JPH04209630A - Functional resin microparticle - Google Patents

Abstract

PURPOSE:To obtain the title microparticle having a function of improving the cleanability of a developing solution or a function of giving a coating material for improving hiding power and elasticity by forming a shell substance around the surface of a core substance by a specified process to form ruggedness on the surface of a resin particle. CONSTITUTION:A shell substance [e.g. a urethane resin prepared from a polyisocyanate (Takenate D-102, a product of Takeda Pharm. Ind. Co., Ltd.) and hexamethylenediamine] is formed around a core substance (e.g. a styrene/n- butyl methacrylate copolymer) by interfacial polymerization or in-situ polymerization to form ruggedness on the surface of a resin particle.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention relates to functional resin fine particles that are used in various fields as additives added to plastics, developing side, paints, etc., and as abrasives. be.

[Prior art and its problems] In recent years, efforts have been made to improve the mechanical properties of plastics, improve the cleaning properties of developers without changing their chargeability, and improve the hiding power of paints. Functional resin fine particles have come to be widely used for various purposes such as polishing objects that cannot be polished with conventional polishing agents.

Here, in producing such functional resin fine particles, conventionally, the resin particles are generally produced by granulating them in a wet state by a chemical polymerization method such as a suspension polymerization method, and then drying the granules. That's what I was doing.

However, when producing functional resin particles in this way, only resin particles with a shape close to a perfect sphere can be obtained, and their uses are limited, and resin particles can be used for various purposes in a wide range of fields. There was a problem that it could not be used accordingly.

[Problems to be Solved by the Invention] It is an object of the present invention to solve the problems in functional resin fine particles as described above.

In other words, the present invention is limited to those whose shape is close to a true sphere, like conventional functional resin fine particles produced by chemical polymerization methods such as suspension polymerization, and its applications are limited. It is an object of the present invention to provide functional resin fine particles that can be used in a wide range of fields and for various purposes, with unevenness formed on the surface of the resin fine particles.

[Means and effects for solving the problem] In order to solve the above problems, the present invention provides fine resin particles in which a shell material is provided around a core material by an interfacial polymerization method or an in-situ polymerization method. They developed functional resin particles with irregularities formed on their surfaces.

In producing the functional resin fine particles according to the present invention, the resin monomer constituting the core material, the resin monomer forming the shell material, a polymerization initiator, and other various additives are usually mixed in a suitable solvent. dissolve or disperse;
This solvent is poured into an aqueous solution and stirred at high speed using a mixer or the like to disperse it, thereby granulating it into oil droplets of an appropriate size while preventing the oil droplets from coagulating with each other.

In addition, in order to granulate oil droplets to an appropriate size in this way, the conditions for stirring the above solvent with a mixer etc. are adjusted depending on the use of the functional resin fine particles, and the oil droplets are granulated to an appropriate size. Let it granulate.

After dispersing the solvent in the aqueous solution and granulating it into oil droplets of a desired size, the resin monomer that makes up the core material is polymerized to form the core material, while the shell material is formed. The resin monomer to be
It is polymerized to form a shell material by an itu polymerization method.

According to the experimental knowledge of the present inventors, when functional resin fine particles are produced in this way, interfacial polymerization or in-situ polymerization occurs.
The resin monomer that forms the shell material is polymerized in a short time through u-polymerization, and the shell material is formed first.Then, inside this shell material, the polymerization of the resin monomer that constitutes the core material progresses, and on this resin It is thought that irregularities are formed on the surface of the resin fine particles due to internal contraction due to polymerization of the resin particles.

As mentioned above, the functional resin particles according to the present invention have an irregular shape with irregularities formed on the surface of the resin particles, so by adding a small amount to the developer,
The cleaning performance of the developer can be improved without changing the chargeability of the developer, and when added to the paint, its hiding power and elasticity are improved compared to when resin fine particles with a shape close to a perfect sphere are added. The strength is improved, and when added as a filler to plastics, mechanical properties such as tensile strength and flexural modulus of plastics can be improved.

In addition, by appropriately selecting the resin material that forms the shell material, the hardness of its surface can be controlled, making it possible to apply it to abrasives and the like.

Furthermore, in the functional resin fine particles according to the present invention, resin fine particles having a particle size of 0.5 μm to 1 mm can be obtained by adjusting the conditions for stirring the solvent with a mixer as described above. In particular, when the functional resin fine particles are used as a cleaning aid added to a developer, it is desirable to use particles having a particle size of 0.5 to 2 μm.

