WO1992003222A1

WO1992003222A1 - Dispersant, surface-treated particulate substance, method of using dispersant, and dispersion composition

Info

Publication number: WO1992003222A1
Application number: PCT/JP1991/001131
Authority: WO
Inventors: Shizuo Kitahara
Original assignee: Nippon Zeon Co., Ltd.
Priority date: 1990-08-28
Filing date: 1991-08-27
Publication date: 1992-03-05

Abstract

A dispersant for use in dispersing fine particles in a medium, which contains at least one polymer selected among a modified polymer obtained by the reaction of an unsaturated polymer with an organic compound having both carboxyl and aldehyde groups in the presence of a proton acid or a Lewis acid, a polymer obtained by the coupling of anionic living polymers through a tin compound, and an isoprene polymer treated with tin tetrachloride. It can be used in the production of a wide variety of products wherein a homogeneous dispersion of various particulate substances is required, for example, magnetic recording medium, thermal transfer ink, coating material, toner for developing electrostatically charged images, and so forth.

Description

Specification

Dispersant, surface-treated particulate matter, method of using dispersant, and dispersion composition

Technical field

The present invention relates to a method for dispersing a particulate material, for example, a filler, a reinforcing agent, an inorganic fine particle such as a magnetic powder or a pigment, an organic pigment, and an organic fine particle such as a single fiber chip in a medium such as a solvent or a polymer. The present invention relates to a dispersant, fine particles surface-treated with a dispersant, a method for using the dispersant, and a dispersion composition of the particulate matter.

Technology background

In various coating compositions such as paints and printing inks, a particulate inorganic substance such as titanium oxide or zinc oxide is blended as a pigment, and a particulate organic substance is added to a pigment or coating film. It is used as a filler. In polymers such as rubber and plastic, inorganic substances such as calcium carbonate and silica are used as fillers and reinforcing agents. Organic fine particles such as single fiber chops and granular polymers are also compounded as reinforcing agents and surface treatment agents.

As described above, the compounding of fine inorganic or organic substances into an organic medium or a polymer has been performed in various fields.

In any case, in order to obtain high performance, it is necessary to uniformly disperse the particulate matter in an organic medium or a polymer. Therefore, various dispersants and coupling agents have been proposed for the purpose of improving the dispersibility or the adhesion at the interface between the medium and the particulate matter.

Among them are, for example, silane coupling agents and titanium coupling agents. There are metal salts of fatty acids and the like. The use of these compounds improves the adhesion between the two at the interface. The force dispersibility is still insufficient, and the type of applicable particulate matter is limited. .

Accordingly, an object of the present invention is to provide a novel dispersant which can be applied to various kinds of fine inorganic and organic substances and improves the dispersibility of the fine particles in a medium such as an organic medium or a polymer. .

Another object of the present invention is to provide a fine particle substance and a stable fine particle substance dispersion composition which are treated with the above dispersant and have improved dispersibility in various media, and provide a method of using the dispersant. It is in.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a specific polymer exhibits an excellent action as a dispersant for a particulate substance in various media.

In addition, the polymer is improved in processability, transportability, filling property, etc. in order to suppress the increase in viscosity of the system to which the particulate material has been added, and furthermore, the particulate material previously surface-treated with the polymer. Showed good dispersibility in various media.

The present invention has been completed based on the above findings.

Disclosure of the invention

According to the present invention, the modified polymer (a) obtained by reacting an unsaturated polymer with an organic compound having a carboxylic acid group and an aldehyde group in the presence of a protonic acid or a Lewis acid, Polymer (mouth) of the union combined with tin compound and isoprene treated with tin tetrachloride A dispersant for dispersing fine particles in a medium, characterized by containing at least one polymer selected from the group consisting of: (c), a particulate material surface-treated with any of the above dispersants A method of mixing a particulate matter and a medium in the presence of any of the above dispersants, or a method of mixing a particulate material surface-treated with any of the above dispersants and a medium. Dispersant composition of fine particles comprising any one of the above-mentioned dispersants, fine particles and medium or dispersion of fine particles comprising a medium and a medium surface-treated with any of the above dispersants Composition provided

The dispersant of the present invention has a function of facilitating uniform dispersion of various inorganic and organic fine particles in various media, and also has a dispersion stabilizing function of preventing reaggregation. In addition, since the increase in the viscosity of the system to which the substance is added is suppressed, the processability and transportability of the dispersion, and the filling property of the substance are improved.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention uses a polymer obtained by the following method as a dispersant. The modified polymer (a) obtained by reacting an unsaturated polymer with an organic compound having a carboxyl group and an aldehyde group in the presence of the protic acid or Lewis acid used in the present invention is disclosed in It is a compound obtained by the method described in Japanese Patent Publication No. 3802.

