CN105860054A - Nonaqueous dispersant and nonaqueous dispersion composition - Google Patents
Nonaqueous dispersant and nonaqueous dispersion composition Download PDFInfo
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- CN105860054A CN105860054A CN201610082936.2A CN201610082936A CN105860054A CN 105860054 A CN105860054 A CN 105860054A CN 201610082936 A CN201610082936 A CN 201610082936A CN 105860054 A CN105860054 A CN 105860054A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
- C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
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Abstract
The invention provides a non-aqueous dispersant allowing particle dispersoid to disperse into the non-aqueous solvent with high concentration, and excellent dispersion stability can be given to the particle dispersoid; the non-aqueous dispersant complies with the formula (1)(see description), wherein R refers to a linear chain or linear chain alkyl with 1-22 carbon atoms, A1O refers to oxygen ethylidene, and m is 1-30; A2O refers to oxygen alkylene with 3-4 carbon atoms, wherein n is 1-30; the following relation is complied with: 0.1<=m/n<=10 and 5<=m+n<=40, wherein a refers to aromatic nucleus number (1-2), and M refers to hydrogen atom, ammonio or alkanol ammonio.
Description
Technical field
The present invention relates to a kind of non-aqueous dispersion agent and the non-aqueous dispersions compositions containing this non-aqueous dispersion agent, institute
State non-aqueous dispersion agent and can be used for the dispersion dispersions in non-aqueous solvent such as organic or inorganic powder body.More specifically, originally
Invention relates to a kind of non-aqueous dispersion agent and contains the non-aqueous dispersions compositions of this non-aqueous dispersion agent, described non-aqueous point
Powder can make dispersion be scattered in non-aqueous solvent with high concentration with a small amount of addition, and the dispersion simultaneously giving excellence is steady
Qualitative.
Background technology
Make the non-aqueous dispersions compositions quilt that the dispersion such as organic powder or inorganic particle is scattered in non-aqueous solvent
In various industrial circles.As organic powder, include, for example out organic pigment, containing the non-aqueous dispersion of organic pigment
Body compositions is used for coating, printing-ink, ink for inking, light filter resist and writing appliance ink etc..Additionally, make
For inorganic particle, include, for example out ceramic powder or metal-powder, the non-aqueous dispersions compositions containing ceramic powder is removed
The electronic units such as dielectric layer, semiconductor substrate, various sensor and the liquid crystal display cells for multilayer ceramic capacitor
In addition, it is additionally operable to grinding-material or refractory material etc..Additionally, the non-aqueous dispersions compositions containing metal-powder is as formation
The electronic material of electrode, such as, be widely used as conductive paste or conductive ink.
In recent years, in electronic unit purposes, it is desirable to the product attributes such as the miniaturization of parts, high capacity and high efficiency
Improvement, in order to meet these requirements, seek the micronized of dispersion, the non-aqueous dispersion such as raw ceramic materials powder body or metal-powder
The high concentration of the dispersion in body compositions.When preparing non-aqueous dispersions compositions, due to organic powder or inorganic powder
The body situation that dispersibility is insufficient under independent state is more, therefore to improve mobility and the storage of non-aqueous dispersions compositions
For the purpose of hiding stability, generally use dispersant.As this dispersant, up to now, there has been proposed many high score subclasses to divide
The copolymer etc. of powder, such as polyacrylic acid or their copolymer, polyoxyalkylene derivative and maleic anhydride.
But along with micronized, in conventional high score subclass dispersant, dispersant is through absorption between particle, easily produces
Bridge joint cohesion, thus produces the problem that initial stage dispersibility reduces.Additionally, due to the surface area of dispersion increases, the table of dispersion
Face free energy increases, and dispersion easily becomes unstable.Therefore, i.e. allow to temporary dispersion, if attempting to reduce dispersion
Apparent surface is amassed, then dispersion is condensed again, it is difficult to stably keep dispersity.Initial stage dispersibility and dispersion stabilization are with dividing
The micronized of a prose style free from parallelism and reduce, thus produce the problem such as non-aqueous dispersions compositions retrogradation or dispersion deposition.Creating
In the non-aqueous dispersions compositions of these problems, not only cause the reduction of productivity, processing characteristics and operability, also result in
The quality of whole goods reduces.
Therefore, for dispersant, it is desirable to be obtained in that and contain dispersion and low viscous non-aqueous dispersions with high concentration
While compositions, dispersion warp is long-time without depositing, it is possible to the performance of stable dispersion.
In order to solve the problems referred to above, in patent documentation 1, it is proposed that a kind of polyoxyethylene monophenyl ether and ring type carboxylic acid
Carboxylate, but it can not fully meet effect for the non-aqueous dispersions compositions containing microparticle dispersion.Additionally,
In patent documentation 2, propose the carboxylate of the high polyoxypropylene monomethacrylate ether of lipophile and trimellitic anhydride respectively,
But to the effect of described compositions not fully satisfactory.
