TW202003611A - Block copolymer - Google Patents

Abstract

The present invention provides a novel block copolymer which is able to be used as a surface treatment agent that is capable of imparting objects such as inorganic particles with various characteristics such as dispersibility. A block copolymer according to the present invention comprises a hydrophobic segment and a hydrophilic segment; the hydrophobic segment contains a monomer unit which is composed of at least one monomer that is selected from monomers represented by formula 1 or formula 2; and the hydrophilic segment contains a monomer unit which is composed of a monomer represented by formula 3. In formula 1, R1 represents a hydrogen atom or a methyl group; and m represents an integer of 0-21. In formula 2, R1 represents a hydrogen atom or a methyl group; each of R2 and R3 independently represents an alkyl group having 1-6 carbon atoms; m represents an integer of 1-6; and n represents an integer of 5-70. In formula 3, R1 represents a hydrogen atom or a methyl group.

Description

Block copolymer

The present invention relates to a novel block copolymer.

In recent years, various surface modification techniques using polymer materials and the like for imparting antifouling properties, antifogging properties, dispersibility of inorganic particles, etc. are being studied.

Patent Document 1 discloses an ink for inkjet recording, which contains water, a water-soluble compound, a pigment, and a (meth)acrylic acid ester system in which the pigment dispersion acid value is 100 mgKOH/g or more and 160 mgKOH/g or less. Random copolymer.

Patent Document 2 discloses a block polymer capable of imparting anti-fog properties, antistatic properties, etc. to various members, which includes at least a hydrophobic segment and a hydrophilic segment, and the hydrophilic segment includes at least a cationic monomer And anionic monomer monomer units.

Patent Document 3 discloses a pigment dispersion liquid containing a pigment, a liquid medium, and a polymer dispersant. The polymer dispersant is a block polymer represented by AB or ABC. The A block and C block include The polymer block of the ethylenically unsaturated monomer having an amine group and a hydroxyl group, the B block is connected to the polymer block containing a monomer having a glycidyl group or isocyanate group via a glycidyl group or isocyanate bond A polymer block having any one of an amine compound and a compound having a hydroxyl group. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-052058 [Patent Document 2] Japanese Patent Laid-Open No. 2017-179112 [Patent Document 3] International Publication No. 2010/016523

[Problems to be solved by the invention]

There are various expectations for polymers used as surface treatment agents. For example, in sunscreen cosmetics using inorganic particles such as titanium oxide to scatter ultraviolet rays, the polymerization has been expected to further improve the dispersibility of the inorganic particles. Thing.

Therefore, the subject of the present invention is to provide a novel block copolymer that can be used as a surface treatment agent that can impart various properties such as dispersibility to inorganic particles and the like. [Technical means to solve the problem]

…式1 式1中， R¹ 為氫或甲基，且 m為0~21之整數， [化2]

…式2 式2中， R¹ 為氫或甲基， R² 及R³ 分別獨立地為碳原子數1~6之烷基， m為1~6之整數，且 n為5~70之整數， [化3]

…式3 式3中， R¹ 為氫或甲基。 ＜態樣2＞ 如態樣1所記載之嵌段共聚物，其中上述式1之R¹ 為甲基，m為10~15之整數， 上述式2之R¹ 及R² 為甲基，R³ 為丁基，m為1~3之整數，n為10~60之整數，且 上述式3之R¹ 為甲基。 ＜態樣3＞ 如態樣1或2所記載之嵌段共聚物，其中上述疏水性鏈段之比率為50~99莫耳%，且上述親水性鏈段之比率為1~50莫耳%。 ＜態樣4＞ 一種如態樣1~3中任一項所記載之嵌段共聚物之製造方法，其使用選自式1及式2中之至少一種單體並藉由活性自由基聚合法形成疏水性鏈段，繼而，使用式3之單體並藉由活性自由基聚合法形成親水性鏈段，或 使用式3之單體並藉由活性自由基聚合法形成親水性鏈段，繼而，使用選自式1及式2中之至少一種單體並藉由活性自由基聚合法形成疏水性鏈段。 ＜態樣5＞ 如態樣4所記載之方法，其中活性自由基聚合法係將碘化合物作為起始化合物，將磷化合物、氮化合物或氧化合物作為觸媒之聚合法。 [發明之效果]<Aspect 1> A block copolymer comprising a hydrophobic segment and a hydrophilic segment, the hydrophobic segment comprising at least one monomer selected from the following Formula 1 and Formula 2 Monomer unit, the above-mentioned hydrophilic segment includes a monomer unit composed of the monomer of the following formula 3:

… Formula 1 In Formula 1, R ¹ is hydrogen or methyl, and m is an integer from 0 to 21, [Chem 2]

… Formula 2 In Formula 2, R ¹ is hydrogen or methyl, 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, and n is an integer of 5 to 70 , [化3]

... Formula 3 In Formula 3, R ¹ is hydrogen or methyl. <Aspect 2> The block copolymer as described in Aspect 1, wherein R ¹ of the above formula 1 is a methyl group and m is an integer of 10 to 15, R ¹ and R ² of the above formula ² are a methyl group, and R ³ is butyl, m is an integer of 1 to 3, n is an integer of 10 to 60, and R ¹ of the above formula 3 is a methyl group. <Aspect 3> The block copolymer according to aspect 1 or 2, wherein the ratio of the above-mentioned hydrophobic segment is 50 to 99 mol%, and the ratio of the above-mentioned hydrophilic segment is 1 to 50 mol% . <Aspect 4> A method for producing a block copolymer as described in any one of Aspects 1 to 3, which uses at least one monomer selected from Formula 1 and Formula 2 by living radical polymerization Forming a hydrophobic segment, and then, using the monomer of Formula 3 and forming a hydrophilic segment by living radical polymerization, or using a monomer of Formula 3 and forming a hydrophilic segment by living radical polymerization, and then , Using at least one monomer selected from Formula 1 and Formula 2 and forming a hydrophobic segment by a living radical polymerization method. <Aspect 5> The method described in Aspect 4, wherein the living radical polymerization method is a polymerization method using an iodine compound as a starting compound and a phosphorus compound, a nitrogen compound, or an oxygen compound as a catalyst. [Effect of invention]

According to the present invention, it is possible to provide a novel block copolymer which can be used as a surface treatment agent capable of imparting various characteristics such as dispersibility to objects such as inorganic particles.

Hereinafter, the embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist of the 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 Formula 1 and Formula 2, and is hydrophilic The block segment contains a block copolymer of monomer units composed of monomers of formula 3 below.

…式1 式1中， R¹ 為氫或甲基，且 m為0~21之整數， [化5]

…式2 式2中， R¹ 為氫或甲基， R² 及R³ 分別獨立地為碳原子數1~6之烷基， m為1~6之整數，且 n為5~70之整數， [化6]

…式3 式3中， R¹ 為氫或甲基。[Chemical 4]

… Formula 1 In Formula 1, R ¹ is hydrogen or methyl, and m is an integer from 0 to 21, [Chem 5]

… Formula 2 In Formula 2, R ¹ is hydrogen or methyl, 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, and n is an integer of 5 to 70 , [化6]

... Formula 3 In Formula 3, R ¹ is hydrogen or methyl.

Although not limited by the principle, it is believed that such a block copolymer can impart surface treatment properties to an object as follows. In addition, the case where inorganic particles are used as an object is illustrated here.

For example, when a random copolymer is made from a hydrophobic monomer and a hydrophilic monomer, the copolymer is randomly arranged in the copolymer because the hydrophobic part and the hydrophilic part are random. The copolymer as a whole exhibits intermediate properties such as a mixture of hydrophobicity and hydrophilicity. On the other hand, in the case of a block copolymer, since the hydrophobic segment containing the hydrophobic monomer and the hydrophilic segment containing the hydrophilic monomer are formed separately in the copolymer, the block Copolymers impart different properties such as hydrophobicity and hydrophilicity.

For example, when an oil component containing inorganic particles surface-treated with a low-molecular-type surface treatment agent that has been used conventionally is formulated into cosmetics and emulsified, agglomeration and sedimentation are likely to occur. The reason for this is considered to be that part of the low-molecular-weight surface treatment agent is easily detached from the inorganic particles and migrates to the cosmetics, and a peeling portion is generated on the surface of the inorganic particles, which lacks stability. On the other hand, the block copolymer of the present invention has a specific hydrophobic segment and a specific hydrophilic segment, wherein at least a part of the hydrophilic segment is adsorbed to the inorganic particles via a plurality of adsorption points, or is entangled It is adsorbed on the surface of the inorganic particles and, depending on the situation, hydrogen bonds are also generated between the inorganic particles and the hydrophilic segment. Therefore, it is considered that the copolymer is not easy to fall off from the inorganic particles, and the dispersion stability of the inorganic particles is improved.

In addition, it is considered that in the oil phase, the hydrophobic segment in the copolymer has, for example, a comb-like structure as shown in FIG. 2 and is oriented outward with respect to the inorganic particles. As a result, it is considered that the steric hindrance is improved compared to the random copolymer and the low-molecular surface treatment agent as shown in (b) and (c) of FIG. 1, and the aggregation of inorganic particles in the oil phase can be further suppressed And Shendian, so the dispersion of inorganic particles is more improved.

Also, for example, in the case of mixing inorganic particles in a water-drop type cosmetic in oil, the inorganic particles obtained by the previous surface treatment usually have a tendency to greatly increase the viscosity of the cosmetic, but the surface of the block copolymer of the present invention The treated inorganic particles will not greatly increase the viscosity of the cosmetics.

It is considered that the reason is that, for example, the inorganic particles treated by the surface of the random copolymer, as shown in FIG. 1(b), have a hydrophilic and hydrophobic part wrapped around the particle structure, and the steric hindrance is low. The affinity layer with the oil phase is thin, so the particles are dispersed in the oil phase close to each other.

In addition, it is considered that the inorganic particles surface-treated by the previous low-molecular-type surface treatment agent also have a shorter hydrophobic part as shown in FIG. 1(c), and a lower steric hindrance. The affinity layer based on the hydrophobic part and the oil phase is lower Thin, so the particles are dispersed in the oil phase close to each other. As a result, it is considered that the inorganic particles subjected to the surface treatment of these materials are in a state of being tightly packed with oil between the particles, so that the viscosity of cosmetics and the like is increased.

On the other hand, it is considered that the inorganic particles subjected to the surface treatment of the block copolymer of the present invention cover the hydrophobic chain based on the thicker structure of the random copolymer and the low molecular surface treatment agent as shown in FIG. 1(a). The affinity layer of the segment and the oil phase, and the particles are dispersed relatively apart from each other, so the oil existing between the particles can flow more freely. As a result, it is considered that the increase in viscosity of cosmetics and the like can be suppressed.

Therefore, for example, if the block copolymer of the present invention is used for surface treatment of titanium oxide and the like, the particles can be highly formulated with good dispersibility without greatly increasing the viscosity of sunscreen cosmetics and the like, and thus the coating on the skin can be improved Properties such as cloth properties and sun protection properties.

"Block Copolymer" In the block copolymer of the present invention, considering the performance based on the performance of the hydrophobic segment, the ratio of the hydrophobic segment of Formula 1 or Formula 2 in the copolymer can be set to 50 mol% or more and 55 mol % Or more or 60 mol% or more, and can be set to 99 mol% or less, 95 mol% or less or 90 mol% or less. Considering the adsorption to the object, etc., the ratio of the hydrophilic segment of Formula 3 can be set to 1 mol% or more, 5 mol% or more, or 10 mol% or more, and can also be set to 50 mol% Below, below 45 mol% or below 40 mol%.

The molecular weight of the block copolymer of the present invention is not particularly limited. For example, the number average molecular weight in terms of polystyrene in gel permeation chromatography measurement can be set in the range of 1,000 to 80,000, preferably 5,000 to 20,000 Scope. Moreover, the ratio of the number average molecular weight to the weight average molecular weight, that is, the molecular weight distribution can be set in the range of 1.05 to 5, preferably in the range of 1.05 to 1.7.

<hydrophobic segment> Regarding the monomer unit composed of at least one monomer selected from Formula 1 and Formula 2 in the hydrophobic segment, the desired surface treatment performance and the object to be surface treated with the block copolymer can be considered The affinity of the dispersion medium is appropriately selected.

…式1(Monomer of Formula 1) The monomer of Formula 1 below is preferably used when, for example, a dispersion medium such as polar oil is used. [化7]

…Formula 1

In Formula 1, R ¹ is hydrogen or methyl, and m is an integer of 0-21. From the viewpoint of performance such as dispersibility and viscosity reduction, 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, and more preferably 20 or less , An integer below 18 or below 15. Here, the position of (CH ₂ ) _{m in} Formula 1 may be either linear or branched, and preferably linear.

…式2(Monomer of Formula 2) The monomer of Formula 2 below is preferably used, for example, in a dispersion medium such as silicone oil. [Chem 8]

…Form 2

In Formula 2, R ¹ is hydrogen or methyl, 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, and n is an integer of 5 to 70. From the viewpoint of dispersibility and low viscosity, R ¹ and R ^{2 in} Formula 2 are preferably methyl, R ^{3 is} preferably butyl, m is preferably an integer of 1 to 3, and n is preferably 6 or more , An integer of 8 or more, or 10 or more, and preferably an integer of 60 or less, 50 or less, or 40 or less. Here, the position of (CH ₂ ) _{m in} Formula 1 may be either linear or branched, and preferably linear.

…式3<Hydrophilic Segment> (Monomer of Formula 3) The monomer of Formula 3 below constitutes the monomer unit of the hydrophilic segment and forms a site that is adsorbed on the surface of the object. [化9]

…Form 3

In Formula 3, R ¹ is hydrogen or methyl. From the viewpoint of the polymerizability of the block copolymer and the like, R ^{1 is} preferably a methyl group.

<Any monomer> The block copolymer of the present invention may further have a monomer unit composed of monomers other than the monomers of Formula 1 to Formula 3 as long as the effect of the present invention is not impaired. The ratio of the monomer unit can be set within a range of 30 mol% or less, 20 mol% or less, 10 mol% or less, or 5 mol% or less of the total monomer units constituted. Examples of the monomer include acrylic amide, methacrylamide, methacrylamide, methylmethacrylamide, dimethylmethacrylamide, ethylacrylamide, ethyl Methacrylamide, diethylmethacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, ε-caprolactam, vinyl alcohol, maleic anhydride, N, N'-dimethylaminoethyl methacrylic acid, diallyl dimethyl ammonium chloride, alkyl acrylate, alkyl methacrylate, N,N'-dimethyl acrylamide, benzene Ethylene etc.

<Manufacturing method of block copolymer> The block copolymer of the present invention can be obtained by a known living radical polymerization method. For example, it is possible to use at least one monomer selected from the above formula 1 and formula 2 and form a hydrophobic segment by a living radical polymerization method, and then, use the monomer of the above formula 3 and form a living radical polymerization method The block copolymer is obtained by hydrophilic segment. Alternatively, use the monomer of the above formula 3 and form a hydrophilic segment by the living radical polymerization method, and then, use at least one monomer selected from the above formula 1 and formula 2 and form the hydrophobic by the living radical polymerization method Block copolymer.

The living radical polymerization method is a method of simulating active polymerization by controlling the reactivity of terminal active radicals by adding a catalyst, a chain transfer agent, etc. to the previous radical polymerization method. Compared with the usual free radical polymerization, the molecular weight distribution can be narrowed and the molecular weight can be controlled. As a known living radical polymerization method, specifically, the living radical polymerization method using a non-metal catalyst disclosed in International Publication No. 2010/016523, etc., and the disclosure disclosed in International Publication No. 96/030421, etc. Tempo (2,2,6,6-Tetramethyl-1) introduction of thermally dissociable groups is disclosed by the ATRP (Atom Transfer Radical Polymerization) method of adding metal complexes, US Patent No. 4,581,429, etc. -RAFT (Reversible Addition-Fragmentation) with the addition of a reversible addition cleavage chain transfer agent disclosed in the piperidinyloxy, 2,2,6,6-tetramethylpiperidine-nitrogen oxide method, International Publication No. 98/001479, etc. Chain Transfer (reversible addition cleavage chain transfer) polymerization method, Chem. Express 5 (10), 801 (1990), etc. disclosed initiation-transfer-termination (Iniferte) method with photo-thermal dissociation group, etc.

Among them, a living radical polymerization method using a non-metallic catalyst that is inexpensive and has little environmental load is preferred. This polymerization method is implemented using, for example, the above-mentioned various monomers, starting compounds, catalysts, radical polymerization initiators, and polymerization solvents.

…式4(Starting compound) As the starting compound, an iodine compound represented by Formula 4 below is preferably used. [化10]

…Form 4

The iodine atom in the starting compound is bound to the secondary or tertiary carbon atom, and X, Y and Z may be the same or different, preferably selected from hydrogen, hydrocarbyl, halo, cyano, alkoxy Carbonyl, allyloxycarbonyl, acetyloxy, allyloxy, alkoxy, alkylcarbonyl, and allylcarbonyl.

Considering the dissociability of iodine, the iodine atom is preferably bonded to a secondary or tertiary carbon atom. As a result, at least two of X, Y, and Z are not hydrogen atoms. Hereinafter, X, Y, and Z will be specifically exemplified, but not limited to these.

Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups. Specific examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-methylpropyl, tertiary butyl, pentyl, and dodecyl; Vinyl, allyl, 2-methylvinyl, butenyl, butadienyl and other alkenyl groups containing double bonds; acetylene, methylacetylene and other alkynyl groups containing triple bonds; phenyl, naphthyl, methyl Aryl groups such as phenyl, ethyl phenyl, propyl phenyl, dodecyl phenyl, biphenyl, etc. and may also include pyridyl, imidazolinyl and other heterocyclic aryl groups; phenylmethyl , 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl and other aralkyl groups.

Examples of the halogen group include fluorine atom, chlorine atom, bromine atom, and iodine atom.

Examples of the alkoxycarbonyl group or allyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propylcarbonyl group, a cyclohexylcarbonyl group, a benzyloxycarbonyl group or a phenoxycarbonyl group, and a naphthoxycarbonyl group.

Examples of the acetyloxy group or allyloxy group include acetoxy group, ethylcarbonyloxy group, cyclohexylcarbonyloxy group, benzoyloxy group, and naphthylcarboxyoxy group.

Examples of the alkoxy group include methoxy, ethoxy, methoxyethoxy, and phenoxyethoxy groups.

Examples of the alkylcarbonyl group or allylcarbonyl group include methylcarbonyl group, ethylcarbonyl group, and phenylcarbonyl group.

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.

Also, in this polymerization method, the molecular weight of the copolymer can be controlled by the amount of the starting compound. The arbitrary molecular weight, or the size of the molecular weight, can be controlled by setting the molar number of the monomer relative to the molar number of the starting compound. The molar ratio of the starting compound to the monomer is not particularly limited, and can be appropriately determined depending on the required molecular weight and the like. For example, in the case of using 1 molar starting compound and 500 molar monomers with a molecular weight of 100 to perform polymerization, a theoretical molecular weight of 1×100×500=50,000 can be provided.

(catalyst) As the catalyst, a non-metallic compound that can capture iodine of the starting compound or iodine at the end of the polymer to become a radical, for example, a phosphorus compound, a nitrogen compound, or an oxygen compound having such properties can be used.

Although not limited to the following, for example, as the phosphorus compound, phosphorus halide containing an iodine atom, phosphite-based compound, phosphite-based compound, etc. may be mentioned; as the nitrogen compound, amide imide-based compound, ethyl Internal urea, barbituric acid, cyanuric acid, etc.; examples of oxygen compounds include phenolic compounds, iodooxyphenyl compounds, and vitamins. These can be used alone or in combination of two or more.

Specifically, the phosphorus compound is a phosphorus halide containing an iodine atom, a phosphite-based compound, or a phosphite-based compound, and examples thereof include phosphorus iodide, phosphorus dibromide, phosphorus triiodide, and dimethyl. Phosphite, diethyl phosphite, dibutyl phosphite, bis(perfluoroethyl) phosphite, diphenyl phosphite, dibenzyl phosphite, bis(2-ethylhexyl ) Phosphite, bis(2,2,2-trifluoroethyl) phosphite, diallyl phosphite, ethylidene phosphite, ethylphenyl phosphite, phenylphenyl phosphite Phosphate, ethyl methyl phosphite, phenyl methyl phosphite, etc.

As the nitrogen compound, examples of the amide imines include succinimide, 2,2-dimethyl succinimide, and α,α-dimethyl-β-methyl succinimide. , 3-ethyl-3-methyl-2,5-pyrrolidinedione, cis-1,2,3,6-tetrahydrophthalimide, α-methyl-α-propylbutane Diimide, 5-methylhexahydroisoindole-1,3-dione, 2-phenylbutanediimide, α-methyl-α-phenylbutanediimide, 2,3 -Diethylacetoxybutadieneimide, maleimide, phthalimide, 4-methylphthalimide, N-chlorophthalimide , N-bromophthalimide, N-bromophthalimide, 4-nitrophthalimide, 2,3-naphthalenecarboximide, pyromellitic acid diamine Acetylene imide, 5-bromoisoindole-1,3-dione, N-chlorobutadiene imide, N-bromobutadiene imide, N-iodobutadiene imide, etc. Examples of the hydantoins include hydantoin, 1-methylhydantoin, 5,5-dimethylhydantoin, 5-phenylhydantoin, and 1,3-dihydantoin. Iodine-5,5-dimethylhydantoin, etc. Examples of barbituric acids include barbituric acid, 5-methylbarbituric acid, 5,5-diethylbarbituric acid, 5-isopropylbarbituric acid, and 5,5-dibarbituric acid. Butyl barbituric acid, thiobarbituric acid, etc. Examples of the cyanuric acid include cyanuric acid, N-methyl cyanuric acid, and triiodocyanuric acid.

The oxygen compound is a phenolic compound having a phenolic hydroxyl group having an aromatic ring as a hydroxy group, an iodoxyphenyl compound as an iodide of the phenolic hydroxyl group, and vitamins. For example, as phenols, phenol and p Hydroquinone, 4-methoxyphenol, 4-tert-butylphenol, 4-tert-butyl-2-methylphenol, 2-tert-butyl-4-methylphenol, catechol, Resorcinol, 2,6-di-tert-butyl-4-methylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-di-third Butyl-4-methoxyphenol, a polymer obtained by polymerizing 4-hydroxystyrene or its polymer fine particles carrying hydroxyphenyl, 3,5-di-third butyl-4-methacrylate Monomers with phenolic hydroxyl groups such as hydroxyphenyl ethyl ester. These systems are added to the ethylenically unsaturated monomer as a polymerization inhibitor. Therefore, the commercially available ethylenically unsaturated monomer can be used directly without purification, which can also exert its effects. Examples of the iodooxyphenyl compound include resveratrol iodide, and examples of vitamins include vitamin C and vitamin E.

The amount of catalyst used usually does not reach the number of moles of the radical polymerization initiator, and can be arbitrarily determined in consideration of the control state of polymerization and the like.

(Free radical polymerization initiator) As the radical polymerization initiator, previously known ones can be used without particular limitation, and for example, organic peroxides or azo compounds can be used. Specific examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, and tertiary Hexyl peroxybenzoate, third butyl-2-ethylhexanoate peroxide, third hexyl-2-ethylhexanoate peroxide, 1,1-bis (third butyl peroxide) 3,3,5-trimethylcyclohexane, hydroperoxide 2,5-dimethyl-2,5-bis (third butyl peroxide) hexyl-3,3-isopropyl, hydroperoxide Tertiary butyl, dicumyl hydroperoxide, acetoxy peroxide, bis(4-tertiary butylcyclohexyl) peroxydicarbonate, isobutyl peroxide, 3,3,5 peroxide -Trimethylhexylanyl, lauryl peroxide, 1,1-bis (third butyl peroxide) 3,3,5-trimethylcyclohexane, 1,1-bis (third hexyl peroxide ) 3,3,5-trimethylcyclohexane, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (isobutyrate), etc.

From the viewpoint of polymerizability, the number of moles of the radical polymerization initiator relative to the monomer can be used within a range of 0.001 mole times or more, 0.002 mole times or more, or 0.005 mole times or more. Use within the range of 0.1 mole times or less, 0.05 mole times or less or 0.01 mole times or less.

(Polymerization solvent) As the polymerization solvent, a solvent that does not show reactivity with respect to the functional group of the monomer is appropriately selected. Although not limited to the following, for example, hydrocarbon systems such as hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, and cumene Solvents; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, benzyl alcohol, cyclohexanol and other alcohol solvents; 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, butyl carbitol, butyl triethylene glycol, methyl dipropylene glycol and other hydroxyl-containing diols Ether; Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl ether acetate, diethylene glycol monobutyl ether Glycol solvents such as acetate; diethyl ether, dimethyl ether, dipropyl ether, methylcyclopropyl ether, tetrahydrofuran, dioxane, anisole and other ether solvents; dimethyl ketone, diethyl ketone, Ketone solvents such as ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, isophorone, and acetophenone; methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl butyrate, butyric acid Ethyl ester, caprolactone, methyl lactate, ethyl lactate and other ester solvents; chloroform, dichloromethane, dichloroethane, o-dichlorobenzene and other halogen solvents; methylamine, N,N-dimethyl Acetamide-based solvents such as methylamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam; dimethyl sulfoxide, Glyphosate, tetramethylurea, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, nitromethane, acetonitrile, nitrobenzene, dioctyl phthalate, etc.

(Polymerization temperature) The polymerization temperature can be appropriately adjusted according to the half-life of the radical polymerization initiator, and is not particularly limited. For example, it can be set to 0°C or higher or 30°C or higher, or 150°C or lower or 120°C or lower.

(Aggregation time) The polymerization time is preferably continued until the monomer disappears, and is not particularly limited. For example, it can be set to 0.5 hours or more, 1 hour or more, or 2 hours or more, and can be set to 48 hours or less, 24 hours or less, or 12 hours or less. .

(Aggregation atmosphere) The polymerization atmosphere is not particularly limited, and the polymerization can be carried out directly in an atmospheric atmosphere, that is, oxygen can be present in the polymerization system within a normal range, and can also be carried out under a nitrogen atmosphere in order to remove oxygen if necessary. Various materials can be used to remove impurities by distillation, activated carbon or alumina, etc., or commercially available products can also be used directly. In addition, the polymerization can be carried out under light shielding or in a transparent container such as glass.

"Use of Block Copolymers" The block copolymer of the present invention can be used as a surface treatment agent, for example. The surface treatment of the object using the block copolymer of the present invention may be any conventional treatment method, and the method is not particularly limited. For example, the block copolymer of the present invention can be dissolved in an appropriate dispersion medium, and the object can be mixed and stirred in the solution to obtain a dispersion containing the surface-treated object. The surface-treated object can be used in the state of dispersion, or it can be used in the form of powder after drying.

When the block copolymer of the present invention is applied to an object as a surface treatment agent, the ratio between the object and the block copolymer is not particularly limited as long as it exhibits required properties such as dispersibility, for example, in terms of mass ratio , Can be set in the range of 100:5~100:40, and more preferably in the range of 100:7~100:30, more preferably in the range of 100:10~100:20.

In addition, the content of the object in the dispersion liquid can be set to a range of 10% by mass or more, 20% by mass or more, or 30% by mass or more of the entire dispersion, and can also be set to 90% by mass or less, 80% by mass or less Or 70% by mass or less.

<Object> 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 kinds. For example, an object having a hydrophilic surface and inorganic particles having a hydroxyl group on the surface are preferred , Such as metal oxides. Such hydroxyl groups on the surface of the object can form hydrogen bonds with the hydroxyl groups of the hydrophilic segment. The inorganic particles are not particularly limited, and examples thereof include silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide, and magnesium oxide. Zinc oxide, titanium oxide, cerium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine blue, iron blue, chromium oxide, chromium hydroxide, carbon black and their composites Wait for particles. In addition, regarding the shape of the particles, for example, any shape such as a plate shape, a block shape, a scaly shape, a spherical shape, a porous spherical shape, and the like, and the particle size is not particularly limited.

(Dispersion medium) As the dispersion medium, organic solvents, especially various oils, can be used. Although not limited to the following, for example, liquid paraffin, squalane, isoalkanes, branched light paraffin, petrolatum, ceresin, etc. may be mentioned. Hydrocarbon oil, isopropyl myristate, cetyl isooctanoate, glyceryl tricaprylate and other ester oils, decamethylpentasiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, etc. Silicone oil, etc. These can be used alone or in combination of two or more.

Among them, polysiloxane oil can be preferably used from the viewpoint of the sense of use when making cosmetics and the like. Specifically, the 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 relative to the entire dispersion medium, and can also be used in the range of 100% by mass or less.

The polysiloxane oil is not limited to the following, but for example, chain polysiloxane, cyclic polysiloxane, modified polysiloxane, polysiloxane-based resin, etc. can be used, preferably under normal pressure The boiling point is below 200 ℃. For example, chain polysiloxanes such as dimethyl polysiloxane, methylphenyl polysiloxane, methylhydropolysiloxane, etc.; octamethylcyclotetrasiloxane, decamethylcyclopenta Cyclic polysiloxanes such as silicone, dodecylcyclohexasiloxane, tetramethyltetrahydrocyclotetrasiloxane, etc.

Among them, volatile chain polysiloxanes such as low polymerization degree dimethyl polysiloxane (polymerization degree 3 to 7) or decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane and other rings are used In the case of volatile polysiloxane oil such as volatile polysiloxane, for example, it is not easy to leave a greasy feeling when applied to the skin as a cosmetic, etc., and it can obtain a refreshing sense of use, so it is particularly preferred.

"Use of Inorganic Particle Dispersion" Compared with the inorganic particle dispersion system obtained by the previous surface treatment, the dispersion liquid of the inorganic particles subjected to the surface treatment of the block copolymer of the present invention can greatly suppress the increase in viscosity accompanying the preparation of the inorganic particles, and therefore can be highly formulated without restricting the formulation. Inorganic particles. Therefore, the dispersion liquid can be used for various applications such as cosmetics, resin compositions, paints, inks, and coating compositions. Among them, it is preferably used for cosmetics, especially cosmetics for sunscreen. Although the present invention is not limited, specifically, the cosmetics using the dispersion liquid of inorganic particles surface-treated with the block copolymer of the present invention will be described below.

<Makeup> When the inorganic particle dispersion of the present invention is applied to a cosmetic, it can be directly or diluted with an oily component to make an oily cosmetic, and the aqueous component can also be emulsified by a known method. After treatment, the oil-in-water or oil-in-water emulsion cosmetics, especially the oil-in-water emulsion cosmetics are prepared.

Cosmetics containing the dispersion of inorganic particles of the present invention, especially cosmetics for sunscreen, can be highly formulated into cosmetics with good dispersibility, such as titanium oxide, zinc oxide, cerium oxide, iron oxide, mica, etc., without greatly increasing the viscosity in. As a result, the cosmetic has excellent applicability to the skin, and can increase the SPF (Sun Protection Factor) value based on the scattering and shielding effect of ultraviolet rays by the uniformly dispersed scattering agent.

The SPF value is a value that varies according to the degree of dispersion of the inorganic particles, so the SPF value can also be used as an indicator of dispersion stability. The SPF value and viscosity of the cosmetics are not limited to the following, for example, as the SPF value, it can be set to 15 or more, 20 or more, or 25 or more, and can also be set to 60 or less, 55 or less, or 50 or less as the viscosity, Can be set below 50000 Pa·s, below 30000 Pa·s, or below 10000 Pa·s, especially below 3000 Pa·s, below 2800 Pa·s, or below 2500 Pa·s The viscosity can be set to 100 Pa·s or more, 150 Pa·s or more, or 200 Pa·s or more. Here, the term "viscosity" means the shear rate of the object to be measured when measuring at 32°C and 1 atmosphere using VDA-2 or VS-H1 (all manufactured by SHIBAURA SYSTEM) as a Vismetron viscometer. Time viscosity.

The inorganic particle dispersion liquid of the present invention can be highly formulated with inorganic particles in cosmetics. Although not limited to the following, for example, the amount of inorganic particles to be formulated in cosmetics can be adjusted to 5 mass% relative to the total amount of cosmetics Above, 10% by mass or more, or 15% by mass or more, 50% by mass or less, 48% by mass or less, or 45% by mass or less can be prepared.

The dosage form of the cosmetic of the present invention is arbitrary, and can be provided in any form such as solution system, solubilization system, emulsification system, water-oil two-layer system, gel, aerosol, mist, and capsule. In addition, the product form of the cosmetics of the present invention is also arbitrary, as long as it is a cosmetics such as lotion, lotion, cream, mask, etc.; foundation, powder, blush, lipstick, lipstick, eye shadow, eyeliner, mascara, sunscreen, etc. Make-up cosmetics; body cosmetics; aromatic cosmetics; skin cleansers such as makeup removers, facial cleansers, shower gels; hair cosmetics such as hair creams, shampoos, shampoos, conditioners, shampoos, etc. Since it has been used as an external preparation for skin, it can be applied in any form. In particular, it can be preferably used as a product for preventing ultraviolet rays.

(Optional) The cosmetic of the present invention can be appropriately formulated with various ingredients within a range that does not affect the effect of the present invention. Examples of the various components include additives that can be generally formulated in cosmetics, such as oils and fats such as liquid oils, solid oils, waxes, and higher fatty acids, higher alcohols, anionic surfactants, cationic surfactants, and amphoteric surfactants. Nonionic surfactants, moisturizers, water-soluble polymers, tackifiers, film agents, metal ion blocking agents, lower alcohols, polyols, various extracts, sugars, amino acids, organic amines, polymer latex, Chelating agents, ultraviolet absorbers, pH adjusters, skin nutrients, vitamins, water-soluble agents that can be used in pharmaceuticals, quasi-drugs, cosmetics, antioxidants, buffers, preservatives, antioxidant aids, organic powders , Pigments, dyes, pigments, spices, water, etc.

In the case of making sunscreen cosmetics, one or two or more water-soluble or oil-soluble organic ultraviolet absorbers can also be formulated.

Examples of water-soluble ultraviolet absorbers include: 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methyl Oxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4' -Phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, 4-hydroxy-3-carboxybenzophenone and other benzophenone ultraviolet absorbers ; Phenylbenzimidazole-5-sulfonic acid and its salts, phenylene-bis-benzimidazole-tetrasulfonic acid and its salts, benzimidazole-based ultraviolet absorbers; 3-(4'-methylbenzylidene) Radical)-d,l-camphor, 3-benzylidene-d,l-camphor, urinary acid, urinary acid ethyl ester, etc.

Examples of the oil-soluble ultraviolet absorber include p-aminobenzoic acid (PABA), PABA monoglyceride, N,N-dipropoxy ethyl PABA, N,N-diethoxy PABA ethyl ester, N , N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester and other benzoic acid-based ultraviolet absorbers; N-acetyl anthranilic acid homomethyl ester and other o-aminobenzoic acid-based ultraviolet absorbers Agents; amyl salicylate, yl salicylate, homoyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, phenyl p-isopropyl alcohol salicylate, etc. Acid-based ultraviolet absorber; octyl cinnamate, ethyl 4-isopropylcinnamate, methyl 2,5-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, 2,4- Methyl diisopropylcinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate, p-methoxy 2-ethylhexyl cinnamate, 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenylcinnamate, α-cyano -Β-phenylcinnamic acid 2-ethylhexyl ester, glyceryl mono-2-ethylhexyl-di-p-methoxycinnamic acid ester, 3,4,5-trimethoxycinnamic acid 3-methyl Benzyl-4-[methylbis(trimethylsilyloxy)silyl] butyl ester and other cinnamic acid ultraviolet absorbers; 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy- 5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-third octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenylbenzene Pyrogallazole, dibenzhydrazine, dianisyl methyl methane, 4-methoxy-4'-third butyl dibenzoyl methane, 5-(3,3-dimethyl-2-methylene (Lower 𦯉基)-3-pentane-2-one, octocrylene, etc. [Example]

The following examples illustrate the present invention in further detail, but the present invention is not limited to these. In addition, unless otherwise stated in advance, the formulation amount is expressed in parts by mass.

"Examples 1 to 5 and Comparative Examples 1 to 8"

<Synthesis method of copolymer> (Copolymer 1) 30 parts by mass of propylene glycol monomethyl ether acetate, 110 parts by mass of monomer of the following formula 2, 0.25 parts by mass of iodine, 2,2' were added to the reaction vessel equipped with a stirrer, a countercurrent condenser, a thermometer, and a nitrogen introduction tube -0.3 parts by mass of azobis (isobutyronitrile), while introducing nitrogen gas, and polymerizing at 80°C for 2 hours to produce a hydrophobic segment.

…式2 式2中，R¹ 及R² 為甲基，R³ 為丁基，m為3，且n為10。[Chem 11]

... Formula 2 In Formula 2, R ¹ and R ² are methyl, R ³ is butyl, m is 3, and n is 10.

Next, 15 parts by mass of methacrylic acid was added, and further polymerized at this temperature for 2 hours to form a hydrophilic block portion to obtain a block copolymer having a hydrophobic segment and a hydrophilic segment. If the molar ratio of the block copolymer obtained is converted according to the usage amount of each monomer raw material, the ratio of the monomer unit of the above formula 2 is about 80.5 mol%, and the ratio of the monomer unit of methacrylic acid is about 19.5 mol%.

(Copolymer 2) The block copolymer of copolymer 2 was produced by the same method as copolymer 1 except changing n of the monomer of the said Formula 2 from 10 to 30.

(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.

…式1 式1中，R¹ 為甲基，且m為11。[化12]

... Formula 1 In Formula 1, 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 above.

<Preparation method of surface-treated inorganic particle dispersion liquid> (Dispersion 1) 20 g of copolymer 1 was dissolved in 200 g of butanediol, and then 80 g of titanium oxide (ST-485WD, manufactured by Titan Kogyo Co., Ltd.) was added to the solution, and stirred at room temperature for 1 hour, A titanium oxide dispersion 1 containing 50% by mass of surface-treated titanium oxide was prepared.

(Dispersion 2~4) Instead of copolymer 1, copolymers 2 to 4 were used, and otherwise, dispersions 2 to 4 of titanium oxide were prepared in the same manner as dispersion 1.

<Evaluation of Viscosity and SPF Value> The viscosity of the emulsified product obtained by the formulations and manufacturing methods of Tables 1 to 2 shown below and the SPF value called UV protection index were evaluated. Here, regarding the viscosity, the following viscosity is adopted, that is, VDA-2 is used as the VISMETRON viscometer in the case of low viscosity, and VS-H1 is used as the VISMETRON viscometer in the case of high viscosity, measured at 32°C and 1 atmosphere Measure the viscosity of the object at a shear rate of 1/s. In addition, the SPF value was obtained by applying the obtained emulsion to a transparent tape at a coating amount of 2 mg/cm ² to prepare an evaluation sample, and inserting the evaluation sample as having ultraviolet rays in the ultraviolet region The SPF value is calculated by comparing the spectrum obtained based on the presence or absence of the evaluation sample between the solar simulator manufactured by SolarLight Corporation and the spectrophotometer of the light source of approximately the same spectrum. The calculation method based on each spectrum is the same as the method described in paragraph numbers "0076" and "0077" of Japanese Patent Publication No. 6-27064.

<Methods for producing emulsions of Examples 1 to 2 and Comparative Examples 1 to 6> (Example 1) The titanium oxide powder obtained by drying cyclopentasiloxane as an oil component and the dispersion 1 of titanium oxide was stirred and mixed at room temperature to prepare a mixture A. Then, PEG-10 dimethicone as an interfacial agent 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 emulsion of Example 1 was prepared. In addition, the composition of this emulsion is summarized in Table 1.

(Example 2) Except that cyclopentasiloxane and cetyl isooctanoate were used as oil components, the emulsion of Example 2 was prepared in the same manner as Example 1. In addition, the composition of this emulsion is summarized in Table 1.

(Comparative examples 1~2, 4 and 5) The various components and blending ratios described in Table 1 were used; and Dispersions B and C were used directly without drying, and otherwise, Comparative Examples 1 to 2, 4 and 5 were prepared in the same manner as in Example 1, respectively. Emulsion. In addition, the composition of this emulsion is summarized in Table 1. Here, the so-called powder A in Table 1 is titanium oxide powder surface-treated with aluminum stearate, and the so-called dispersion B is a surface treatment containing 40% by mass of aluminum stearate in cyclopentasiloxane. A dispersion liquid of titanium oxide and 10% by mass of surfactant, and the so-called dispersion liquid C contains 40% by mass of titanium oxide surface-treated with hydrogen dimethyl polysiloxane and 10% by mass in cyclopentasiloxane. Dispersion of surfactant with mass %.

(Comparative Examples 3 and 6) The oil-containing cyclopentasiloxane, ion-exchanged water, and Dispersion B or Dispersion C were stirred and mixed at 60°C to prepare the emulsified products of Comparative Examples 3 and 6, respectively. In addition, the composition of this emulsion is summarized in Table 1.

[Table 1]

<Result> It is clear from Table 1 that the emulsified system of Comparative Examples 1 to 6 using titanium oxide surface-treated with materials that have been used conventionally has a high viscosity of about 6700 Pa·s or higher, or the separation of oil and water, etc. It is unstable, but Examples 1 and 2 using titanium oxide surface-treated with the block copolymer of the present invention, in addition to having excellent dispersibility of titanium oxide, can greatly reduce the viscosity of the emulsion compared to Comparative Examples 1 to 6. Also, for example, according to Comparative Examples 2 and 4, it is clearly found that when titanium oxide that has been surface-treated with the previous material is used, the viscosity greatly changes depending on the type of oil, but the emulsified products of Examples 1 and 2 are hardly affected. The impact of different types of oil. Therefore, it can also be seen that titanium oxide and other objects subjected to the surface treatment of the block copolymer of the present invention are not easily restricted by the type of oil.

<Methods for producing emulsions of Examples 3 to 5 and Comparative Examples 7 to 8> (Example 3) The oil component described in Table 2 and the dry powder of the dispersion liquid 2 as a UV (ultraviolet) scattering agent were stirred and mixed in an atmosphere at 80° C. at the formulation ratio described in Table 2 to prepare a mixture C. Then, the water, alcohol, tackifier, moisturizer, surfactant, UV absorber, and other components described in Table 2 were stirred and mixed in the atmosphere at 80° C. at the formulation ratio described in Table 2 to prepare Mixture D , While stirring at 80°C, the mixture C was added to the mixture D to prepare the emulsion of Example 3. In addition, the composition of this emulsion is summarized in Table 2.

(Examples 4 and 5) Except that the UV scattering agent was changed from the dry powder of the dispersion liquid 2 to the dry powder of the dispersion liquid 3 or the dry powder of the dispersion liquid 4, the emulsified products of Examples 4 and 5 were prepared in the same manner as in Example 3, respectively. In addition, the composition of this emulsion is summarized in Table 2.

(Comparative example 7) The water, alcohol, tackifier, moisturizer, oil, surfactant, UV absorber, and other components described in Table 2 were stirred and mixed in the atmosphere at 80°C at the formulation ratio described in Table 2 to make a comparison Emulsion of Example 7. In addition, the composition of this emulsion is summarized in Table 2.

(Comparative Example 8) The emulsified product of Comparative Example 8 was prepared in the same manner as in Example 3 except that the UV scattering agent was changed from the dried powder of Dispersion Liquid 2 to Powder A. In addition, the composition of this emulsion is summarized in Table 2.

[Table 2]

<Result> It is clear from Table 2 that when a part of the UV absorber of Comparative Example 7 that does not contain a UV scattering agent is replaced with a UV scattering agent, usually as shown in Comparative Example 8, there is a substantial increase in viscosity accompanied by UV. The dispersion of the scattering agent tends to decrease and the SPF value also decreases. On the other hand, it can be seen that in the case of Examples 3 to 5 using titanium oxide surface-treated with the block copolymer of the present invention, even if a part of the UV absorber is replaced with a UV scattering agent, the viscosity will not increase but may be reduced. Viscosity can also increase the SPF value.

In addition, according to the results of Comparative Example 7 and Examples 3 to 5 in Table 2, it is considered that if a UV scattering agent containing titanium oxide or the like surface-treated with the block copolymer of the present invention is used, it can be obtained in a state of lower viscosity. The SPF value of the system without the UV scattering agent shown in Comparative Example 7 is equal to or higher than that of the system. Therefore, when the UV scattering agent is formulated at a higher concentration until the viscosity of the system without the UV scattering agent, it can be easily estimated that The SPF value is further improved than this system.

1‧‧‧hydrophobic segment 2‧‧‧Hydrophilic segment 3‧‧‧Object

Fig. 1 (a) is a schematic diagram of an object treated with a block copolymer surface, (b) is a schematic diagram of an object treated with a random copolymer surface, (c) is a surface treated with a low-molecular surface treatment agent Model diagram of the object to be processed. FIG. 2 is a schematic diagram of an object subjected to the surface treatment of a block copolymer according to an embodiment of the present invention.

1‧‧‧hydrophobic segment

2‧‧‧Hydrophilic segment

3‧‧‧Object

Claims (5)

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 contains monomer units composed of monomers of the following formula 3: [Chem 1]

… Formula 1 In Formula 1, R ¹ is hydrogen or methyl, and m is an integer from 0 to 21, [Chem 2]

… Formula 2 In Formula 2, R ¹ is hydrogen or methyl, 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, and n is an integer of 5 to 70 , [化3]

... Formula 3 In Formula 3, R ¹ is hydrogen or methyl. According to the block copolymer of claim 1, wherein R ¹ of the above formula 1 is a methyl group, m is an integer of 10 to 15, R ¹ and R ² of the above formula ² are a methyl group, R ³ is a butyl group, and m is An integer of 1 to 3, n is an integer of 10 to 60, and R ¹ of the above formula 3 is a methyl group. The block copolymer according to claim 1 or 2, wherein the ratio of the above-mentioned hydrophobic segment is 50 to 99 mol%, and the ratio of the above-mentioned hydrophilic segment is 1 to 50 mol%. A method for manufacturing a block copolymer according to any one of claims 1 to 3, which uses at least one monomer selected from Formula 1 and Formula 2 and forms a hydrophobic segment by a living radical polymerization method, and then , Using monomers of formula 3 and forming a hydrophilic segment by living radical polymerization, or The monomer of Formula 3 is used and a hydrophilic segment is formed by a living radical polymerization method, and then, at least one monomer selected from Formula 1 and Formula 2 is used and a hydrophobic segment is formed by a living radical polymerization method. The method according to claim 4, wherein the living radical polymerization method is a polymerization method using an iodine compound as a starting compound and a phosphorus compound, a nitrogen compound, or an oxygen compound as a catalyst.

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