The unsaturated polymer L in the molecular chain is a polymer having a carbon-carbon double bond at the terminal of the molecular chain.

Examples of the polymer having the bond in the molecular chain include conjugated diene such as butadiene, isoprene, and piperylene, dicyclopentadiene, and ethylene. Homopolymers and copolymers of lidennorbornene; copolymers of conjugated gens and vinyl monomers such as polybutadiene, polyisoprene, styrene butter copolymers [random copolymers, block copolymers (A-B, A — B— Type A, etc., where A represents a polybutadiene block and B represents a polystyrene block.)], Styrene-isoprene copolymer [random copolymer, block copolymer (A-B type, A — B— Type A, etc., where A is a polyisoprene block and B is a polystyrene block.)], Acrylonitrile-butadiene copolymer, butadiene-propylene copolymer, ethylene-propylene-gen monomer ternary copolymer And the like, and partially hydrides thereof.

Examples of the polymer having the bond at the terminal of the molecular chain include low molecular weight polymers such as low molecular weight polyethylene, polypropylene, and oligomers of polyolefin, or oligomers; polybutene, polyethylene glycol diacrylate, and polypropylene glycol. Examples include macromers such as diacrylate, polypropylene glycol dimethacrylate, polystyrene methacrylate, and polystyrene diacrylate.

As exemplified above, a polymer having a carbon-carbon double bond in the molecular chain or at the molecular chain terminal may be used.The molecular weight is not particularly limited, and the number average molecular weight in terms of standard polystyrene measured by GPC is 3 Oligomers from 1000 to 100,000 to high molecular weight polymers are included.

The organic compound having a carboxyl group and an aldehyde group to be reacted with the above polymer has at least one of each group in the molecule, and is a linear aliphatic compound having up to 20 carbon atoms, a benzene ring, Naphthalene ring, pi It is selected from compounds having an aromatic ring such as a lysine ring and a furan ring, and alicyclic compounds such as a cyclopentane ring, a cyclopentene ring and a cyclohexane ring. In these compounds, an oxygen atom, a sulfur atom, a nitrogen atom or a multiple bond can be appropriately contained in a molecular chain. Further, the hydrogen atom in the molecule can be replaced with an arbitrary substituent such as an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an amino group or the like as long as the reaction is not adversely affected.

Specifically, glyoxylic acid, formyl acetic acid,

Compounds having an aromatic ring, such as 2-formylacrylic acid, 6-formylhexanoic acid, formylmethoxyacetic acid, 2-formylbutyric acid, and 3- (carboxymethoxy) propioaldehyde, are 2-, 3-, or 4-carboxy. Sivenzaldehyde, 2-formyl-1-5-acetyl-benzoic acid, 2-

3- or 4-monoformylphenylacetic acid, 1,8-naphthaldehyde, 3- (2-formylphenyl) propionic acid, 2-formyl-14-methyl-phenyloxyacetic acid, 6- (2-, 3- or 4-formyl) Phenoxy) hexanoic acid, 2-formyl 3- or 4-formylphenylthioacetic acid, and other alicyclic compounds such as 2-formylcropentanecarboxylic acid, 4-formyl-12-cyclopentenecarboxylic acid, —Formylcyclohexanecarboxylic acid and the like.

Among these compounds, a compound having an aromatic ring in which a carboxyl group or an atomic group containing this group and an aldehyde group or an atomic group containing this group are located adjacent to each other on the ring has a higher reaction rate. Particularly preferred in terms of

The amount of organic compounds containing carboxyl and aldehyde groups is It is usually 0.01 to 20 parts by weight per 100 parts by weight of the compound having a sum bond.

The catalyst used for the reaction is selected from protonic acids and Lewis acids. Examples of the protic acid include sulfuric acid, nitric acid, chlorosulfonic acid, p-toluenesulfonic acid, and hydrogen halide.

Representative examples of Lewis acids include metal or metalloid halides. For example, Be, B, Al, Si, P, S, Ti, V, Fe, Zn, Ga, As, Se, Zr, Nb, Mo, Cd, Sn, Sb, Te, Ta, W, hg, B i, elements such as U or PO, S eO, 'S_〇, S0 _2, VO although such as oxygen one element conjugate halide or organic halide or these complexes, such as, and a carboxyl group Those which form a coordination bond with an organic compound having an aldehyde group are preferred. More specifically _{_{_{BF 3, (CH 3) 2}}} BF, BC 1 3, A 1 C 1 3, A 1 B r 3, (C 2 H 5) A 1 C 1 2, POC 1 3, T i C _{1 VC 1 4, Mo C 1} 6, S n C 1 4, (CH 3) S n C 1 3, S b C 1 5, T e C 1 4 and WC 1 ₆ like _c Here, a protonic acid Alternatively, two or more Lewis acids may be used in combination, or both acids may be used in combination. The amount of these catalysts to be used is usually 0.01 to 5 mol per 1 mol of the organic compound having the group.

