JPS63110220A - Dispersible high polymer particle - Google Patents

Abstract

PURPOSE:To obtain the titled particles, having excellent water dispersibility and suitable as cosmetics, coating materials, etc., by ionic adsorption of a chain organic compound containing sulfone group or carboxyl group onto high polymer particles having amino groups on the surface thereof. CONSTITUTION:Particles obtained by precipitation polymerization of an uncured epoxy compound, e.g. glycidyl ether of bisphenol A etc., and an amine based curing agent, e.g. piperazine, etc., in a stationary state to give high polymer particles having amino groups on the surface as well as preferably 0.1-1,000mum average particle diameter and subjecting the resulting high polymer particles to adsorption treatment in, e.g. an aqueous solution, of a chain organic compound obtained by sulfonating or carboxylating one terminal of polyoxyethylene having >=300 molecular weight and containing the component (B) in an amount of preferably >=0.5wt% adsorbed on the particles of the component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polymer particles suitable for use as a compounding agent for cosmetics, coatings, and inks.

[Prior Art] The present inventor has already disclosed Japanese Patent Application Laid-open No. 59-170114, Japanese Patent Application Laid-Open No. 60-156717, and Japanese Patent Application Laid-open No. 60-163.
In Japanese Patent No. 916, a technique was proposed in which spherical fine particles were created by adding a specific amino curing agent to an emulsion of uncured epoxy resin.

In addition, the present inventor has disclosed a technique in JP-A-61-166827 in which a compound having an anionic group is absorbed into epoxy particles cured with an amino curing agent to impart ultraviolet absorption ability to the particles. proposed.

Also, YU-HUI HUANG et al. ,+,pol
y+n.

Sci: Polym Chem, Edi, Vo
1, 23.795 (1985), H2N < ch2
He has published research on improving the stability of latex by covalently bonding Ct-t2>, +-+ under an alkali catalyst.

[Problems to be solved by the invention] However, since particles having at least an amino group on their surface generally have both hydrophilicity and hydrophobicity to some extent, their dispersibility in water is also poor in highly hydrophobic dispersion media such as hydrocarbons. There was also a problem that the dispersibility was not always good.

Further, even when a compound having an anionic group is adsorbed onto particles cured with an amino-based curing agent, there is a problem in that the dispersibility of the particles is not satisfactory.

The present invention aims to solve the drawbacks of such prior art, and by adsorbing a highly hydrophilic or highly hydrophobic chain-like compound onto particles, it becomes water-dispersible or hydrophobic in organic solvents. The purpose of the present invention is to provide polymer particles with improved dispersibility.

Means for Solving Problem L] In order to achieve the above object, the present invention has the following structure.

That is, the present invention is characterized in that a chain organic compound having one or more sulfone groups or carboxyl groups in the molecule is ion-adsorbed in particles made of a polymer having at least 7-mino groups on the surface. The present invention relates to dispersible polymer particles. Examples of the polymer having at least an amino group on the surface used in the present invention include epoxy resin powder cured with at least an amino curing agent, and acrylic resin having an amino group such as 2-aminoethyl (meth)acrylate. At least one of the copolymerization components is acrylic resin powder, chitozan powder, etc., and these are used in spherical or amorphous shapes.

Regarding the amount of amino groups present on the surface, it is preferable that the polymer chains near the surface contain 1 mol % or more, more preferably 5 mol % or more of the amino group-containing polymer (or curing agent).

In the present invention, although there are no particular limitations on the components, epoxy resin particles will be mainly described as one of the components that can easily embody the invention.

The epoxy compounds that can be used in the present invention are preferably those containing two or more epoxy groups in the molecule.

Examples include bisphenol A-type glycidyl ethers, diglycidyl ethers of polyethylene glycol, polyglycidyl ethers of phenol novolac-type compounds, N,N,N'', N-tetraglycidyl m-xylene diamino, etc. They can be used alone or in combination.

Furthermore, if necessary, it is possible to add a small amount of a compound having one epoxy group in the molecule, such as glycidyl methacrylate-1-. Also used in the present invention is a modified epoxy compound in which a part of the epoxy group is bonded to a compound such as a 7-mino group.

A method for obtaining epoxy resin particles having at least an amino group on the surface of the present invention from the above-mentioned epoxy compound will be described below.

An uncured epoxy compound that is solid at room temperature (= near I, or [
Mechanically crushed particles of an epoxy compound that have been partially or fully cured with an amino-based curing agent are spheroidized by a method such as gravity falling in a heating cylinder, and then hardened by a method such as contact with an amino-based curing agent. There is a way to complete this (method 1).

Another method is to suspend an uncured epoxy compound in an aqueous Pi body and then cure it (referred to as the second method).

Another method is to carry out stationary precipitation polymerization of an uncured epoxy compound and an amino curing agent in a liquid polyol (referred to as the third method).

In the present invention, the above-mentioned first to third methods are not particularly limited, but the second method and the third method are particularly preferred from the viewpoint of particle uniformity, nacreousness, etc. Among these, the second method, particularly the method using an emulsion using a surfactant, is preferable in terms of productivity.

In the first method, the above-mentioned epoxy compounds that are solid at around room temperature are mechanically pulverized or partially or completely cured with a curing agent containing at least an amino curing agent such as piperazine or metaxylylene diamino. It is prepared by mechanically crushing a solid resinous material at around room temperature. These particles are then heated to an internal temperature of approximately 60-400'
It can be made into spheres by charging it from the top of the heating cylinder C and letting it fall by gravity. Particles can be immersed in an aqueous solution of an amino-based curing agent such as piperazine, edgelene diamino or metaxylylene diamino or an organic solvent solution such as dioxane, or mixed directly with the curing agent and further heated if necessary. This allows the amino curing agent to be introduced into the particles and hardened roughly.

In these curing reactions, a curing agent other than the amino curing agent such as phthalic anhydride may coexist.

In the second method, particles of an epoxy compound suspended in an aqueous liquid are cured with a curing agent containing at least an amino curing agent. In this method, the curing agent and curing method are not particularly limited, but (1) a method in which an epoxy compound to which a curing agent has been added in advance is suspended in an aqueous liquid and cured as it is; (2) There is a method of curing by adding a water-soluble amino curing agent to an aqueous suspension of an epoxy compound.

For the former method, ethylene diamino, diethylene triamino, N(2-aminoethyl) piperazine, and the like, which are liquid at room temperature, are particularly suitable as curing agents.

Approximately 0.2 to 1.2 equivalents of these curing agents are added to the epoxy compound to form an aqueous suspension.

Regarding the method of curing an aqueous suspension of an epoxy compound by adding a water-soluble amino curing agent to it (the latter method), the following methods are recommended.

When adding a water-soluble curing agent to an emulsion of an epoxy compound and curing it into particles, mix an equivalent amount of the water-soluble curing agent with the above epoxy compound (not in an emulsion) at room temperature, and leave it for 8 hours before mixing. Shore A hardness of the body is 50
A method of adding 0.3 equivalent or more of this amino compound to the epoxy compound.

The amino curing agent used in the second method generally includes the following compounds, but is not particularly limited thereto. These include piperazine, hydrazine, polyethylene polyaminos such as ethylenediamino, diethylenetriamino, and triethylenetetramine, alcohol aminos such as monoethanolamino, and piperazine (formerly 2-aminoethyl).

In the second method, an aqueous suspension of an epoxy compound with or without a curing agent is prepared, an example of which is given below.

(1) A method in which an epoxy compound containing or not containing a curing agent or its solution is continuously discharged from a nozzle that moves in the air or in a liquid, cutting it into droplets and collecting it in the liquid. .

(2) A method in which an epoxy compound containing or not containing a curing agent or its solution is ejected in pulses from a nozzle in the air or in a liquid, and the epoxy compound or its solution is collected in the liquid.

(3) A method in which a surfactant is mixed and emulsified using a combination of an epoxy compound containing or not containing a hardening agent and water.

(4) A method of emulsifying the object'fI using a combination of an epoxy compound with or without an inhibitor and a hardening agent and water.

(5) A method of converting into 1L using a combination of water containing the protective colloid T1 and an epoxy compound containing or not containing a curing agent.

Among the above methods, methods (3) to (5) are preferably used in the present invention from the viewpoint of productivity, but a combination of methods (1> to (5)) is also preferably used in the present invention.

When using a surfactant, the HL B value is 12
Good results are often obtained when the above compounds are used in an amount of 3% or more based on the epoxy compound. If the surfactant does not satisfy this range, it tends not to be cured into particles.

In general, the types of surfactants preferably used in the second method include polyoxynyletine/phenol-substituted ether type, polyoxyethylene/polyoxypropylene block,
Examples include ether type nonionic surfactants such as polyether type, and ester type nonionic surfactants such as higher fatty acid esters of polyethylene glycol and fatty acid esters of polyhydric alcohols.

When using a juvenile emulsifier such as crystalline cellulose or barium sulfate, this method is suitable for producing particles with a relatively large average particle size.

In the present invention, instead of a surfactant, a method of emulsifying with a substance exhibiting a protective colloid action such as polyvinyl alcohol, hydroxymethyl cellulose, or sodium alginate is also possible.

When emulsifying an epoxy compound using a surfactant, powder emulsifier, or protective colloid, use an epoxy compound containing them or water and gradually add water to the epoxy compound being stirred at high speed. is common. The concentration of the produced emulsion is usually 10 to 80% by weight.

The general method for adding an amino curing agent to a suspension of an epoxy compound is to add the curing agent directly or in the form of an aqueous solution. The curing agent may be a mixture of other amino-based curing agents or other types of curing agents, but in that case, it is preferable that the specific curing agent satisfies the specific usage conditions mentioned above.

In the second method, (1) if the curing agent is added to the epoxy compound in advance and then made into an aqueous suspension, then (2) if the curing agent is added after the epoxy compound is made into an aqueous suspension; After adding the curing agent, the curing reaction is allowed to occur while standing still or being gently stirred. If you want to obtain a cured state of
There is a way to heat the whole thing.

In the third method, an epoxy compound having two or more epoxy groups and an amino curing agent are dissolved in a polyester polyol or a polyalkylene polyether polyol, and the mixture is subjected to stationary precipitation polymerization.

In the first method and the second method, additives such as pigments may be added to the epoxy compound as a raw material if necessary, and ketones or diluents for the epoxy compound may be used to lower the viscosity. There is no problem even if it contains.

The polymer particles used in the present invention have an average particle diameter of 0°1 to 1
Particularly good results are obtained when the thickness is 0.000 μm, preferably 0.5 to 500 μm. When the average particle diameter is less than 0.1 μm, it becomes difficult to collect the particles, and when it exceeds 1000 μm, it becomes unsuitable for use as a compounding agent in cosmetics, paints, etc. due to the feeling of foreign bodies and sedimentation.

Next, a chain organic compound having a sulfone group or a carboxyl group used to achieve the present invention will be explained.

Examples of hydrophilic chain organic compounds used for the purpose of improving the dispersibility of particles in water include polyoxyalkylene chains in which polyoxyethylene chains, polyoxypropylene chains, etc. are combined as a single component or in blocks. There are sulfonated compounds with ethylene and propylene groups, which often exhibit favorable hydrophilic properties when the alkylene groups are ethylene and propylene groups. Since a polyoxyalkylene chain usually has an OH group at both ends or one end, it can be made into a sulfonated product by converting this part into a sulfuric acid ester. Among these, there are sulfonated particles at both ends and sulfonated particles at one end, but sulfonated particles at one end, which do not cause ionic bonding between particles, tend to have better water dispersibility. Furthermore, some compounds having a polyoxyalkylene chain have one or both ends phenyl etherified or alkyl etherified. Those in which a part of the phenyl group or alkyl group is replaced with a sulfone group or a carboxyl group can also be used in the present invention.

In the present invention, the water dispersibility of the particles tends to be significantly improved when the molecular weight of the polyoxyalkylene chain is 300 or more.

Examples of hydrophobic chain organic compounds used to improve dispersibility in hydrophobic dispersion media such as hydrocarbons include waxy linear hydrocarbons, sulfonated products of linear hydrocarbons such as polyethylene and polypropylene, and There are carboxylated products. Among these, higher fatty acids and sulfuric acid esters of linear hydrocarbons having OH groups are preferably used in the present invention.

In the present invention, the dispersibility of particles in a hydrophobic dispersion medium tends to be significantly improved when the molecular weight of the linear hydrocarbon is 300 or more.

Next, an example of a method for causing the above-mentioned chain organic compound having a sulfone group or a carboxyl group to be ion-adsorbed onto the above-mentioned polymer particles will be explained.

The chain organic compound having a sulfonic group or a carboxyl group may form a salt with sodium chloride, potassium, etc., and any of them can be used. A general method of ion adsorption is to add a compound having one or more sulfone or carboxyl groups and a polyoxyethylene chain to an aqueous dispersion of polymer particles, either directly or in an aqueous solution, to improve the water dispersibility of the particles. and adsorption treatment at room temperature or heating. At this time, if a relatively strong acid such as phosphoric acid, sulfuric acid, or vinegar is allowed to coexist, adsorption often becomes easier.

To improve the dispersibility of particles in a hydrophobic dispersion medium, disperse polymer particles in a dispersion medium such as benzene or toluene,
A compound having a sulfone group or a carboxyl group and a linear hydrocarbon moiety is added directly or as a solution in benzene, toluene, etc., and adsorbed at room temperature or by heating. in this case,
As the epoxy resin particles, it is preferable to use solvent-resistant particles that have been previously treated with a polybasic acid such as phosphoric acid.

The amount of adsorption is generally 0.1% or more based on the particles,
Preferably, when the content is 1% or more, a significant improvement effect on dispersibility tends to be observed.

In the above-mentioned adsorption treatment, if polymer particles are used that ionically adsorb or physically encapsulate pigments such as acid dyes and ultraviolet absorbers, even better particles can be obtained for use in cosmetics and paint formulations. It will be done.

The particles after the above-mentioned ion adsorption treatment for improving dispersibility can be taken out as a dry powder by removing the dispersion medium by means such as filtration and drying.

[Example] (1) Preparation of particles Preparation of epoxy resin particles (Particles 1) Commercially available bisphenol A diglycidyl ether type epoxy resin (Epicote 828, manufactured by Yuka Shell Epoxy) 10 (
7 in a 100 cc polycup, and add Neugen EA-137 (manufactured by Dai-Kogyo Co., Ltd.), which is a commercially available polyoxyethylene/phenol replacement ether surfactant with an HLB of 13.
l! l! ′! O, sg of A) was added. The mixture was kneaded for 1 minute at 80 rpm using a stirring rod equipped with a Teflon plate blade at the tip. Subsequently, 1.5 cc of water in a syringe was sequentially added at 1 minute intervals while stirring at ao-o-rpm.

1q of milky white emulsion was placed in the polycup.

A curing solution prepared by dissolving 0.6 equivalents of piperazine in Bcc water was added to this uncured epoxy emulsion and homogenized by gentle stirring.

This liquid was allowed to stand at 25°C for 5 days to harden into spherical particles with an average particle diameter of about 6 μm.

The cured particles were separated by suction filtration using filter paper, and after washing, the particles were redispersed in water to obtain a dispersion containing 10% by weight of particles.

Preparation of epoxy resin particles (particles 2) Epicote 8
28.40Q was placed in a 300 cc polycup, 6 g of the surfactant Neugen EA-137 was added thereto, and 24 cc of water was added in four portions in the same manner as in Particle No. 1 to prepare an uncured epoxy emulsion. Add 1.5 equivalents of hydrated hydrazine dissolved in 30Q water, and add 1.5 equivalents of hydrated hydrazine dissolved in 30Q water,
17 for spherical particles with an average particle diameter of 1.5 μm after being left to stand for 0 days.

After filtration and washing, the hardened particles were redispersed in water at 400C.

Preparation of epoxy resin particles (particles 3) Epicote 8
28 and an equivalent amount of N(2-aminoethyl)piperazine were mixed and the epoxy resin cured at 100'C for 14 hours was crushed to obtain amorphous particles with an average particle diameter of about 1 μm as measured by an image analyzer. Ta.

Preparation of Acrylic Resin Particles (Particle No. 4) Methyl methacrylate and 2-dimethylaminoethyl methacrylate were polymerized in dimethyl sulfoxide using azohisisobutyronitrile as a polymerization initiator. Elemental analysis of the resulting polymer recovered by reprecipitation in water revealed that the polymerization ratio of methyl methacrylate and 2-dimethylaminoethyl methacrylate was approximately 84:16.

The polymer was dried, freeze-pulverized, and further classified to obtain a powder having an average particle diameter of approximately 26 μm as measured by an image analyzer.

(2) Synthesis of a compound to be adsorbed onto particles Synthesis of a compound having a sulfone group and a polyoxyalkylene chain (Synthesis 1) Coniox M-2000 (manufactured by NOF Co., Ltd., molecular weight approx. 2000) IOQ was heated to 50'C, and while stirring, 1Ω of concentrated sulfuric acid was added to carry out a sulfuric acid esterification reaction for 1 hour. The reaction rate was about 50%.

The reaction mixture was diluted with methanol, neutralized with sodium methylate, and precipitated sodium sulfate was temporarily separated.

Remaining methanol in the solution was removed using a rotary evaporator to recover a sulfuric acid ester containing unreacted Uniox M-2000.

This solution was dissolved in water and used for adsorption tests on particles.

Synthesis of a compound with a sulfone group and a polyoxyalkylene chain (synthesis part 2) Coniox M- instead of Uniox M-2000
400 (molecular weight approximately 400>) was used, and was sulfuric acid esterified with a sulfuric acid in almost the same manner as Part 1.

In this case, 2.50% of concentrated sulfuric acid was used for Uniox M-400, 10C]. The reaction rate was about 30%.

Synthesis of a compound having a sulfonic group and a linear hydrocarbon (synthesis part 3) Unilin Alcohol 425 (manufactured by Toyo Ink, molecular weight approximately 425 > 10), a primary alcohol of linear saturated hydrocarbons
g was heated and dissolved at about 95° C., 3 g of concentrated sulfur M was added, and the mixture was reacted for 1 hour to form a sulfuric acid ester. The reaction rate was about 45%.

The reaction mixture was dissolved in toluene and neutralized with sodium methylate. The precipitated sodium sulfate was subjected to r-separation and then used as it was for an adsorption test on particles.

Examples 1 and 2 The particle slurry of (Particles No. 1) and the polyethylene glycol having sulfone groups (Synthesis No. 1) were mixed at room temperature for 30 minutes, and the polyethylene glycol having sulfone groups was adsorbed onto the particles. The particles were then filter-dried and dried at 50°C. The dried particles were redispersed in water, and the particle size distribution was measured using a centrifugal sedimentation type particle size distribution analyzer CAPA-500 (Hitachi-Horiba, Ltd.). Table 1 shows the results. Table 1 shows the relationship between the adsorption rate of polyethylene glycol having a sulfone group and the v1 ratio (vo1%) of particles of 10 μm or more contained in the dispersion.

When no adsorption treatment is performed (Reference example 1) or Uniox M
In Reference Example 2, in which only -2000 was treated with a treatment solution in which particles were dissolved at 10% (in this case, nothing was adsorbed), redispersion was not sufficient and large numbers of aggregates were redispersed. I know what you're doing.

For redispersion, put 0.10 g of dry particles and 14 g of water into a 5 ml glass sample tube containing 5 g of glass beads with a diameter of 2 mm.
This was done by treating it for 10 minutes.

Examples 3 and 4 The sulfonic group-containing polyethylene glycol of (Synthesis Part 2) was adsorbed to the particle slurry of (Particles Part 2) in the same manner as in Example 1, and the results were evaluated in the same manner by redispersing it in water. It is shown in Table 2.

Examples 5 and 6 The sulfonic group-containing polyethylene glycol of (Synthesis Part 1) was adsorbed to the water slurry of the particles of (Particles Part 3) in the same manner as in Example 1, and it was similarly redispersed in water and evaluated in the same manner. The results are shown in Table 3.

Particle 10C was added to the particle slurry prepared in Example 7.8 (Particle No. 1).
4N phosphoric acid was added at a ratio of 1 part to 20 parts, and the mixture was treated at 98°C for 1 hour with stirring. After neutralization; filtration, redispersion in ethyl alcohol and filtration were performed twice to replace ethyl alcohol, and then redispersion in toluene and filtration were performed twice to replace toluene. Finally, it was redispersed in toluene to form a slurry.

To this slurry, add a toluene solution of the compound having a sulfone group and a straight hydrocarbon chain (Synthesis 3), and
The mixture was stirred for a minute to be adsorbed onto the particles.

Table 4 shows the results of evaluating the dispersion of the particles in the same manner as in Example 1 when the particles were filtered and then redispersed in toluene using air or water in the same manner as in Example 1.

Example 9 Polyethylene glycol having a sulfone group (synthesis part) was added to the slurry of particles prepared in (particles part 4) in the same manner as in example 1, dispersed in water, and evaluated in the same manner. It is shown in Table 5.

Table 1 Table 2 Table 3 Table 4 Table 5 [Effects of the Invention] According to the present invention, a highly hydrophilic or highly hydrophobic chain organic compound is applied to polymer particles having at least an amino group on the surface using an ion adsorption method. By adsorption using such a simple method, polymer particles with significantly improved dispersibility in water or hydrophobic organic solvents can be provided.

As a result, the particles of the present invention blended into cosmetics and paints have a good dispersion state, making it possible to produce uniform, high-quality cosmetics and paints.

Claims (3)

[Claims] (1) Highly dispersible particles characterized in that a chain organic compound having one or more sulfone groups or carboxyl groups in the molecule is ion-adsorbed in particles made of a polymer having at least an amino group on the surface. molecular particles. (2) The chain organic compound has a molecular weight of 3 as a chain structure part.
The dispersible polymer particles according to claim (1), having a polyoxyalkylene chain of 00 or more. (3) The chain organic compound has a molecular weight of 3 as a chain structure part.
The dispersible polymer particles according to claim (1), having a hydrocarbon chain of 00 or more.