyester-polyurethane; Tg=50 ℃; 50meq NaSO 3 -/ kg) 10 weight parts
Stearic acid 1 weight part
Stearic acid butyl ester 1 weight part
Tetrahydrofuran (THF) 230 weight parts
Diox 230 weight parts
Dispersion prepares in a usual manner, wherein grinds in horizontal agitating ball mill and carries out.
Binding agent B and lubricant only add afterwards reaching gloss 120 (60 ℃).Filter by a strainer subsequently with hole dimension 2 μ m.
Before applying, stir the 50% concentration solution that adds 6 weight part linking agents (TMP/TDI-based isocyanate) with functionality 2.6.Coating utilizes Scraper applicator to carry out having in advance on the thick PET film of 14 μ m of backing coating.Magnetic layer thickness is 2.5 μ m.At press polish (2 steel/steel and 3 PU/ steel riders; 60 ℃; 200kp/cm) afterwards, will apply piece and store 3 days down at 60 ℃.
Material is cut into 1/2 inch wide band, on non-woven fleece and blade, is wound into the Magstar tape after the cleaning then.
Comparative Examples:
As embodiment 1, but use 20 weight part binding agent B to substitute binding agent 10.The gloss that is obtained: 110 (60 °)
Endurance test
With 2 tapes 31 ℃ with 85% relative humidity under store 2 days respectively and in the IBM3590 driving mechanism, under identical temperature and humidity condition, carry out endurance test in 8 hours (location recoil test) subsequently.
Omit (%) Interim mistake Permanent error
Before Afterwards Before Afterwards Before Afterwards
Embodiment 1
Tape 1 ????8 ????7 ????0 ????0 ????0 ????0
Tape 2 ????5 ????6 ????0 ????0 ????0 ????0
Comparative Examples
Tape 1 ????6 ???20 ????0 ????3 ????0 ????1
Tape 2 ????8 ???30 ????0 ????4 ????0 ????1
The tape of Comparative Examples shows manifest error to be increased; The weather resistance deficiency of layer.

Claims (14)

