JPS60262828A - Rodlike fine polymer powder and its dispersion in nonaqueous medium - Google Patents

Abstract

PURPOSE:To titled dispersion which little causes coagulation and gives a smooth touch to the skin, obtained by polymerizing a polymerizable monomer in a specified aqueous surfactant solution and removing the water and the surfactant. CONSTITUTION:A polymerizable monomer (e.g., styrene) is added to an aqueous surfactant solution having a dynamic modulus of elasticity >=0.01dyn at a vibration frequency of 0.05-1.0Hz (e.g., aqueous solution of hexadecenylsuccinic acid) and the polymerization of the resulting mixture is started at 50-90 deg.C in the presence of a radical polymerization initiator. Next, a polymerizable monomer is added thereto at such a rate at which the dynamic modulus of elasticity of the aqueous surfactant solution will not be outside the above range, and the mixture is polymerized for 5-50hr and then subjected to freeze drying, centrifugation or a like operation to remove the water and the surfactant. In this way, a rodlike fine polymer powder having a major axis of 0.1-100mum and a minor axis one third or below the major axis. This fine powder is dispersed in a nonaqueous medium, e.g., methanol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fine polymer powder having a novel rod-like shape and a dispersion of the same in a non-aqueous medium.

[Conventional technology]

Traditionally, kaolin, goethite, γ-iron oxide, silica stone,
Rod-shaped inorganic fine powders such as light calcium carbonate are used for makeup cosmetics and paints.

It is widely used as a pigment and thickener for paper processing, etc. However, these are all natural inorganic substances.
Therefore, their properties are relatively similar and there are no major differences. For example, in terms of surface properties, all of them are hydrophilic and sticky, so if a hydrophobic surface is required, such as extender pigments for make-up azo products, the current situation is that a hydrophobic treatment is purposely applied. . In the case of products (for example, oil-based paints) that have a high specific gravity and are used by being dispersed in a non-aqueous medium because they are made of machinery, cauterization measures are required to completely prevent sedimentation. In addition, these products have the problem of inconsistent quality, which is a disadvantage peculiar to natural products. For example, in the case of silica stone, the long diameter is 1μm for small diameter ones, and 50mm for large diameter ones.
There is some fluctuation at around 0 μm. Furthermore, since these natural rod-shaped inorganic powders usually contain impurities, they often go through many purification steps, which poses many problems when effectively utilizing these natural fine powders.

[Problem that the invention seeks to solve]

In view of the above-mentioned circumstances, the present inventors set out to obtain a rod-shaped fine polymer powder having a new shape that has a uniform particle size compared to natural inorganic powders and overcomes the drawbacks of the above-mentioned natural inorganic powders. As a result of extensive research, we have found that the desired rod-shaped fine polymer powder can be obtained by removing water and, if necessary, a surfactant from the polymer latex obtained using the solubilization polymerization method described below. Furthermore, the present inventors have found that a dispersion can be obtained by dispersing the above fine polymer powder in an aqueous medium, and have completed the present invention.

[Means to solve all problems]

That is, in the present invention, the long axis is 0.1 to 100 μm.

All rod-shaped fine polymer powders whose short axis is 173 or less of the long axis are provided. Furthermore, the present invention provides a dispersion in which the rod-shaped fine polymer powder is dispersed in a non-aqueous medium.

The rod-shaped fine polymer powder of the present invention has an imaging frequency of 0.05 H.
z ~1.0 Dynamic elastic modulus dfO,01d at H2
After solubilizing the polymerizable monomer in a surfactant water bath solution with ynθ/country 2 or higher and initiating polymerization in water, the dynamic elastic modulus of the surfactant aqueous solution does not deviate from the above range. Water and, if necessary, a surfactant t-
Manufactured by wire removal.

The dynamic elastic modulus of the surfactant aqueous solution is 0.01 aynθ
/R or higher is fine, but especially 0.5~” “I”37
cm” is preferable, and the dynamic elastic modulus is 0.01 dynθ/α
! When it is larger than 7CI Qdyne/J%, the rod-shaped micelles are destroyed by the addition of the monomer, and when it is larger than 7CI Qdyne/J%, it is possible to produce rod-shaped polymer latex, but it is difficult to stir during production. This is a difficult point.

As surfactants with such riding properties, the following (
-) to (f) are mentioned.

(a) General formula an, cooz / -OH \ 00Y (where R is a hydrocarbon group having 6 to 24 carbon atoms, X and Y are hydrogen atoms, alkali metals, ammonium, alkanolamines or bases having 2 to 3 carbon atoms) General formula (where R1 is a hydrocarbon group of carbon a8-24, R,, R
s and R4 are a hydrocarbon group having 1 to 3 carbon atoms, a hydroxyl hydrocarbon group, or a pencil group, and ρ represents a phantom anion.

(e) General formula % formula % ) ( ) (where R,, R6 is a hydrocarbon group having 6 to 24 carbon atoms, n
is an integer of 1 to 50, A is 1 of a hydrocarbon group having 2 to 4 carbon atoms
(indicates a mixture of two or more types).

(d) Contains all of the following two ingredients (A) and (B), (~
The weight ratio of the component and (Bl component is 1oo: 20 to 30:
100% essential surfactant composition.

body) (1) R8O,K.

(s5 R804Xl (3) ROCAO)nsday03x1 or (where R is a hydrocarbon group having 6 to 24 carbon atoms, nl is 1 to
An integer of 20, M represents a hydrocarbon having a carbon number of 2 to 4, an alkali metal, an alkaline earth metal, an alkanolamine having a carbon number of 2 to 3, or a basic amino acid group) (11 (1) Ry -N -(OH,) n, Box9 C2 R7-N -(OH20HOH1)n280B
R9OH8 (() R,-N-(am,)n,co.

9 R.

Kuzu (4) By-N→0 9 (where Ryt'i is a hydrocarbon group having 6 to 24 carbon atoms, R
8, R, and R10 are a hydrocarbon group having 1 to 3 carbon atoms, a hydroxyl hydrocarbon group, or a benzyl group, f+! is 1-1
An integer of 0, Shio indicates a counter anion) ←) A compound represented by the general formula % (where R7, Aki, and R9 are the same as above).

(f) General formula % formula %) (Here, RIO is a hydrocarbon group having 6 to 24 carbon atoms, Ru
F'i is a hydrocarbon group having 1 to 24 carbon atoms, Rlm is a carbon number 1
-4 hydrocarbon group, and m is the same as above) A compound represented by:

Preferred surfactants include alkyl or alkenyl succinates having 6 to 24 carbon atoms in the hydrocarbon chain, such as dodecylsuccinic acid, octadecylsuccinic acid, dodecenylsuccinic acid, and octadecenylsuccinic acid. Partially neutralized acid, N,N-dimethyl-N-(carboxymethyl)alkyl ammonium inner salt having 6 to 24 carbon atoms in the hydrocarbon chain and alkyl having 6 to 24 carbon atoms in the hydrocarbon chain (pft acid) l) Mixture of WAM, N,N-dimethyl(3-sulfozolobyl)alkylammonium internal salt with 6 to 24 carbon atoms in the hydrocarbon chain and 6 to 24 carbon atoms in the hydrocarbon chain mixtures of alkyl sodium sulfates, halogenated benzoates or salicylates of alkyl trimether ammoniums having 6 to 24 carbon atoms in the hydrocarbon chain, and sialkylglycerin ethers having 6 to 24 carbon atoms in the hydrocarbon chain. Examples include ethylene oxide adducts and ethylene oxide adducts of Guerbet alcohol.

In addition, as the polymerizable monomer, any of the known monomers used in emulsification can be used, such as ethylenically unsaturated monomers such as ethylene, propylene, isobutyne, butene-1, and styrene. , α-methylstin, vinyltoluene, halogenated styrene, aromatic vinyl monomers such as divinylbenzene, ethyl acrylate, butyl acrylate, acrylic I! 111! Acrylic acid esters whose alkyl group has 1 to 20 carbon atoms such as 2-ethylhexyl, methacrylic esters whose alkyl group has 1 to 20 carbon atoms such as methyl methacrylate, butyl methacrylate, walyl methacrylate, vinyl acetate , vinyl esters such as vinyl propionate, vinyl needles having 1 to 20 carbon atoms such as ethyl vinyl ether, sotervinyl ether, menalpinyl katon,
Vinyl ketones with 1 to 20 carbon atoms such as ethyl vinyl ketone, vinyl cyanogens such as acrylonitrile, methacrylic acid)'J/L-, vinyl halides such as vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene beautification. and fatty 117+ group conjugated zoenes such as vinylidene halide, 1,3-butadiene, and 2-methyl-1,3-butadiene. These monomers can be used alone or in combination with
It is also possible to use a mixture of the above monomers, and further add maleic anhydride or a water-soluble monomer, styrene sulfone Wl (salt), vinylnaphthalene sulfonic acid (salt), acrylic acid (salt), etc. to the above monomers. You can also do both. Furthermore, as a polycondensable monomer, azobic acid (chloride)
Monomers such as , terephthalic acid (chloride), alkylene cyamine, and alkylene glycol can be used.

The most preferred method for producing the rod-shaped polymer latex according to the present invention is to prepare a viscoelastic aqueous solution by adding a surfactant to a reaction vessel containing JL7 with water, heating and stirring the mixture, While maintaining the properties of the solution, add an aqueous solution of a monomerizable monomer and, if necessary, a radical polymerization initiator to completely initiate polymerization. In this method, polymerizable monomers are gradually added to carry out polymerization.

Here, as the radical 1 initiator, for example, perVt salts such as potash persulfate, sodium persulfate, pert[ltammoniumwum, etc.], 2,2'-7zobis(2-amizonodero, Qn) mineral acid salts, etc. , azo compounds such as azobiscyanobuanphosphate and its alkali metal salts and ammonium salts, redox initiators such as toriteric acid-hydrogen peroxide, Rongalitto peroxide, ascorbic acid-peroxide, etc. Among these, 2,2'-azobis(2-amizonozolonon9one) mineral acid salt is suitable when used as a cationic surfactant copolymerization system, and persulfate is suitable for other monopolymerization systems. Used for. The amount of radical i initiator is 0.1 to 5 parts per 100 parts of monomers constituting the entire polymer;
Preferably it is 0.1 to 3N parts.

The reaction temperature is preferably in the range of 6.9.5°C to 90°C at the highest temperature at which these properties are not lost by heating. −
1k, the time required for polymerization depends on the type of monomer, composition, degree of agglomeration,
Although it varies depending on the line range of the radical 1 initiator and the polymerization temperature, it is usually preferably in the range of 5 to 50 hours.

By completely removing water and, if necessary, surfactant from the fL7C rod-shaped cloudy molecular latex thus obtained, the rod-shaped fine polymer powder of the present invention can be obtained.

Methods for completely removing water and surfactant from rod-shaped polymer latex include methods such as freeze-dry storage, centrifugation, precipitation with an organic solvent miscible with water, and precipitation by salting out. Which of these methods to use for removing water gold is determined by the intended use of the resulting powder. For example, if there is no problem even if the surfactant remains in the powder, it is easy to powder it by freeze-drying. −
However, a method in which a bath medium such as ethanol is added to the latex to completely precipitate the rod-shaped polymer fine powder allows the surfactant soluble in ethanol to be removed with relative ease. In this way, the powder removed from the surfactant is used in makeup cosmetics that come into direct contact with the skin. Suitable for waders, etc.

In addition, the non-aqueous medium in which the rod-shaped polymer fine powder is dispersed may be selected depending on the properties of the target product.
Monoalcohols such as methanol, ethanol, chrycerin, and ethylene glycol - p, I'! J-ol, glycol ethers, nitriles such as acetonitrile and butyronitrile, halogenated methane such as chloroform and bromoform, halogenated ethane, ketones such as acetone and methyl ether ketone, aromatic solvents such as benzene and toluene, castor Examples include triglycerides such as oil, olive oil, and rapeseed oil, as well as vaseline and NoQ Laugh-In.

〔Effect of the invention〕

The rod-shaped fine polymer powder of the present invention and the liquid obtained by dispersing it in a non-medium are particularly useful as a base material for make-up cosmetics because they have relatively little aggregation and give a smooth feel when applied to the skin.

In addition, this dispersion may further contain commonly used cosmetic raw materials.

〔Example〕

Next example? List and explain.

Example 1゜300-glass container with stirrer, Q-Lab/L/7
:7S:I VC'4% hexatecenylconohydric acid (
Neutralize with sodium hydroxide. After preparing the entire viscoelastic solution by adding 200 parts by weight (hereinafter referred to as "VA") with a degree of neutralization of 0.7, the solution was sufficiently purged with nitrogen and heated to 60 DEG C. with stirring. 20 parts of styrene and overlaW! ammonium 0
．． An aqueous radical initiator solution prepared by dissolving 5 parts in 10 parts of distilled water was added dropwise over 2 hours while maintaining the viscoelasticity of the solution. Polymerization was further carried out at the same temperature for 6 hours.

When 100 parts of this latex solution is added to 200 parts of ethanol, a glue-like latex is precipitated. The entire solution was transferred to a centrifugal tube and centrifuged at 11,000 rpm for 15 minutes.The resulting cake-like latex was redispersed in ethanol and centrifuged again under the same conditions. obtained nπ
Does latex look like a rod when kept dry? Risti Von powder is obtained. The obtained rod-shaped styrene fine powder was analyzed using a scanning Hiroko microscope in FIG. 1. The properties of the fine powder are shown in Table 1.

Example 2゜Example 1. Polymerization was carried out in the same manner as above using styrene and sodium styrene sulfonate as monomers in the amounts shown in f-ff-1. The results are shown in Table-1.

Example 3.4゜ Styrene and sodium styrene sulfonate as monomers in the amounts shown in Table 1-1 Example 1, T for Ia H Instead of gisadecenylsuccinic acid, 4% octadecyltrimethylammonium A polymerization reaction was carried out in accordance with the method of Example 1.0 except for using the 2θθ part of benzoic acid converted into a wamm-formed benzoic acid, and a rod-shaped ? Listerene/sodium sulfonate fine powder 'lr was obtained. The results are shown in Table-1.

Example 5 As polymerizable monomers, 20 parts of styrene and 0.25 parts of styrene sulfone sodium t-m9 were used. Carry out the polymerization reaction according to the method of ? A listerene/sodium sulfonate latex was obtained. Next, 100 parts of the latex was immersed in a total acetone-dry ice bath, frozen, and then vacuumed. Freeze-dry for 24 hours 11! A fine powder of sodium styrene sulfonate was obtained. This fine powder has a smooth feel! It was shown. The average particle diameter of this fine powder and the degree of wettability with water are shown in Table IK.

The following margins fi-1t4 Properties of polymer imitation powder a)--1 Completely repel water, -: Slightly repel water, +
: Slightly wet. ++: Completely wet. Monomer number gjL
indicates the part.

Example 6. Lipstick (υNiseika Titanium 2.0 (wt%) (2) Red No. 204 2.5 C3) Red No. 220 0.5 (4) Yellow No. 4 Muluki 0.2 G) Rod-shaped? Listileno powder 8.0 (Example 2) (6) Upper chill lactate 10.0 4° (η lanolin 5.0 (8) Castor oil 52.7 (匈Karnawa Varova 2.0 aυ Ceresin 4.0 u3 Mitsurowa 4.0 u3 Fragrance Appropriate amount aXu Antioxidant Appropriate amount Add ingredients (1) to (4) to a part of castor oil and heat and melt the homogenized pigment ingredient and remaining other ingredients. All of the ingredients were mixed and dispersed uniformly using a homomixer.After dispersion, the lipstick was poured into a mold and cooled, allowing it to be applied evenly.

[Brief explanation of drawings]

FIG. 1 shows Example 1. The n7'c rod shape of the present invention? The kinetics of Listerno fine powder is explained by electron microscopy. that's all

Claims (1)

[Claims] 1. The major axis is 0.1 to 100+”m + the minor axis is 17 of the major axis.
Rod-shaped polymer fine powder with a particle size of 3 or less. 2. Solubilize the polymerizable monomer in an aqueous surfactant solution whose dynamic elastic modulus in the vibration frequency range of 0.05 Hz to 1, QHz is greater than 1 d7ne /at" and start polymerization in water. After the dynamic elastic modulus of the aqueous surfactant solution deviates from the above range, water and, if necessary, the surfactant are removed from the rod-shaped polymer latex obtained by adding a polymerizable monomer at a rate that exceeds the above range. The rod-shaped fine polymer powder according to claim 1 obtained by removing K. 3.11 Claims in which the polymerizable monomer is a vinyl polymer monomer or an allyl polymerizable monomer The rod-shaped fine polymer powder according to item 2. 4. The long axis is 0°1 to 100 μm, and the short axis is 1/3 of the long axis.
A dispersion liquid in which the rod-shaped fine polymer powder described below is dispersed in a non-aqueous medium. 5. The dispersion according to claim 4, further containing a cosmetic raw material.