The reaction between the compound having an unsaturated bond and the organic compound having the group is usually performed in the presence of a solvent. As the solvent, those which are inert to the catalyst and dissolve both compounds are particularly suitable. For example, aromatic solvents such as benzene and toluene, aliphatic solvents such as butane and hexane, and halogenated hydrocarbon solvents such as chloroform and dichloroethane are exemplified. The reaction is usually performed at a temperature of 0 to 100 ° C., for a reaction time of 10 seconds to several tens hours. By adding a large amount of alcohol or hot water to the reaction system, it is possible to simultaneously stop the reaction and coagulate the reaction product. If necessary, remove the remaining catalyst by washing. Thus, the modified polymer (a) used in the present invention is obtained.

The polymer (mouth) obtained by force-pulling the anion living polymer used in the present invention with a tin compound can be produced by a known method described in JP-B-44-4996.

Anion polymerization is usually carried out using an alkali metal compound, especially an organolithium compound as a catalyst, but an alkaline earth metal compound can also be used.

Examples of the organic lithium compound include methyllithium, ethyllithium, butyllithium, octyllithium, 1,4-dilithiobutane, 1,5-dilithiopentane, and 1,10-dilithiodecane. Examples of the alkaline earth metal compound catalyst include, for example, JP-A-51-115590, JP-A-52-9090, 30543, 48910, 98

Examples of the catalyst system include compounds such as barium, strontium, and calcium disclosed in JP-A No. 077, JP-A-56-112916, JP-A-118403, and JP-A-57-100146.

The amount of these anion polymerization catalysts used is determined in relation to the molecular weight of the produced polymer. Usually, it is about 0.1 to 200 millimol per 100 grams of monomer.

The monomers constituting the polymer are completely controlled as long as they can be anionically polymerized. Not limited.

For example, conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentene, styrene, 1-vinylnaphthalene, 1-methylstyrene, 2-vinylnaphthalene, 3— Examples thereof include monovinyl aromatic compounds such as methylstyrene, and esters of (meth) acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate. These monomers may be used alone or in combination of two or more.

The polymerization is usually carried out in a temperature range of from 120 ° C to 150 ° C. Examples of the polymerization solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene, xylene, and toluene; and alicyclic solvents such as cyclohexane and methylcyclopentane. One or more selected from hydrocarbon solvents are used.

The coupling with the tin compound can be performed during the polymerization, but is usually performed after the polymerization is completed.

The tin compounds used for coupling are methyltrichlorotin, dimethyldichlorotin, tetrachlorotin, dichlorotin, ethyltriclotin, tin, getyldichlorotin, tetrafluoros, methyltribromotin, dimethyldibutin, tin, phenyltrichlorotin, and phenyltrichlorotin. Tin halides such as tin, 1,2 bis (trichlorostannyl) ethane, 1,4 bis (methyldichlorostannyl) butane, getyldiaryltin, propyltriaryltin, dibutyldimethoxytin, dibutylbis (octyloxy) tin, Tetramethylthiotin, tetradodeci Examples thereof include non-tin compounds such as luthiotin, dimethyltin oxide and dimethyltin sulfide, and tin halide compounds, and tin halide compounds are usually used.

The force coupling reaction is carried out at a temperature of 0 to 150 ° C for a period of 0.5 minutes to 20 hours. The amount of the tin compound used is, for example, 1 to 1.5 equivalents of a halogen atom of an organolithium compound per equivalent of a lithium atom of the organolithium compound, taking a tin halide compound as an example.

The force coupling reaction is carried out in an atmosphere of an inert gas by adding a halide to the solution of the living polymer after completion of the polymerization. After completion of the reaction, the tin-coupling polymer is recovered from the reaction solution by using a usual polymer recovery method such as steam stripping. Thus, a polymer (mouth) obtained by coupling the anion living polymer with the tin compound is obtained.

Finally, a method for producing an isoprene-based polymer (c) treated with tin tetrachloride will be described.

The polymer (c) is obtained by adding tin tetrachloride to a solution of an isoprene-based polymer in a solvent inert to tin tetrachloride, and treating the mixture with stirring.

Examples of isoprene-based polymers include natural rubber, polyisoprene, isoprene-butadiene copolymer (including random and block copolymers), isoprene-styrene copolymer [random copolymer and block copolymer (SI, SIS, Isoprene-acrylonitrile copolymer, isoprene-butadiene-acrylonitrile copolymer, and partially hydrides of these conjugated gen units. This In these copolymers

It is desirable that isoprene forms two or more chains.

Any solvent can be used as long as it dissolves the polymer and is inert to tin tetrachloride, and is not particularly limited. Examples thereof include aromatic hydrocarbon solvents such as benzene and toluene, alicyclic hydrocarbon solvents such as cyclohexane, and halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride. Alcohols, ketones and ethers which have chemical conversion to tin tetrachloride can also be used if the amount used is limited. The concentration of the polymer in the solution is usually in the range of 1 to 50% by weight. The water content in the solution is desirably 4 O O Ppm or less.

The amount of tin tetrachloride used varies depending on the type of solvent, water content and the like, but is usually in the range of 0.05 to 5 parts by weight per 100 parts by weight of the polymer. Reducing the amount of tin tetrachloride by coexisting an appropriate amount of a compound having active hydrogen such as trichloroacetic acid, tribromoacetic acid, water or methanol, or a halogen compound such as t-butyl chloride or benzyl chloride. Is possible.

The processing is usually performed at 120 to 100 ° C, preferably 0 to 60 ° C. C The processing time is about 1 minute to 10 hours. It is desirable to perform the treatment so that the glass transition temperature of the isoprene-based polymer after the treatment is increased by 3 ° C or less. After completion of the treatment, the reaction can be stopped and the reaction product can be separated at the same time by adding a large amount of alcohol or hot water to the reaction mixture or by steam stripping. Thus, an isoprene-based polymer (c) treated with tin tetrachloride is obtained. The particulate matter targeted by the present invention is not particularly limited, and the C-particle system which is an inorganic or organic substance having a granular form, a flake form, or a fibrous form is not particularly limited. as preferably 0 0 1 to 5 _c inorganic fine particles is 0 m, for example, metal whiskers as reinforcing agents, Kure one, carbon black, silica, glass fibers, carbon fibers, carbide Geiso fiber維等;. as fillers Calcium carbonate, barium sulfate, mica, zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium fluoride, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, dosonite, calcium sulfate, talc , Calcium gayate, pumice, montmoronite, bentonite, glass bal

ン, shirasu balloon, glass powder, barium titanate, tin oxide, zinc borate, zirconium titanate, etc .; titanium dioxide as pigment, iron oxide (including bengara), carbon black, zinc chromate, etc .; reactivity Examples of the material include metal compounds such as zinc, magnesium, lead, and aluminum.

Examples of the organic fine particles include low-molecular-weight organic compounds such as anthracene, pyrene, and fluorene; petroleum such as pitch; oil residue from naphtha under normal pressure; and asphalten; azo pigments, mordant dye lakes, phthalocyanine pigments, Pigments such as fluorescent pigments; fine particles of resins such as benzoguanamine resin, methacrylic acid resin, silicone resin, polyamide resin, polyester resin, polyphenylene xide, and fuynol-based thermosetting resin; aramid fiber, polyester fiber, polyamide fiber Single fiber chops of fibers such as 0 The medium in the present invention is not particularly limited as long as the above-mentioned particulate matter does not dissolve or is hardly compatible, and includes liquid and solid media _c, for example, water, tetrahydrofuran, Various solvents such as acetonitrile, benzene, toluene, xylene, hexane, methyl ethyl ketone, ethyl acetate, and alcohols; carnauba wax, montan wax, caster wax, paraffin wax, microcrystal wax And natural or synthetic waxes such as oxidized wax, low molecular weight polyethylene wax, low molecular weight polypropylene wax; stearic acid, palmitic acid, aluminum stearate, zinc stearate, barium panolemitate, lead palmitate, methyl hydride Loxastearate, glycerol steer Derivatives of higher fatty acids and their metal salts, esters, etc .; Base oils of various lubricating oils (mineral base oils, synthetic base oils such as monoolefins); naphthenic paraffins and aromatic process oils Plasticizers such as octyl phthalate and dibutyl phthalate; polymers (including oligomers to high molecular weight polymers), for example, polyvinyl chloride, vinyl chloride-vinyl acetate-copolymer, vinyl chloride- Vinyl chloride polymer such as vinylidene chloride copolymer, polyvinyl acetate such as polyvinyl acetate, vinyl acetate-ethylene copolymer, acryl resin such as polymethyl methacrylate

Styrene-based polymers such as polystyrene, impact-resistant polystyrene resin, ABS resin, and AS resin; polyethylene polymers, polypropylene, polyisobutylene, and other olefin-based polymers; gen-based rubber [natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer (Including random and block), styrene-isoprene copolymer (same as left), etc.] And partially hydrides thereof, engineering plastics such as polyethylene terephthalate, polycarbonate, polysulfone ether, and polyamides, celluloses such as cell acetate, acetate, and nitrocellulose, phenolic resins, epoxy resins, unsaturated polyester resins, polyurethane resins, and silicon. curable resin such as a resin, petroleum resin, terpene resin, synthetic resins such as polybutene, but not limited to _c

The amount of the dispersant of the present invention varies depending on the type of the medium for dispersing the inorganic and / or organic fine particles, the surface area per weight of the substance or the type of the dispersant, the molecular weight, and the like. The amount is at least 0.05 part by weight, preferably 0.05 to 100 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the substance.

Examples of the method of using the dispersant include the following methods.

How (1) was added to the pre-medium a dispersant, then adding particulate matter, stirred if needed, be mixed ^s focus.

(2) A method in which a dispersant and a particulate material are added together in a medium, and if necessary, stirred and mixed.

(3) The dispersant and the particulate matter are stirred and mixed at a temperature of 50 to 300 ° C, and the surface of the substance is treated with the dispersant, and then added to a medium, and if necessary, stirred and mixed. how to. -When using a particulate material that has been previously surface-treated with a dispersant, in order to achieve the effects of the present invention, the amount of surface treatment (adhesion) of the dispersant to the substance, the amount of the dispersant Although it varies depending on the type, molecular weight, etc., it is at least 1% by weight, preferably 3% by weight or more based on the weight of the substance. C The method of surface treatment of the particulate matter with a dispersant is not particularly limited. Examples thereof include the method of dry blending of the above (3), the method of immersing the substance in a solution of a dispersant of an inert organic solvent, the method of A method of spraying and applying a suspension of a dispersant using an inert solvent such as water to the substance may be used.

In order to produce a dispersion in which the substance is uniformly dispersed in a polymer using the dispersant of the present invention or the particulate substance surface-treated with the dispersant, it is necessary to sufficiently mix the polymer and the substance. is necessary. Preferred mixing conditions depend on the type of polymer, chemical structure, and the like. The dispersant and the substance are surface-treated with a dispersant using a conventional mixer such as a Henschel mixer, a Hobart mixer, a Banbury mixer, or a twin-screw extruder, and then mixed with the polymer. You may.

Processing of the polymer, eg, high shear mixing, is generally performed at a temperature well above the glass transition temperature of the polymer, preferably at a temperature at which the polymer has a low melt viscosity. The temperatures at which good processing takes place are, for example, in the temperature range of 170-230 ° C for low-density polyethylene, in the temperature range of 200-250 ° C for high-density polyethylene, and for polystyrene. In the temperature range of 230 to 260, in the temperature range of 230 to 270 ° C for polypropylene, and in the temperature range of 240 to 292 ° C for ABS resin (medium impact resistance) The temperature conditions for mixing the polymer and the particulate matter other than those exemplified in _c, such as the temperature range, may be a temperature range known to those skilled in the art for the target polymer.

A commonly used mixer can be used and is not particularly limited. For example, two-roll mill, _c which include Wari ring blender Chancellor When manufacturing by dissolving or dispersing various substances in a liquid medium (at room temperature or when heated) such as paints and inks, it is difficult to disperse them evenly. It is convenient to prepare in advance a dispersion in which an agent, various pigments (for example, described in Kiki Color Index, Third Edition) and the like are dispersed in a suitable solvent such as water or an organic solvent. The use of the above-mentioned dispersant of the present invention makes it possible to produce a dispersion composition of fine particulate matter having excellent dispersibility and dispersion stability.

Since the type and amount of the fine particle substance to be used vary depending on the application, the substance and the amount suitable for the purpose may be selected. In the present invention, the substance and the amount used are not particularly limited. Uses include carbon black, inorganic pigments, organic pigments and dyes, and toner (using a toner for electrostatic copying as a dispersion).

The medium of the dispersion composition is also selected according to the use of the dispersion composition, and is not particularly limited in the present invention.

As a method of dispersing the particulate matter in a liquid medium (for example, a solvent), a method in which the substance is added to a solvent to which a necessary amount of a dispersant is added, a method in which the necessary amount of a dispersant and the substance are added to the solvent, Or a method in which the substance previously surface-treated with a dispersant is added to a solvent as described above, but other methods may be used. By using the dispersant of the present invention, mixing under a high shearing force such as a ball mill in the production of a conventional dispersion liquid becomes unnecessary, and the mixture is uniformly dispersed only by mixing with a stirrer having an ordinary stirring blade. This has the advantage that labor saving can be achieved.

The dispersant of the present invention can be used in various media of various inorganic and organic fine particles. It has a function of stabilizing the dispersion, which makes it easy to uniformly disperse the particles and prevents reaggregation. Further, since the increase in the viscosity of the system to which the substance is added is suppressed, the processability and transportability of the dispersion or the filling property of the substance are improved. C.

The thermal transfer ink contains at least one of the above-mentioned dispersant polymers (a) to (c), carbon black and a binder as main components, and the polymers (a) to (c) contain carbon black as the binder. It works to disperse it evenly, and as a result, the image obtained by using this thermal transfer ink becomes high quality and excellent in durability. As the binder, a binder conventionally used for this purpose is used. Examples of the above-mentioned waxes, higher fatty acids and various polymers of metal salts thereof, and the like. Carbon blacks conventionally used for this purpose are also used. Carbon black is usually used in the ink in the range of 5 to 40% by weight. If desired, other additives can be used. The thermal transfer ink is produced by melt-kneading a binder and carbon black and, if necessary, other additives in the presence of the dispersant of the present invention. Due to the presence of the dispersant, it is extremely easy to disperse the carbon black into the binder.It is only necessary to mix with low shear using a stirrer such as a conventional stirrer with various shapes and a static mixer. It is enough. If a polymer having a monomer composition and a molecular weight suitable for the binder is selected as the dispersant of the present invention, the dispersant of the present invention can be used without adding another binder.

The prepared thermal transfer ink is represented by polyethylene terephthalate film, polyimide film, condenser paper, silk fabric, aluminum foil, etc. It can be applied to the support by a conventionally used method such as hot melt coating, reverse roll coating, and gravure opening coating, so that a thermal transfer sheet of excellent quality can be obtained. it can

Since the thermal transfer ink using the dispersant of the present invention is uniformly dispersed in the carbon black binder component, an image recorded using this ink is compared with an image using the conventional thermal transfer ink. The quality is remarkably high and the image durability is excellent.

Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples, but the present invention is not limited to these examples.

The number of parts in each example is based on weight unless otherwise specified.

Production Example 1

100 g of the polymer shown in Table 1 was dissolved in 400 ml of toluene and placed in a reaction vessel equipped with a stirrer, an internal heating device, a vapor condenser, and a liquid-solid supply port. Heat to 30 ° C with stirring. Then, 1 mol of each of reagents A and B shown in Table 1 was added, and the mixture was reacted for about 1 hour.c.The reaction was stopped by adding a small amount of methanol, and then 500 ml of an aqueous solution of sodium carbonate was added. The mixture was added, stirred, and allowed to stand. The organic layer was separated and washed with water 500 ml. After standing, the organic layer was separated, and the solvent was removed to obtain a reaction product. These are referred to as dispersants A to C.

Production Example 2

100 g of the polymer described in Table 2 was dissolved in 50 O ml of xylene, placed in the reaction vessel of Reference Example 1, and heated to 30 ° C. with stirring. Next, 1 mol of each of reagents A and B described in the first description was added, and the reaction was carried out for about 1 hour. A small amount of The reaction was stopped by adding ethanol, and the content was poured into 1000 ml of methanol, and the reaction product was separated and dried under reduced pressure. The resulting reaction products are referred to as dispersants D to F. _c

Production Example 3

Polystyrene-polysoprene block copolymer (SZ I = 80/2

(0 weight ratio, Mn = 73,000) Dissolve 140 g in 2.81 dehydrated toluene, add 22 millimoles of tin tetrachloride in a separable flask under a nitrogen atmosphere, and react at 70 ° C for 70 minutes I let it. The reaction was stopped by adding 100 ml of methanol. The reaction solution was poured into a 1% methanol solution 31 of BHT (2 ', 6-di-tert-butyl-4-methyl-phenol), and the reaction product was separated. After washing, dried under reduced pressure to obtain Dispersant G c

Production Example 4

In a stainless steel reaction vessel under a nitrogen atmosphere, cyclohexane 11 and styrene 150 g were charged, and after adjusting the internal temperature to 30 ° C., 0.09 g of n-butyllithium was added to initiate polymerization. After _c their that polymerization was carried out for 1 hour under elevated temperature, the addition of tin tetrachloride 0. 07 g, was subjected to 30 minutes coupling reaction at 70 ° C. BHT was added to the reaction solution, the reaction product was separated by steam stripping, and dried under reduced pressure. This is designated as Dispersant H (Mn = l 20,000).

Before the coupling reaction was performed by the above method, a small amount of 1,3-butadiene was added to continue the polymerization. After the polymerization was completed, tin tetrachloride coupling was performed. The obtained reaction product is used as dispersant I

Production Example 5 140 g of liquid polyisoprene (λ4η = 6,600) was dissolved in 2.81 dehydrated toluene, and reacted with 7 mmol of tin tetrachloride in the same manner as in Reference Example 3. At that time, 7 millimoles of acetic acid with trichloride was added. The obtained reaction product is referred to as Dispersant J.

