JPH0474521A - Dispersant, surface treated minute particle and use of dispersant - Google Patents

Abstract

PURPOSE:To obtain a dispersant well dispersing a fine particulate substance by incorporating a polymer of polymerizable monomer having a functional group such as an oxazine group or an oxazolone group into the dispersant. CONSTITUTION:A dispersant is composed of a polymer of a polymerizable monomer having a functional group such as an oxazine group or an oxazolone group and a copolymer of the above monomer and a monomer copolymerizable therewith. Various fine particulate inorg. substances and/or fine particulate org. substances are mixed with the dispersant in an org. medium or a medium such as a polymer. When the surfaces of the fine particulate substances are treated with the dispersant, said substances are uniformly and stably dispersed in the medium and the re-flocculation thereof is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dispersant, and more specifically, the present invention relates to a dispersant, and more particularly, to a medium such as an organic medium or a polymer, a particulate material such as a filler, a reinforcing agent, a magnetic powder, a pigment, etc. This invention relates to a dispersant for uniformly dispersing inorganic fine particles such as organic pigments, chopped single fibers, etc., and preventing re-agglomeration.

The invention also relates to particulate materials treated with the dispersant and methods of using the dispersant.

[Conventional technology]

In various coating compositions such as paints and printing inks,
Particulate inorganic substances such as titanium oxide and zinc oxide are blended as pigments, and particulate organic substances are used as pigments and coating film modifiers. For polymers such as rubber and plastics, inorganic substances such as calcium carbonate and silica are used as reinforcing agents and fillers, and organic fine particles such as chopped single fibers and granular polymers are blended as reinforcing agents and surface treatment agents. has been done.

In this way, blending particulate inorganic substances and organic fine particles into organic media and polymers is practiced in a wide range of fields.

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

Among them, there are, for example, silane coupling agents, titanium coupling agents, metal salts of fatty acids, and the like. Although the use of these compounds improves adhesion, etc. at the interface between particulate matter and polymer, the effect of improving dispersibility is not sufficient, and the types of applicable particulate matter are also limited. There is a problem that

[Problem to be solved by the invention]

An object of the present invention is to provide a novel dispersant that can be applied to various particulate inorganic substances and/or particulate organic substances and improves the dispersibility of particulate substances in organic media or media such as polymers. There is a particular thing.

Another object of the present invention is to provide a particulate material which is treated with the above-mentioned dispersant and has improved dispersibility in a medium such as an organic medium or a polymer.

Another object of the present invention is to provide a method for using the above-mentioned dispersant.

As a result of intensive research aimed at achieving the above object, the present inventors have found that a compound with a structure in which a specific heterocyclic structure is introduced into the molecule (inside the molecular chain or at the end of the molecular chain) can be used in various types of organic media or polymers. It has been found that it exhibits excellent effects as a dispersant for inorganic substances and organic fine particles.

In addition, the compound suppresses the increase in viscosity of the system to which inorganic and/or organic fine particles have been added, improving processability, transportability, or filling properties. It has been found that/or organic fine particles exhibit good dispersibility in organic media and polymers.

The present invention has been completed based on these findings.

[Means to solve the problem]

Thus, according to the invention, for dispersing particulate material in a medium containing a polymer of polymerizable monomers having functional groups selected from oxazine groups, oxacylone groups, oxazinium ions and oxazolonium ions. A dispersant is provided.

Further, according to the present invention, a particulate material whose surface is treated with the dispersant is provided.

Furthermore, the present invention provides a method for using a dispersant, which comprises mixing particulate matter with the dispersant in a medium.

Hereinafter, the configuration of the present invention will be explained in detail.

(Dispersant) The dispersant of the present invention has an onitosazine group in the molecule [general formula (
1)] or an oxacylone group [general formula (2)], and these groups are preferably contained in an amount of about 0.01 to 10% by weight in the polymer.

R.

(In the formula, R1 to R4 represent hydrogen or a substituent.) The dispersant of the present invention has an oxazinium ion structure [general formula (3)] or an oxazolonium ion structure [general formula (4)] in the molecule. It is a polymer, and these ionic structures are preferably contained in an amount of about 0.01 to 10% by weight in the polymer.

R.

R1 -(-C-CI(2→- 10C-CH2→- (wherein R1 to R6 are hydrogen or a substituent, R5 is a substituent,
Z represents an electrophilic group. ) Manufacturing method of dispersant The dispersant having the above structure of the present invention can be produced by (1) a method of polymerizing the polymerizable monomer having the above functional group together with other polymerizable monomers if necessary, f21 (
A method in which the polymer having an oxazine group or oxacylone group obtained in 1) is treated with an alkylating agent, etc., and the nitrogen atom in the group is converted into a quaternary ammonium to generate an oxazinium ion or an oxazinium ion. There is.

Examples of the polymerizable i-mer having an oxazine group include 2-vinyl-2-oxazine, 2-vinyl-4methyl-2-oxazine, 2-vinyl-4-ethyl-2-oxazine, 2-vinyl-4-ethyl-2-oxazine,
-isopropenyl-2oxazine, 2-impropenyl-4-methyl 2-oxazine, 2-isopropenyl-4
-ethyl-2-oxazine, 2-isopropenyl-4,
Examples include 5-dimethyl-2-oxazine.

Examples of polymerizable monomers having an oxacylone group include 2-vinyl-5-oxasilon, 2-vinyl-4-methyl-5
-Oxacilone, 2-vinyl-4ethyl-5-oxacilone, 2-isopropenyl-5-oxacilone, 2-isopropenyl-4methyl-5-oxacilone, 2-isopropenyl-4-ethyl-5-oxacilone, 2- Examples include isopropenyl-4,4-dimethyl-5-oxacilone. 1. Polymerizable monomers having an oxazinium ion structure include N-methyl-2-vinyl-2-oxazinium salt, N
-methyl-2-isopropenyl 2-oxazinium salt,
N~methyl-2-vinyl 4-methyl-2-oxazinium salt, N-methyl-2-isopropenyl-4-methyl-
Examples include 2-oxazinium salts.

Examples of the polymerizable monomer having an oxazinium ion structure include oxazolonium ion salts of the above-mentioned polymerizable monomers having an oxacilone group.

Monomers used as necessary with these monomers are not particularly limited as long as they can be copolymerized, such as styrene-based polymers such as styrene, p-methylstyrene, and p-methoxystyrene; acrylics; Acrylic acid or methacrylic acid monomers such as acid, methyl acrylate, butyl acrylate, stearyl acrylate, methacrylic acid, methyl methacrylate; ethylene, propylene, vinyl chloride, vinyl acetate, acrylamide, acrylonitrile, N-vinylpyrrolidone etc., and one or more of these may be used.

As the polymerization initiator used for polymerization, commonly used oil-soluble peroxide-based or azo-based initiators can be used.

For example, peroxide initiators such as benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2.2'-azobisisobutyronitrile, 2.2' Azobis=(2,4-dimethylvaleronitrile), 2°2'-azobis-2,3,3-trimethylbutyronitrile, 1,1'-azobis-(cyclohexane-1-carbonitrile), 4.4' There are peroxide-based initiators such as -3azobis-4cyanovaleric acid and dimethyl-2,2'-azobisisobutyrate. Further, ordinary anionic polymerization catalysts (for example, organic lithium compounds, etc.) can also be used.

When using a peroxide-based initiator as a polymerization solvent, acetonitrile, nitromethane, toluene, benzene, xylene, etc. are used, and when using an anionic polymerization catalyst, a solvent that is inert to acid catalysts is usually used. be done. Polymerization is usually carried out at a temperature of -20°C to 150°C.

In order to convert an oxazine group into an oxazinium ion or an oxacylone group into an oxazolonium ion, an N-alkylating agent such as an alkyl halide, methyl p-t~luenesulfonate, or dimethyl sulfate is used. Although the ion is introduced into the polymer chain by this method, a functional group to which the -Tomasei ion is not introduced may be included.

(Fine particulate matter) The particulate matter targeted by the present invention is an inorganic or organic substance having a powder, flake, or fibrous shape. Although the particle size is not particularly limited, it is usually 0.1 mm or less, preferably 0.01 to 50 μm.

Specific examples of inorganic fine particles include metals, clay, carbon blanks, calcium carbonate, barium sulfate, silica, mica, glass, ashest, etc. as inorganic reinforcing materials; zinc, magnesium, lead aluminum and the like as reactive inorganic materials. , and other metal compounds. Titanium dioxide, iron oxide (including red iron oxide), pigment carbon, zinc chromate, etc. as inorganic pigments. Zinc oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, helium oxide, pumice as inorganic fillers,
Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, dawsonite, calcium sulfate, talc, mica, glass balloon, shirasu balloon, glass powder, glass fiber, calcium silicate, montmoroni l-, bentonite, carbon fiber, titanium Examples include barium acid, tin oxide, zinc borate, silicon carbide fiber, zirconium titanate, and the like.

Specific examples of organic fine particles include anthracene, pyrene,
Low-molecular weight organic compounds such as ferrocene, residual oil from ordinary or vacuum distillation of petroleum and naphtha such as pinch, asphaltene, etc.; organic pigments such as azo pigments, mordant dye lakes, phthalocyanine pigments, and organic fluorescent pigments; benzoguanamine resins, Examples include fine particles of methacrylic acid resin, silicone resin, polyamide resin, polyester resin, polyphenylene oxide, phenolic thermosetting resin, etc.; chopped single fibers such as aramid fiber, polyester fiber, polyamide fiber, etc.

(Medium) The medium in the present invention does not dissolve the above-mentioned particulate matter, and
Further, there are no particular limitations as long as they are not easily compatible with each other, and liquid or solid media are included. Specific examples include various solvents such as water, tetrahydrofuran, acetonitrile, benzene, 1 to toluene, xylene, hexano, methyl ethyl ketone, acetone, ethyl acetate, and alcohol; known carnahawasox, montan wax, paraffin wax, microcrystalline wax, and oxidized Natural or synthetic waxes such as waxes, low molecular weight polyethylene waxes, and low molecular weight polypropylene waxes; spindle oil base oils for various lubricating oils, α-olefin synthetic base oils, etc.; aromatic, naphthenic, and paraffinic process oils; Light oil, hydraulic oil; Plasticizers such as dioctyl phthalate-1 and dibutyl phthalate; Oligomers or high molecular weight polymers, such as vinyl chloride polymers, vinyl chloride resins such as vinyl chloride/vinylidene chloride copolymers; Acetic acid Vinyl ester resins such as vinyl polymers, ethylene/vinyl acetate copolymers, vinyl acetate/methyl methacrylate copolymers; (meth)acrylic ester (co)polymers, (meth)acrylic ester/acrylonitrile copolymers, etc. Polymers, (meth)acrylic ester resins such as (meth)acrylic ester/styrene copolymers; styrene resins such as polystyrene, ABS resins, and AS resins, polyethylene, chlorinated polyethylene, polypropylene, polyisobutylene, polybutadiene , polyisoprene, partially hydrogenated polybutadiene, partially hydrogenated polyisoprene, etc.; general purpose engineering plastics such as polyethylene terephthalate, polycarbonate 1~, polyamide, polyester; cellulose derivatives such as cellulose acetate, nitrocellulose; silicone resins; Acrylic resin; alkyd resin, phenolic resin, epoxy resin, unsaturated polyester resin, polyurethane resin; natural rubber, styrene-butadiene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene diene and 1-riblock Examples include elastomers such as copolymers, acrylonitrile-butadiene copolymers, and partially hydrogenated products thereof, but are not limited to these examples.

(How to use the dispersant) The amount of the dispersant containing the polymer having the oxazine group, oxacilone group, and oxazinium ion of the present invention is as follows:
Although it differs depending on the type of medium in which inorganic and/or organic fine particles (hereinafter referred to as "dispersed material") are dispersed, the content of oh-1-zazine groups, oh-1-resolon groups, oxazinium ions in the dispersant, etc. Usually at least 0.05 parts by weight, preferably from 0.5 to 100 parts by weight of the material to be dispersed.
The amount is 100 parts by weight, more preferably 3 to 50 parts by weight.

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

(2) A method in which a dispersant is added to the medium in advance, and then the material to be dispersed is added.

■ A method in which a dispersant is added to the medium together with the material to be dispersed.

■ After adding the material to be dispersed to the medium, add the dispersant,
How to mix and stir.

(2) A method in which a material to be dispersed whose surface has been previously treated with a dispersant is added to a medium by stirring and mixing at a temperature of 50 to 300°C.

When using a material to be dispersed whose surface has been previously treated with the dispersant of the present invention, in order to achieve the object of the present invention, the amount of surface treatment (adhered amount) of the dispersant to the material to be dispersed, Although it varies depending on the molecular weight of the molecule and the content of the functional group, it is at least 1% by weight, preferably 3% by weight or more.

The method of surface treatment using a dispersant for the object to be dispersed is not particularly limited, but methods include dissolving the dispersant in an inert organic solvent and immersing the object to be dispersed in this solution, or using a solution of the dispersant or an inert solution such as water. Examples include a method of applying a suspension using a medium to the object to be dispersed, a method of triblending, and the like.

In order to produce a dispersion in which the dispersant is uniformly dispersed in the polymer using the dispersant of the present invention and the surface-treated dispersant, it is necessary to sufficiently mix the polymer and the N+ material to be dispersed. is necessary. Preferred mixing conditions depend on the type of polymer, whether it is thermoplastic or thermoset, its chemical structure, etc.

Alternatively, the dispersant and the material to be dispersed may be subjected to a surface treatment using a conventional kneading machine such as a Henschel mixer, a Boppart mixer, a Banbury mixer 1 double concentric screw, etc. May be mixed with polymers.

Polymer processing, such as high shear mixing, is generally carried out at temperatures well above the second order transition temperature of the polymer, preferably at temperatures at which the polymer has a low melt viscosity. For example, low density polyethylene has a temperature range of 170-230°C, high-density polystyrene has a temperature range of 200-250°C, polystyrene has a temperature range of 230-260°C and polypropylene has a temperature range of 230-270°C.
C, epoxy resin is 120-150°C, nylon 6 is 244-292°C, ABS resin (medium impact resistance) is 244-292°C, polycarbonate is 267°C.
~361°C, and polybutylene terephthalate is 2
Processes best at 60°C.

Regarding the temperature conditions for mixing the other polymer and the material to be dispersed, mixing devices of a type well known to those skilled in the art may be used, such as a two-roll mill or a Waring blender.

(Effects of the Invention) The dispersant of the present invention facilitates uniform dispersion of various inorganic and/or organic fine particles (substances to be dispersed) in a medium, and has a dispersion stabilizing function of preventing re-agglomeration.

Furthermore, since the increase in the viscosity of the system to which the dispersed material is added is suppressed, the processability and transportability of the mixture or the filling properties of the dispersed material are improved.

Examples of the dispersant of the present invention include bonded magnets, magnetic recording media (toner for electrostatic image development, disks, tapes), magnetic materials such as magnetic fluids, EMI-compatible paints and molded products, thermal transfer inks, conductive inks, etc. ink; conductive and electrostatic composite materials; flame-retardant materials for electric wires and building materials; anti-reflection materials (bank light materials), antifriction materials for laminated heat sinks, FRP and FRTP materials; dispersion and dispersion of pigments, dyes, catalysts, etc. Stabilizer: Suitable for use as a dispersant (sludge dispersant or cleaning dispersant) with lubricating oils and heavy oils.

〔Example〕

The present invention will be described in more detail below with reference to Examples, Synthesis Examples, and Comparative Examples, but the present invention is not limited to these Examples.

Note that parts and percentages in Examples, Comparative Examples, and Reference Examples are based on weight unless otherwise specified.

Synthesis Example 1 3 parts of vinyloxazine and 9 parts of styrene were placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer.
250 parts of toluene in which 7 parts were dissolved was charged. Furthermore, 10 parts of hensin ruber oxide was added. It was heated to 80 to 100° C. while blowing nitrogen gas, and polymerized in this state for 5 hours while stirring. After returning to room temperature and removing the solvent by evaporation, the mixture was poured into 500 parts of methanol, solidified, and dried to obtain a polymer having an oxazine group as a functional group. This polymer was designated as Dispersant A.

Synthesis Example 2 In Synthesis Example 1, the polymerizable monomer used was styrene 98
The same method as in Synthesis Example 1 was repeated except that 1 part and 2 parts of isopropenyloxacylone were used to obtain a polymer having an oxacylone group as a functional group.

This polymer was designated as Dispersant B.

Synthesis Example 3 In Synthesis Example 1, the polymerizable monomer used was styrene 70
A polymer having an oxazinium ion structure as a functional group was obtained by repeating the same method as Synthesis 1 except that 25 parts of stearyl methacrylate and 1 to 5 parts of N-methylisobropenyloxazinium 1-silane were used. This polymer was designated as Dispersant C.

Synthesis Example 4 Styrene-vinyloxazine copolymer 1 obtained in Synthesis Example 1
00 parts was dissolved in 300 parts of benzene, and methyl chloride was dissolved in 5 parts of methyl chloride.
1 part and 1 part of sodium iodide were added, and the mixture was reacted under reflux for 12 hours. The obtained reaction solution was poured into 1,000 parts of methanol, reprecipitated, and then dried. A portion of the obtained polymer was dissolved in chloroform, and the UV-visible spectrum of the polymer component was measured using GPC connected to a UV-visible multi-wavelength spectrometer (MULTI-330 manufactured by JASCO Corporation).
An absorption attributed to oxazinium of max = 310 parts m was obtained. It was confirmed that the obtained polymer contained an oxazinium ion structure. This polymer was used as a dispersant.

Example 1 This example shows the effect of the dispersant of the present invention on inhibiting aggregation of various inorganic and organic fine particles dispersed in toluene.

The experiment was conducted using the ratio of the average particle size when dispersed under ultrasonic operation (median diameter D50: particle size relative to 50% of the cumulative distribution of particle sizes) and the average particle size 10 minutes after the ultrasonic wave was stopped. The dispersion effect of the compound was measured. The average particle size was measured using a laser diffraction granulometer (SK L manufactured by Seishin Enterprise Co., Ltd.).
ASERMICRON SIZER PRO-700O3)
This was done using

The conditions for measuring particle size are as follows.

Amount of inorganic and organic fine particles: 50 to 100 ■ Amount of toluene: 300 ml Ratio of particle sizes 0 minutes and 10 minutes after stopping ultrasonication (050 (10) 1050 (
0) ) was taken as the degree of aggregation. Table 1 shows the measurement results for various particles. The amount of dispersant added is expressed as a weight fraction of fine particles.

The results in Table 1 clearly show that the dispersant of the present invention prevents agglomeration of inorganic and organic fine particles and has the effect of stabilizing dispersion.

Example 2 The viscosity of calcium carbonate (NS#100, manufactured by Nitto Funka Co., Ltd.) dispersed in a liquid epoxy resin (Epimart 828, manufactured by Shell Chemical Co., Ltd.) was measured using a B-type viscometer. The results are shown in Table 2.

Table 2 Addition of dispersant resulted in approximately 50% to 60% viscosity reduction of calcium carbonate dispersion in liquid epoxy resin.

Example 3 100 μm of various inorganic fine particles and 20 μm of benzene were placed in a stoppered test tube, and a predetermined amount of Hensen's solution of the dispersant was added thereto. After shaking the test tube vigorously for 1 minute, the test tube was allowed to stand still and the degree of sedimentation of the fine particles was observed.

◎ No sedimentation even after 1000 minutes 0 No settling even after 300 minutes × Sediments within 3 minutes From this experiment, The dispersant causes agglomeration of inorganic fine particles, Shen It can be seen that it has the effect of preventing rain.

Claims (4)

[Claims] (1) Particulate matter in a medium containing a polymer of a polymerizable monomer having a functional group selected from an oxazine group, an oxazolone group, an oxazinium ion-containing group, and an oxazolonium ion-containing group. A dispersant for dispersing. (2) The dispersant according to claim 1, wherein the polymer is a copolymer of the monomer and a monomer copolymerizable with the monomer. (3) A particulate material surface-treated with the dispersant according to claims (1) and (2). (4) A method for using a dispersant, which comprises mixing particulate matter in a medium in the presence of the dispersant according to claims (1) and (2).