JPH03212444A - Spherical resin particle and its production - Google Patents

Abstract

PURPOSE:To provide the subject spherical resin particle composed of an ionic group-containing polyester and a polymer containing ionic groups forming an ion-pair with the former ionic group, having a substantially spherical shape and a narrow dispersion range of particle size and suitable for a matting agent, a carrier for chromatography, etc. CONSTITUTION:To a system in which an ionic group (e.g. carboxyl group or sulfonate group)-containing polyester is finely dispersed, a vinyl monomer containing ionic groups forming an ion-pair with the above-mentioned ionic group is added in an amount of 0.8-2.0, preferably 0.85-1.5 equivalent ratio of former/latter ions and the resultant mixture is subjected to polymerization to obtain the objective substantially spherical resin particle having 0.1-100mum average particle size. The particle size of the resultant resin particle can be readily controlled by the equivalent ratio of the ionic groups, polymerization temperature, polymerization time, etc.

Description

Detailed Description of the Invention (Industrial Application! l'l-) The present invention provides polyester resin particles (resin particle group) that are substantially spherical and have a narrow particle size distribution on the micron order.
and its manufacturing method.

(Prior art) In recent years, polymer beads (polymer J'-), matting agents, blocking anti-maturity agents, organic pigments, carriers for chromatography, pharmaceutical phases, powder coatings, thickness and gap adjustment materials, toners. It is widely used as such. The particle size of polymer beads used for such applications is 1.0 to 100μ.
It is required to be spherical and have a narrow particle/size distribution.

Conventionally, known methods for producing such polymer beads include the use of a special suspension stabilizer or the so-called suspension polymerization method in which vinyl monomers are dispersed and polymerized under high-speed stirring.

Furthermore, in recent years, it has become known to make particles larger by impregnating existing fine particles with monomers and polymerizing them. However, all of these are limited to polymers that can be polymerized to vinyl.

(Problems to be Solved by the Invention) However, in the suspension polymerization method, it is necessary to carry out polymerization in a stable suspension system without polymerization, and it is necessary to carry out the polymerization in a stable suspension system without polymerization.
It is technically difficult to obtain particles (particularly 20 μm or smaller) with a certain particle size.

For this reason, poorly soluble inorganic powders such as BaSO4, Mg
CO, talc, viscous l-, water-soluble polymers such as polyvinyl alcohol, gelatin starch, etc. are added to the polymer thread as suspension stabilizers to prevent the coalescence of polymer particles (this is sometimes done, but it is not necessary to do so). 1- The disadvantage is that the particles become smaller or become gelled, making it impossible to obtain particles. Even if gelation can be prevented, the particle size of 4J is broad and a classification operation after polymerization is required. .

In addition, polycondensation resins such as polyesters and polyamides, and polyaddition resins such as polyurethane cannot be formed by suspension polymerization, and condensation polymer powders containing polyester cannot be used. Although it is obtained by pulverizing a polymer, it has an amorphous shape and a broad particle size distribution. Moreover, when the particles become fine, the cost of the pulverization process increases, which is a drawback of the method itself. Therefore,
Although it is possible to dissolve the resin in a solvent and drop the solution into a precipitant to solidify it, it is difficult to form substantially spherical particles in such a one-step process, and the solvent Recovery I-grade is 7 points lower.

(First stage for solving the problem) The L1 object of the present invention is to provide resin particles having a polyester resin as a component which is substantially spherical, has an arbitrary particle size, and has a narrow particle size distribution; An object of the present invention is to provide a manufacturing method. That is, in the present invention, the average grain -r diameter is from 0.1 to
1001i! R, substantially bispherical resin particles, containing an ionic group-containing polyester, and also containing a polymer containing an ionic group that forms a counter ion with the polyester-containing ion, and contains both particles that form a counter ion. Spherical resin particles characterized by an ion equivalent ratio of 0.8 to 2.0.
In addition, in a system in which the ionic group 34'1 polyester is finely dispersed, a vinyl monomer containing an ionic group that forms a pair with the ion is added so that the equivalent ratio of both ions forming the counter ion is 0. This is a method for producing spherical resin particles characterized by adding and polymerizing so that the particle diameter is 8 to 2.0.

The polyester of the present invention is not particularly limited, but polyesters containing a dicarboxylic acid component and a glycol component are preferably used.

Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1.5--)-phthalic acid, p-oxynebenzoic acid, p-(hydroxyethoxy/)benzoic acid, etc. aromatic oxy-7-carboxylic acids, succinic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid,
These include unsaturated aliphatic and ring dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid, and tetrahydrophthalic acid. If necessary, it may contain small amounts of tri- and tetracarboxylic acids such as trimellinotic acid, trimesic acid, and biromellitic acid.