Here, in the functional resin fine particles according to the present invention,
Generally, various vinyl resins such as polystyrene resins and poly(meth)acrylic resins, or copolymers and mixtures thereof are used as the resin constituting the core material, and the resin monomers are monomers. Functional and multifunctional monomers can be used.

Here, examples of monofunctional monomers include styrene,
α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, p-n-butylstyrene,
p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p- Styrenic monomers such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, 1so-
Propyl acrylate, n-butyl acrylate, 1s
o-Butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl Acrylic monomers such as acrylate, diethyl phosphate, ethyl acrylate, ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-
Butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate,
Methacrylate monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, Vinyl monomers such as vinyl esters such as vinyl formate, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropyl ketone can be used. .

In addition, examples of polyfunctional monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1.6-
Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate,
2,2'-bis'4-(acryloxy-jethoxy)phenyl]propane, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate,
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,
3-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2″-bis[4-(methacryloxy)
jetoxy)phenyl]propane, 2,2°-bis[4
-(methacryloxy polyethoxy)phenyl]propane, trimethylolpropane trimethacrylate, tetramethylolmethane trimethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, etc. can be used.

In addition, the above monofunctional monomers can be used alone or in combination of two or more, or a monofunctional monomer and a polyfunctional monomer can also be used in combination.

Further, in polymerizing the above monomers, an oil-soluble polymerization initiator that can be dissolved in the above-mentioned solvent is used as a polymerization initiator.

Here, typical examples of this oil-soluble polymerization initiator include 2,2'-azobisisobutyronitrile, 2
．． 2'-azobis-2,4-dimethylvaleronitrile,
2. Azo compounds such as 2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxydicarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide,
Propionyl peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate,
Peroxides such as benzoyl peroxide, t-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, etc. Examples include initiators.

When using these polymerization initiators, if the amount is too small, the polymerization rate will be slow, while if the amount is too large, it will be difficult to control the polymerization. 0.01 for part
~5 parts by weight, preferably 0.5 to 2 parts by weight.

In addition, when performing such a polymerization reaction, usually 5
It is carried out at a temperature of 0 to 95°C, preferably 60 to 85°C. This is because if the temperature of the polymerization reaction is lower than 50"C, the polymerization rate will be slow, but if it is higher than 95"C, the monomer and solvent will evaporate, the outer shell will become porous, and the low molecular weight polymer will This is because the stability over time may deteriorate.

Further, the time for carrying out such a polymerization reaction varies depending on the temperature at which the polymerization reaction is carried out, etc., but generally 4 to 10 hours is sufficient.

On the other hand, as the resin forming the shell material, epoxy resin, urethane resin, urea resin, polystyrene resin, poly(meth)acrylic resin, etc. can be used.

In addition, as the above-mentioned resin material forming the shell substance, urethane resin or urea resin obtained by polymerizing incyanate with amine or polyol is generally used.

The isocyanate used to form the shell material made of urethane resin or urea resin is
For example, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, ethylidene diisocyanate, cyclohexylidene-1 , 2-diisocyanate, cyclohexylidene-1,4-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
2.6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1°4-diisocyanate, diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, triphenylmethane diisocyanate, polymethylene polyphenylisocyanate, 4, 4'-dimethyldiphenylmethane-2,2'
, 5.5'-tetraisocyanate, an adduct of hexamethylene diisocyanate and hexanetriol, 2.
adduct of 4-tolylene diisocyanate and catechol,
Examples include adducts of tolylene diisocyanate and trimethylolpropane, and adducts of xylene diisocyanate and trimethylolpropane, which can be used alone or in combination.

In addition, examples of the polyol to be polymerized with the above-mentioned isocyanate include ethylene glycol, propylene glycol, 1,4-butanediol, catechol, resorcinol, hydroquinone, 1,2-dihydroxy-4-
Methylbenzene, 1,3-dihydroxy-5-methylbenzene, 3,4-dihydroxy-1-methylbenzene,
3,5-dihydroxy-1-methylbenzene, 2,4-
Dihydroxy-1-ethylbenzene, 1,3-naphthalenediol, 1゜5-naphthalenediol, 2,3-naphthalenediol, 2,7-naphthalenediol, 0゜0'-bisphenol, p,p'-bisphenol,
1.1″-bis-2-naphthol, bisphenol A,
Use 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-bentanediol, 1,7-bentanediol, 1,8-octinediol, glycerin, water, etc. I can do it.

