CN1019582B - Magnetic coating formulations and usage thereof - Google Patents
Magnetic coating formulations and usage thereofInfo
- Publication number
- CN1019582B CN1019582B CN 89108186 CN89108186A CN1019582B CN 1019582 B CN1019582 B CN 1019582B CN 89108186 CN89108186 CN 89108186 CN 89108186 A CN89108186 A CN 89108186A CN 1019582 B CN1019582 B CN 1019582B
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Abstract
A magnetic coating formulation is composed principally of magnetic particles and a binder. At least a portion of the binder is a polyurethane resin synthesized from a reactant mixture of specific phosphorus compound, epoxy compound, isocyanate compound and polyfunctional hydroxy compounds. The reactant mixture may optionally contain a chain extender. The polyurethane resin contains one phosphoric acid group or one residual group derived from phosphoric acid per 3,000-200,000 number average molecular weight of the polyurethane resin, and has a number average molecular weight of 4,000-150,000. A magnetic recording medium with a magnetic coating layer formed from the magnetic coating formulation is also disclosed. The magnetic coating layer features not only excellent dispersion of magnetic particles, in other words, excellent magnetic characteristics but also superb durability.
Description
The present invention relates to the magnetic coating prescription, from another viewpoint, the present invention relates to have mainly the magnetic record medium of the magnetosphere that constitutes by magnetic particle and tackiness agent.For instance, magnetic record medium can comprise tape, disk, magnetic card or the like.
In general, magnetic record medium is loaded with one deck magnetosphere, and this magnetosphere is by forming with a kind of coating that contains the dry then coating thus of magnetic coating prescription coating basement membrane (as polyester film) of magnetic particle and tackiness agent.
The tackiness agent that wherein is mixed with different resins has been commonly used for the tackiness agent of magnetic record medium.Wherein, effectively urethane resin, vinyl chloride-vinyl acetate copolymer resin, Nitrocellulose etc.But these tackiness agents do not have enough dispersive abilities, and its dispersive ability depends on dispersion agent as a result, as soybean lecithin or phosphate cpd.But, often produce deleterious effect (as bleed) by tackiness agent and the system that the dispersion agent that mixes forms, unfavorable during life-time service to the magnetosphere weather resistance.
In order to improve the problems referred to above, tackiness agent with the high dispersive ability has been proposed, wherein introduce hydrophilic polar group, to improve magnetic particulate affinity (is seen that Japanese Patent discloses unsettled 92422/1982 as hydroxyl, carboxyl, phosphate, sulfonic group etc., 30235/1984,154633/1984,15473/1985,20315/1985 and 1110/1987).
From present technological standard, be starved of and develop a kind of magnetic particles dispersed and all good magnetic pipe recording material of magnetosphere weather resistance.
But nobody successfully provides a kind of magnetic record medium that this two aspect requires that satisfies so far, i.e. the high-wearing feature (being weather resistance) of magnetic particulate polymolecularity while magnetosphere.In addition, do not propose to can be used for preparing the magnetic coating prescription of this magnetic record medium so far as yet.
One object of the present invention addresses the above problem exactly.
The inventor finds, under the situation of the mechanical property of not damaging urethane resin, can prepare the good magnetic record medium of magnetic particles dispersed, promptly when the urethane resin of phosphoric acid modification prepares magnetic record medium as tackiness agent, the urethane resin of described phosphoric acid modification is a synthetic by the following method: with the isocyanate compound and the number-average molecular weight of bifunctional isocyanate compound and/or trifunctional is 400-5,000 polyfunctional oxy-compound and chain extension agent (if need) are added in a kind of polyol of phosphoric acid modification (this compound is to be added to a kind of epoxy compounds and/or a kind of epoxy compounds that contains an epoxy group(ing) and at least one hydroxyl that contains two epoxy group(ing) at least by the specific compound with a kind of phosphorous acidic group to produce), carry out polyurethane-reinforcement then and react.This has just finished the present invention.
In addition, the inventor also finds, can provide a kind of magnetic record medium with phosphoric acid modification and epoxide modified urethane resin (by in the presence of epoxy compounds, carrying out polyurethane-reinforcement reaction synthetic) as tackiness agent with magnetosphere, because cross-linkage of resin is very high, described magnetic not only magnetic particulate dispersiveness is good, and wear resistance and weather resistance are also good, and this discovery also causes having finished the present invention.
So, the invention provides magnetic record medium, this medium contain the magnetosphere that one deck mainly is made of magnetic-particle and tackiness agent.At least a portion tackiness agent is reaction mixture synthetic urethane resin (the every 3000-200 by the following component that provides (1), (2), (3), (4) and/or (5), the urethane resin of 000 number-average molecular weight contains a phosphate or one by phosphoric acid deutero-residual group, have 4,000-150,000 number-average molecular weight) or wherein phosphate or by phosphoric acid deutero-residual group (being included in the urethane resin) by alkali part neutral urethane:
(1) phosphorus compound of representing by following structural formula (a) or the phosphorus compound (b) represented by following structural formula:
Phosphorus compound (a): independent compound (a
1) or compound (a
1) and another kind of compound (a
2) mixture:
R wherein
1Be hydrogen atom, phenyl, C
1-4Alkyl or C
1-40Alkyl phenyl, n are integers between 0-30,
Phosphorus compound (b):
R wherein
2Be phenyl, C
1-40Alkyl or C
1-40Alkyl phenyl;
(2) has the epoxy compounds of two epoxy group(ing) and/or have the epoxy compounds of an epoxy group(ing) and at least one hydroxyl at least;
(3) isocyanate compound of the isocyanate compound of bifunctional and/or trifunctional; And
(4) number-average molecular weight is 400-5,000 multi-functional oxy-compound.
The reaction mixture that is used for composite adhesives can further contain a kind of chain extension agent as component (5).
The present invention has made provides the magnetic record medium that to have with the good and super weather resistance of magnetic particles dispersed be the magnetisable coating of feature to become possibility.
Term used herein " by phosphoric acid deutero-residual group " means the residual group of phosphoric acid ester (as phosphoric acid one ester, phosphodiester or phosphotriester).
Phosphorus compound
In the present invention, compound (a) both can be independent compound (a
1), also can be compound (a
1) and compound (a
2) mixture.With regard to mixture, compound (a
1) and compound (a
2) ratio can be 100: 0-10: between 90.Concrete example comprises " Gafac RE-410 ", " Gafac RE-610 ", " Gafac RE-210 ", " Gafac RP-710 ", " Gafac RD-510Y ", " Gafac RB-410 ", " Gafac RS-410 ", " Gafac RS-610 " and " Gafac RB-510 " (trade mark and product of Toho chemistry public industry company limited and GAF chemical company), and phosphoric acid-isodecyl ester of producing by Daihachi chemical industry company limited.The example of the compound that can mention (b) has phenyl-phosphonic acid and octyl phosphonic acid (producing by Nissan chemical industry company limited).
Epoxy compounds
The example of epoxy compounds has " Epicoat828 ", " Epicoat834 ", " Epicoat1001 ", " Epicoat1002 ", " Epicoat1003 " and " Epicoat1004 " (all being trade marks of the dihydroxyphenyl propane-epichlorohydrin epoxy of producing by Yuka Shell Epoxy Kabushiki Kaisha) and " Epicoat152 " and " Epicoat154 " (all being trade marks) and " SmiepoxyELPN-180 " and " SmiepoxyESPN-180 " (all be by " phenolic resin varnish of Sumitoma chemical industry company limited production) by the phenolic resin varnish of Yuka Shell Epoxy Kabushiki Kaisha production; " SmiepoxyESCN220L ", " Smiepoxy220F ", " Smiepoxy220HH " and " SmiepoxyESMN-220L " (all be by " trade mark of the cresols phenolic resin varnish that Sumitomo chemistry company limited produces); " EOCN-102 "; " EOCN-103 " and " EOCN-104 " (all be trade mark and " Epicoat180s " (trade mark of the cresols phenolic resin varnish that YukaShellEpoxyKabushikiKaisha produces) of the cresols phenolic resin varnish produced by NipponKayaku company limited; " Epicoat604 " (trade mark of the Resins, epoxy of the four-functional group of the glycidic amine type of YukaShellEpoxyKabushikiKaisha production), two sweet sour diglycidylethers; Bisphenol-S diglycidyl ether; Spiral shell glycol diglycidylether; Resorcinol diglycidyl ether; The hexanodioic acid 2-glycidyl ester; Triglycidyl group trihydroxyethyl isocyanic ester; The tetramethylolmethane polyglycidyl ether; Terephthalic acid diglycidyl ester; O-phthalic acid diglycidyl ester; Neopentylglycol diglycidyl ether; The dibromoneopentyl glycol diglycidylether; 1, the 6-hexanediol diglycidyl ether; The sorbyl alcohol polyglycidyl ether; Glycerin diglycidyl ether; Two glycerin diglycidyl ethers; T 55; The TriMethylolPropane(TMP) diglycidylether; Trihydroxymethylpropanyltri diglycidyl ether; The glycol ether triglycidyl ether; The vinyl cyclohexene dioxide; The Dicyclopentadiene (DCPD) dioxide; 3,4-epoxy-6-methylcyclohexane carbonic acid-3,4-epoxy-6-methylcyclohexyl methyl esters; Alicyclic ring bicyclic oxygen adipic acid ester; Tetrahydrochysene phthalic acid 2-glycidyl ester; Hexahydrobenzene dioctyl phthalate 2-glycidyl ester; Diglycidyl is to oxybenzoic acid; Trihydroxy-biphenyl triglycidyl ether; Four glycidyl group benzo benzoquinones; Benzenedio four glycidyl ethers; Biphenol Perfluoroacetone diglycidylether; 1, two (4-(2, the 3-epoxy group(ing) propoxy-) phenyl of 1-) hexanaphthene; Hydroxyl Dicyclopentadiene (DCPD) monoxide; Two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester; With 3,4-epoxy cyclohexane carboxylic acid-3,4-epoxycyclohexyl methyl esters.
As single palace energy epoxy compounds, that can mention has by Nip-PonOil﹠amp; The Racemic glycidol (2) that Fats company limited produces.
Isocyanate compound
As isocyanate compound, can adopt following example:
Two isocyanic acids-2,4-toluene ester (can be abbreviated as TDI); Two isocyanic acids-2,6-toluene ester; Two isocyanic acids are to the phenylene ester; Two isocyanic acid phenylbenzene methyl esters (can be abbreviated as " MDI "); Two isocyanic acid metaphenylene esters; Two isocyanic acid hexa-methylene esters; Two isocyanic acid tetramethylene esters; Two isocyanic acids-3,3 '-dimethoxy-4 ', 4 '-the diphenylene ester; Two isocyanic acids-2,4-naphthylidene ester; Two isocyanic acids-3,3 '-dimethyl-4,4 '-the diphenylene ester; Two isocyanic acids-4,4 '-the diphenylene ester; 4,4 '-two isocyanato-diphenyl ethers; Two isocyanic acids-1,5-naphthylidene ester; Two isocyanic acids are to the xylylene ester; Xylylene ester between two isocyanic acids; 1,3-two isocyanato-methylcyclohexanes; 1,4-two isocyanato-methylcyclohexanes; 4,4 '-two isocyanato-bicyclohexane; 4,4 '-two isocyanato-dicyclohexyl methyl hydrides; With different fluorine sym.-diisopropylideneacetone vulcabond.
Need, also can use 2,4,4 '-three isocyanato-biphenyl, three phenylcarbimides or analogue on a small quantity.
Multifunctional hydroxy compounds
Polyester polyol, polyether polyol etc. can be used as multifunctional hydroxy compounds, i.e. polyol among the present invention.
The example of polyester polyol compound has the adipic acid ester polyol, as poly-hexanodioic acid second ester polyol, poly-hexanodioic acid fourth ester polyol, the poly-how pure and mild hexanodioic acid cyclohexanedimethanoester ester of hexanodioic acid ethylidene propyl ester; The many alkylol cpds of terephthalic acid are as " Vyron RUX " and " VYron RV-200 " (all be trade mark and produced by Toyobo company limited); With the many alkylol cpds of polycaprolactone, as " Placcel212 ", " Placcel220 ", " Placcel208 " and " Placcel210 " (all be trade mark and produce by Daicel chemical industry company limited).