The IJ call component includes, for example, ethylene glycol,
Propylene glycol, 1,3-propanediol, ■
, 4-butanediol, 1,5-bentanediol, 1
, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2.2
．． 4-trimethyl-1,3-bentanediol, 1.4
-7 Clohexanenomethanol, spiroglycol, 1
14-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A
ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, and diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. If necessary, a small amount of triol and tetraol such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol may be included.

Other polyester polyols include lactone-based polyester polyols obtained by ring-opening polymerization of lactones exclusively for ε-caprolactone.

The ionic groups contained in the polyester include anionic groups such as carboxyl groups, sulfonic acid groups, sulfuric acid groups, phosphoric acid groups, or salts thereof, or cationic groups such as primary to tertiary amino groups. , preferably a sulfonic acid metal base.

Sulfonic acid metal base 3 capable of copolymerizing r+J with polyester
(17J Group 8 nocarboxylic acids include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid,
4-sulfonaphthalate-2,7 dicarboxylic acid, 5[4
Metal salts such as -sulfophthalic acid/]isophthalic acid can be mentioned. As a metal salt, Lit Na+ k+
Examples include salts such as Mg+Ca+Cu+Fe.

Particularly preferred is pentasodium sulfoisophthalate. The amount of the aromatic dicarboxylic acid containing a sulfonic acid metal group is not limited as long as the dispersion can be obtained, but it is suitably in the range of approximately 20 to 500 equivalents/10'g.

In the present invention, the polyester can be used in a medium type, or if necessary, can be used in combination, and furthermore, in a molten state,
It can be mixed with amino resins, epoxy resin incyanate compounds, etc. in a solution state, or it can be partially reacted with these compounds, and the resulting partial reaction product can also be used as a raw material for dispersion. It is also possible.

The dispersion containing the ionic group-containing polyester of the present invention as a main component can be produced by any known method. That is, (A) polyester and (B) water-soluble batter compound are mixed in advance at 50 to 200°C, and (C) water is added to this, or a mixture of (A) and (B) is added to water. Manufactured by stirring at 40-120°C.

Alternatively, it can also be produced by adding (A) polyester to a mixed solution of (C) water and (B) water-soluble organic compound, and stirring and dispersing it at 40 to 100°C.

The counterionic group that forms a counterion is an ionic group that is the opposite of the ionic group that is present in polyester (when it is an ionic group or an anionic group, the counterionic group is a cationic group, or a cationic group). When the counterionic group is anionic) A,
) means. Such an ionic group is essential in 1-1 for forming a stable dispersion system of polyester, especially an aqueous dispersion.

The amount of counterionic groups in the polymer obtained by polymerizing a monomer capable of vinyl polymerization is 0.8 to 0.8 to the amount of counterionic groups in polyester to the amount of ionic groups in polyester.
2.0, preferably in the range of 0.85 to 1.5.

If the limit of this range is not reached, coalescence and growth of the fine particles may occur.Also, even if the upper limit is exceeded, it not only does not contribute to the growth of the fine particles, but also causes disadvantages such as low water resistance of the resin particles. Sometimes.

There are no particular restrictions on the polymerization initiator used when polymerizing vinyl monomers; examples include organic peroxides such as benzoyl peroxide and acetyl peroxide; 2.2'-azobisisobutylonitrile; 2+4 7 Azo compound exclusively for methylvaleronitrile; inorganic peroxides such as persulfate, hydrogen peroxide, permanganate; the above inorganic peroxides and sulfites, bisulfites, metasulfites, hydrosulfites,
Examples include water-soluble redox initiators with reducing agents such as thiosulfates, iron salts, and oxalic acid, but water-soluble redox initiators are preferred from safety, 1', and industrial viewpoints. The amount of polymerization initiator used is approximately 0.1 to 0.1 to vinyl monomer.
It is within the range of 3%.

Although it is difficult to define the polymerization temperature unambiguously, polyester fine particles dispersed in a medium, preferably an aqueous medium, are coalesced and grown into a spherical shape as the vinyl monomer is polymerized. It is desirable to adopt a temperature condition of -F below the transition point (Tg); conditions below this temperature tend to produce irregularly shaped particles. In addition, by using a polyester solvent or a plasticizer in combination, the apparent Tg (or minimum film forming temperature) of the polyester can be lowered, and polymerization can be carried out under conditions at or above this temperature. There are no limitations on the types of solvents and plasticizers, and they are appropriately selected from known ones depending on the type of polyester (A) as long as they do not interfere with polymerization.

Other polymerization conditions are carried out according to conventional methods, but the first step of charging vinyl monomer into the dispersion of polyester fine particles and then adding 4 volumes of a polymerization initiator causes rapid coalescence and aggregation of the polyester fine particles. This is preferable because there are no problems with this.

j The dispersion of the ground resin particles is taken out as a dry powder by a conventional method such as filtration, freeze drying, spray drying or the like.

In addition, when the vinyl thread picker is a cationic carbon-containing vinyl monomer (hereinafter referred to as a cationic monomer), for example, 2-aminoethyl (meth)acrylic L'-), 2-N,
N-dimethylaminoethyl (meth)acrylate, 2-
N,N-diethylaminoethyl (meth)acrylate,
2-N,N-dipropylamino(meth)acrylate,
Examples include 2-N, t-butylaminoethyl (meth)acrylate, 2-(4-morpholino)-ethyl (meth)acrylate, 2-vinylpyridine, 4-vinylpyridine, aminostyrene, and anionic groups. Containing vinyl monomers (hereinafter referred to as anionic monomers) include (meth)acrylic acid, itaconic acid, furotic acid, maleic acid,
Seven polymers containing a carboxyl group or a salt thereof such as fumaric acid, styrenesulfonic acid, vinyltoluenesulfonic acid, vinylethylbenzenesulfonic acid, isopropenylbenzenesulfonic acid, 2-chlorostyrenesulfonic acid,
2.4-dichlorostyrenesulfonic acid, 2-methyl-4
- Sulfonic acid groups such as chlorostyrene sulfonic acid, vinyloxybenzenesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, sulfoethyl or sulfopropyl ester of (meth)acrylic acid, 2-acrylamido-2-methylpropanesulfone, or Monomer azidophosphoquine ethyl (meth)acrylate, azidophosphoquine/propyl (meth)acrylate, containing ff salts thereof;
3-chloro-2-azidophosphoquinepropyl methacrylate, bis(meth)acrywaki/ethyl phosphate,
Examples include monomers containing a phosphoric acid group (vinyl phosphate) or a salt thereof.

A combination of a 1- and anionic group-containing 1-polyester and a cationic monomer that achieves the object of the present invention is more desirable. Moreover, there is no problem in appropriately using a known nonionic monomer in combination.

In the present invention, "substantially spherical" means 1 of sphericity as described later.
．． Represents particles close to 0.

In this way, \V average particle diameter [)) is 0.1 to 10
Any size within the range of 0 μm, and 0.
70% or more of 1- particles exist within the range of 5D to 2[],
Polyester resin particles having a narrow diameter distribution can be produced industrially.

The particle size is determined by the ratio of the amount of counterionic groups in the vinyl polymer to the amount of ionic groups in the polyester, the polymerization i'
&1 degree, can be easily controlled by polymerization time, etc.
For example, the size of the resin particles can be increased by increasing the warming within the range of 0.8 to 2.0, increasing the polymerization temperature, and increasing the aging time.

In addition, in consideration of the industrial polymerization conditions of the vinyl monomer, it is preferable that the polyester is within the range of 30 to 90 degrees per 1 g, and from the viewpoint of sphericity of proofreading and shortening of aging time. It is desirable to set the polymerization temperature to Tg+10°C or higher. Thus, if the sphericity of the particles is 0.7 or more,
Resin particles are formed in which - particles account for 70% or more of it on the number average.

(Example) Hereinafter, the present invention will be specifically explained by referring to an example.
The scope of the present invention is not limited by the description of these Examples.

Parts and percentages given in the examples are given on a weight basis unless otherwise specified. The average particle diameter is island/I! The sphericity was measured using an automatic particle size distribution measuring device CAPA700 model manufactured by Seisakusho.The sphericity was measured using an optical microscope, the major axis and the minor axis were measured from the projected diagram of the sphere, and the ratio of the minor axis to the long axis was determined as a true sphere. If it is 1.0, it is a perfect sphere, and if it is 1.0 or more, it is deformed. Further, the amount of %-r was measured using a 115-type molecular spear measuring device manufactured by Ichiri Seisakusho, and the particle size of the dispersion was measured using a grindmeter and an optical microscope.

Polyester.