Table 1

Dispersant A Dispersant B Dispersant C

Liquid unsaturated polyisoprene S-I block E.PDM②

Compound (Mn = 4000) Copolymer (Mn = 8500)

(Mn = 10000)

Reagent A 2-forminole 5-formyl 1-honoleminole

Phenoxyacetic acid 2-naphthyl pentanoate

Oxyacetic acid

5 formula b Tin tetrachloride Antimony pentachloride Tin tetrachloride Note) ① Polystyrene-polyisoprene block copolymer

Styrene / isoprene = 8Z2 (weight ratio)

M n is the number average molecular weight in terms of standard polystyrene measured by GPC.

②Ethylene-propylene-gen terpolymer

〇2- Table 2

s

Note) ③ Styrene / isoprene = 9Z1 (weight ratio)

④Styrene Z isoprene = 2Z8 (weight ratio)

Iodine value 20

Example 1

In order to confirm the dispersing effects of the above dispersants C to J, the inorganic particulate substances shown in Table 3 were dispersed in toluene, and the aggregation suppressing effect was evaluated.

50-100 mg of inorganic fine particles were added to 300 ml of toluene, and dispersed by the action of ultrasonic waves (by a transmitter attached to the following granulometer). Average particle diameter (median diameter, [D ₅ Q] o) immediately after the ultrasonic wave action stops when the average particle diameter (median diameter, [D _5fl] ₁₀₎ 1 0 minutes after the stop of the ultrasonic lasers The measurement was performed using a one-diffraction type particle sizer (SK LASER MI CRON SI ZER PRO-70000 manufactured by Seishin Enterprise Co., Ltd.).

Aggregation inhibiting effect _{_{[D 5 ()] 10 /}} [D 50]. Where [D ₅₀ ] is the particle diameter corresponding to 50% of the cumulative distribution of particle diameters.

The amount of the dispersant added is% by weight with respect to the inorganic fine particles.

Table 3 shows the results.

Example 2

Add 10 parts of dispersant A or G and 50 parts of HAF Rikibon black (Asahi Rikibon Co., Ltd. Asahi # 70) to 140 parts of toluene and irradiate with ultrasonic wave (same as in Example 1) for 5 minutes Thereafter, the mixture was uniformly stirred at 300 rpm to prepare a dispersion of carbon black. This dispersion was centrifuged to separate carbon blacks, and then dried under reduced pressure to obtain carbon blacks (I) and (II) surface-treated with a dispersant. In the same manner, instead of the dispersant, a male black polyisoprene was used to obtain carbon black (III) having been subjected to a surface treatment. '

Using these surface-treated carbon blacks (I) to (III), A vulcanized compound of polyisoprene rubber (Nip012200, manufactured by Nippon Zeon Co., Ltd.) was prepared, and the vulcanization properties were improved by improving the dispersibility of carbon black.

According to the following formulation, the rubber was first mixed with carbon black using a small Banbury mixer, and sulfur and a vulcanization accelerator were added to the mixture using a small roll and mixed.

This compound was press-vulcanized at 140 ° C for 25 minutes to obtain a vulcanized product, and the strength characteristics and rebound resilience (using a Dunlop trypsometer at room temperature) were measured. The results are shown in Table 4. c

Combination method

Rubber 100 parts Carbon black (I)-(III) 0 Aromatic process oil 0 Zinc oxide 0 Stearic acid 9

2.δ

N-oxydiethylene mono-2-benzothiazyl

Sulfenamide 0.8 N-isopropyl-N'-phenyl- p-

Phenylamine 1.0 Example 3

Dispersant Β or Η Add 10 parts of azo organic pigment lake C (manufactured by Dainichi Seika) and 20 parts to 200 parts of toluene / methylethyltoluene (1/1) Then, after irradiating with ultrasonic waves (same as in Example 1) for 1 minute, the mixture was stirred under the condition of 300 rpm to prepare a dispersion liquid (dispersion composition) of the organic pigment.

The dispersibility of this dispersion was evaluated by the amount of the organic pigment remaining on the filter after passing through a N03 glass filter, and the dispersion stability was evaluated from the sedimentation state of the organic pigment over time of the dispersion passed through the filter.

The dispersibility was indicated by “場合” when excellent without residual amount, and “X” when the residual amount was inferior. Dispersion stability was indicated by 〇 when it was excellent without sedimentation even after one month, and X when it settled and was inferior after one week. The results are shown in Table 5.