Prior art literature
Patent documentation
Patent documentation 1: JP 62-106838 publication
Patent documentation 2: JP 2007-144402 publication
Summary of the invention
The technical problem to be solved in the present invention
In sum, it is an object of the invention to solve described technical problem, be specially and a kind of non-aqueous dispersion agent is provided,
It can make particle diameter be that 1 μm particles below dispersion is scattered in non-aqueous solvent with high concentration, can give it excellent simultaneously
Different dispersion stabilization.
Solve the technological means of technical problem
In order to solve described technical problem, present inventor etc. is through conscientiously studying, found that by having specific knot
The polyether ester compound that the polyethers of structure is formed with tricarboxylic acid anhydride can solve the problem that described technical problem.
That is, the present invention is following [1]～[3].
[1] the non-aqueous dispersion agent shown in following formula (1),
[chemical formula 1]
In formula (1), R is the alkyl of the straight or branched of carbon number 1～22；A1O is oxygen ethylidene (オ キ シ エ チ
レ Application base), m be A1The average addition molal quantity of the oxygen ethylidene shown in O, is 1～30；A2O is the oxygen alkylene of carbon number 3～4
Base (オ キ シ ア Le キ レ Application base), n is A2The average addition molal quantity of the oxyalkylene shown in O, is 1～30；M Yu n meets
0.1≤m/n≤10 and the relation of 5≤m+n≤40；A is the quantity of aromatic rings, is 1～2；M represents hydrogen atom, ammonium
Or alkanol ammonium (alkanolammonium) (ammonium).
[2] according to the non-aqueous dispersion agent described in [1], it is characterised in that A2O be carbon number be the oxygen propylidene (オ of 3
キ シ プ ロ ピ レ Application base).
[3] a kind of non-aqueous dispersions compositions, it contains by the non-aqueous dispersion agent described in [1] or [2], non-aqueous molten
Agent and by the described scattered dispersion of non-aqueous dispersion agent.
Invention effect
In accordance with the invention it is possible to the microparticle dispersion such as the organic powder making particle diameter be below 1 μm or inorganic particle is with highly concentrated
Degree is scattered in non-aqueous solvent, can give the dispersion stabilization of its excellence simultaneously.
Detailed description of the invention
Hereinafter the non-aqueous dispersion agent of the present invention and the embodiment of non-aqueous dispersions compositions are illustrated successively.
(non-aqueous dispersion agent)
The non-aqueous dispersion agent of the present invention contains the polyether ester chemical combination that the polyethers shown in following formula (1) is formed with tricarboxylic acid anhydride
Thing, additionally, the ester compounds that the polyethers shown in formula (1) and tricarboxylic acid anhydride are formed the most also is only called " polyethers esters chemical combination
Thing ".
[chemical formula 2]
R is the alkyl of the straight or branched of carbon number 1～22.As R, can list methyl, ethyl, propyl group, butyl,
The straight-chain such as hexyl, heptyl, octyl group, lauryl, myristyl, palmityl, stearyl, behenyl base (behenyl group) are satisfied
And alkyl, isopropyl, isobutyl group, the tert-butyl group, isopentyl, iso-octyl, 2-ethylhexyl, different nonyl, 3,5,5-trimethyl,
The branched saturated hydrocarbyls such as isodecyl, iso stearyl, 2-octyl-decyl, 2-octyldodecyl, 2-hexyl decyl, pi-allyl,
The unsaturated alkyls etc. such as (methyl) acrylic, palmityl, oleyl, sub-oil base.These groups can use one or two
Plant use mixed above.From the point of view of to the dissolubility of non-aqueous solvent and initial stage dispersibility, preferably carbon number 4～
The straight or branched saturated hydrocarbyl of 18 or unsaturated alkyl, the most preferably branched of carbon number 4～18 are saturated
Alkyl.
A1O and A2O is polyoxy alkylidene, it is possible to when being adsorbed in dispersion, by repelling (steric as steric hindrance
Repulsion) position acts on, and makes dispersion fine dispersion, can improve the dissolubility to non-aqueous solvent simultaneously.
A1O be carbon number be the oxygen ethylidene of 2, A2O be carbon number be the oxyalkylene of 3～4, preferably carbon number
It it is the oxygen propylidene of 3.M represents the average addition molal quantity of oxygen ethylidene, and n represents the average of the oxyalkylene of carbon number 3～4
Addition molal quantity, m is 1～30, and n is 1～30.
From the point of view of initial stage dispersibility and dispersion stabilization, more preferably m is more than 3, particularly preferably more than 4.This
Outward, m is more preferably less than 25, and particularly preferably less than 20.
Additionally, from the point of view of initial stage dispersibility and dispersion stabilization, particularly preferred n is more than 3.Additionally, n is more preferably
It is less than 25, more preferably less than 20, particularly preferably less than 15.
A1Average addition molal quantity m and A of the oxygen ethylidene shown in O2The average addition molal quantity n of the oxyalkylene shown in O
There is 0.1≤m/n≤10 and the relation of 5≤m+n≤40.
M/n represents in polyether ester compounds, the A that the hydrophilic of polyether chain is strong1The A that O is strong with lipophile2The balance of O.
If m/n is less than 0.1, lipophile is too high, and therefore polyether chain expansion in non-aqueous solvent, polyether chain is easily wound around, at the beginning of therefore having
The possibility that phase dispersibility or dispersion stabilization reduce.Additionally, if m/n is more than 10, then hydrophilic is too high, therefore at non-aqueous solvent
In dissolubility reduce, therefore polyether chain shrink, steric hindrance repel effect reduce, have the possibility that initial stage dispersibility reduces.
Considering from above-mentioned angle, m/n is more preferably more than 0.2, more preferably more than 0.5, particularly preferably 0.7 with
On.Additionally, m/n is more preferably less than 8, particularly preferably less than 7.
M+n represents polyether chain length, meets 5≤m+n≤40.If m+n is less than 5, then, it is difficult to obtain sufficient steric hindrance and repel
Effect, if additionally, more than 40, then polyether chain is the most mutually wound around, having the possibility that initial stage dispersibility reduces.From initial stage dispersibility and
From the point of view of dispersion stabilization, m+n is particularly preferably more than 6.Additionally, m+n is more preferably less than 35, more preferably 30
Hereinafter, particularly preferably less than 25.
A represents the quantity of aromatic rings, is 1～2.Aromatic rings in polyether ester compounds, from tricarboxylic acid anhydride, is bonded to
The carboxyl of aromatic rings works as the adsorption site being adsorbed in dispersion.Same aromatic rings has carboxyl, will more
It is prone in dispersion absorption, so from the perspective of initial stage dispersibility, preferably a=1.
Shown in chemical formula in the case of a=1 such as formula (1A), shown in the such as formula of the chemical formula in the case of a=2 (1B).
[chemical formula 3]
[chemical formula 4]
M is hydrogen atom or ammonium or alkanol ammonium, preferably hydrogen atom or alkanol ammonium, the most preferably hydrogen atom.
Then, the preparation method of the polyether ester compounds shown in formula (1) is illustrated.
Polyether ester compounds shown in formula (1) by preparing the first operation of polyethers and can make in the first operation
The second operation that the polyethers obtained and tricarboxylic acid anhydride react and prepare.
First operation is illustrated.
Can pass through on the alcohol with the straight or branched alkyl that carbon number is 1～22, addition alkylene oxide (ア Le
キ レ Application オ キ サ イ De) and prepare polyethers.
As the catalyst of the additive reaction for alkylene oxide, base catalyst can be listed, such as can use alkali metal or
The alkanolamines such as alkanamine class, triethanolamine such as the oxide of alkaline-earth metal or hydroxide, alcoholates, triethylamine.Additionally, except
Outside described base catalyst, it is possible to use the lewis acid catalyst such as boron trifluoride or butter of tin.Relative to additive reaction
Quality after completing, the consumption of catalyst is usually 0.01～5.0 mass %.
The additive reaction of alkylene oxide can be carried out in the following manner: such as, in the inactive gas atmosphere such as argon or nitrogen
Under, with 50～200 DEG C, 0.02～1.0MPa, persistent pressure is while adding alkylene oxide.
Then, the second operation is illustrated.
As in the second operation use tricarboxylic acid anhydride, can list trimellitic anhydride, 1,2,3-benzene tricarbonic acid's acid anhydrides, 1,
2,5-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, the aromatic series tricarboxylic of 1,2,8-naphthalene tricarboxylic acid anhydride
Anhydride.
Reaction ratio in the second operation, the molal quantity at the hydroxyl with monoalkyl polyethers is (H), with tricarboxylic acid anhydride
When molal quantity is (T), preferably 0.7 ＜ (H)/(T) ＜ 1.2, further it is preferably (H)/(T)=1.
Catalyst can be used in the second operation.Tertiary amine compound can be listed as catalyst, include, for example out
Triethylamine, triethylene diamine, N, N-dimethyl benzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-11 carbon
Alkene, 1,5-diazabicyclo-[4.3.0]-5-nonene etc..
Can carry out under solvent-free in the first operation, the second operation, it is possible to use suitable dehydrated organic solvent.?
The solvent used in reaction, can be removed by operations such as distillations after completion of the reaction, or can be directly as a part for goods
And use.Reaction temperature is 80～180 DEG C, preferably 90～160 DEG C, further preferably 100～140 DEG C.
The polyether ester compounds of the present invention can be neutralized by amine.As amine, can list ammonia, methylamine, dimethylamine,
The alkanolamines such as the alkanamines such as ethamine or monoethanolamine, diethanolamine, triethanolamine, can use one or both that select from them
Above.
(non-aqueous dispersions compositions)
The non-aqueous dispersions compositions of the present invention contains non-aqueous dispersion agent, dispersion and non-aqueous solvent.
Here, the gross mass of non-aqueous dispersion agent, dispersion and non-aqueous solvent is designated as 100 mass %.
In this case, the content of non-aqueous dispersion agent is preferably 0.05～20 mass %.If not containing of aqueous dispersion
Amount less than 0.05 mass %, then possibly cannot obtain sufficient initial stage dispersibility and dispersion stabilization, and content is even more than 20 matter
Amount %, it is also possible to the effect matched with content cannot be obtained.From the point of view of initial stage dispersibility and dispersion stabilization, non-aqueous
The content of dispersant is preferably 0.1～15 mass %, the most preferably 0.5～10 mass %.
As the dispersion contained in the non-aqueous dispersions compositions of the present invention, organic powder or inorganic powder can be listed
Body.
Azo, two azos, condensation azo, thioindigo class, indanthrone class (イ is include, for example out as organic powder
Application ダ ス ロ Application), quinacridine ketone, Anthraquinones, benzimidazole ketone, class, phthalocyanines, anthracene pyridines and diazines etc. have
Machine pigment.
As inorganic particle, include, for example tap a blast furnace, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, stannum, palladium, zirconium, titanium, copper, silver,
The alloy powder of metal-powder, two or more metals or the metals such as gold, platinum and nonmetal composition, to metal-powder or alloyed powder
Body carries out the mixed powder that the composite granule of Composite, two or more inorganic particles or inorganic particle mix with other powder body.
It addition, as inorganic particle, silicate mineral, other silicate compound, carbonate compound, sulphuric acid can be listed
Each powder body such as compound, oxyhydroxide, oxide, nitride, carbide, titanic acid compound.Such as, kaolinite can be listed
Soil, clay, Talcum, Muscovitum, bentonite, dolomite, calcium silicates, aluminium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, brium carbonate, sulfur
Acid calcium, barium sulfate, aluminum sulfate, aluminium hydroxide, hydrated ferric oxide., zirconium oxide, magnesium oxide, aluminium oxide, titanium oxide, ferrum oxide, oxidation
Zinc, antimony trioxide, Indium sesquioxide., tin indium oxide, carborundum, tungsten carbide, aluminium nitride, silicon nitride, boron nitride, Barium metatitanate., calcium titanate,
Strontium titanates, carbon black, glass fibre, carbon fiber, carbon nano-fiber, CNT are (SWCN, double-walled carbon nano-tube, many
Wall carbon nano tube) etc. each powder body.
As dispersion, the preferably metal-powder such as nickel, cobalt, palladium, copper, silver, gold, platinum, zirconium oxide, magnesium oxide, aluminium oxide,
The powder body of the oxides such as ferrum oxide, zinc oxide, tin indium oxide, the powder body of the titanium oxygen compound such as Barium metatitanate., calcium titanate, strontium titanates.
From the point of view of serviceability, the mean diameter of dispersion is preferably 0.01～1 μm, and the most preferably 0.01
～0.7 μm, particularly preferably 0.01～0.5 μm.Additionally, the mean diameter of dispersion can (scanning electron shows by using SEM
Micro mirror) or the electron microscope method of TEM (transmission electron microscope) or Microtrack method (laser diffraction and scattering method) enter
Row measures.
In the case of the total amount of non-aqueous dispersion agent, dispersion and non-aqueous solvent is designated as 100 mass %, dispersion
Content usually 10～90 mass % in non-aqueous dispersions forms, preferably 30～85 mass %, the most preferably
It is 55～80 mass %.
As the non-aqueous solvent making the scattered disperse medium of dispersion in the non-aqueous dispersions compositions of the present invention
The varsols such as (organic solvent), include, for example out the aromatic hydrocarbon solvent such as toluene or dimethylbenzene, hexamethylene, acetone, first
The ketones solvents such as ethyl ketone, methyl iso-butyl ketone (MIBK) and Ketohexamethylene, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate
And the esters solvent such as gamma-butyrolacton, ethylene glycol monoethyl ether, ethyleneglycol monopropylether, ethylene glycol mono-n-butyl ether, diethylene glycol list second
Ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether,
The glycol ethers such as dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether are molten
Agent, ethylene glycol monoethylether acetate, ethylene glycol list isopropyl acetate, ethylene glycol mono-n-butyl ether acetas, diethylene glycol list second
Ether acetic acid ester, diethylene glycol mono-n-butyl ether acetas, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol
Single positive propyl ether acetas, propylene glycol mono-n-butyl ether acetas, DPE acetas, dipropylene glycol list positive propyl ether acetic acid
The diol alcohol esters solvents such as ester and dipropylene glycol mono-n-butyl ether acetas, terpineol, dihydroterpineol, terpinenyl aceatae and two
The terpene type solvents such as hydroacetic acid Oleum Pini ester, the alcohols such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol and tert-butyl alcohol is molten
Agent, can use one or more that select from these non-aqueous solvents.
From improve dispersion dispersibility and with the intermiscibility of polyether ester compounds the present invention from the point of view of, non-aqueous
The property preferred solubility parameter of solvent (SP value) is 8.5～12.5 (cal/cm3)1/2's.Additionally, the dissolubility ginseng of non-aqueous solvent
Number (SP value) can be calculated by Hansen formula, and its detailed content is recorded in " SP value base application and computational methods " (Yamamoto
Elegant tree writes, and information institution society prints, distribution in 2006), obtain according to this record.
If particular instantiation solubility parameter (SP value) is at the non-aqueous solvent of described scope, can list toluene, butanone,
Methyl iso-butyl ketone (MIBK), Ketohexamethylene, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethylene glycol monoethyl ether, second
Glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, second two
Alcohol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetas, diethylene glycol monoethyl ether acetas, diethylene glycol mono-n-butyl ether acetic acid
Ester, propylene glycol methyl ether acetate, propylene glycol mono-n-butyl ether acetas, terpineol, dihydroterpineol, terpinenyl aceatae, dihydro
Terpinenyl aceatae, isopropanol, n-butyl alcohol.Can be used alone the one selected from these non-aqueous solvents, it is possible to use two kinds
Above mixture.
Even additionally, solubility parameter (SP value) is at 8.5～12.5 (cal/cm3)1/2Extraneous non-aqueous solvent,
Also by combining two or more non-aqueous solvents, SP value can be adjusted to described scope.
The SP value of mixed solvent can experimentally be obtained, or, as easy method, can be by each non-aqueous solvent
The long-pending summation of mol ratio and SP value and calculate.In the non-aqueous dispersions compositions of the present invention, can use by these sides
Method adjusted the mixed solvent of SP value.
In non-aqueous dispersions compositions, the content of non-aqueous solvent is usually 5～50 mass %, preferably 10～40
Quality %, the most preferably 10～30 mass %.
Do not damaging in the range of its purpose, other surfaces can added in the non-aqueous dispersions compositions of the present invention and live
The various additives such as property agent, binding agent, plasticizer and defoamer.
The non-aqueous dispersions compositions of the present invention, can the preparation method of known non-aqueous dispersions compositions be base
Standard is prepared.Such as, can list after adding dispersion in the non-aqueous solvent be dissolved with dispersion, at room temperature carry out
The method of stirring mixing, after adding non-aqueous solvent and dispersant in dispersions, the method being at room temperature stirred mixing
Deng.
As being used for stirring, mixing or scattered dispensing machine, known dispersion machine can be used.Such as, roller can be listed
Grinding machine, ball mill, ball mill, sand mill, homogenizer, disperser, rotation-revolution type blender etc..In addition, it is possible at ultrasound wave
Occur bath carries out dispersion process.
Embodiment
Then, by embodiment and comparative example, the present invention is further described in detail.
(synthesis example 1: the synthesis of polyether ester compounds 1)
To being provided with blender, piezometer, thermometer, relief valve, gas insufflation tube, exhaustor, cooling coil and vapour jacket
Stainless steel 5 liter capacity pressure vessel in, add 288g (2mol) 3,5,5-trimethyl-1-hexanol (trade name:
NONANOL, KHneochem Co., Ltd. system) and 2g potassium hydroxide, after nitrogen is replaced, stir and be warming up to 120 DEG C.
Under agitation, 120 DEG C, 0.05～0.50MPa (gauge pressure) under conditions of, by gas insufflation tube from the pressure vessel additionally prepared
Middle 705g (16mol) oxirane nitrogen is pressurizeed while adding.After the addition was complete, make it anti-under the same conditions
Should to the most intrinsic pressure necessarily.Then, in the process, 349g (6mol) expoxy propane is added, after the addition was complete, at the same terms
Under make its react to intrinsic pressure necessarily.Then, from pressure vessel, take out reactant, be neutralized with hydrochloric acid to pH6～7, in order to remove
Contained moisture, carries out 100 DEG C, the reduced pressure treatment of 1 hour, removes desalination finally by filtration, obtain 1270g polyethers.Gained
To the hydroxyl value of polyethers be 84, the molecular weight obtained from hydroxyl value is 668.
Then, in being provided with the reaction vessel of glass system 0.5 liter capacity of agitating device, thermometer, gas insufflation tube, add
Enter 267g (0.4mol) polyethers obtained above and 77g (0.4mol) trimellitic anhydride (Northeast chemistry (strain) system), at 120 DEG C
React 4 hours.Confirm that the anhydride of more than 98% is half-esterification by measuring of acid number, terminate reaction.Thus, polyethers esters is obtained
Compound 1.
Additionally, by 3 in synthesis example 1,5,5-trimethyl-1-hexanols, oxirane and expoxy propane are suitably changed to it
His compound, operates on the basis of synthesis example 1, thus the polyether ester compounds 2 of synthesis table 1～7 and the polyethers of formula (2)
Ester type compound 8.
The polyether ester compounds 1～7 of synthesis is shown in table 1, and compound 8 is shown in formula (2).
[table 1]
| Compound | R | (A1O)m | A2O | m+n | m/n | a | M |
| 1 | 3,5,5-trimethyl-1-hexyl | (C2H4O)8 | (C3H6O)3 | 11 | 2.7 | 1 | Hydrogen atom |
| 2 | 3,5,5-trimethyl-1-hexyl | (C2H4O)4 | (C3H6O)3 | 7 | 1.3 | 1 | Hydrogen atom |
| 3 | 3,5,5-trimethyl-1-hexyl | (C2H4O)20 | (C3H6O)3 | 23 | 6.7 | 1 | Hydrogen atom |
| 4 | Isodecyl | (C2H4O)3 | (C3H6O)8 | 11 | 0.4 | 1 | Hydrogen atom |
| 5 | Isodecyl | (C2H4O)3 | (C3H6O)15 | 18 | 0.2 | 1 | Hydrogen atom |
| 6 | Oleyl | (C2H4O)12 | (C3H6O)1 | 13 | 12 | 1 | Hydrogen atom |
| 7 | Stearyl | (C2H4O)0 | (C3H6O)15 | 15 | 0 | 1 | Hydrogen atom |
[chemical formula 5]
R is the mixture of the straight-chain/branched alkyl of carbon number 10～16.
(embodiment 1～5, comparative example 1～3)
Polyether ester compounds 1～8 is used as dispersant, in the following manner preparation non-aqueous dispersions compositions.
In 50mL corrugated tubing, (mean diameter: 0.05 μm, by using the electronics of SEM to weigh 20.0g barium carbonate powder
Microscopic method measures), 5.0g propylene glycol methyl ether acetate and 1.4g dispersant, use rotation-revolution type mixer to carry out 5 points
Clock stirs, and carries out pre-dispersed.Then, use the zirconium oxide bead of 0.5mm, by carrying out dispersion in 4 hours with ball mill, obtain serosity
The non-aqueous dispersions compositions of shape.Additionally, the SP value of propylene glycol methyl ether acetate is 8.7 (cal/cm3)1/2。
The non-aqueous dispersions compositions obtained by use polyether ester compounds 1～5, as embodiment 1～5, will use
The non-aqueous dispersions compositions that polyether ester compounds 6～8 obtains is as comparative example 1～3.
(distributed test)
Use embodiment 1～5 and the non-aqueous dispersions compositions of comparative example 1～3, carry out distributed test.
For each non-aqueous dispersions compositions, use dynamic viscoelastic device (Paar Physica MCR-300,
Anton Paar society system) measure temperature 20 DEG C, shear rate is the shear viscosity of 0.1～100 (1/s).Shear rate is 1 (1/
S) shear viscosity time is as shown in table 2.
Additionally, measure the shear viscosity of each non-aqueous dispersions compositions standing a week in room temperature with the same terms.Cut
Cutting speed degree is that shear viscosity time 1 (1/s) is shown in table 2 in the lump.
[table 2]
With the addition of the non-aqueous dispersions compositions of the embodiment 1～5 of the polyether ester compounds 1～5 of the present invention, all exist
Show good dispersibility immediately after preparation, even if after one week, be also hardly visible through time viscosity B coefficent.
On the other hand, with the addition of m/n at extraneous polyether ester compounds 6 and 7 or with the addition of and have and the present invention
The comparison of the polyether ester compounds 8 of the addition mode inverse structure of the alkylene oxide in the polyether ester compounds shown in formula (1)
The non-aqueous dispersions compositions of example 1～3, shear viscosity the most immediately after preparation is high, and through time viscosity B coefficent big, therefore
Understanding bad dispersibility the most immediately after preparation, dispersion stabilization is the poorest.
(embodiment 6～9, comparative example 4～6)
Polyether ester compounds 1～4,6,7,8 is used as dispersant, by following preparation non-aqueous dispersions compositions.This
Outward, the non-aqueous dispersions compositions obtained by use polyether ester compounds 1～4, as embodiment 6～9, will use polyethers
The non-aqueous dispersions compositions that ester type compound 6～8 obtains is as comparative example 4～6.
In 50mL corrugated tubing, (mean diameter: 0.05 μm, by using the electronics of SEM to weigh 20.0g barium carbonate powder
Microscopic method measures), 5.0g toluene/ethanol mixed solvent (1/1, mass ratio) and 1.4g dispersant, use rotation-revolution type to mix
Conjunction machine carries out stirring in 5 minutes, carries out pre-dispersed.Then, the zirconium oxide bead of 0.5mm is used, by carrying out for 4 little time-divisions with ball mill
Dissipate, obtain the non-aqueous dispersions compositions of slurry.Additionally, the SP value of toluene/ethanol mixed solvent (1/1, mass ratio) is
11.4(cal/cm3)1/2。
(distributed test)
Use embodiment 6～9 and the non-aqueous dispersions compositions of comparative example 4～6, carry out distributed test.
For each non-aqueous dispersions compositions, use dynamic viscoelastic device (Paar Physica MCR-300,
Anton Paar society system) measure temperature 20 DEG C, shear rate is the shear viscosity of 0.1～100 (1/s).It is 1 by shear rate
(1/s) shear viscosity time is shown in table 3.
Additionally, measure the shear viscosity of each non-aqueous dispersions compositions standing a week in room temperature with the same terms.Will
Shear rate is that shear viscosity time 1 (1/s) is shown in table 3 in the lump.
[table 3]
It is added with the non-aqueous dispersions compositions of the embodiment 6～9 of the polyether ester compounds 1～4 of the present invention, all exists
Show good dispersion immediately after preparation, though do not find after one week through time viscosity B coefficent.
On the other hand, with the addition of m/n at extraneous polyether ester compounds 6 and 7 or with the addition of and have and the present invention
The comparison of the polyether ester compounds 8 of the addition mode inverse structure of the alkylene oxide in the polyether ester compounds shown in formula (1)
The non-aqueous dispersions compositions of example 4～6, shear viscosity the most immediately after preparation is high, and through time viscosity B coefficent big, therefore
Understanding bad dispersibility the most immediately after preparation, dispersion stabilization is the poorest.
(embodiment 10～12, comparative example 7～9)
Polyether ester compounds 1,3,4,6,7,8 is used as dispersant, by following preparation non-aqueous dispersions compositions.This
Outward, use, as embodiment 10～12, is gathered by the non-aqueous dispersions compositions obtained by use polyether ester compounds 1,3,4
The non-aqueous dispersions compositions that ether-ether compounds 6～8 obtains is as comparative example 7～9.
In 50mL corrugated tubing, (mean diameter: 0.1 μm, by using the electronic display of SEM to weigh 20.0g barium carbonate powder
Micro mirror method measures), 5.0g toluene/ethanol mixed solvent (3/7, mass ratio) and 0.4g dispersant, use the mixing of rotation-revolution type
Machine carries out stirring in 5 minutes, carries out pre-dispersed.Then, the zirconium oxide bead of 1.0mm is used, by carrying out for 3 little time-divisions with ball mill
Dissipate, obtain the non-aqueous dispersions compositions of slurry.Additionally, the SP value of toluene/ethanol mixed solvent (3/7, mass ratio) is
12.0(cal/cm3)1/2。
(distributed test)
Use embodiment 10～12 and the non-aqueous dispersions compositions of comparative example 7～9, carry out distributed test.
For each non-aqueous dispersions compositions, use dynamic viscoelastic device (Paar Physica MCR-300,
Anton Paar society system) measure temperature 20 DEG C, shear rate is the shear viscosity of 0.1～100 (1/s).It is 1 by shear rate
(1/s) shear viscosity time is shown in table 4.
Additionally, measure the shear viscosity of each non-aqueous dispersions compositions standing a week in room temperature with the same terms.Will
Shear rate is that shear viscosity time 1 (1/s) is shown in table 4 in the lump.
[table 4]
It is added with the non-aqueous dispersions compositions of the embodiment 10～12 of the polyether ester compounds 1,3 and 4 of the present invention,
All showing good dispersibility immediately after preparation, though do not find after one week through time viscosity B coefficent.
On the other hand, with the addition of m/n at extraneous polyether ester compounds 6 and 7 or with the addition of and have and the present invention
The comparison of the polyether ester compounds 8 of the addition mode inverse structure of the alkylene oxide in the polyether ester compounds shown in formula (1)
The non-aqueous dispersions compositions of example 7～9, shear viscosity the most immediately after preparation is high, and through time viscosity B coefficent big, therefore
Understanding bad dispersibility the most immediately after preparation, dispersion stabilization is the poorest.