On the other hand, the example of useful polyether polyol has polyoxyethylene glycol; The polyoxy propylene glycol; Polyoxyethylene polyoxy propylene glycol; With the many alkylol cpds of polyoxy tetramethylene, as " PTG1000 " and " PTG2000 " (all be trade mark and produce by Hodogaya chemistry company limited).
The typical example of the multifunctional hydroxy compounds that other is useful comprises how pure polycarbonate is, as " Desmophen 2020E " (commodity, Bayer AG, W, the product of Germany) and " Carbodiol D-1000 " T " CarbodiolD-2000 " (trade mark, the product of Toagosei chemical industry company limited); How pure polyhutadiene is, as " G-1000 ", " G2000 " and " G-3000 " (trade mark, the product of Nippon Soda company limited); The 3-methyl isophthalic acid, 5-pentane hexylene glycol ester polyol is as " PMPA 1000 " and PMPA2000 " (trade mark, the product of Kuraray company limited); How pure polyprene is; How pure Viscotrol C is; And how pure Beta-methyl-δ-Wu Neizhi is, as PMVL1000 " and PMVL2000 " (commodity, the product of Kuraray company limited).
These polyvalent alcohols both can use separately, also can mix use.
The polyol of phosphoric acid modification
In the present invention, can be by at 40-120 ℃, preferably 60-100 ℃ and exist or do not exist and make epoxy compounds and above compound (a) and (b) polyol of prepared in reaction phosphoric acid modification under the condition of solvent.
Preferred solvent has methylethylketone, methyl iso-butyl ketone (MIBK), toluene, pimelinketone, tetrahydrofuran (THF) etc.These solvents can be used alone or as a mixture.
As for compound (a) and (b) and the feed molar ratio of epoxy compounds, to compound (a), recommend 2: 1 mol ratios, and, recommend 1: 1 mol ratio compound (b).But epoxy compounds can excessively add.In addition, above-mentioned reaction can be carried out in the presence of multifunctional polyol and/or chain extension agent.
Chain extension agent
The example of chain extension agent have molecular weight be 500 or following two sense to six palaces can how alcohol, and to contain one or two uncle or Zhong Duan oxygen base and molecular weight be 500 or following diamines and alcamines.
The typical example of suitable chain extension agent comprises following compound:
(a) polyvalent alcohol:
Ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1, the 4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), 3-methyl-3-hydroxyl-1,5-pentanediol, tetramethylolmethane, sorbyl alcohol, 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol, xylylene-glycol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,3-hexylene glycol, 3-methyl isophthalic acid, 3-butyleneglycol.
(b) diamines:
Hydrazine, quadrol, tetramethylene-diamine, hexamethylene-diamine and 1, the diamines of 4-cyclohexane diamine one class.
(c) hydramine:
Ethylene glycol amine, the hydramine of diethanolamine and trolamine one class.(d) quinhydrones, burnt roasting phenol, 4,4-isopropylidene biphenol, dihydroxyphenyl propane and by propylene oxide and/or oxyethane are added to the polyvalent alcohol (molecular weight is 500 or following) that obtains in above-mentioned many alcohol, diamines and the hydramine with random order.
(e) dihydroxyl hydroxy acid, as 2,2-dihydroxypropionic acid and tartrate.
The polyurethane-reinforcement reaction
Existing or not existing under the condition of solvent, with bifunctional isocyanate's compound and/or trifunctional isocyanates compound and number-average molecular weight 400-5,000 many palaces energy oxy-compound and chain extension agent (if needs) are added in the oxy-compound of phosphoric acid modification.Then, by mode well-known in the art, carry out the polyurethane-reinforcement reaction by feeding method or the legal mixture that makes of pre-polymerization, thereby synthesized the urethane resin of phosphoric acid modification.In this reaction, also can use the polyurethane reaction catalyzer, as dibutyl tin dilaurate, stannous octoate or triethylenediamine.
In addition, can prepare and have the higher branched structure and phosphoric acid modification and the epoxide modified resin of high hydroxyl content more, condition is to add a kind ofly to have the epoxy compounds of two epoxy group(ing) at least and/or have an epoxy group(ing) and the epoxy compounds of at least one hydroxyl carries out the polyurethane-reinforcement reaction.
When adding epoxy compounds, the temperature of reaction of polyurethane-reinforcement can be 50-160 ℃, preferably 70-120 ℃ having under the condition of solvent; Not having to be 70-240 ℃ under the condition of solvent, be preferably 120-220 ℃.
In addition, for the polyol of the above-mentioned phosphoric acid modification of preparation, epoxy compounds can excessively add, with remaining a part of unreacted epoxy compounds or epoxy group(ing).Then, this remaining epoxy compounds or epoxy group(ing) partly can be used as epoxy compounds and carry out polyurethane-reinforcement reaction.
The synthetic phosphoric acid modification as stated above have very high cross-linking density and very high hydroxy radical content with epoxide modified urethane resin.In the drying step of gained magnetic coating prescription, make in its molecular chain or can low-molecular-weight isocyanate compound reaction, thereby can obtain having the more magnetic record medium of high crosslink density and excellent wear and weather resistance magnetic coating in the hydroxyl at exposed terminated groups place and many palaces.
Representational reaction solvent has tetrahydrofuran (THF), methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, dimethyl formamide, toluene and dimethylbenzene.These solvents both can be used alone, but also also mix together.
Urethane resin
In the present invention, the number-average molecular weight of urethane resin can be 4,000-150, and 000, with 5,000-60,000 is good.If number-average molecular weight is too low, then it will be difficult to give play to the weather resistance that sufficient effectiveness is improved magnetic coating.On the other hand, too high number-average molecular weight can be very inconvenient, because the viscosity of gained magnetic formulation for coating material will be very high.
By the way, phosphate or can partly or entirely neutralize with a kind of alkali by phosphoric acid deutero-residual group (they are included in and are used for urethane resin of the present invention).
