TW202003642A - Block copolymer - Google Patents

Abstract

Provided is a novel block copolymer that can be used as a surface treatment agent capable of continuously imparting various characteristics. The block copolymer according to the present invention has a hydrophobic segment and a hydrophilic segment, wherein the hydrophobic segment has a monomer unit constituted by a monomer represented by formula 1, and the hydrophilic segment has a monomer unit constituted by a monomer represented by formula 2. In formula 1: R1 represents hydrogen or a methyl group, R2 and R3 independently represent a C1-6 alkyl group, m is an integer from 1 to 6 and n is an integer from 5 to 70. In formula 2: R1 represents hydrogen or a methyl group, m is an integer from 1 to 6 and R4 independently represents a hydrolyzing crosslinking functional group.

Description

Block copolymer

The present invention relates to a novel block copolymer.

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

Patent Document 1 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 2 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 a polymer block containing a monomer having a glycidyl group or isocyanate group via a glycidyl group or isocyanate group The polymer block to which any of the amine compound and the compound having a hydroxyl group is bonded.

Patent Document 3 discloses a hair treatment composition in which a random copolymer having a silane group bonded with at least one reactive functional group is blended. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-179112 [Patent Literature 2] International Publication No. 2010/016523 [Patent Document 3] Japanese Patent Laid-Open No. 11-302129

[Problems to be solved by the invention]

There are various expectations for polymers used as surface treatment agents. For example, in the field of hair cosmetics, polymers that have been continuously imparted with properties such as smoothness have been expected.

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 continuously impart various characteristics. [Technical means to solve the problem]

…式1 式1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2]

…式2 式2中， R¹ 為氫或甲基， m為1~6之整數，且 R⁴ 分別獨立地為水解行交聯反應之官能基。 ＜態樣2＞ 如態樣1所記載之嵌段共聚物，其中上述式1之R¹ 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2之R¹ 為甲基，R⁴ 為選自氫原子、烷氧基、鹵素原子、醯氧基及胺基中之至少一種，m為1~3之整數。 ＜態樣3＞ 如態樣1或2所記載之嵌段共聚物，其中嵌段共聚物中，上述式1之疏水性鏈段之比率為10~90莫耳%，且上述式2之親水性鏈段之比率為5~70莫耳%。 ＜態樣4＞ 如態樣1~3中任一項所記載之嵌段共聚物，其中上述親水性鏈段進而具有由下述式3之單體所構成之單體單元： [化3]

…式3 式3中， R¹ 為氫或甲基， m為1~6之整數，且 R⁵ 分別獨立地為碳原子數1~6之烷基。 ＜態樣5＞ 如態樣4所記載之嵌段共聚物，其中嵌段共聚物中，上述式3之親水性鏈段之比率為70莫耳%以下。 ＜態樣6＞ 一種如態樣1~5中任一項所記載之嵌段共聚物之製造方法，其使用式1之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2及於存在之情形時使用式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2及於存在之情形時使用式3之單體並藉由活性自由基聚合法形成親水性鏈段，繼而，使用式1之單體並藉由活性自由基聚合法形成疏水性鏈段。 ＜態樣7＞ 如態樣6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，且將磷化合物、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 having a hydrophobic segment and a hydrophilic segment, the hydrophobic segment having a monomer unit composed of a monomer of the following formula 1, the hydrophilic chain The segment has a monomer unit composed of monomers of the following formula 2: [Chem 1]

... Formula 1 In Formula 1, 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2]

… Formula 2 In Formula 2, R ¹ is hydrogen or methyl, m is an integer from 1 to 6, and R ^{4 is} independently a functional group for hydrolysis crosslinking reaction. <Aspect 2> The block copolymer as described in Aspect 1, wherein R ¹ and R ^{2 in the} above formula 1 are methyl, R ³ is butyl, m is an integer of 1 to 3, and n is 10 to 60 Integer, and R ^{1 in the} above formula 2 is a methyl group, R ⁴ is at least one selected from a hydrogen atom, an alkoxy group, a halogen atom, an oxy group, and an amine group, and m is an integer of 1-3. <Aspect 3> The block copolymer as described in Aspect 1 or 2, wherein in the block copolymer, the ratio of the hydrophobic segment of the above formula 1 is 10 to 90 mol%, and the hydrophilicity of the above formula 2 The ratio of sexual segments is 5 to 70 mol%. <Aspect 4> The block copolymer as described in any one of Aspects 1 to 3, wherein the hydrophilic segment further has a monomer unit composed of a monomer of the following formula 3:

... Formula 3 In Formula 3, R ¹ is hydrogen or methyl, m is an integer of 1 to 6, and R ^{5 is} independently an alkyl group having 1 to 6 carbon atoms. <Aspect 5> The block copolymer as described in Aspect 4, wherein the ratio of the hydrophilic segment of the above formula 3 in the block copolymer is 70 mol% or less. <Aspect 6> A method for producing a block copolymer as described in any one of Aspects 1 to 5, which uses the monomer of Formula 1 and forms a hydrophobic segment by a living radical polymerization method, and then, Use Formula 2 and use the monomer of Formula 3 in the case of existence and form a hydrophilic segment by living radical polymerization, or use Formula 2 and use the monomer of Formula 3 in the case of existence and free by activity The radical polymerization method forms a hydrophilic segment, and then, the monomer of Formula 1 is used and the hydrophobic segment is formed by a living radical polymerization method. <Aspect 7> The method as described in Aspect 6, 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 that can be used as a surface treatment agent that can continuously impart various characteristics.

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 has a hydrophobic segment and a hydrophilic segment, the hydrophobic segment has a monomer unit composed of the monomer of the following formula 1, and the hydrophilic segment has the following formula 2 Block copolymer of monomer units composed of monomers.

…式1 式1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5]

…式2 式2中， R¹ 為氫或甲基， m為1~6之整數，且 R⁴ 分別獨立地為水解行交聯反應之官能基。[Chemical 4]

... Formula 1 In Formula 1, 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 , [Chem 5]

… Formula 2 In Formula 2, R ¹ is hydrogen or methyl, m is an integer from 1 to 6, and R ^{4 is} independently a functional group for hydrolysis crosslinking reaction.

Although not limited by the principle, it is considered that the action principle of such a block copolymer to continuously impart surface treatment performance is as follows.

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.

The block copolymer of the present invention has a specific hydrophobic segment and a specific hydrophilic segment, wherein the hydrophilic segment is shown in FIG. 1 and is hydrolyzed after being adsorbed on the surface of the object to be surface-treated, and at least Form a cross-linked structure between the copolymers. It is considered that the copolymer having the cross-linked structure is easily entangled in the object, so the copolymer is not likely to fall off from the object. Especially in the case where the object is a surface having a hydroxyl group such as hair, it is considered that the functional group of the hydrophilic segment in the cross-linking reaction of hydrolysis will also react and bond with the hydroxyl group on the surface of the hair, so the copolymer is more difficult Fall off from the object.

In the case of a random copolymer, since the cross-linked part is close to the hydrophobic part and randomly arranged, as the cross-linked structure is formed, the hydrophobic part is also wrapped around the object at the same time, the result is It is considered that the performance based on the hydrophobic part cannot be sufficiently exerted on the object. On the other hand, the block copolymer of the present invention, as shown in FIG. 1, because the hydrophobic segment 2 and the hydrophilic segment 3 of the cross-linking site are separately and independently arranged, it is considered to be able to fully exhibit the object Based on the performance of the hydrophobic segment.

"Block Copolymer" The block copolymer of the present invention takes into consideration the performance based on the performance of the hydrophobic segment, etc., and the ratio of the hydrophobic segment of Formula 1 in the copolymer can be set to 10 mol% or more, 15 mol% or more 20 mol% or more, and it can be set to 90 mol% or less, 80 mol% or less, or 70 mol% or less. Considering the adsorption to the object, the formation of the cross-linked structure, etc., the ratio of the hydrophilic segment of Formula 2 can be set to 5 mol% or more, 10 mol% or more, or 15 mol% or more, and, It can be set to 70 mol% or less, 60 mol% or less, or 50 mol% or less.

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 100,000, preferably 2,000 to 50,000 The range is more preferably 5,000~20,000. In addition, 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 5.0, preferably in the range of 1.05 to 3.0.

…式1 尤其是於對象物為毛髮之情形時，可提高順滑性、速乾性等性能。<Hydrophobic Segment> (Monomer of Formula 1) The monomer of Formula 1 below constitutes the monomer unit of the hydrophobic segment, and can impart properties such as smoothness and water repellency to the object to which the copolymer is applied. [化6]

…Equation 1 Especially when the object is hair, performance such as smoothness and quick-drying can be improved.

In Formula 1, 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 viewpoints of performance such as smoothness and quick-drying properties, R ¹ and R ^{2 in} Formula 1 are preferably methyl, R ^{3 is} preferably butyl, m is preferably an integer of 1 to 3, n It is preferably an integer of 10-60, more preferably an integer of 20-60, and particularly preferably an integer of 20-50. Here, the position of (CH ₂ ) _{m in} Formula 1 may be either linear or branched, and preferably linear.

…式2<Hydrophilic Segment> (Monomer of Formula 2) The monomer of Formula 2 below constitutes the monomer unit of the hydrophilic segment, adsorbs on the surface of the object and hydrolyzes, forming a cross-linked structure at least between the copolymers . [化7]

…Form 2

In Formula 2, R ¹ is hydrogen or methyl, m is an integer of 1 to 6, and R ^{4 is} independently a functional group for the cross-linking reaction of hydrolysis. From the viewpoint of the adsorption of the target object and the formation of the cross-linked structure, R ^{1 of} Formula 2 is preferably a methyl group, and R ^{4 is} preferably selected from a hydrogen atom, an alkoxy group, a halogen atom, and an oxy group And at least one of amine groups, of which, methoxy or ethoxy is more preferred, and m is preferably an integer of 1 to 3. Here, the position of (CH ₂ ) _{m in} Formula 2 may be either linear or branched, and preferably linear.

…式3 該單體單元容易離子化成N⁺ 而吸附於毛髮等對象物，因此嵌段共聚物容易配向於對象物。<Arbitrary monomer> The hydrophilic segment of the present invention may further have a monomer unit composed of the monomer of Formula 3 below. [Chem 8]

... Formula 3 The monomer unit is easily ionized into N ⁺ and adsorbed to an object such as hair, so the block copolymer is easily aligned to the object.

In Formula 3, R ¹ is hydrogen or methyl, m is an integer of 1 to 6, and R ^{5 is} independently an alkyl group having 1 to 6 carbon atoms. From the standpoint of the adsorbability of the object, R ¹ and R ^{5 are} preferably methyl groups, and m is preferably an integer of 1 to 3. Here, the position of (CH ₂ ) _{m in} Formula 3 may be either linear or branched, and preferably linear.

In the block copolymer, the ratio of the hydrophilic segment of Formula 3 can be set to 70 mol% or less, 60 mol% or less, or 50 mol% or less from the viewpoint of adsorption to the object.

As long as the effect of the present invention is not impaired, the block copolymer of the present invention may further have a monomer unit composed of monomers other than the above formulas 1 to 3. 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, diene Propyl dimethyl ammonium chloride, alkyl acrylate, alkyl methacrylate, N,N'-dimethylacrylamide, styrene, 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, the monomer of Formula 1 above can be used and a hydrophobic segment can be formed by the living radical polymerization method, and then, the monomer of Formula 3 can be used by the living radical polymerization method and the living radical polymerization method can be used A block copolymer is obtained by forming a hydrophilic segment. Alternatively, Formula 2 and, where present, monomers of Formula 3 can be used to form a hydrophilic segment by living radical polymerization, and then, monomers of Formula 1 can be used to form a hydrophobic by living radical polymerization 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 any polymerization solvent.

…式4(Starting compound) As the starting compound, an iodine compound represented by Formula 4 below is preferably used. [化9]

…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, phthalimide, 4-methylphthalimide, N-chlorophthalimide , N-bromophthalimide, N-bromophthalimide, 4-nitrophthalimide, 2,3-naphthalenecarboximide, pyromethylenetetramine 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 compounds are phenolic compounds which are phenolic hydroxyl groups having a hydroxyl group in the aromatic ring, iodoxyphenyl compounds which are iodides of the phenolic hydroxyl groups, 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) If necessary, a polymerization solvent can be used. As the polymerization solvent, a solvent that does not exhibit 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 object to which the surface treatment agent can be applied is not particularly limited. For example, an object having a hydrophilic surface, an inorganic particle having a hydroxyl group on the surface, hair and the like are preferred, and hair is particularly preferred. Such hydroxyl groups on the surface of the object can react with the functional groups of the hydrophilic segment on the surface of the object to form a strong bond. Although the present invention is not limited, specifically, a hair cosmetic using the block copolymer of the present invention will be described below.

<hair cosmetics> The block copolymer of the present invention can be dissolved or dispersed in a non-aqueous solvent and used as a hair cosmetic, for example.

(Solvent) When the hair cosmetic is a non-aqueous composition, as the solvent, alcohols such as aliphatic hydrocarbons, aromatic hydrocarbons, chloro compound hydrocarbons, ether solvents, and aliphatic 1-4 alcohols having 1 to 4 carbon atoms can be used Cell-based solvents, ethyl cellosolve, butyl cellosolve and other cellosolve-based solvents, dioxane, methyl acetate, dimethylamide, etc. Among them, methanol, ethanol, isopropanol, propylene glycol, etc., which are aliphatic 1- to 2-valent alcohols, are preferred, and in terms of safety, ethanol and isopropanol are more preferred.

When the hair cosmetic is an aqueous composition, water such as ion-exchanged water or distilled water can be used as a solvent.

(Provision amount) The amount of the block copolymer used in hair cosmetics is not particularly limited. For example, it can be adjusted to 0.1% by mass, 0.2% by mass, or 0.3% by mass relative to the total amount of cosmetics. It is preferably 50% by mass or less, 25% by mass or less, or 10% by mass or less, and is preferably prepared in the range of 0.5% by mass to 3% by mass.

(Dosage form) The dosage form of the hair cosmetics is not particularly limited, as long as it is a form that can exert the effects of the present invention, it may be any dosage form. Examples include liquid, emulsion, cream, gel, mist, spray, aerosol, mousse, and the like.

(Optional) The hair cosmetics can be properly formulated with various ingredients within a range that does not affect the effects of the present invention. Examples of various components include additives that can be generally formulated in cosmetics, such as liquid oils, solid oils, waxes, higher fatty acids, rosehip oil, camellia oil, etc.; higher alcohols, anionic surfactants, cationic interface activities Agents, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymers, tackifiers, polysilicon oxide polysaccharides and other film forming agents, metal ion blocking agents, lower alcohols, polyols, various extracts , Sugar, amino acids, organic amines, polymer latex, chelating agents, ultraviolet absorbers, pH adjusters, skin nutrients, royal jelly extracts, vitamins, water-soluble agents that can be used in pharmaceuticals, quasi-drugs, cosmetics, etc. , Antioxidants, buffers, preservatives, antioxidant aids, sprays, organic powders, pigments, dyes, pigments, fragrances, water, acid components, alkali components, etc. Here, water, acid, and alkali are preferably prepared in a dosage form different from the block copolymer in advance.

<hair treatment method> As a hair treatment method using hair cosmetics, the cosmetics are applied to the hair so that the functional groups of the cross-linking reaction in the block copolymer contained in the cosmetics undergo cross-linking reaction at least on the hair surface. As the crosslinking method, for example, a method using a reaction by water, an acid or a base, a reaction by heat, or the like can be mentioned. Specifically, there is a method of applying hair cosmetics to hair using a known method such as coating, and then hydrolyzing the hair by contacting the hair with water, water vapor, acid, or alkali, or by heating. Methods, etc. Alternatively, hair cosmetics can also be applied to hair previously treated with water, acid, or alkali for hydrolysis and cross-linking.

Also, a method of mixing water, acid, or alkali in the hair cosmetic and applying it immediately is also conceivable, but a method of applying the hair cosmetic to the hair separately from water, acid, or alkali is also preferable. Although the reaction by water, acid or alkali usually proceeds at room temperature, it can also be heated to promote the reaction. When the cross-linking reaction can also proceed slowly, natural cross-linking can also be carried out only by moisture in the atmosphere. In addition, in order to uniformly apply and process in all cases, tools such as brushes, combs, and brushes are appropriately used as necessary.

The acid and base used in the hair treatment method are not particularly limited as long as they are functional groups that can promote the hydrolysis crosslinking reaction in the block copolymer, and organic or inorganic acid or base can be used . These acids and alkalis can be used alone or in combination of two or more, or they can be a mixture with water. [Example]

Hereinafter, the present invention will be described in further detail with examples, 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 2" <Synthesis of copolymers> (Copolymer 1) To a reaction vessel equipped with a stirrer, a countercurrent condenser, a thermometer, and a nitrogen introduction tube, add 25 parts by mass of the monomer of the following formula 1, 0.167 parts by mass of iodine, and 0.3 parts by mass of 2,2'-azobis(isobutyronitrile) Parts, and 0.082 parts by mass of N-iodobutanediimide, while introducing nitrogen gas, and performing polymerization at 60°C for 2 hours to produce a hydrophobic segment.