1. adhesive composition, it comprises at least and can make and have segmented copolymer and at least a magnetic or the magnetisable pigment that at least two monomers are formed different blocks by Raolical polymerizable.
2. according to the desired adhesive composition of claim 1, wherein segmented copolymer has 2-6 kind block.
3. according to claim 1 or 2 desired adhesive compositions, wherein segmented copolymer is by may further comprise the steps (i) at least and method is (ii) made:
(i) under condition of free radical, the reaction mixture reaction that will comprise following material obtains reaction product (A):
-at least a monomer (a) that can radical polymerization,
-at least a radical initiator and
-structural formula (I) compound
Figure A0181125900021
R wherein 1-R 4Be hydrogen in each case independently of each other, distinguish alkyl group unsubstituted or that replace, group of naphthene base or aromatic alkyl group, or aromatic hydrocarbon radical unsubstituted or that replace, prerequisite is at least two radicals R 1-R 4Be aromatic hydrocarbon radical unsubstituted or that replace, or R 1And R 2Or R 3And R 4Be in couples in each case have 6-18 carbon atom replacement or unsubstituted aromatic hydrocarbon and have between carbon atom and heteroatoms and with structural formula I in the two key conjugated multikeys of C-C functional group and
(ii) the reaction product (A) that will in step (i), obtain under condition of free radical with at least a can radically homo or monomer (b) reaction of copolyreaction, obtain reaction product (B).
4. according to the desired adhesive composition of claim 3, the radical initiator electric weight that wherein is used for one or more monomers (a) is a 0.5-50% weight, based on the total amount of initiator and monomer (a).
5. according to claim 3 or 4 desired adhesive compositions, wherein use diphenylethlene, the alkoxyl group diphenylethlene, dinaphthyl ethene, 4,4-vinylidene two (N, accelerine), 4,4-vinylidene two (1-amino-benzene), cis-stilbene, trans-stilbene, α-Ben Jibingxisuan methyl ester, α-phenyl methyl methyl acrylate, α-phenyl vinyl cyanide, two or more mixture of α-phenyl methyl vinyl cyanide or its is as the compound of structural formula (I).
6. according to each desired adhesive composition of claim 3-5, wherein reaction mixture comprises the vinylbenzene as first monomer (a), acrylic or methacrylic acid, C 1-to C 4-alkyl or hydroxyl-C 1-to C 4-alkyl acrylate or methacrylic ester, vinyl-acetic ester, that replace or unsubstituted vinyl pyrrolidone, its two or more mixture, or this first monomer (a) with at least a can radically homo or other monomeric mixture of copolyreaction.
7. according to each desired adhesive composition of claim 3-6, wherein 10% weight or lower water are present in reaction mixture in reaction process.
8. according to each desired adhesive composition of claim 1-7, wherein segmented copolymer is made by the method that may further comprise the steps at least (iii):
(iii) will reaction product (B) that step obtains in (ii) under the condition of free radical at least a can radically homo or the monomer (c) of copolyreaction in the presence of reaction, this reaction repeats several times with identical or different monomers (c) if desired in proper order.
9. method that is used to prepare adhesive composition wherein can be made and have at least two monomers and form the segmented copolymer of different blocks and at least a non magnetic and non-magnetisable inorganic or pigment dyestuff and mix or have at least a non magnetic and non-magnetisable inorganic or pigment dyestuff in the process for preparing the segmented copolymer that can make by Raolical polymerizable by Raolical polymerizable.
10. each desired adhesive composition or in claim 1-9 according to the application of the described adhesive composition of making of claim 10 in producing magnetic recording medium.
11. a magnetic recording medium, it is included among the claim 1-8 each and requires or according to the described adhesive composition of making of claim 9.
12. according to the desired magnetic recording medium of claim 11, wherein magnetic or magnetisable pigment are ferromagnetic metal pigment or ferromagnetic metal alloy pigment.
13. according to claim 11 or 12 desired magnetic recording mediums, wherein adhesive composition comprises at least a other magnetic or non-magnetic pigment.
14. according to each desired magnetic recording medium among the claim 11-13, it is recording, video-tape, data tape, floppy disk, or magnetic card.
CN01811259A 2000-06-16 2001-06-13 Magnetic or magnetisable bonding agent composition Pending CN1436204A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10029699A DE10029699A1 (en) 2000-06-16 2000-06-16 Binding composition, useful in magnetic recording materials, comprises radical-polymerized block copolymer and magnetic or magnetizable pigment
DE10029699.8 2000-06-16

Publications (1)

Publication Number Publication Date
CN1436204A true CN1436204A (en) 2003-08-13

Family

ID=7645967

Family Applications (1)

Application Number Title Priority Date Filing Date
CN01811259A Pending CN1436204A (en) 2000-06-16 2001-06-13 Magnetic or magnetisable bonding agent composition

Country Status (8)

Country Link
EP (1) EP1294797A1 (en)
JP (1) JP2004503641A (en)
KR (1) KR20030031497A (en)
CN (1) CN1436204A (en)
AU (1) AU2001272472A1 (en)
DE (1) DE10029699A1 (en)
NO (1) NO20026009L (en)
WO (1) WO2001096455A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101283414B (en) * 2005-09-09 2011-09-14 巴斯夫欧洲公司 Dispersion containing two different metals for applying a metal layer