In an autoclave equipped with a thermometer and a stirrer, 402 parts of dimethyl terephthalate and 40 parts of dimethyl isophthalate were added.
2 parts, 322 parts of Oude Rangelicol, 558 parts of neopentyl glycol, and 0.6 parts of tetrabutquin titanate.
8 parts were charged and heated at 150 to 230°C for 120 minutes to carry out a transesterification reaction. Then ampic acid 7
3 parts and 65 parts of 5-sodium sulfoisophthalic acid were added, and the reaction was further carried out at 220 to 230°C for 1 hour. After raising the temperature of the reaction system to 250°C for 30 minutes, the pressure of the system was gradually reduced to 5 mmHg after 45 minutes, and then lowered to 6 mmHg.
The reaction continued for 0 minutes. The resulting copolymerized polyester had a molecule Ia of 4500 and a Tg of 41° C. The sulfonic acid metal base in the resin was 197 equivalent irt/106 g.

M of the sulfonic acid metal base is sulfur M' in the polyester
It was determined by measurement at 1M degrees.

34 parts of this polyester, 10 parts of butyl cellosolve in 1 part
After dissolving at 00°C, 56 parts of water at 80°C was added to form an aqueous polyester dispersion (A)-I with a particle size of 0.07μ.
I got it.

1,000 parts of water dispersion (A)-I was placed in a distillation flask, distilled until the distillate temperature reached 100°C, cooled, and 250 parts of deionized water was added to obtain a water dispersion (A)-I that does not contain butyl cellosolve. A) −■ was obtained.

In an autoclave equipped with a thermometer and a stirrer, 564 parts of dimethyl terephthalate and 57 parts of dimethyl isophthalate were added.
0 parts, ethylene glycol 534 parts, neopentyl glycol 480 parts, and tetrabutquinol titanium) 0.6
il was charged and heated at 120 to 230°C for 120 minutes to carry out a transesterification reaction.

Then, 5-natriuno, sulfoisophthalic acid 40.2
The reaction was continued at 220-230°C for an additional 60 minutes.

After heating the reaction system to 250°C for 30 minutes,
The polycondensation reaction was carried out at 00 to 260° C. and 10 to 0.1 degrees of Hg for 60 minutes. The resulting copolymerized polyester had a molecular weight of 15,000, a Tg of 59°C, and a metal sulfonic acid base in the resin of 121 equivalents (l5) of 101'g.

34 parts of this polyester, 10 parts of butyl cellosolve in 1 part
After dissolving at 00°C, 56 parts of water at 80°C was added to prepare an aqueous polyester dispersion (B)-I with a particle size of 0.9tt.
I got it.

Put 1000 parts of water dispersion (B)-I into a distillation flask, distill until the distillation temperature reaches 100°C, cool it, and add 250 parts of deionized water to obtain an aqueous dispersion that does not contain butyl cellosolve. (B)-■ was obtained.

1 of polyester, equipped with a meter, a condenser, and a stirring blade.
In a Q separable flask, 834 aqueous dispersions, 35ffiζ of deionized water, and the cationic monomers shown in Table 1 (
B) was added, and the temperature was raised to the temperature shown in Table 1.

Next, 0.2 g of ammonium persulfate (aqueous I&L containing <
The OO part was added dropwise over a period of 40 minutes and then kept at that temperature for the aging time shown in Table 1.

Next, the dispersion was filtered and vacuum dried to obtain polyester resin particles.

The evaluation results of particle shape, particle diameter, etc. are shown in Table 1.

Table 1 shows that by controlling the equivalent weight of the cationic group, the polymerization temperature, and the aging time, resin particles that are spherical, have a narrow particle shape distribution, and have an arbitrary average particle size can be obtained.

Margins below (Effects of the Invention) According to the present invention, it is presumed that polyester fine particles stabilized by ionic groups are associated, coalesced, and spheroidized via a vinyl polymer having a counterionic group.

In this way, we were able to independently provide polyester resin particles whose average particle diameter was controlled to any size within the range of 0.1 to 100μ, were substantially spherical, and had a narrow particle size distribution. This is a noteworthy effect of the present invention.

Claims (2)

[Claims] (1) Substantially spherical resin particles having an average particle diameter of 0.1 to 100 μm, containing an ionic group-containing polyester, and containing an ionic group that forms a counter ion with the polyester-containing ions. Spherical particles that also contain a polymer and have an equivalent ratio of both counterions of 0.8 to 2.0. (2) In a system in which the ionic group-containing polyester is microdispersed, a vinyl monomer containing an ionic group that pairs with the ion is added so that the equivalent ratio of both ions forming the counter ion is 0.8 to 2. A method for producing spherical resin particles, characterized by adding and polymerizing the particles so that the particle size is .0.