In addition, examples of amines to be polymerized with the above isocyanate include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine,
hexamethylenediamine, p-phenylenediamine, m
- Using phenylenediamine, piperazine, 2-methylbiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, amine adducts of epoxy compounds, etc. I can do it.

When interfacially polymerizing the above-mentioned isocyanate with polyol or amine, the temperature is set at 50 to 95°C.
, preferably at 60 to 80°C. This is because if the polymerization temperature is higher than 95°C, the solvent will evaporate and pores will be formed in the shell material formed on the surface of the resin particles, while if it is lower than 50°C, the reaction rate will be slow.
This is because the reaction time is long.

Here, the thickness of the shell material thus formed is usually 0.01 to 0.8 μm, preferably 0.1 to 0.4 μm.
m.

Note that as the amount of the resin monomer that forms the shell material increases, the depth of the unevenness formed on the surface of the resin fine particles becomes shallower. It is preferable to adjust the amount of monomer added.

[Example] Hereinafter, a method for producing functional resin fine particles according to an example of the present invention will be specifically explained, and a comparative example will be given. Reveal that something is different. (In addition,
If there is a result of comparison with that of a comparative example (?), it will be clarified that it is superior to the functional resin fine particles of the comparative example. ) (Example 1) In this example, 70 parts by weight of styrene monomer, 30 parts by weight of n-butyl methacrylate, polyisocyanate (manufactured by Takeda Pharmaceutical Company Ltd.; Takenate D-102)
) and 5 parts by weight of AIBN (azobisisobutyronitrile) were thoroughly mixed with a sand stirrer,
A polymerizable composition was prepared.

Then, this polymerizable composition was poured into an aqueous gum arabic solution with a concentration of 5% by weight, and the mixture was stirred at a rotation speed of 500 using a stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd.; T-Auto Homomixer).
While stirring at 0 rpm, the temperature was maintained at 60 ° C and dispersed for 4 hours, and then an aqueous solution of hexamethylene diamine with a concentration of 10% by weight was added at a ratio of 15 parts by weight to 100 parts by weight of styrene monomer. , temperature 85℃
The polymerization reaction was carried out for 1 hour while stirring at a rotational speed of 3000 rpm.

After the polymerization reaction was completed, the reaction system was cooled and washed with pure water, filtered, and dried to obtain fine resin particles.

After that, the resin particles were classified by air, and the average particle size was 1 μm.
Functional resin fine particles having a particle diameter of m were obtained.

Here, Example 1 obtained in this manner.

When the functional resin particles were observed by SEM, as shown in the photograph of FIG. 1, the resin particles had an irregular shape with irregularities on the surface.

(Example 2) In this example, 70 parts by weight of cyclohexyl methacrylate, 30 parts by weight of diethylene glycol diacrylate, polyisocyanate manufactured by Takeda Pharmaceutical Company Ltd.; Takenate D-102>20 parts by weight, and 3 parts by weight of AIBN. were sufficiently mixed using a sand stirrer to prepare a polymerizable composition.

Then, while using this polymerizable composition, a concentration of 10
% by weight of hexamethylene diamine aqueous solution was added at a ratio of 15 parts by weight to 100 parts by weight of cyclohexyl methacrylate, and other than that, the average particle size was determined in the same manner as in Example 1 above. Functional resin fine particles with a diameter of 1 μm were produced.

Note that, like the functional resin fine particles of Example 1, the functional resin fine particles obtained in this example also had an irregular shape with irregularities on the surface of the resin fine particles.

(Comparative Example 1) In this comparative example, 70 g of styrene and n-
A mixture of 30 g of butyl methacrylate and 2 g of azobisisobutyronitrile was heated to a concentration of 5% by weight under cooling.
were added to an aqueous solution of gum arabic lp, and the homomixer was rotated at a high speed of 9000 rpm to stir these to obtain fine suspended particles.

Next, the temperature was raised to 60'C for 3 hours, and then 90°C.
The temperature was raised to ℃ and suspension polymerization was carried out for 3 hours, and the average particle size was 1μ.
Resin fine particles having a diameter of m were obtained.