(embodiment 13～15, comparative example 10～12)
Polyether ester compounds 1,3,4,6,7,8 is used as dispersant, by following preparation non-aqueous dispersions compositions.This
Outward, use, as embodiment 13～15, is gathered by the non-aqueous dispersions compositions obtained by use polyether ester compounds 1,3,4
The non-aqueous dispersions compositions that ether-ether compounds 6～8 obtains is as comparative example 10～12.
In 50mL corrugated tubing, weigh 20.0g alumina powder jointed (mean diameter: 0.4 μm, use laser diffractometry survey
Fixed), 5.0g toluene/ethanol mixed solvent (1/1, mass ratio) and 0.2g dispersant, use rotation-revolution type mixer to carry out 5 points
Clock stirs, and carries out pre-dispersed.Then, use the zirconium oxide bead of 1.0mm, by carrying out dispersion in 3 hours with ball mill, obtain serosity
The non-aqueous dispersions compositions of shape.
(distributed test)
Use embodiment 13～15 and the non-aqueous dispersions compositions of comparative example 10～12, carry out distributed test.
For each non-aqueous dispersions compositions, use dynamic viscoelastic device (Paar Physica MCR-300,
Anton Paar society system), measure temperature 20 DEG C, shear rate is the shear viscosity of 0.1～100 (1/s).It is 1 by shear rate
(1/s) shear viscosity time is shown in table 5.
Additionally, measure the shear viscosity of each non-aqueous dispersions compositions standing a week in room temperature with the same terms.Will
Shear rate is that shear viscosity time 1 (1/s) is shown in table 5 in the lump.
[table 5]
It is added with the non-aqueous dispersions compositions of the embodiment 13～15 of the polyether ester compounds 1,3 and 4 of the present invention,
All showing good dispersibility immediately after preparation, even if displaying that good dispersion stabilization after one week.
On the other hand, with the addition of m/n at extraneous polyether ester compounds 6 and 7 or with the addition of and have and the present invention
The comparison of the polyether ester compounds 8 of the addition mode inverse structure of the alkylene oxide in the polyether ester compounds shown in formula (1)
The non-aqueous dispersions compositions of example 10～12, shear viscosity the most immediately after preparation is high, and through time viscosity B coefficent big, because of
This understands bad dispersibility the most immediately after preparation, and dispersion stabilization is the poorest.
Claims (3)
1. the non-aqueous dispersion agent shown in following formula (1),
In formula (1), R is the alkyl of the straight or branched of carbon number 1～22；A1O be oxygen ethylidene, m be A1Oxygen shown in O
The average addition molal quantity of ethylidene, is 1～30；A2O is the oxyalkylene of carbon number 3～4, and n is A2Oxygen alkylene shown in O
The average addition molal quantity of base, is 1～30；M Yu n meets the relation of 0.1≤m/n≤10 and 5≤m+n≤40；A is aromatic rings
Quantity, is 1～2；M represents hydrogen atom, ammonium or alkanol ammonium.
Non-aqueous dispersion agent the most according to claim 1, it is characterised in that A2O be carbon number be the oxygen propylidene of 3.
3. a non-aqueous dispersions compositions, it contains non-aqueous dispersion agent according to claim 1 and 2, non-aqueous
Solvent and by the described scattered dispersion of non-aqueous dispersion agent.
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| CN111902882A (en) * | 2018-03-28 | 2020-11-06 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN112334995A (en) * | 2018-09-27 | 2021-02-05 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN113227233A (en) * | 2018-12-25 | 2021-08-06 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN113227246A (en) * | 2018-12-25 | 2021-08-06 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| JP5135760B2 (en) * | 2005-11-02 | 2013-02-06 | 東洋インキＳｃホールディングス株式会社 | Dispersant and production method thereof |
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| US20050031566A1 (en) * | 2001-10-17 | 2005-02-10 | Cooper Julie Hutchison | Cosmetic and personal care compositions |
| CN102906060A (en) * | 2010-05-26 | 2013-01-30 | 第一工业制药株式会社 | Dispersant and dispersion composition |
| CN103282110A (en) * | 2010-12-22 | 2013-09-04 | 第一工业制药株式会社 | Dispersant and dispersion composition |
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| CN111902882A (en) * | 2018-03-28 | 2020-11-06 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN111902882B (en) * | 2018-03-28 | 2022-08-26 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN112334995A (en) * | 2018-09-27 | 2021-02-05 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN112334995B (en) * | 2018-09-27 | 2023-01-10 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN113227233A (en) * | 2018-12-25 | 2021-08-06 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN113227246A (en) * | 2018-12-25 | 2021-08-06 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN113227246B (en) * | 2018-12-25 | 2023-09-12 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
| CN113227233B (en) * | 2018-12-25 | 2023-12-12 | 住友金属矿山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| CN105860054B (en) | 2020-10-09 |
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