Third dispersant Comparative example

Inorganic fine particles

Cohesion C D Γ G H I J Carbon black CDsoJo (// m) 1.1 1.1 1.1 1.1 1.1

① [D ₅ o] i. _{() 9. s 5 1.0 3.5 1.0} 3.5

[D ₅ o] io / [D ₅₀ ] ₀ 8.6 0.9 3.4 0.9 3.4

Zinc oxide ② [D ₅₀ ] o (lim) 2.0 2.0. 0

N n 2.0 2.0

[D50T10 () 8.5 2.3 5

2.3 5.3

[D ₅₀ ] ₁₀ / [D ₅₀ ] ₀ 3.3 1.2 L 7 1.2 97 Magnetic powder ③ [D ₅₀ ] ₀ (/ im) 2.0 2.0 9 nu, n U 2.0 2.0 2 n

[D ₅ o] io (/ im) 16.0 1.8 3.0 3.0 1.8 3.0 2.5

[D ₅₀ ] ₁₀ / [D ₅₀ ] ₀ 8.0 0.9 1.5 1.5 0.9 1.5 1.3 Calcium carbonate [D ₅₀ ] ₀ dim) 7.8 7.8 7.8 7.8 7.8 7.8

④ [D ₅₀ ] io () 23.0 7.6 16.5 16.5 7.6 16.5

[D ₅₀ ] ₁₀ / [D ₅₀ ] ₀ 3.0 1.0 2.1 2.1 1.0 2.1 Glass powder [D ₅₀ ] _o (// m) 10.3 10.3 10.3 10.3 10.3

⑤ [D ₅₀ ] i. () 12.5 10.3 10.9 10.3 10.9

[D ₅₀ ], o / [D ₅₀ ] ₀ 1.2 1.0 1.0 1.0 1.0

Note) (1) HAF carbon black Asahi # 70 manufactured by Asahi Carbon

② Activated zinc flower manufactured by Shodo Chemical Co., Ltd.

③ Ba-flight

Average particle size 0.04 m

(By electron microscope observation)

④Says NS # 100 manufactured by Dongpo Chemical Co., Ltd.

⑤Toshibo PF AO 01

Table 4

Note) (*) Use 50 parts of carbon black without surface treatment with dispersant.

Table 5-

Example 4

Using each of the above dispersants, according to the formulation in Table 6, the mixture was stirred and mixed at 100 ° C for 30 minutes to prepare a thermal transfer ink. Each of the obtained inks was thinly applied on a glass plate, and the dispersibility of carbon black was observed with an optical microscope. Good or bad dispersibility was indicated by 〇 and X. Each ink was coated on a 6〃m-thick biaxially stretched polyethylene terephthalate (PET) film so that the dry thickness of the ink was 5 // m. It was applied using. The inks were heated so that each of them was in an optimal flow state. The resulting thermal transfer sheet was mounted on a thermal printer and printed on plain paper. The quality of the print was evaluated on a 5-point scale, including the resolution and the presence or absence of white spots.

The raw materials for dispersants A, D and J were used as dispersants A ', D' and J ', respectively, and these were used to prepare and evaluate a thermal transfer ink in the same manner in accordance with the formulation shown in Table 6. Furthermore, a thermal transfer ink (Nol 7) without using a dispersant was prepared and evaluated. The results are shown in Table 6.

Table 6

I

r

Note) CB: Ribonbon Black [ΜΛ- 100 R (Mitsubishi Chemical Industries)].

Industrial applicability

The dispersant of the present invention can be used in the manufacture of a wide range of products that require uniform dispersion of various particulate substances. For example, bonded magnets using magnetic materials (various magnetic powders), magnetic recording media [toner for electrostatic image development, discs, tapes (magnetic powder in magnetic recording layer and back coat layer, binder such as carbon black) ^ The dispersion has been improved)? Paints and molded articles using EMI materials; inks using pigments (printing inks, thermal transfer inks, conductive inks, etc.); thermal transfer ink ribbon coating agents: paints, conductive materials, etc. Conductive and electrostatic composite materials used: Wires, building materials, etc. using arrogant materials; Dyes, catalysts, etc. dispersion and stabilizing materials; Fillers, reinforcing agents, antifriction materials, etc. Rubber and plastic molded products, FRP, FRTP, etc .; used to manufacture various oils (for example, lubricating oils, engine oils, etc.) to which oil additives such as sludge dispersants, detergent dispersants, and load additives are added. be able to.

Claims

The scope of the claims

1. A modified polymer obtained by reacting an unsaturated polymer with an organic compound having a carboxyl group and an aldehyde group in the presence of a protonic acid or a Lewis acid. Dispersion for dispersing particulate matter in a medium characterized by containing a ring polymer (mouth) and at least one polymer (c) selected from isoprene polymers treated with tin tetrachloride Agent.

2. The dispersant according to claim 1, wherein the number average molecular weight of the polymer is from 300 to 100,000.

3. A method for using a dispersant, comprising mixing a particulate matter and a medium in the presence of the dispersant according to claim 1.

A method for using a dispersant, comprising mixing a particulate material surface-treated with the dispersant according to claim 1 with a medium.

5. A dispersion composition comprising the dispersant according to claim 1, a particulate substance, and a medium.

6. A dispersion composition comprising a particulate material surface-treated with the dispersant according to claim 1 and a medium. .

7. A thermal transfer ink comprising the dispersion composition according to claim 5 or 6.