Used alkali can be any organic bases or mineral alkali, as long as described alkali can the neutralising phosphoric acid base or by phosphoric acid deutero-group.This organic and mineral alkali can be used alone or as a mixture.
The example of mineral alkali has lithium hydroxide, sodium hydroxide, potassium hydroxide and ammoniacal liquor.
On the other hand, the example of organic bases has the amine or derivatives thereof, as Monomethylamine, dimethylamine, Trimethylamine 99, monoethylamine, diethylamine, triethylamine, Tributylamine, trioctylamine, tridecylamine, dimethylethanolamine, Monoethanolamine MEA BASF, diethanolamine, trolamine, morpholine pyridine, piperazine, piperidines, aniline, xylidine and picoline; Bulky amine is as dimethyl amber ester-1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl--piperidines polycondensate; Cation type polymer is as polyvinylamine; And quaternary ammonium hydroxide, as hydroxide dodecyl ethyl propyl ammonium.
When use by adopt separately or blended alkali with in and the urethane resin that obtains of form during as tackiness agent, can improve the useful interaction between tackiness agent and magnetic particle surface.And, can also obtain better dispersive ability, this depends on magnetic particulate kind.
With regard to the urethane resin of polyester type, in and acidic group can prevent that resin from reducing in the frequent quality of long-time storage.
Though these urethane resins itself are extremely effective tackiness agents, they can work with one or more different materials (as known tackiness agent) that the preparation magnetic coating is used always.The object lesson of the tackiness agent that can use with above-mentioned urethane resin comprises the urethane resin of phosphoric acid end modification, phenoxy resin, celluosic resin, Resins, epoxy, the vinyl chloride-vinyl acetate copolymer resin, polyvinylidene chloride resin, vibrin, polyethylene butyral resin and chloro vinyl chloride resin.
In addition, can play the poly-isobutyrate compound of linked effect in addition usually with other tackiness agent that urethane uses.In the middle of them, particularly preferably be the low-molecular-weight isocyanate compound of trifunctional.The example of this kind isocyanate compound that can mention has " Colonate L " (trade mark, the product of Nippon polyurethane industrial company limited), " Desmodule L " (trade mark, the product of BayerAG) and " TakenateD102(trade mark, the product of Takeda chemical industry company limited).
As for phosphate or by the content of phosphoric acid deutero-residual group (they are included in the urethane resin), per 3,000-200,000, best 5,000-40, the urethane resin of 000 number-average molecular weight must contain a phosphate or one by phosphoric acid deutero-residual group.If content is lower than lower limit or is higher than the upper limit, can estimate the influence that magnetic particulate dispersiveness is not had.
The preparation method of magnetic record medium
Can anyly prepare magnetic record medium of the present invention with the similar mode of traditional method.For example, the additive that the magnetic particle is different with one or more (if needs) mixes with a kind of organic solvent, preparation magnetic formulation for coating material.Then, with the basement membrane of this magnetic formulation for coating material coated polyester film one class.After the drying, carry out surface treatment (as calendering).
As magnetic particle, α-Fe
2O
3, r-Fe
2O
3And Fe
3O
4Mixed crystal, be doped with the r-Fe of cobalt
2O
3And Fe
3O
4, CrC
2, barium ferrite, pure iron, other ferrimag particle (as Fe-Co, Co-Ni, Fe-Co-Ni, Fe-Co-B, Fe-Co-Cr-B, Mn-Bi, Mn-Al, Fe-Co-V), nitrided iron and other similar ferromagnetic particle all can use.
The additive in being added to the magnetic formulation for coating material on demand, preparation magnetic formulation for coating material all should use as additive multiple material commonly used, for example lubricant, anti-wear agent, dispersion agent, static inhibitor and filler.
In addition, the example of the solvent that preparation magnetic formulation for coating material is used comprises ketone, as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) and pimelinketone; Alcohols is as methyl alcohol, ethanol, propyl alcohol and butanols; The ester class is as ritalin, vinyl acetic monomer and N-BUTYL ACETATE; Glycol ethers is as propylene glycol monomethyl ether, glycol monoethyl ether He diox; The acetates of glycol ethers is as glycol monoethyl ether acetic ester and propylene glycol one methyl ethyl ether acetic ester; Aromatic hydrocarbons is as benzene, toluene and dimethylbenzene; Aliphatic hydrocarbon is as hexane and heptane; Nitropropane; Tetrahydrofuran (THF); N,N-DIMETHYLACETAMIDE; And dimethyl formamide.
Below will be described more specifically the present invention with embodiment.Should point out that the present invention is not limited to following embodiment.
Embodiment 1
In 2 liters of flasks being furnished with thermometer, agitator, nitrogen inlet tube and reflux exchanger, add 316 gram phosphenylic acids (product of Nissan chemical industry company limited) and 316 gram methylethylketones, restrain " Epicoat828 " (trade marks in 70 ℃ of droppings by 372 then, the product of Yuka Shell Epoxy Kabushiki Kaisha, 186) and the solution that constitutes of the methylethylketone of equivalent epoxy equivalent (weight):, last 30 minutes.Mixture was in 70 ℃ of reactions 5 hours.
Afterwards, remove solvent, obtain acid number and be 160 heavy-gravity reaction product with rotatory evaporator.
Embodiment 2
Obtaining acid number by embodiment 1 similar fashion is 184 reaction product, different is with the 306 diacid 2-glycidyl ester (trade marks: " Dinacol EX701; the product of Nagase chemistry company limited, epoxy equivalent (weight): 153) replace " Epicoat 828 " of restraining oneself.
Embodiment 3
Obtaining acid number by embodiment 1 similar fashion is 195 reaction product, and different is with 252 grams 3,4-epoxy cyclohexane carboxylic-acid-3, and 4-epoxycyclohexyl methyl esters (trade mark: " Chissonox CX221 ", the product of Chisso company) replaces " Epicoat828 "
Embodiment 4
Obtaining acid number by the similar fashion of embodiment 1 is 42.4 reaction product, different is respectively with 764 gram " Gafac RE610 " (trade marks, the product of Tcho chemical industrial company) and 200 the gram " Epicoat1001 " (trade marks, the product of Yuka Shell Epoxy Kabushiki Kaisha, epoxy equivalent (weight): 470) replacing phosphenylic acid and " Epicoat828 " and reaction is to carry out 3 hours at 60 ℃.