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2859210B1 (en) * 2003-09-01 2008-05-09 Oreal ETHYLENIC COPOLYMER SEQUENCES COMPRISING A VINYLLACTAM SEQUENCE, COSMETIC COMPOSITIONS CONTAINING THEM, AND THE USE OF THESE COPOLYMERS IN COSMETICS
JP2005139437A (en) * 2003-10-15 2005-06-02 Kansai Paint Co Ltd Light-colored water-borne coating for automotive body
JP2007262325A (en) * 2006-03-29 2007-10-11 Mitsui Chemicals Inc Polymer blend comprising olefinic block polymer
EP2006326A4 (en) * 2006-03-29 2009-07-22 Mitsui Chemicals Inc Resin composition containing olefin block polymer and use of the same
JP2008024794A (en) * 2006-07-19 2008-02-07 Mitsui Chemicals Inc Polymer blend containing olefin-based block polymer
JP2007321026A (en) * 2006-05-31 2007-12-13 Mitsui Chemicals Inc Polymer blend containing olefin-based block polymer
JP2007321025A (en) * 2006-05-31 2007-12-13 Mitsui Chemicals Inc Polymer blend containing olefin-based block polymer
KR101647352B1 (en) * 2009-02-27 2016-08-11 연세대학교 산학협력단 Paint for measuring deformation of structure, tape comprising the same and deformation measuring method of structure using the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1260132B (en) * 1966-07-27 1968-02-01 Basf Ag Process for the production of magnetogram carriers
US5118580A (en) * 1990-06-25 1992-06-02 Minnesota Mining And Manufacturing Company Magnetic recording media prepared from polyurethane copolymers formed utilizing an interferter compound
US5891971A (en) * 1997-08-15 1999-04-06 Xerox Corporation Polymerization processes
DE19945400A1 (en) * 1999-09-22 2001-04-05 Emtec Magnetics Gmbh Block copolymer polyurethane, process for its production and binders and moldings produced therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101283414B (en) * 2005-09-09 2011-09-14 巴斯夫欧洲公司 Dispersion containing two different metals for applying a metal layer

Also Published As

Publication number Publication date
KR20030031497A (en) 2003-04-21
NO20026009D0 (en) 2002-12-13
WO2001096455A1 (en) 2001-12-20
DE10029699A1 (en) 2001-12-20
EP1294797A1 (en) 2003-03-26
JP2004503641A (en) 2004-02-05
AU2001272472A1 (en) 2001-12-24
NO20026009L (en) 2003-02-13

Similar Documents

Publication Publication Date Title
CN1121726A (en) Carboxylic-acid functional polyurethane polymers and their use in magnetic recording media
CN1310988C (en) Resin composition and optical elements
CN1436204A (en) Magnetic or magnetisable bonding agent composition
CN1067479C (en) Binder system for magnetic medium
CN1774482A (en) Flake pigment, coating material and powder coating composition each containing the same, and surface-treating agent for flaky particle for use therein
CN1161412C (en) Polypropylene graft copolymers with improved scratch and mar resistance
CN101037558A (en) Aqueous compositions comprising polymeric duller particle
CN87105636A (en) The non-self-crosslinking adhesive composition contains the water japanning liquid and the application thereof of this binder composition
CN1346858A (en) Aqueous graft copolymer pigment dispersant
CN1106416A (en) Silane-modified floor finish vehicles
CN1950440A (en) Resin composition
JP2010100835A (en) Adherence substance and adhesive sheet
CN1311026C (en) Thermoplastic polymer material for audio and/or optical data recording media
CN1440988A (en) Aquious carbaminate-olefine hybrid polymer dispersing liquid and its prepn and use
JPH05266459A (en) Magnetic recording carrier
CN1093726A (en) Magnetic recording media
CN112048057A (en) Epoxy resin, application and high-leveling ultralow-temperature curing type pure powder coating
CN115160908B (en) Solvent-free UV matte coating and preparation method thereof
CN1309158A (en) Adhesive composition for magnetic recording medium
CN1255488C (en) Thickeners
CN1090591A (en) The radiation-hardenable oligopolymer reaches the magnetic recording material with its preparation
CN1200319A (en) Lapping tape
JP6776637B2 (en) UV ink made of active energy ray-polymerizable composition and its production method
CN1784470A (en) Additive for optical resins, and optical resin composition
JP2825594B2 (en) Binder composition used for magnetic recording medium

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication