WO2019230289A1 - Copolymère séquencé - Google Patents

Copolymère séquencé Download PDF

Info

Publication number
WO2019230289A1
WO2019230289A1 PCT/JP2019/017780 JP2019017780W WO2019230289A1 WO 2019230289 A1 WO2019230289 A1 WO 2019230289A1 JP 2019017780 W JP2019017780 W JP 2019017780W WO 2019230289 A1 WO2019230289 A1 WO 2019230289A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
monomer
block copolymer
group
integer
Prior art date
Application number
PCT/JP2019/017780
Other languages
English (en)
Japanese (ja)
Inventor
宮沢　和之
祐仁 伊東
後藤　淳
Original Assignee
株式会社 資生堂
ナンヤン テクノロジカル ユニヴァーシティー
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社 資生堂, ナンヤン テクノロジカル ユニヴァーシティー filed Critical 株式会社 資生堂
Priority to JP2020521804A priority Critical patent/JP7304037B2/ja
Publication of WO2019230289A1 publication Critical patent/WO2019230289A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule

Definitions

  • the present invention relates to a novel block copolymer.
  • Patent Document 1 discloses an inkjet recording ink containing water, a water-soluble compound, a pigment, and a (meth) acrylate random copolymer having an acid value of 100 mgKOH / g or more and 160 mgKOH / g or less in which the pigment is dispersed. Is disclosed.
  • Patent Document 2 includes at least a hydrophobic segment and a hydrophilic segment, and the hydrophilic segment includes at least a monomer unit of a cationic monomer and an anionic monomer.
  • the block polymer which can provide property etc. is disclosed.
  • Patent Document 3 discloses a pigment dispersion containing a pigment, a liquid medium, and a polymer dispersant, wherein the polymer dispersant is a block polymer represented by AB or ABC.
  • the block and the C block are polymer blocks composed of an ethylenically unsaturated monomer having no amino group and hydroxyl group
  • the B block is a polymer block composed of a monomer having a glycidyl group or an isocyanate group via a glycidyl group or an isocyanate group.
  • a pigment dispersion which is a polymer block to which one of an amino compound and a compound having a hydroxyl group is bonded, is disclosed.
  • the subject of the present invention is to provide a novel block copolymer that can be used as a surface treating agent that can impart various properties such as dispersibility to an object such as inorganic particles.
  • a block copolymer comprising a hydrophobic segment and a hydrophilic segment
  • the hydrophobic segment includes a monomer unit composed of at least one monomer selected from Formula 1 and Formula 2 below
  • the hydrophilic segment includes monomer units composed of monomers of the following formula 3.
  • Block copolymer In Formula 1, R 1 is hydrogen or a methyl group, and m is an integer of 0 to 21, In Equation 2, R 1 is hydrogen or a methyl group; R 2 and R 3 are each independently an alkyl group having 1 to 6 carbon atoms, m is an integer from 1 to 6, and n is an integer from 5 to 70, In Formula 3, R 1 is hydrogen or a methyl group.
  • R 1 in Formula 1 is a methyl group
  • m is an integer of 10 to 15
  • R 1 and R 2 in Formula 2 are a methyl group
  • R 3 is a butyl group
  • m is an integer of 1 to 3
  • n is an integer of 10 to 60
  • ⁇ Aspect 3 The block copolymer according to embodiment 1 or 2, wherein the proportion of the hydrophobic segment is 50 to 99 mol%, and the proportion of the hydrophilic segment is 1 to 50 mol%.
  • ⁇ Aspect 4> Using at least one monomer selected from Formula 1 and Formula 2 to form a hydrophobic segment by living radical polymerization, and then using the monomer of Formula 3 to form a hydrophilic segment by living radical polymerization, or Using the monomer of formula 3 to form a hydrophilic segment by a living radical polymerization method, then using at least one monomer selected from formula 1 and formula 2 to form a hydrophobic segment by a living radical polymerization method, The method for producing a block copolymer according to any one of embodiments 1 to 3.
  • the living radical polymerization method is a polymerization method in which an iodine compound is used as a starting compound and a phosphorus compound, a nitrogen compound, or an oxygen compound is used as a catalyst.
  • (A) is a schematic diagram of an object surface-treated with a block copolymer
  • (b) is a schematic diagram of an object surface-treated with a random copolymer
  • (c) is a low molecular surface. It is a schematic diagram of the target object surface-treated with the processing agent. It is a schematic diagram of the target object surface-treated with the block copolymer of one embodiment of the present invention.
  • the block copolymer of the present invention includes a hydrophobic segment and a hydrophilic segment, the hydrophobic segment includes a monomer unit composed of at least one monomer selected from the following formulas 1 and 2, and is hydrophilic.
  • R 1 is hydrogen or a methyl group, and m is an integer of 0 to 21,
  • R 1 is hydrogen or a methyl group;
  • R 2 and R 3 are each independently an alkyl group having 1 to 6 carbon atoms, m is an integer from 1 to 6, and n is an integer from 5 to 70,
  • R 1 is hydrogen or a methyl group.
  • a random copolymer is made from a hydrophobic monomer and a hydrophilic monomer
  • the hydrophobic copolymer and the hydrophilic site are randomly arranged in the copolymer. It exhibits an intermediate performance that mixes hydrophobicity and hydrophilicity.
  • a block copolymer a hydrophobic segment composed of a hydrophobic monomer and a hydrophilic segment composed of a hydrophilic monomer are separately formed in the copolymer. Parts having different properties such as sex can be imparted.
  • the block copolymer of the present invention has a specific hydrophobic segment and a specific hydrophilic segment, and at least a part of the hydrophilic segment adsorbs to the inorganic particles through a plurality of adsorption points.
  • the hydrophobic segments in the copolymer are considered to have a comb-like structure and are oriented outward with respect to the inorganic particles, for example, as shown in FIG. .
  • the steric hindrance action is improved as compared with the random copolymer and the low molecular type surface treatment agent as shown in FIGS. 1B and 1C, and the aggregation of the inorganic particles in the oil phase and Since precipitation can be further suppressed, it is considered that the dispersibility of the inorganic particles is further improved.
  • the inorganic particles obtained by conventional surface treatment generally tend to greatly increase the viscosity of the cosmetic.
  • the inorganic particles surface-treated with this block copolymer do not significantly increase the viscosity of the cosmetic.
  • inorganic particles surface-treated with a random copolymer have a structure in which hydrophilic and hydrophobic portions are clung to the particles as shown in FIG. It is low, and since the affinity layer with the oil phase based on the hydrophobic portion is thin, the particles are considered to be close to each other and dispersed in the oil phase.
  • the inorganic particles surface-treated with the conventional low molecular surface treatment agent also have a short hydrophobic part and a low steric hindrance as shown in FIG. Since the affinity layer is thin, it is considered that the particles are close to each other and dispersed in the oil phase. As a result, it is considered that the inorganic particles surface-treated with these materials increase the viscosity of cosmetics and the like because they are in a state where oil is tightly packed between the particles.
  • the inorganic particles surface-treated with the block copolymer of the present invention have a random copolymer and a low molecular-type surface treatment agent as shown in FIG. It is considered that the oil existing between the particles can flow more freely because the particles are relatively thickly dispersed and are relatively separated from each other. As a result, it is considered that an increase in viscosity of cosmetics and the like can be suppressed.
  • titanium oxide or the like when titanium oxide or the like is surface-treated with the block copolymer of the present invention, such particles can be highly blended with high dispersibility without significantly increasing the viscosity of sunscreen cosmetics and the like. I think that it can improve the performance such as the coating property to the sun and the sun protection performance.
  • the block copolymer of the present invention takes into consideration the performance of the hydrophobic segment, and the proportion of the hydrophobic segment of Formula 1 or Formula 2 in the copolymer is 50 mol% or more, 55 mol% or more, or 60 mol%. Further, it can be 99 mol% or less, 95 mol% or less, or 90 mol% or less. Considering the adsorptivity to the object, the ratio of the hydrophilic segment of Formula 3 can be 1 mol% or more, 5 mol% or more, or 10 mol% or more, and 50 mol% or less, 45 mol % Or less or 40 mol% or less.
  • the molecular weight of the block copolymer of the present invention is not particularly limited.
  • the number average molecular weight in terms of polystyrene in gel permeation chromatography can be in the range of 1,000 to 80,000. , Preferably in the range of 20,000 to 20,000.
  • the molecular weight distribution which is the ratio between the number average molecular weight and the weight average molecular weight, can be in the range of 1.05 to 5, and is preferably in the range of 1.05 to 1.7.
  • the monomer unit composed of at least one monomer selected from Formula 1 and Formula 2 in the hydrophobic segment takes into account the required surface treatment performance, affinity with the dispersion medium that mixes the target surface treated with the block copolymer, etc. And can be selected as appropriate.
  • the monomer of formula 1 below is for example, it is preferably employed when a dispersion medium such as polar oil is used.
  • R 1 is hydrogen or a methyl group, and m is an integer of 0-21. From the viewpoints of dispersibility, performance such as viscosity reduction, etc., R 1 is preferably a methyl group, and m is preferably an integer of 3 or more, 5 or more, 8 or more, or 10 or more. Moreover, it is preferable that it is an integer of 20 or less, 18 or less, or 15 or less.
  • the site of (CH 2 ) m in Formula 1 may be either linear or branched, but is preferably linear.
  • the monomer of formula 2 below is for example, it is preferably employed when a dispersion medium such as silicone oil is used.
  • R 1 is hydrogen or a methyl group
  • R 2 and R 3 are each independently an alkyl group having 1 to 6 carbon atoms
  • m is an integer of 1 to 6
  • N is an integer of 5 to 70.
  • R 1 and R 2 in Formula 2 are preferably methyl groups
  • R 3 is preferably a butyl group
  • m is an integer of 1 to 3.
  • n is an integer of 6 or more, 8 or more, or 10 or more, and is preferably an integer of 60 or less, 50 or less, or 40 or less.
  • the site of (CH 2 ) m in Formula 1 may be either linear or branched, but is preferably linear.
  • ⁇ Hydrophilic segment> (Monomer of Formula 3)
  • the monomer of formula 3 below is It forms a monomer unit of the hydrophilic segment and forms a site that is adsorbed on the surface of the object.
  • R 1 is hydrogen or a methyl group. From the viewpoint of polymerizability of the block copolymer, R 1 is preferably a methyl group.
  • the block copolymer of the present invention may further have a monomer unit composed of monomers other than the monomers of the above formulas 1 to 3 as long as the effects of the present invention are not impaired.
  • the ratio of such monomer units can be in the range of 30 mol% or less, 20 mol% or less, 10 mol% or less, or 5 mol% or less of the total amount of monomer units constituting the monomer unit.
  • Examples of such monomers include acrylamide, methacrylamide, methyl acrylamide, methyl methacrylamide, dimethyl methacrylamide, ethyl acrylamide, ethyl methacrylamide, diethyl methacrylamide, N-isopropyl acrylamide, N-vinyl pyrrolidone, ⁇ -caprolactam, vinyl alcohol.
  • the block copolymer of the present invention can be obtained by a known living radical polymerization method. For example, using at least one monomer selected from Formula 1 and Formula 2 above, forming a hydrophobic segment by a living radical polymerization method, and then using the monomer of Formula 3 above to make a hydrophilic segment by a living radical polymerization method Segments can be formed to obtain block copolymers. Alternatively, a hydrophilic segment is formed by the living radical polymerization method using the monomer of the above formula 3, and then hydrophobic by the living radical polymerization method using at least one monomer selected from the above formulas 1 and 2. Segments can be formed to obtain block copolymers.
  • the living radical polymerization method is a method of controlling the reactivity of the terminal active radical by adding a catalyst, a chain transfer agent, or the like to the conventional radical polymerization method and proceeding the polymerization in a pseudo living manner. Compared to normal radical polymerization, the molecular weight distribution can be narrowed and the molecular weight can be controlled.
  • a living radical polymerization method specifically, a living radical polymerization method using a nonmetallic catalyst disclosed in International Publication No. 2010/016523 or the like, or a metal complex disclosed in International Publication No. 96/030421 or the like. Addition of ATRP method by addition, TEMPO method for introducing thermally dissociable group disclosed in US Pat. No.
  • RAFT polymerization method Chem. Examples include the iniferter method having a photo / thermal dissociation group disclosed in Express 5 (10), 801 (1990) and the like.
  • the living radical polymerization method using a nonmetallic catalyst is preferable because it is inexpensive and has a low environmental burden.
  • Such a polymerization method is performed using, for example, the above-described various monomers, starting compounds, catalysts, radical polymerization initiators, and polymerization solvents.
  • the iodine atom in the starting compound is bonded to a secondary or tertiary carbon atom, and X, Y and Z may be the same or different, and may be hydrogen, hydrocarbon group, halogen group, cyano group, It is preferably selected from an alkoxycarbonyl group, an allyloxycarbonyl group, an acyloxy group, an allyloxy group, an alkoxy group, an alkylcarbonyl group, and an allylcarbonyl group.
  • the iodine atom is preferably bonded to a secondary or tertiary carbon atom in consideration of the dissociation property of iodine.
  • X, Y and Z are not hydrogen atoms. Specific examples of X, Y and Z are shown below, but are not limited thereto.
  • hydrocarbon group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an arylalkyl group.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-methylpropyl, t-butyl, pentyl, dodecyl; double groups such as vinyl, allyl, 2-methylvinyl, butenyl, butadienyl
  • halogen group examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxycarbonyl group or allyloxycarbonyl group examples include methoxycarbonyl, ethoxycarbonyl, propylcarbonyl, cyclohexylcarbonyl, benzyloxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl and the like.
  • acyloxy group or allyloxy group examples include acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, naphthylcarboxyoxy, and the like.
  • alkoxy group examples include methoxy, ethoxy, methoxyethoxy, phenoxyethoxy and the like.
  • alkylcarbonyl group or allylcarbonyl group examples include methylcarbonyl, ethylcarbonyl, phenylcarbonyl and the like.
  • Preferred specific examples of the starting compound include 1-iodo-1-phenylethane, 2-iodo-2-cyanopropane, 2-iodo-2-cyano-4-methylpentane and the like.
  • the molecular weight of the copolymer can be controlled by the amount of the starting compound.
  • an arbitrary molecular weight or the magnitude of the molecular weight can be controlled.
  • catalyst As the catalyst, it is possible to use a nonmetallic compound that becomes a radical capable of extracting iodine of the starting compound or iodine of the polymer terminal, for example, a phosphorus compound, a nitrogen compound, or an oxygen compound having such properties.
  • a nonmetallic compound that becomes a radical capable of extracting iodine of the starting compound or iodine of the polymer terminal for example, a phosphorus compound, a nitrogen compound, or an oxygen compound having such properties.
  • phosphorus compounds include phosphorus halides containing iodine atoms, phosphite compounds, phosphinate compounds, etc.
  • nitrogen compounds include imide compounds, hydantoins, Examples include barbituric acids and cyanuric acids.
  • oxygen compounds include phenolic compounds, iodooxyphenyl compounds, and vitamins. These can be used alone or in combination of two or more.
  • the phosphorus compound is a phosphorus halide containing an iodine atom, a phosphite compound, a phosphinate compound, such as dichloroiodolin, dibromoiodrine, phosphorus triiodide, dimethylphosphite, Diethyl phosphite, dibutyl phosphite, di (perfluoroethyl) phosphinate, diphenyl phosphite, dibenzyl phosphite, bis (2-ethylhexyl) phosphite, bis (2,2,2-trifluoroethyl) phosphite Diallyl phosphite, ethylene phosphite, ethyl phenyl phosphinate, phenyl phenyl phosphinate, ethyl methyl phosphinate, phenyl methyl phosphinate and the
  • nitrogen compounds include imides such as succinimide, 2,2-dimethylsuccinimide, ⁇ , ⁇ -dimethyl- ⁇ -methylsuccinimide, 3-ethyl-3-methyl-2,5-pyrrolidinedione, cis-1, 2,3,6-tetrahydrophthalimide, ⁇ -methyl- ⁇ -propylsuccinimide, 5-methylhexahydroisoindole-1,3-dione, 2-phenylsuccinimide, ⁇ -methyl- ⁇ -phenylsuccinimide, 2,3- Diacetoxysuccinimide, maleimide, phthalimide, 4-methylphthalimide, N-chlorophthalimide, N-bromophthalimide, N-bromophthalimide, 4-nitrophthalimide, 2,3-naphthalenecarboximide, pyromellitic diimide, 5-bromoisoindole -1,3 Dione, N- chlorosuccinimide, N-
  • hydantoins include hydantoin, 1-methylhydantoin, 5,5-dimethylhydantoin, 5-phenylhydantoin, 1,3-diaiodo-5,5-dimethylhydantoin and the like.
  • barbituric acids include barbituric acid, 5-methylbarbituric acid, 5,5-diethylbarbituric acid, 5-isopropylbarbituric acid, 5,5-dibutylbarbituric acid, thiobarbituric acid, and the like.
  • cyanuric acids include cyanuric acid, N-methyl cyanuric acid, triiodo cyanuric acid and the like.
  • oxygen compound examples include a phenolic compound that is a phenolic hydroxyl group having a hydroxyl group in an aromatic ring, an iodooxyphenyl compound that is an iodide of the phenolic hydroxyl group, and vitamins.
  • phenols such as phenol, hydroquinone, 4-methoxyphenol, 4-tert-butylphenol, 4-tert-butyl-2-methylphenol, 2-tert-butyl-4-methylphenol, catechol, resorcin, 2,6-di-tert-butyl-4-methyl
  • phenolic hydroxyl group such as Russia hydroxyphenyl ethyl.
  • the effect can be exhibited by using a commercially available ethylenically unsaturated monomer as it is without purification.
  • the iodooxyphenyl compound include thymol iodide, and examples of vitamins include vitamin C and vitamin E.
  • the amount of the catalyst used is generally less than the number of moles of the radical polymerization initiator, and can be arbitrarily determined in consideration of the polymerization control state and the like.
  • radical polymerization initiator As the radical polymerization initiator, conventionally known ones can be used and are not particularly limited.
  • organic peroxides or azo compounds can be used. Specifically, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate , T-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butyl Peroxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-but-butyl per
  • the radical polymerization initiator can be used in a range of 0.001 mol times or more, 0.002 mol times or more, or 0.005 mol times or more with respect to the number of moles of the monomer from the viewpoint of polymerizability and the like. Moreover, it can be used in the range of 0.1 mol times or less, 0.05 mol times or less, or 0.01 mol times or less.
  • polymerization solvent a solvent that does not exhibit reactivity with the functional group of the monomer is appropriately selected.
  • hydrocarbon solvents such as hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, cumene; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Alcohol solvents such as hexanol, benzyl alcohol, cyclohexanol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether
  • the polymerization temperature is appropriately adjusted depending on the half-life of the radical polymerization initiator and is not particularly limited.
  • the polymerization temperature can be 0 ° C or higher or 30 ° C or higher, and can be 150 ° C or lower or 120 ° C or lower. .
  • the polymerization time is preferably continued until the monomer runs out, and is not particularly limited, but can be, for example, 0.5 hours or more, 1 hour or more, or 2 hours or more, and 48 hours or less, 24 hours or less. Or it can be made into 12 hours or less.
  • the polymerization atmosphere is not particularly limited, and the polymerization may be carried out as it is in an air atmosphere, that is, oxygen may be present within the normal range in the polymerization system, and nitrogen may be removed to remove oxygen as necessary. It may be performed in an atmosphere. Various materials to be used may remove impurities by distillation, activated carbon, alumina, or the like, but commercially available products may be used as they are. Further, the polymerization may be performed under light shielding or in a transparent container such as glass.
  • the block copolymer of the present invention can be used as, for example, a surface treatment agent.
  • the surface treatment of the object with the block copolymer of the present invention may be performed using a normal treatment method, and the method is not particularly limited.
  • the block copolymer of the present invention can be dissolved in a suitable dispersion medium, and an object can be mixed and stirred in this solution to obtain a dispersion containing the surface-treated object.
  • the surface-treated object may be used in the state of a dispersion, or may be used in the form of a dried powder.
  • the ratio of the object and the block copolymer is not particularly limited as long as desired performance such as dispersibility is exhibited. : 5 to 100: 40, and a range of 100: 7 to 100: 30 is preferable, and a range of 100: 10 to 100: 20 is more preferable.
  • content of the target object in a dispersion liquid it can be made into the range of 10 mass% or more of the whole dispersion liquid, 20 mass% or more, or 30 mass% or more, and is 90 mass% or less, 80 mass%. Or less than 70% by mass.
  • the object to which the block copolymer of the present invention can be applied is not particularly limited, and can be used alone or in combination of two or more.
  • an object having a hydrophilic surface, in particular, a hydroxyl group on the surface Inorganic particles having, for example, metal oxides are preferred. Such hydroxyl groups on the surface of the object can form hydrogen bonds or the like with the hydroxyl groups of the hydrophilic segment.
  • the inorganic particles include, but are not limited to, for example, silicic acid, anhydrous silicic acid, magnesium silicate, talc, kaolin, mica (mica), bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, and oxidation.
  • Particles such as zinc, titanium oxide, cerium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, bitumen, chromium oxide, chromium hydroxide, carbon black, and composites thereof Is mentioned.
  • the shape of the particles can be any shape such as, for example, a plate shape, a block shape, a scale shape, a sphere shape, a porous sphere shape, and the particle size is not particularly limited.
  • an organic solvent in particular, various oils can be used, and is not limited to the following.
  • hydrocarbons such as liquid paraffin, squalane, isoparaffin, branched light paraffin, petroleum jelly and ceresin
  • oils include oils, ester oils such as isopropyl myristate, cetyl isooctanoate, and glyceryl trioctanoate, silicone oils such as decamethylpentasiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane. These can be used alone or in combination of two or more.
  • silicone oil is preferably used from the viewpoint of the feeling of use in the case of cosmetics.
  • silicone oil can be used in the range of 10% by mass or more, 50% by mass or more, or 70% by mass or more, and in the range of 100% by mass or less with respect to the entire dispersion medium. Can do.
  • silicone oil examples include, but are not limited to, for example, chain polysiloxanes, cyclic polysiloxanes, modified silicones, silicone resins, and the like. Particularly, the boiling point at normal pressure is 200 ° C. or less. Those are preferred.
  • chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, etc.
  • cyclic polysiloxane examples include, but are not limited to, for example, chain polysiloxanes, cyclic polysiloxanes, modified silicones, silicone resins, and the like. Particularly, the boiling point at normal pressure is 200 ° C. or less. Those are preferred
  • volatile silicone oils such as volatile chain polysiloxanes such as low-polymerization degree dimethylpolysiloxane (polymerization degree 3 to 7) and cyclic volatile polysiloxanes such as decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane are used.
  • volatile chain polysiloxanes such as low-polymerization degree dimethylpolysiloxane (polymerization degree 3 to 7)
  • cyclic volatile polysiloxanes such as decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane are used.
  • it is particularly suitable because it is difficult to leave an oily feeling when applied to the skin as a cosmetic or the like, and a refreshing feeling is obtained.
  • the dispersion of the inorganic particles surface-treated with the block copolymer of the present invention can greatly suppress the increase in viscosity accompanying the blending of the inorganic particles compared to the conventional inorganic particle dispersion system by the surface treatment, and therefore limits the formulation.
  • Inorganic particles can be highly blended without any problems. Therefore, the dispersion can be used for various applications such as cosmetics, resin compositions, paints, inks, coating compositions, etc., among others, used for cosmetics, in particular, sunscreen cosmetics. It is preferable to do.
  • the present invention is not limited, but specifically, a cosmetic using a dispersion of inorganic particles surface-treated with the block copolymer of the present invention will be described below.
  • the inorganic particle dispersion of the present invention When the inorganic particle dispersion of the present invention is applied to a cosmetic, it can be used as it is or diluted with an oil component to obtain an oil-type cosmetic, and these are emulsified with a water phase component by a known method.
  • an oil-in-water or water-in-oil emulsified cosmetic particularly an oil-in-water emulsified cosmetic can be used.
  • Cosmetics containing the inorganic particle dispersion liquid of the present invention especially cosmetics for sunscreen, disperse UV scattering agents such as titanium oxide, zinc oxide, cerium oxide, iron oxide, mica, etc. without significantly increasing the viscosity. It can be well blended in cosmetics. As a result, such cosmetics are excellent in applicability to the skin and can increase the SPF value based on the scattering and shielding effect of ultraviolet rays by the uniformly dispersed scattering agent.
  • the SPF value is a numerical value that varies depending on the degree of dispersion of inorganic particles, the SPF value can also be used as an index of dispersion stability.
  • the SPF value and viscosity of the cosmetic are not limited to the following, but for example, the SPF value can be 15 or more, 20 or more, or 25 or more, and is 60 or less, 55 or less, or 50 or less.
  • the viscosity can be 50,000 Pa ⁇ s or less, 30000 Pa ⁇ s or less, or 10000 Pa ⁇ s or less, particularly 3000 Pa ⁇ s or less, 2800 Pa ⁇ s or less, or 2500 Pa ⁇ s or less.
  • the viscosity can also be lowered, and can be 100 Pa ⁇ s or more, 150 Pa ⁇ s or more, or 200 Pa ⁇ s or more.
  • the viscosity refers to the shear rate 1 / s of the measurement object when measured at 32 ° C. and 1 atm using a VDA-2 or VS-H1 (both manufactured by Shibaura System Co., Ltd.) as a vistometron viscometer. Intended for viscosity of time.
  • the inorganic particle dispersion liquid of the present invention can highly blend inorganic particles in cosmetics, and is not limited to the following.
  • the blending amount of inorganic particles in cosmetics is the total amount of cosmetics.
  • 5 mass% or more, 10 mass% or more, or 15 mass% or more can be mix
  • the dosage form of the cosmetic of the present invention is arbitrary, and can be provided in any form such as a solution system, a solubilization system, an emulsification system, a water-oil two-layer system, a gel, an aerosol, a mist, and a capsule.
  • the product form of the cosmetic of the present invention is also arbitrary, and is a facial cosmetic such as lotion, emulsion, cream, pack, etc .; makeup base, foundation, blusher, lipstick, lip balm, eye shadow, eyeliner, mascara, sun Makeup cosmetics such as screens; body cosmetics; aromatic cosmetics; skin cleansing agents such as make-up removers, facial cleansers, body shampoos; hair cosmetics such as hair sprays, hair creams, hair lotions, hair rinses, shampoos, etc. Any form can be applied as long as it is used for an external preparation for skin. In particular, it is suitably used as a product for the purpose of preventing ultraviolet rays.
  • the cosmetic of the present invention can be appropriately blended with various components as long as the effects of the present invention are not affected.
  • additive components that can be usually blended in cosmetics, for example, oils such as liquid fats and oils, solid fats and oils, waxes, higher fatty acids, higher alcohols, anionic surfactants, cationic surfactants, amphoteric surfactants , Nonionic surfactant, moisturizer, water-soluble polymer, thickener, film agent, sequestering agent, lower alcohol, polyhydric alcohol, various extracts, sugar, amino acid, organic amine, polymer emulsion, chelate , UV absorbers, pH adjusters, skin nutrients, vitamins, pharmaceuticals, quasi-drugs, water-soluble drugs applicable to cosmetics, antioxidants, buffers, preservatives, antioxidant aids, organic Examples thereof include powder, pigment, dye, pigment, fragrance, and water.
  • one or more water-soluble or oil-soluble organic ultraviolet absorbers may be blended.
  • water-soluble ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4.
  • oil-soluble ultraviolet absorber examples include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N Benzoic acid UV absorbers such as N-dimethyl PABA butyl ester; Anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl Salicylic acid UV absorbers such as salicylate and p-isopropanolphenyl salicylate; octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylsilane Namate
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
  • the blending amount is expressed in parts by mass.
  • R 1 and R 2 are methyl groups, R 3 is a butyl group, m is 3, and n is 10.
  • Copolymer 3 A block copolymer of Copolymer 3 was produced in the same manner as Copolymer 1 except that 80 parts by mass of the monomer of Formula 1 below was used instead of the monomer of Formula 2 above.
  • R 1 is a methyl group and m is 11.
  • Copolymer 4 A block copolymer of Copolymer 4 was produced in the same manner as Copolymer 1 except that it was changed to methyl methacrylate instead of the monomer of Formula 2.
  • Dispersion 1 20 g of copolymer 1 was dissolved in 200 g of butyl diglycol, and then 80 g of titanium oxide (ST-485WD, manufactured by Titanium Industry Co., Ltd.) was added to this solution and stirred at room temperature for 1 hour. Then, a dispersion 1 of titanium oxide containing 50% by mass of the surface-treated titanium oxide was produced.
  • Dispersions 2 to 4 of titanium oxide were prepared in the same manner as dispersion 1, except that copolymers 2 to 4 were used instead of copolymer 1, respectively.
  • the viscosity and SPF value also called UV protection index, of the emulsions obtained by the formulations and production methods shown in Tables 1 and 2 below were evaluated.
  • the viscosity is a shear rate 1 of the measurement object when measured at 32 ° C. and 1 atm using VDA-2 for a low viscosity and VS-H1 for a high viscosity as a vistometron viscometer.
  • the viscosity at / s was adopted.
  • the SPF value is obtained by applying the obtained emulsion on a transparent tape at an application amount of 2 mg / cm 2 to obtain an evaluation sample, and the evaluation sample has almost the same spectrum as sunlight in the ultraviolet region.
  • the SPF value was calculated by inserting between a solar simulator manufactured by Solar Light Co., which is a light source, and a spectrophotometer, and comparing the spectra with and without the evaluation sample.
  • the calculation method from each spectrum is the same as the method described in paragraph numbers “0076” and “0077” of Japanese Patent Publication No. 6-27064.
  • Example 1 The mixture A was prepared by stirring and mixing the titanium oxide powder obtained by drying the oil dispersion cyclopentasiloxane and the titanium oxide dispersion 1 at room temperature. Next, the surfactant PEG-10 dimethicone and ion-exchanged water were stirred and mixed at 60 ° C. to prepare a mixture B. While stirring at 60 ° C., the mixture A was added to the mixture B and the mixture of Example 1 was added. An emulsion was prepared. The composition of the emulsion is summarized in Table 1.
  • Example 2 The emulsion of Example 2 was produced in the same manner as in Example 1 except that cyclopentasiloxane and cetylisooctanoate were used as oil components.
  • the composition of the emulsion is summarized in Table 1.
  • Comparative Examples 1-2, 4 and 5 Comparative Examples 1 and 2, in the same manner as in Example 1, except that the various components and blending ratios shown in Table 1 were employed, and that the dispersions B and C were used as they were without being dried. 4 and 5 emulsions were prepared, respectively.
  • the composition of the emulsion is summarized in Table 1.
  • the powder A in Table 1 is a titanium oxide powder surface-treated with aluminum stearate
  • the dispersion B is 40 masses of titanium oxide surface-treated with aluminum stearate in cyclopentasiloxane.
  • the dispersion C contains 40% by mass of titanium oxide surface-treated with hydrogen dimethicone in cyclopentasiloxane and 10% by mass of a surfactant. It is a dispersion.
  • Example 3 A mixture C was prepared by stirring and mixing the oils described in Table 2 and the dry powder of Dispersion 2 as a UV scattering agent in an atmosphere of 80 ° C. at the blending ratios described in Table 2. Next, water, alcohol, thickener, moisturizer, surfactant, UV absorber and other components described in Table 2 are stirred and mixed at an blending ratio described in Table 2 in an atmosphere of 80 ° C. A mixture D was prepared, and the mixture C was added to the mixture D while stirring at 80 ° C. to prepare an emulsion of Example 3. The composition of the emulsion is summarized in Table 2.
  • Examples 4 and 5 The emulsions of Examples 4 and 5 were prepared in the same manner as in Example 3 except that the UV scattering agent was changed from the dry powder of Dispersion 2 to the dry powder of Dispersion 3 or the dry powder of Dispersion 4. did.
  • the composition of the emulsion is summarized in Table 2.
  • Comparative Example 7 Water, alcohol, thickener, moisturizer, oil, surfactant, UV absorber and other components described in Table 2 are stirred and mixed at a blending ratio described in Table 2 in an atmosphere of 80 ° C. Thus, an emulsion of Comparative Example 7 was produced. The composition of the emulsion is summarized in Table 2.
  • Comparative Example 8 An emulsion of Comparative Example 8 was produced in the same manner as in Example 3 except that the UV scattering agent was changed from the dry powder of Dispersion 2 to Powder A.
  • the composition of the emulsion is summarized in Table 2.
  • Comparative Example 7 when a UV scattering agent containing titanium oxide and the like surface-treated with the block copolymer of the present invention is used, a UV scattering agent as shown in Comparative Example 7 is used. Since an SPF value equivalent to or higher than that of a system containing no UV scattering agent can be obtained in a lower viscosity state, when a UV scattering agent is blended at a higher concentration up to the viscosity of a system containing no UV scattering agent, the SPF value is higher than that of the system. It can be easily estimated that the SPF value can be further increased.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un nouveau copolymère séquencé, lequel peut être utilisé en tant qu'agent de traitement de surface permettant de conférer à des objets tels que particules inorganiques et similaires, diverses caractéristiques telles que dispersibilité et similaires.　Plus spécifiquement, ce copolymère séquencé contient: un segment hydrophobe et un segment hydrophile, le segment hydrophobe contenant une unité monomère constituée d'au moins une sorte de monomère choisie dans le groupe contenant les monomères représentés par les formules 1 et 2 ci-dessous; et le segment hydrophile contenant une unité monomère constituée d'un monomère représenté par la formule 3 ci-dessous. Dans la formule 1, R1 représente hydrogène ou un groupe méthyle, m est un nombre entier de 0 à 21 et n est un nombre entier de 5 à 70; dans la formule 2, R1 représente hydrogène ou un groupe méthyle, et R2 et R3 représentent chacun indépendamment un groupe alkyle dont le nombre d'atomes de carbone est compris entre 1 et 6, et m est un nombre entier de 1 à 6; et dans la formule 3, R1 représente hydrogène ou un groupe méthyle.
PCT/JP2019/017780 2018-05-29 2019-04-25 Copolymère séquencé WO2019230289A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020521804A JP7304037B2 (ja) 2018-05-29 2019-04-25 ブロックコポリマー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-102625 2018-05-29
JP2018102625 2018-05-29

Publications (1)

Publication Number Publication Date
WO2019230289A1 true WO2019230289A1 (fr) 2019-12-05

Family

ID=68698130

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/017780 WO2019230289A1 (fr) 2018-05-29 2019-04-25 Copolymère séquencé

Country Status (3)

Country Link
JP (1) JP7304037B2 (fr)
TW (1) TW202003611A (fr)
WO (1) WO2019230289A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012013962A (ja) * 2010-06-30 2012-01-19 Fujifilm Corp 感光性組成物、パターン形成材料、並びに、これを用いた感光性膜、パターン形成方法、パターン膜、低屈折率膜、光学デバイス、及び、固体撮像素子
JP2014162880A (ja) * 2013-02-26 2014-09-08 Kyoto Univ セルロース及び分散剤を含む組成物
JP2017132931A (ja) * 2016-01-29 2017-08-03 大日精化工業株式会社 水酸化鉱物分散体、有機無機複合材料、及びそれらの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012013962A (ja) * 2010-06-30 2012-01-19 Fujifilm Corp 感光性組成物、パターン形成材料、並びに、これを用いた感光性膜、パターン形成方法、パターン膜、低屈折率膜、光学デバイス、及び、固体撮像素子
JP2014162880A (ja) * 2013-02-26 2014-09-08 Kyoto Univ セルロース及び分散剤を含む組成物
JP2017132931A (ja) * 2016-01-29 2017-08-03 大日精化工業株式会社 水酸化鉱物分散体、有機無機複合材料、及びそれらの製造方法

Also Published As

Publication number Publication date
JP7304037B2 (ja) 2023-07-06
JPWO2019230289A1 (ja) 2021-06-10
TW202003611A (zh) 2020-01-16

Similar Documents

Publication Publication Date Title
JP4782025B2 (ja) シリコーン共重合体およびそれを含有する化粧料
JP4563855B2 (ja) 睫用化粧料
EP2630948B1 (fr) Préparation externe de type huile-dans-eau pour les soins de la peau
KR102596805B1 (ko) 유중수형 유화 화장료
US8119108B2 (en) Dispersion of microparticulate titanium oxide and cosmetics containing the same
JP5084021B2 (ja) 日焼け止め化粧料
KR20160110125A (ko) 겔 페이스트 조성물 및 이 겔 페이스트 조성물을 이용한 화장료
WO2017130257A1 (fr) Résine absorbant l'eau comportant un squelette siloxane, et produit cosmétique comprenant celle-ci
WO2019230289A1 (fr) Copolymère séquencé
WO2019230378A1 (fr) Dispersion de particules inorganiques contenant un copolymère séquencé pour produits cosmétiques
JP2001278982A (ja) 新規高分子およびこれを用いた化粧料
JP5203075B2 (ja) シクロアルキル基含有アクリル系共重合体及びそれを含有する化粧料
CN107811887B (zh) 化妆材料及化妆材料的制造方法
TW202112338A (zh) 油中水型乳化組合物
JP2005290036A (ja) 化粧料
WO2022009738A1 (fr) Agent de base pour compositions cosmétiques en émulsion eau dans huile, et composition cosmétique en émulsion eau dans huile contenant ledit agent de base
JP7316604B2 (ja) 化粧料用オイル増粘剤及び油溶性共重合体
JP7277414B2 (ja) 化粧料
JPH08268857A (ja) 日焼け止め化粧料
WO2019230290A1 (fr) Copolymère séquencé
WO2019230326A1 (fr) Produit cosmétique capillaire comprenant un copolymère séquencé
JP2022151781A (ja) 組成物
JP2019089715A (ja) 化粧料の製造方法
JP2005350366A (ja) 油中水型皮膚外用組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19812434

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020521804

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19812434

Country of ref document: EP

Kind code of ref document: A1