Embodiment 5
95%) and 200 grams " Epicoat1001 " and to react be to carry out 2 hours at 60 ℃ obtaining acid number by the similar fashion of embodiment 4 is 48.5 reaction product, and different is adds 321.7 gram " Gafac RE610 "-ester derivatives (purity:.
Embodiment 6
Obtaining acid number by the similar fashion of embodiment 4 is 47.2 reaction product, and different is with 100 gram four glycidyl group benzophenone and reaction is to carry out 2 hours at 60 ℃.
Embodiment 7
Obtaining acid number by the similar fashion of embodiment 4 is 45.0 reaction product, the consumption that different is " Gafac RE610 " reduces to 718 grams from 764 grams, with 144 gram phenol phenol aldehyde type " Epicoat 154 " (trade marks, the product of Yuka Shell Epoxy Kabushiki Kaisha, epoxy equivalent (weight): 180) replacing " Epicoat1001 " and reaction is to carry out under 70 ℃.
Embodiment 8
Obtaining acid number by the similar fashion of embodiment 4 is 46.2 reaction product, different is respectively with 696 gram " Gafac RS610 " (trade marks, the product of Toho chemical industry company limited) and 50 gram o-phthalic acid diglycidyl esters (trade mark: " Dinacol EX721 ", the product of Nagase chemistry company limited) replace " Gafac RE610 " and " Epicoat1001 ".
Embodiment 9
Obtaining acid number by the similar fashion of embodiment 4 is 75.8 reaction product, different is respectively with 595 gram " Gafac RE410 " (trade marks, the product of Toho chemical industry company limited) and 75.6 gram glycerine three-glycidyl esters (trade mark: " Dinacol EX314 ", the product of Nagase chemical company) replace " " Gafac RE610 " and " Epicoat 1001 " and to react be to carry out 2 hours at 50 ℃.
Embodiment 10
Obtaining acid number by the similar fashion of embodiment 9 is 71.3 reaction product, different is, and to replace " Dinacol EX314 " and reaction with 102 Keshan pears sugar alcohol polyglycidyl ethers (trade mark: " DinacolEX611 ", the product of Nagase chemistry company limited) be to carry out 3 hours at 50 ℃.
Embodiment 11
In flask similarly to Example 1, pack into 595 grams " Gafac RE410 " and 93 grams " Epicoat828 ".Make them 100 ℃ of reactions 30 minutes, obtain acid number and be the reaction product in 72.9.
Embodiment 12
Obtaining acid number by embodiment 11 similar fashion is 50.2 reaction product, different is that the consumption of " Epicoat828 " reduces to 74.4 grams and reacts from 93 grams is to carry out 2 hours at 70 ℃ with 718 gram " Gafac RE610 " replacements " Gafac RE410 ".
Embodiment 13
In flask similarly to Example 1, pack into 158.1 gram phosphenylic acids and 632 gram tetrahydrofuran (THF)s at the solution that drips 74.1 gram Racemic glycidols in 296.4 gram tetrahydrofuran (THF)s under 50 ℃, last about 2 hours then.Under 50 ℃, make their reactions 1 hour.Using silica gel thin-layer chromatography (" Merck Art 5715 ", trade mark, an agent is sent out in exhibition: 1: 1 the chloroform and the mixed solvent of methyl alcohol) confirm to have eliminated after a little Racemic glycidol raw material, decompression steams solvent from reaction mixture, obtains acid number and be 280 heavy-gravity reaction product.
Embodiment 14
In 1 liter of removable flask being furnished with thermometer, agitator, nitrogen inlet tube and reflux exchanger, 100.9 grams of packing into gather (hexanodioic acid-1, the 4-ethyl ester) (molecular weight: 1,000), 7,3 grams 1, the reaction product that 4-butyleneglycol, 9.2 gram embodiment 4 obtain, 45.0 gram MDI, 270 gram tetrahydrofuran (THF)s and 270 gram toluene are that 80-85 ℃ of reaction is after 12 hours, add 100 gram methylethylketones, make solid content be adjusted to 20%.
The acid number of the urethane resin of gained phosphoric acid modification is the 2.2(polymkeric substance) and number-average molecular weight be 39,000.
At polyurethane resin solution, the cobalt improved r-Fe of 600 grams with 750 gram phosphoric acid modifications
2O
3(trade mark: " AX-3000 ", the product of TitanKogyoK.K., specific surface are 31m
2/ g), after 350 gram pimelinketone and 650 gram methylethylketones mix in ball mill and kneaded 72 hours, add 20 grams " Desmodule L " with gained mixture remix with kneaded 30 minutes, thereby obtain the magnetic formulation for coating material.
Thick with magnetic formulation for coating material coating is that the polyester film of 9 μ M is to obtain the coating of 4 μ M thick (dry back), then in 90 ℃ of dryings 8 hours.After the drying, the film that is coated with thus is cut into the wide tape of 4.0mm.
Embodiment 15
294.6 grams " the PTG-1000 " (trade mark of the polyether polyol of producing by Hodogaya chemistry company limited of in 1 liter of removable jew flask being furnished with thermometer, agitator and nitrogen inlet tube, packing into, molecular weight: 1000), 16.3 restrain 1, the reaction product that obtains among 4-butyleneglycol, 18.9 gram neopentyl glycol and the 24.9 gram embodiment 12.After reaction product is heated to 80 ℃, adds 162.9 and restrain the MDI that has been heated to 80 ℃.Strong mixing reaction mixture 5 minutes is transferred in the bucket then, makes mixture timeliness 10 hours in 120 ℃ at this.
The acid number of gained resin is 1.9, and number-average molecular weight is 45,000 and is solid-state.It is dissolved in the methylethylketone, and obtaining solid content is 20%, thereby resin solution is provided.
Then, make tape by the mode of embodiment 14.