The resin fine particles of Comparative Example 1 thus obtained had no irregularities on the surface and had a shape close to a perfect sphere.

(Comparative Example 2) In this comparative example, 70 parts by weight of styrene and 30 parts by weight of diethylene glycol diacrylate were thoroughly mixed using a sand stirrer to prepare a polymerizable composition.

Then, this polymerizable composition was poured into an aqueous solution of gum arabic with a concentration of 3% by weight, and the rotation speed was increased to 5.
While stirring at 000 rpm, the temperature was raised to 60°C and polymerization reaction was carried out for 6 hours, and the temperature was further raised to 85°C to carry out polymerization reaction.

After the polymerization reaction was completed, the reaction system was cooled and washed with water five times.
This was filtered and dried to obtain fine resin particles having an average particle size of 2 μm.

Note that, similarly to the resin fine particles of Comparative Example 1, the resin fine particles of Comparative Example 2 obtained in this manner had no irregularities on the surface and had a shape close to a pearl.

Next, the functional resin fine particles obtained in Example 1 above were
The effect of adding it to a developer as a cleaning aid was investigated.

Here, the toner and carrier in the developer were manufactured as follows.

(Manufacture of toner) Ingredients Weight/
Styrene 70g, n-butyl methacrylate 30g, azobisisobutyronitrile 2g, Nigrosine base-EX 5
g (manufactured by Orient Kagaku Kogyo ■) - Carbon black 7 g (manufactured by Cabot, R-40OR) The above mixture was poured into 1 p of a gum arabic aqueous solution with a concentration of 5% by weight under cooling, and a homomixer was rotated at high speed at 7500 rpm. , these were stirred to obtain suspended particles.

Then, this was heated to 60℃ for 3 hours, and then heated to 90℃ for 3 hours.
Suspension polymerization was carried out for 3 hours at an elevated temperature of °C, and the average particle size was 8.
A black spherical toner with a size of μm was obtained.

(Production of carrier) Ingredients Parts by weight Polyester resin 100 (Softening point 123°C, Glass transition point 65°C, AV23.0HV40) Fe-Zn ferrite fine particles 500MFP-2
(manufactured by TDK) Carbon black 2 (manufactured by Mitsubishi Chemical Industries, MA#8) The above materials were thoroughly mixed and pulverized using a Henschel mixer, and then the cylinder part was heated to 180°C and the cylinder head was heated to 170°C.
Melt and knead using an extrusion kneader set at ℃.

Next, this kneaded material was left to cool, and then coarsely ground using a feather mill, and further finely ground using a jet mill.
The functional resin fine particles obtained in Example 1 were classified using a classifier to obtain a carrier having an average particle size of 60 μm.
It was added at a rate of 0.1% by weight to the above spherical toner having an average particle size of 8 μm, and these were mixed.

Next, the above-mentioned binder-type carrier having an average particle size of 60 μm is mixed with the spherical toner mixed with the resin fine particles at a toner mixing ratio of 6% by weight to form a developer. adjusted.

When this developer was supplied to a commercially available plain paper copying machine (manufactured by Minolta Camera ■, EP-8600) and copies were made, the cleaning defects that occurred when the fine resin particles were not added completely disappeared and the results were good. Images are now available.

[Effects of the Invention] As detailed above, the functional resin fine particles according to the present invention have irregular shapes with irregularities formed on the surface of the resin fine particles. When added in small amounts, it does not change the chargeability of the developer.
The cleaning performance could be improved.

Further, when the functional resin fine particles according to the present invention were added to a paint, the hiding power and elastic force were improved compared to when resin fine particles having a shape close to a perfect sphere were added.

Furthermore, when the functional resin fine particles according to the present invention were added to plastic as a filler, mechanical properties such as tensile strength and flexural modulus of the plastic could be improved.

In addition, the surface hardness of the functional resin fine particles according to the present invention can be controlled by appropriately selecting the resin material forming the shell material, and can be widely applied to abrasives, etc. Ta.

[Brief explanation of the drawing]

FIG. 1 is a photograph showing the state of functional resin fine particles in Example 1 of the present invention.

Claims (1)

[Claims] 1. Functional resin microparticles characterized by having irregularities formed on the surface of resin microparticles, in which a shell material is provided around a core material by an interfacial polymerization method or an in-situ polymerization method.