JP2005298541A - Fluoroalkyl group-containing polymer particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluoroalkyl group-containing polymer particle having a narrow particle size distribution and a water-repellent, oil-repellent surface, and a method for simply and inexpensively manufacturing the polymer particle. <P>SOLUTION: The polymer particle is obtained by polymerizing a monomer component containing a fluoroalkyl group-containing vinyl monomer whose content is at least 20 wt% based on the total amount of monomers bearing one polymerizable group. The manufacturing method thereof and a gelatinizing agent for a fluorine oil comprising the polymer particle are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to fluoroalkyl group-containing polymer particles having water and oil repellency, excellent monodispersibility, and useful for cosmetics, information materials, paints, lubricants, and the like, a production method thereof, and uses.

  Conventionally, polymer particles having a water- and oil-repellent surface have been synthesized by suspension polymerization. The particle size distribution of the particles obtained by the suspension polymerization method was wide, and the skin feel was not so good when used in cosmetics. Moreover, when the ratio of the vinyl monomer which has a fluoroalkyl group is high, there was no dispersing agent suitable for a suspension polymerization method, and it was difficult to synthesize particles.

Examples of a method for producing fluoroalkyl group-containing polymer particles using a dispersion polymerization method include methods described in Patent Document 1, Patent Document 2, Patent Document 3, and the like. However, the copolymerization ratio of the vinyl monomer having a fluoroalkyl group described in these patent documents is at most about 10% by weight, and it has not been possible to produce particles rich in a fluoroalkyl group.
Japanese Patent No. 2615252 Japanese Patent No. 2726333 JP 05-27476 A

  An object of the present invention is to provide fluoroalkyl group-containing polymer particles having a water / oil repellent surface, and to provide a method for producing such polymer particles simply and inexpensively.

  The present invention polymerizes a monomer component containing a vinyl monomer having a fluoroalkyl group (hereinafter referred to as a fluoroalkyl group-containing monomer) and having a content of 20% by weight or more based on the total amount of monomers having one polymerizable group. Polymer particles obtained by the method, a production method thereof, and a fluorine oil gelling agent comprising the polymer particles.

  The particles described in Patent Documents 1 and 2 have a low ratio of the fluoroalkyl group-containing monomer and are copolymerized with 50% by weight or more of a monomer having a hydrophilic group, whereas it is difficult to say that the particles are water-repellent particles. These fluoroalkyl group-containing polymer particles are excellent in water and oil repellency. Furthermore, while the particles described in Patent Document 3 are mainly composed of styrene and short-chain alkyl (meth) acrylates and have a high refractive index, the fluoroalkyl group-containing polymer particles of the present invention are fluoroalkyls. It is a low refractive index particle having a high content of group-containing monomers, and is useful in cosmetics such as foundations when controlling optical properties (refractive index). Further, the fluoroalkyl group-containing polymer particles of the present invention enable gelation of fluorine oil such as perfluoropolyether, which has been impossible with conventional particles.

[Monomer component]
The fluoroalkyl group-containing monomer used in the present invention may have any structure as long as it has one radical polymerizable group and further has at least one fluoroalkyl group.

  In the present invention, the fluoroalkyl group is a group in which at least one of the hydrogen atoms of the alkyl group is substituted with a fluorine atom, preferably a fluoroalkyl group having 1 to 30 carbon atoms, and fluoro having 1 to 15 carbon atoms. An alkyl group is more preferable, and a C1-C15 fluoroalkyl group having a perfluoroalkyl group at the terminal is particularly preferable.

  The fluoroalkyl group-containing monomer preferably has a fluorine atom weight ratio of 35% by weight or more based on the molecular weight of the monomer, and more preferably has a structure represented by the formula (V).

AB (V)
(In the formula, A represents a radical polymerizable group, and B represents a fluoroalkyl group.)
In the formula (V), A includes groups represented by the general formula (VI), (VII), (VIII) or (IX), and B includes the general formula (X), (XI), And a group represented by (XII), (XIII) or (XIV).

(In the formula, R ¹ .R ⁴ represents a hydrogen atom or a methyl group .p represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is a number of 1-6.)

(Wherein, q ₁ is a number of 1 to 15, q ₂ is a number of 1 to 13.)
More preferred as the fluoroalkyl group-containing monomer is a (meth) acrylate represented by the formula (I).

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 4 carbon atoms or — (CH ₂ ) _n N (R ³ ) SO ₂ — (R ³ represents 1 to 4 carbon atoms). An alkyl group or a hydrogen atom, and n represents an integer of 1 to 4.) Rf represents a C 1-15 fluoroalkyl group having a perfluoroalkyl group at the terminal.
As the (meth) acrylate represented by the formula (I), compounds represented by the following formulas (II) to (IV) are preferable.

(Wherein, the number of .m ₁ is 4, 6, 8 or 10 R ¹ is showing a hydrogen atom or a methyl radical, the number of m ₂ is 1 or 2, m ₃ is an number of 2, 4, 6 or 8 Show.)
In the present invention, in addition to the fluoroalkyl group-containing monomer, a monomer copolymerizable therewith can be used. As such a monomer, a normal radical polymerizable vinyl monomer having one polymerizable group is preferably used, and specifically, styrene, an alkyl (meth) acrylate having 1 to 22 carbon atoms, (meth) acrylonitrile, acrylamide. , Vinyl acetate, vinyl pyrrolidone and the like. In addition, α, β-unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and itaconic acid, maleic anhydride, chloroform are used for the purpose of controlling the surface characteristics of the particles to be generated and imparting reactivity. Monomers such as methylstyrene, glycidyl (meth) acrylate, (meth) acryloyloxyethyl isocyanate, 3- (trimethoxysilyl) propyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyridine Can also be copolymerized. These can be copolymerized singly or in combination of two or more.

  In the present invention, the proportion of the fluoroalkyl group-containing monomer is 20% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more based on the total amount of the monomer having one polymerizable group.

[Production method of polymer particles]
The polymer particles of the present invention can be produced by subjecting the monomer component to dispersion polymerization in a solvent in the presence of a polymerization initiator.

  The preferred monomer concentration in the production method of the present invention is preferably 1 to 50% by weight in the reaction system in order not to cause problems such as polymerization delay, dispersion instability, expansion of particle size distribution, runaway polymerization reaction, etc. 2 to 30% by weight is more preferable. The monomer concentration is also a factor for changing the particle diameter, and generally the higher the particle diameter, the larger the particle diameter.

  The monomer is used by mixing the entire amount of the monomer to be used or a part thereof with other components in advance. For example, when obtaining a highly concentrated dispersion, the monomer is continuously fed into the reaction system. Polymerization can be performed. Usually, since a monomer is a good solvent for a polymer to be produced, it often causes aggregation when supplied as it is without being diluted. In such a case, the monomer is supplied after being diluted with a solvent. As a special embodiment, dispersion polymerization can be carried out under reflux of the solvent, and the monomer can be diluted with the condensate and supplied.

  The concentration of the monomer to be supplied is preferably 50% by weight or less, more preferably 30% by weight or less. In order to obtain polymer particles having a narrow particle size distribution, the monomer concentration in the reaction system is 30% by weight or less, preferably 20% by weight or less, and control is performed so that the monomer concentration does not change as rapidly as possible. desirable. In ordinary dispersion polymerization, the polymerization rate increases in proportion to the weight of the already produced polymer particles, so that it is desirable to supply the monomer relatively slowly in the initial stage and faster in the latter half.

  In the present invention, a crosslinking agent can be further used. The cross-linking agent used is a bifunctional cross-linking agent such as divinyl divinylbenzene, di (meth) acrylate ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, or trimethylolpropane tri (meth) acrylate. And polyfunctional crosslinking agents such as tetramethylolmethane tetra (meth) acrylate. Among these, preferred crosslinking agents are divinylbenzene and ethylene glycol di (meth) acrylate.

  The amount of the crosslinking agent is preferably 0 to 50 parts by weight based on 100 parts by weight of the total of monomers having one polymerizable group. When the crosslinking agent is 1 part by weight or more, the solvent-soluble content of the polymer particles decreases, and when it is 10 parts by weight or less, the particles are less likely to be deformed or aggregated.

  The cross-linking agent is added at the start of the reaction and during the reaction in which the polymerization rate of the monomer is 10 to 100%. It is preferable to add continuously. At that time, it is more preferable to dilute with a solvent. When dispersion polymerization is performed under reflux of the solvent, the crosslinking agent can be diluted with the condensate and added.

  The dispersant used in the dispersion polymerization of the present invention is preferably a polysiloxane compound because polymer particles having good monodispersibility can be obtained. Particularly, amino-modified silicone, polyether-modified silicone, aminopolyether-modified silicone, one terminal A polysiloxane compound having a radical polymerizable group is preferred. The compound represented by general formula (XV) is illustrated as a polysiloxane compound which has a radically polymerizable group at one terminal.

[Where:
X: A group represented by CH ₂ ═C (R ¹ ) COO—, CH ₂ ═C (R ¹ ) CONR ⁵ — or CH ₂ ═CH—C ₆ H ₄ —. However, R ¹ = H or CH ₃ , R ⁵ = H or C _b H _{2b + 1} (b = 1 to 4 integer)
Y: A group represented by — (CH ₂ O) _c —C _d H _2d — (c = 0 or 1, d = 1 to 10).
Z: represents a group represented by C _e H _{2e + 1} (e = 1 to 4).
a: Number from 3 to 1500. ]
Among these, a polysiloxane compound represented by the general formula (XVI) is particularly preferable.

[Wherein R ¹ , Y and a have the above-mentioned meanings. R ⁶ represents an alkyl group having 1 to 4 carbon atoms. ]
Such a polysiloxane compound having a radical polymerizable group at one end can be synthesized, for example, by a method using anion living polymerization.

  The number average molecular weight (Mn) of the polysiloxane compound having a radical polymerizable group at one end used in the present invention is 500 to 100, from the viewpoint of dispersion stability of the polymer particles to be produced and operability at the time of production of the polymer particles. 000 is preferable, and 1,000 to 50,000 is more preferable.

  In the present invention, the amount of the dispersant used is appropriately selected depending on the stability of the system and the properties (particle size, surface properties, etc.) required for the particles to be produced. 0.1 to 20% by weight is preferred.

  The solvent used in the present invention is not particularly limited as long as it dissolves the dispersant and the monomer and does not dissolve the produced polymer, but a non-aqueous solvent is preferable. More preferably, it is at least one selected from the group consisting of hydrocarbon solvents and silicone solvents. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as hexane, heptane, dodecane, cyclohexane, methylcyclohexane, isooctane, hydrogenated triisobutylene, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Examples of the solvent include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane and the like. Of these, hexane is particularly preferred.

  The type of solvent is an important factor that affects the size and dispersion stability of the particles produced. In general, the higher the affinity with the polymer produced, the larger particles tend to be formed.

  Examples of the polymerization initiator in the present invention include peroxide initiators such as lauroyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, diisopropyl peroxydicarbonate, azobis (isobutyronitrile), azobis (2, An azo initiator such as 4-dimethylvaleronitrile), azobis (dimethylisobutyrate), azobis (cyclohexanecarbonitrile) is preferably used.

  In general, in dispersion polymerization, it is known that a peroxide-based initiator generates a graft polymer by the action of extracting hydrogen from the dispersant, thereby improving dispersion stability. However, when a polysiloxane compound is used as a dispersant and dispersion polymerization is performed in a hydrocarbon solvent and / or a silicone solvent, dispersion can be stably maintained even in an azo initiator.

  The amount of the polymerization initiator used is preferably 0.03 to 3 mol%, more preferably 0.1 to 1 mol%, based on the monomer.

  The polymerization initiator is used by mixing and dissolving with other components in advance, but for the purpose of reducing the residual monomer, it can be diluted in a solvent or the like during the polymerization and added all at once or continuously.

  In the present invention, a chain transfer agent may be used for the purpose of controlling the molecular weight or particle size. Specific examples of such chain transfer agents include mercaptans such as butyl mercaptan, mercaptoethanol, thioglycolic acid, dodecanethiol, mercapto-modified silicone, carbon tetrachloride, carbon tetrabromide, dimethylaniline, cumene, α-methylstyrene dimer, etc. Is mentioned.

  In the present invention, the polymerization temperature is selected depending on the decomposition rate of the polymerization initiator, the affinity between the monomer and the solvent, and is preferably room temperature to 150 ° C, more preferably 50 to 120 ° C. Performing the reaction under reflux of the solvent is advantageous in that temperature control and removal of heat of polymerization can be easily performed. The polymerization time is appropriately selected depending on the half-life of the polymerization initiator and the reactivity of the monomer, but is preferably 2 hours to 48 hours.

  In dispersion polymerization, the polymerization inhibitor contained in the monomer and the residual amount of oxygen may greatly change the particle size of the generated particles, so the amount of these polymerization inhibition (retardation) factors is higher than when performing normal radical polymerization. It is desirable to control.

  The stirring conditions are preferably such that the dispersion tends to be unstable even if it is too fast or too slow, and the entire system is mixed without applying strong shear.

  In the method of the present invention, various additives can be allowed to coexist within a range that does not adversely affect the dispersion polymerization for the purpose of producing functional particles. Specific examples of such additives include plasticizers, dyes, antibacterial agents, and fragrances.

[Polymer particles]
The polymer particles of the present invention are obtained by polymerizing the above monomer components, and are preferably monodisperse polymer particles having a CV value defined by the following formula of 30% or less, and having a CV value of 10% or less. More preferably it is.

CV value (%) = (standard deviation of particle size / average particle size) × 100
The average particle diameter and the standard deviation of the particle diameter can be measured by analyzing a micrograph of polymer particles with an image analyzer.

  The average particle size of the polymer particles of the present invention is preferably from 0.1 to 10 μm, more preferably from 0.5 to 5 μm.

[Gelling agent]
The polymer particles of the present invention are useful as a gelling agent for fluorine oil. The fluorine oil that is gelled by the polymer particles of the present invention is not particularly limited as long as it is an oil having fluorine atoms, but those having water repellency and oil repellency are preferred.

  A perfluoropolyether represented by the general formula (XVII) is preferred as a readily available high molecular weight fluorine oil.

(Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same or different and represent a fluorine atom, a perfluoroalkyl group or an oxyperfluoroalkyl group. X, y and z are preferably An integer greater than or equal to 0 giving a number average molecular weight of 500 to 100,000, provided that x = y = z = 0 does not occur.
When R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a perfluoroalkyl group or an oxyperfluoroalkyl group, the number of carbon atoms is preferably 1 to 3, and more preferably a trifluoromethyl group. x, y and z are the same or different and are preferably 0 to 300.

  Among these, for example, FOMBLIN HC / 01, HC / 02, HC / 03, HC / 04, HC / 25, and HC / R (manufactured by Augmont) represented by the general formula (XVIII) Can be mentioned.

(Wherein r and s are preferably numbers giving a number average molecular weight of 500 to 10,000, and r / s is 0.2 to 2)
r and s are the same or different and are preferably 1 to 100.

  Moreover, the demnum (DEMNUM) S-20, the same S-65, the same S-100, and the same S-200 (manufactured by Daikin Chemical Industries, Ltd.) represented by the general formula (XIX) are included.

(In the formula, t represents a number of 4 to 500.)
Furthermore, Krytox GPL-100 represented by the general formula (XX), GPL-101, GPL-102, GPL-103, GPL-104, GPL-105, GPL-105, GPL-106, And GPL-107, Krytox 143AB, and 143AC (manufactured by DuPont).

(In the formula, u represents a number of 7 to 60.)
Among these fluorinated oils, perfluoropolyethers having a number average molecular weight of 500 or more and 7,000 or less have good compatibility with the polymer particles of the present invention, and the rheology control and gelation of the fluorinated oil are easy. preferable.

  Further, as easily available as low molecular weight fluorine oil, linear or branched, optionally substituted with a halogen other than a fluorine atom, preferably a fluoroalkane having 6 to 12 carbon atoms, specifically Include perfluorohexane, perfluorooctane, 1-bromoheptadecafluorooctane, perfluorooctadecane, perfluoro-2,7-dimethyloctane, and the like, and hydrofluoroethers represented by the general formula (XXI) .

R ¹² (CH ₂ ) _v —O—R ¹³ (XXI)
(Wherein R ¹² represents a linear or branched perfluoroalkyl group, R ¹³ represents an alkyl group having 1 to 20 carbon atoms which may have a linear or branched substituent, and v represents 0. Indicates the number of ~ 5.)
Specifically, R ¹² is, for example, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluoro-3-methylbutyl group, perfluoro-5-methylhexyl group, perfluoro- A perfluoroalkyl group having 1 to 20 carbon atoms, preferably 4 to 11 carbon atoms, such as a 7-methyloctyl group. R ¹³ is, for example, methyl, ethyl, propyl, isopropyl, butyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, cetyl, stearyl, 2,3-dimethylbutyl. 2,4-dimethylbutyl group and the like.

The gelling agent of the present invention is preferably added in an amount of 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the fluorine oil.
In addition, it is preferable to heat the gelation in the range of room temperature to 150 ° C. to accelerate the gelation rate.

Example 1
In a four-neck flask, 80 g of n-hexane, 0.9 g of amino-modified polysiloxane (TO16 BY16-849), 30 g of a methacrylate having a fluoroalkyl group (Clariant FLUOWET MAE 800), and 0.9 g of lauroyl peroxide at room temperature Stirring was carried out for about 10 minutes while charging and replacing with nitrogen. The temperature was set so that the solvent was refluxed from 30 ° C. in about 1 hour, and the four-necked flask was immersed in an oil bath at 30 ° C. After about 1 hour, the reflux was confirmed, and the polymerization was stopped at 3.5 hours from the start of the reflux and allowed to cool. After standing separation, the supernatant n-hexane was removed by decantation, and then the lower layer precipitate was washed twice with n-hexane and dried under reduced pressure at 30 ° C. to obtain polymer particles (yield 95% ).

The SEM photograph (image of the scanning line electron microscope SE-8000 made from HITACHI) of the obtained polymer particle is shown in FIG. When this SEM photograph was image-analyzed by VH-8000 made from KEYENCE, the average particle diameter, the standard deviation of a particle diameter, and CV value were as follows.
Average particle size 1.54μm
Standard deviation of particle size 0.060μm
CV value 3.9%.

Example 2
560 g of n-hexane in a four-necked flask, 10.5 g of one-terminal methacryloyl-modified polysiloxane (manufactured by Chisso Corp., Silaplane FM-0725: number average molecular weight 10,000), methacrylate having a fluoroalkyl group (FLUOWET MAE 800 manufactured by Clariant) ) 210 g, lauroyl peroxide 6.3 g, and divinylbenzene 0.042 g (0.02 wt% monomer) were charged at room temperature and stirred for about 30 minutes while purging with nitrogen. The temperature was set so that the solvent was refluxed from 30 ° C. in about 2 hours, and the four-necked flask was immersed in a 30 ° C. oil bath. After about 2.5 hours, the reflux was confirmed, and the polymerization was stopped and allowed to cool at 4.5 hours from the start of the reflux. After standing separation, the supernatant n-hexane was removed by decantation, and then the lower layer precipitate was washed twice with n-hexane and dried under reduced pressure at 30 ° C. to obtain polymer particles (yield 97% ).

The SEM photograph (image of the scanning line electron microscope SE-8000 made from HITACHI) of the obtained polymer particle is shown in FIG. When this SEM photograph was image-analyzed by VH-8000 made from KEYENCE, the average particle diameter, the standard deviation of a particle diameter, and CV value were as follows.
Average particle size 1.63 μm
Standard deviation of particle size 0.487μm
CV value 30.0% (the CV value is high because fine particles are mixed).

Formulation Examples 1-3
When the polymer particles obtained in Example 1 are added in the amount shown in Table 1 to Augmont's perfluoropolyether (fomblin HC), heated with a hot stirrer (70 ° C. or higher), and then allowed to cool to room temperature. The appearance of was observed. The results are shown in Table 1.

2 is a SEM photograph of polymer particles obtained in Example 1. 2 is a SEM photograph of polymer particles obtained in Example 2.

Claims (10)

  Polymer particles obtained by polymerizing a monomer component containing a vinyl monomer having a fluoroalkyl group and having a content of 20% by weight or more based on the total amount of monomers having one polymerizable group. The polymer particle according to claim 1, wherein the polymer particle has a CV value defined by the following formula of 30% or less.
CV value (%) = (standard deviation of particle size / average particle size) × 100 The polymer particle according to claim 1 or 2, wherein the vinyl monomer having a fluoroalkyl group is a (meth) acrylate represented by the formula (I).
(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 4 carbon atoms or — (CH ₂ ) _n N (R ³ ) SO ₂ — (R ³ represents 1 to 4 carbon atoms). An alkyl group or a hydrogen atom, and n represents an integer of 1 to 4.) Rf represents a C 1-15 fluoroalkyl group having a perfluoroalkyl group at the terminal. The polymer particle according to claim 3, wherein the (meth) acrylate represented by the formula (I) is any one of compounds represented by the following formulas (II) to (IV).
(Wherein, the number of .m ₁ is 4, 6, 8 or 10 R ¹ is showing a hydrogen atom or a methyl group, the number of m ₂ is 1 or 2, m ₃ is a number of 2, 4, 6 or 8 Show.)   The polymer particle according to any one of claims 1 to 4, wherein the crosslinking agent is polymerized using 0 to 50 parts by weight with respect to 100 parts by weight of the total of monomers having one polymerizable group.   The monomer component containing a vinyl monomer having a fluoroalkyl group in a solvent in an amount of 20% by weight or more based on the total amount of the monomer having one polymerizable group in the presence of a polymerization initiator is dispersedly polymerized. A method for producing the polymer particles according to 1.   The manufacturing method of Claim 6 which uses a polysiloxane compound as a dispersing agent.   The process according to claim 7, wherein the polysiloxane compound is at least one selected from the group consisting of amino-modified silicone, polyether-modified silicone, aminopolyether-modified silicone, and a polysiloxane compound having a radical polymerizable group at one end. .   The method according to any one of claims 6 to 8, wherein the solvent is at least one selected from the group consisting of hydrocarbon solvents and silicone solvents. A gelling agent for fluorine oil comprising the polymer particles according to claim 1.