Embodiment 16
1000), the reaction product that obtains of 23.1 gram 1.4-butyleneglycols and 15.7 gram embodiment 5 in a flask identical, add 318.9 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight: with embodiment 15.With mixture heating up to 110 ℃.
Afterwards, restrain the MDI that has been heated to 110 ℃ with 142.2 and be added in the flask, strong mixing is 3 minutes then.In whipping process, because reaction heat makes temperature of reaction be raised to 220-230 ℃.Reaction mixture is transferred in the bucket, made it in 60 ℃ of timeliness 10 hours at this.The acid number of the resin that obtains thus is 1.6, and number-average molecular weight is 48,000 and is solid-state.It is dissolved in the methylethylketone, obtains 20% solid content, thereby resin liquid is provided.
Then, the similar fashion by embodiment 14 prepares tape.
Embodiment 17
With the poly-(hexanodioic acid-1 of 263.5 grams, the 4-butyl ester) (molecular weight: 2000), 22.1 the gram 1,4-butyleneglycol, 22.7 grams 1, reaction product that 6-hexylene glycol, 31.1 grams " Epicoat828 ", 6.2 gram embodiment 1 obtain and 154.4 gram MDI, by the similar fashion of embodiment 15 obtain that acid number is 2.0, number-average molecular weight is 58,000 solid resin.It is dissolved in the methylethylketone, obtains 20% solid content, thereby resin liquid is provided.Then, prepare tape by embodiment 14 similar fashion.
Embodiment 18
In a flask identical with embodiment 15, add 297.1 grams poly-(1,4-cyclohexanedimethanol adipic acid ester) (molecular weight: 1000), 15.0 grams 1, the 6-hexylene glycol, 13.2 gram neopentyl glycol, 25.3 grams " Epicoat1001 " and 18.3 restrain the reaction product that embodiment 11 obtain.With after the mixture heating up to 110 ℃, add 136.9 gram MDI and also under embodiment 16 conditions of similarities, react.
Reaction mixture is transferred in the bucket, made its cooling then.Afterwards, with it 60 ℃ of timeliness 10 hours.The acid number of the resin that obtains thus is 1.8, and number-average molecular weight is 52,000 and is solid-state.It is dissolved in the methylethylketone, obtains 20% solid content, thereby resin liquid is provided.
Then, the similar fashion by embodiment 14 prepares tape.
Embodiment 19
In a flask identical with embodiment 15,261.4 grams of packing into gather (hexanodioic acid-1, the 4-butyl ester) (molecular weight: 2000), 25.9 restrain 1,6-hexylene glycol, 22.8 gram neopentyl glycol, 32.4 gram glycol ether diglycidylether (trade marks: " YED 205 ", the product of Yuka Shell Epoxy Kabushiki Kaisha, the aliphatic series epoxy compounds, 140) and 10.1 grams " Gafac RE-410 " (Toho chemical industry company limited production phosphoric acid ester) epoxy equivalent (weight):.With mixture heating up to 110 ℃, last about 10 minutes.
Afterwards, under the conditions of similarity of embodiment 16, add 147.4 gram MDI and react, and make reaction mixture carry out timeliness.
The acid number of the resin that obtains thus is 1.8, and number-average molecular weight is 47.000 and is solid-state.It is dissolved in the methylethylketone, obtains 20% solid content, thereby resin liquid is provided.
Then, the similar fashion by embodiment 14 prepares tape.
Embodiment 20
1000), 8.4 gram neopentyl glycol, 0.8 gram " Epicoat828 " and 3.2 restrain " GafacRE410 " in a flask identical, add 640 gram methylethylketones, 100.5 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight: with embodiment 14.Make its reaction 3 hours in 78 ℃.Further add the MDAI(47.1 gram), then in 78 ℃ of reactions 15 hours.The solid content of gained resin solution is 20%.The acid number of polymkeric substance is 1.9, and number-average molecular weight is 45,000.
Then, the similar fashion by embodiment 14 prepares tape.
Embodiment 21
In a flask identical with embodiment 15, add the 290.6 gram many alcohol of polycarbonate (product of Toagosei chemical industry company limited), 16.1 grams 1 in 70 ℃, 4-butyleneglycol, 18.6 grams 1,6-hexylene glycol, 2.5 grams " Epicoat822 " and 11.3 grams " Gafac RS-410 " (product of Toho chemistry company limited).After 10 minutes internal heating to 110 ℃, make reaction mixture in mixture in 110 ℃ of timeliness 10 minutes.
Then, press the similar fashion of embodiment 16, add 160.8 gram MDI and make its reaction, make the reaction mixture timeliness then.
The acid number of gained resin is 2.0, and number-average molecular weight is 45,000 and is solid-state.It is dissolved in the methylethylketone, obtains 20% solid content, thereby resin liquid is provided.
Then, the similar fashion by embodiment 14 prepares tape.
Embodiment 22
Press the similar fashion of embodiment 14, the urethane resin of preparation phosphoric acid modification.It is used and the neutralization of the Ke Xingjia of acid number equivalent.
Use the methylethylketone diluting soln, obtain 20% solid content.Then, prepare tape by embodiment 14 similar fashion.
Embodiment 23
With the poly-(hexanodioic acid-1 of 281.1 grams, the 4-butyl ester) (molecular weight: 1000), 12.2 the gram 1, reaction product that 4-butyleneglycol, 21.2 gram neopentyl glycol, 29.2 gram embodiment 11 obtain and 156.2 gram MDI, by the mode of embodiment 16 obtain that acid number is 5.5, number-average molecular weight is 45,000 solid resin.
Then, the similar fashion by embodiment 14 prepares tape.
Embodiment 24
In a flask identical with embodiment 14, add 94.6 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight: 1000), 8.0 grams 1, the reaction product that 4-butyleneglycol, 1.1 gram embodiment 13 obtain, 103.7 gram MDI and 225 gram tetrahydrofuran (THF)s.It after 10 minutes, is added 375 gram tetrahydrofuran (THF)s in 65 ℃ of reactions.Obtain 20% solid content.
The acid number of the urethane resin of gained phosphoric acid modification is the 1.8(polymkeric substance) and number-average molecular weight be 52,000.
Then, prepare tape by embodiment 14 similar fashion.
Embodiment 25
1000), the reaction product that obtains of 60.7 gram neopentyl glycol and 7.1 gram embodiment 13 in a flask identical, add 226.1 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight: with embodiment 15.Then, with mixture heating up to 110 ℃.
Press the conditions of similarity of embodiment 16, adding 206 gram MDI also react, and make the reaction mixture timeliness then.
The acid number of the resin that obtains thus is 3.1, and number-average molecular weight is 62,000 and is solid-state.It is dissolved in obtains 20% solid content in the methylethylketone, thereby resin liquid is provided.
Then, the mode by embodiment 14 prepares tape.
Embodiment 26
1,000), 60.7 gram neopentyl glycol, 7.1 gram embodiment 13 reaction product and the 5.7 gram tri-n-butylamines that obtain in a flask identical, adds 226.1 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight: with embodiment 15.Then, with mixture heating up to 110 ℃.
Under the conditions of similarity of embodiment 16, adding 206 gram MDI also react, and make the reaction mixture timeliness then.
The acid number of the resin that obtains thus is 3.0, and number-average molecular weight is 59,500 and is solid-state.It is dissolved in the methylethylketone, obtains 20% solid content, thereby resin liquid is provided.
Then, the mode by embodiment 14 prepares tape.
Embodiment 27
Press the mode of embodiment 25, the polyurethane resin solution of preparation phosphoric acid modification uses the triethylamine with acid number equivalent that it is neutralized.Release solution with the methylethylketone cutting edge of a knife or a sword, obtain 20% solid content.
Then, the mode by embodiment 14 prepares tape.
Reference examples 1
With " Estane
The 570FI(trade mark, the product of The B.F.Goodrich company) be dissolved in 70: 30 mixtures of tetrahydrofuran (THF) and pimelinketone, obtain 20% solid content.
With 750 these resin liquid of gram, the cobalt improved r-Fe of 600 grams
2O
3(" A-3000 ", trade mark: Titan, the product of Kogyo K.K.) 650 gram pimelinketone and 350 gram methylethylketones prepare tape by embodiment 14 similar fashion.
Reference examples 2
With " Estane
5703 " (product of The B.F.Goodrich company) is dissolved in the methylethylketone, obtains 20% solid content.
Then, the similar fashion by embodiment 14 prepares tape.
Reference examples 3
1,000), 23.4 grams-1,4-butyleneglycol and 6.1 grams " Epicoat 1001 " in 1 liter of removable jew flask being furnished with thermometer, agitator and nitrogen inlet tube, adds 325.4 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight:.With after the mixture heating up to 80 ℃, add 145.1 grams and be heated to 80 ℃ the MDI and the mixture of strong mixing gained.Afterwards, reaction mixture is transferred in one barrel, made it in 120 ℃ of timeliness 10 hours at this.Obtain number-average molecular weight and be 44,000 solid resin.
Then, prepare tape by embodiment 14 similar modes.
Reference examples 4
In a flask identical with embodiment 14, add 118.4 grams poly-(hexanodioic acid-1,4-butyl ester) (molecular weight: 1000), 2.1 grams-1,4-butyleneglycol, 1.4 grams 2,2-dimethylol propionic acid, 38.1 gram MDI, 270 gram tetrahydrofuran (THF)s and 270 gram toluene.After 12 hours, add 100 gram tetrahydrofuran (THF)s 80-85 ℃ of reaction, obtain 20% solid content.
The acid number of the urethane resin that gained is carboxy-modified is 3.5, and number-average molecular weight is 52,000.
Then, prepare tape by embodiment 14 similar fashion.
Reference examples 5
In a flask identical with embodiment 14, add the poly-(hexanodioic acid-1 of 116.6 grams, the 4-butyl ester) (molecular weight: 1,000), 2.5 grams-1,4-butyleneglycol, 2.8 gram m-phthalic acids-1,3-two (5-hydroxyethyl)-5-sodium sulfonate (Sumitomo chemistry company limited), 38.1 gram MDI, 270 gram tetrahydrofuran (THF)s and 270 gram toluene.After 72 hours, add 100 gram methylethylketones 80 ℃-85 ℃ reactions, obtain 20% solid content.
Sodium sulfonate (the SO of the urethane resin of gained sodium sulfonate modification
3Na) content is 0.05 milligramequivalent/gram, and number-average molecular weight is 48,000.
Prepare tape by embodiment 14 similar fashion.
Reference examples 6
In a flask identical, add 468 gram dimethyl formamides and 115 gram hydroxyl-terminated polyurethanes (" EStane5703 ", trade mark, the product of The B.F.Goobrich company) with embodiment 14.In 80 ℃ this urethane is dissolved in dimethyl formamide after 2 hours, adds the compound that 8.2 gram following formulas are represented.
With 1.6 gram pyridines.Carried out the dehydrogenation H-H reaction 3 hours in 80 ℃ then, thus the two ends of phosphate being introduced each polyurethane chain respectively.After the caustic soda neutralization, polymkeric substance is poured in the methyl alcohol of large volume.In addition, polymkeric substance is washed several times with methyl alcohol again.
After the drying under reduced pressure polymkeric substance, add methylethylketone so that solid content is adjusted to 20%.The sodium phosphate remnants of the urethane resin of the sodium phosphate modification that obtains thus
Content is 1.8 milligramequivalent/grams, and number-average molecular weight is 58,000.
Then, prepare tape by embodiment 14 similar fashion.
With regard to each tape that the foregoing description and reference examples obtain, measure respectively its surface gloss (60 ° of reflectivity) and side than (Br/Bs) to investigate dispersiveness and magnetic.In addition, also measure its wear resistance with the investigation weather resistance.The results are shown in Table 1.
Respectively according to the above characteristic of following determination of test method.
＜surface gloss 〉
Measure the surface luster (60 ° of reflectivity) of the magnetic coating of each tape with glossometer (" AU-SCH-2D-GU3 ", trade mark are produced by Toho Rika Kogyo K.K.).
Good dispersiveness obtains the high glossiness value.
＜side than
With " trade mark of the self-recording unit that Model 3257(is used by the mensuration d.c. magnetic that Yokogawa Electronics Co., Ltd. produces) measure.
Good dispersiveness obtains high side than (Square ratio).
＜resistance to abrasion 〉
The JSPSR(Japan scientific research promotion association that use is produced by Daiei Kagaku SeikiSeisakusho K.K.) the cracking test machine of type.In the environment of 23 ℃ and 65%RH, the surface opposing diameter under the load of 100 grams that makes the magnetic coating of each tape is that the chromed metallic cylinder of 15mm comes and goes and rotates and rub 200 times.Then, in the total surface-area that is rubbed, measure the percentage of any surface-area that grinds off.
Table 1
Surface gloss % side is than wear-resistant rate %
Embodiment 14 88 0.84 3.5
Embodiment 15 93 0.83 4.0
Embodiment 16 92 0.84 1.9
Embodiment 17 90 0.81 1.6
Embodiment 18 85 0.82 1.3
Embodiment 19 74 0.78 2.1
Embodiment 20 70 0.75 5.0
Embodiment 21 80 0.80 4.7
Embodiment 22 90 0.82 3.4
Embodiment 23 95 0.85 3.2
Embodiment 24 92 0.83 2.5
Embodiment 25 93 0.82 3.6
Embodiment 26 96 0.85 3.3
Embodiment 27 98 0.86 3.4
Reference examples 1 16 0.68 1.5
Reference examples 2 20 0.72 3.2
Reference examples 3 17 0.65 2.4
Reference examples 4 50 0.74 3.5
Reference examples 5 68 0.76 8.0
Reference examples 6 52 0.74 5.2
Can obviously find out from table 1, tape of the present invention, promptly the tape dispersiveness of embodiment 14-27 is all good, and particularly the tape of embodiment 16-18 (used respectively phosphoric acid modification with epoxide modified urethane resin) weather resistance is all good.
Claims (4)
1, a kind of magnetic formulation for coating material that mainly constitutes by magnetic particle and tackiness agent, it is characterized in that at least a portion tackiness agent is the reaction mixture synthetic urethane resin by the following component that provides (1), (2), (3) and (4), this resin contains per 3,000-200, phosphate of 000 number-average molecular weight urethane resin or one are 4 by phosphoric acid deutero-residual group and number-average molecular weight, 000-150,000;
(1) a kind of phosphorus compound of representing by following structural formula (a) or the phosphorus compound (b) represented by following structural formula;
Phosphorus compound (a): independent compound (a
1) or compound (a
1) and compound (a
2) mixture:
R wherein
1Be hydrogen atom, phenyl, C
1-4Alkyl, or C
1-40Alkyl phenyl, n are integers between 0-30,
Phosphorus compound (b):
R wherein
2Be phenyl, C
1-40Alkyl or C
1-40Alkyl phenyl;
(2) a kind of have the epoxy compounds of two epoxy group(ing) at least and/or have an epoxy group(ing) and the epoxy compounds of at least one hydroxyl;
(3) isocyanate compound of a kind of difunctionality or trifunctional; And
(4) a kind of number-average molecular weight is 400-5,000 multifunctional hydroxy compounds.
2, according to the magnetic formulation for coating material of claim 1, wherein reaction mixture also contains a kind of chain extension agent as component (5).
3, according to the magnetic formulation for coating material of claim 1 or 2, phosphate or neutralize with alkali at least in part wherein by phosphoric acid deutero-residual group (described group is included in the urethane resin).
4, the purposes of the magnetic formulation for coating material of claim 1 is characterized in that this formulation for coating material is used for magnetic record medium.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP89-271035 | 1988-10-28 | ||
| JP271035/88 | 1988-10-28 | ||
| JP27103588A JPH02209971A (en) | 1988-10-28 | 1988-10-28 | Magnetic coating material and magnetic recording medium |
| JP126580/89 | 1989-05-22 | ||
| JP89-126580 | 1989-05-22 | ||
| JP20373889A JPH03231977A (en) | 1989-05-22 | 1989-08-08 | Magnetic paing and magnetic recording medium |
| JP89-203738 | 1989-08-08 | ||
| JP203738/89 | 1989-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042556A CN1042556A (en) | 1990-05-30 |
| CN1019582B true CN1019582B (en) | 1992-12-23 |
Family
ID=26514088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108186 Expired CN1019582B (en) | 1988-10-28 | 1989-10-26 | Magnetic coating formulations and usage thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019582B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465257C (en) * | 2005-09-15 | 2009-03-04 | 沪东中华造船(集团)有限公司 | Cleaning foam fluid for fault detection and its prepn process |
| CN105584064A (en) * | 2016-01-27 | 2016-05-18 | 蚌埠市众邦包装厂 | Vertical type automatic machining equipment for shallow-bottom compression-molded packaging boxes |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596455B (en) * | 2009-09-30 | 2015-02-04 | 大日本印刷株式会社 | Metal microparticle dispersion, process for production of electrically conductive substrate, and electrically conductive substrate |
| TWI641596B (en) * | 2013-05-15 | 2018-11-21 | Ｄｉｃ股份有限公司 | Method of producing biphenyl skeleton-containing epoxy resin |
| CN104910664A (en) * | 2015-06-08 | 2015-09-16 | 苏州博利迈新材料科技有限公司 | Magnetic paint and preparation method thereof |
| CN107841126A (en) * | 2017-11-14 | 2018-03-27 | 上海多睿电子科技有限公司 | A kind of 3D printing solidifies high luster materials and preparation method thereof with ultraviolet light |
-
1989
- 1989-10-26 CN CN 89108186 patent/CN1019582B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465257C (en) * | 2005-09-15 | 2009-03-04 | 沪东中华造船(集团)有限公司 | Cleaning foam fluid for fault detection and its prepn process |
| CN105584064A (en) * | 2016-01-27 | 2016-05-18 | 蚌埠市众邦包装厂 | Vertical type automatic machining equipment for shallow-bottom compression-molded packaging boxes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042556A (en) | 1990-05-30 |
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