…式1 式1中，R¹ 及R² 為甲基、R³ 為丁基，m為3，且n為10。[化10]

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

Next, 11.7 parts by mass of the monomer of the following formula 2 and 6.4 parts by mass of the monomer of the following formula 3 were added, and polymerization was further performed at this temperature for 2 hours to form a hydrophilic block portion to obtain a hydrophobic segment. And hydrophilic segment block copolymers. 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 1 is about 49.4 mol%, and the ratio of the monomer unit of the above formula 2 is about 25.2 mol%, the ratio of the monomer unit of the above formula 3 is about 25.4 mol%.

…式2 式2中，R¹ 為甲基，m為3，且R⁴ 為乙氧基， [化12]

…式3 式3中，R¹ 及R⁵ 為甲基，m為2。[Chem 11]

…Formula 2 In formula 2, R ¹ is methyl, m is 3, and R ⁴ is ethoxy,

... Formula 3 In Formula 3, R ¹ and R ⁵ are methyl groups, and m is 2.

(Copolymer 2) The addition amount of each monomer is set to 30 parts by mass of the monomer of the above formula 1, 21 parts by mass of the monomer of the above formula 2, and 0 parts by mass of the monomer of the above formula 3, except that it is the same as the copolymer 1. Method to make block copolymer of copolymer 2.

(Copolymer 3) The n of the monomer of the above formula 1 was changed to 60, and the amount of each monomer added was 45 parts by mass of the monomer of the above formula 1, 3.5 parts by mass of the monomer of the above formula 2, and the monomer of the above formula 3 Except for 1.9 parts by mass, a block copolymer of copolymer 3 was produced in the same manner as copolymer 1.

(Copolymer 4) The n of the monomer of the above formula 1 was changed to 30, and the addition amount of each monomer was 45 parts by mass of the monomer of the above formula 1, 5.5 parts by mass of the monomer of the above formula 2, and the monomer of the above formula 3 Other than 0 parts by mass, a block copolymer of copolymer 4 was produced in the same manner as copolymer 1.

(Copolymer 5) The n of the monomer of the above formula 1 was changed to 30, and the amount of each monomer added was 45 parts by mass of the monomer of the above formula 1, 2.8 parts by mass of the monomer of the above formula 2, and the monomer of the above formula 3 Other than 0 parts by mass, a block copolymer of copolymer 5 was produced in the same manner as copolymer 1.

(Copolymer 6) 25 parts by mass of the monomer of Formula 1 above, 11.7 parts by mass of the monomer of Formula 2 above, and 6.3 parts by mass of the monomer of Formula 3 above were added to a reaction vessel equipped with a stirrer, a countercurrent condenser, a thermometer, and a nitrogen gas introduction tube 0.0082 parts by mass of N-iodobutanediimide was passed through nitrogen gas while being polymerized at 60°C for 2 hours to produce a random copolymer.

(Copolymer 7) Dissolve 8.0 g (27 mmol) of 3-methacryloxypropyltriethoxysilane and 4.0 g (40 mmol) of methyl methacrylate in 100 ml of ethanol, and heat at 70°C under a nitrogen gas flow After stirring for 1 hour, 0.05 g of potassium persulfate was added and reacted overnight to complete the copolymerization reaction. The reaction liquid was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol and added to 500 ml of n-hexane. Separate the precipitate to obtain the target random copolymer. The ratio of 3-methacryloxypropyltriethoxysilane monomer units equivalent to y in the obtained random copolymer was 40.3 mol%, and the ratio of methyl methacrylate monomer units was 59.7 Moore%.

<Preparation of cosmetics and evaluation samples> Three parts by mass of copolymers 1 to 7 were collected and dissolved in 97 parts by mass of ethanol, and the obtained persons were filled in spray containers to prepare cosmetics.

Next, after immersing the hair in a wetting liquid containing citric acid for 5 minutes, the hair was taken out from the wetting liquid, and about 0.5 g of cosmetics was spray-applied to the hair. It is fused by a comb, and after being left in the atmosphere for 5 minutes, the hair is dried with a dryer. Then, a hair iron at 180°C was applied to the hair for 15 seconds, and after undergoing a shampoo and a conditioner, an evaluation sample was prepared.

<Evaluation method> (Smoothness evaluation) 20 professional functional inspectors performed a functional evaluation on smoothness. As an evaluation method, a questionnaire was conducted on the smoothness of the hair without the cosmetics applied, the hair immediately after preparation, and the hair that had repeatedly undergone 30 shampoos and conditioners, and the evaluation was performed based on the following criteria. The results are shown in Table 1.

A: Out of 20, 16 or more answered that the smoothness was good. B: Among the 20 people, 12 to 15 answered that the smoothness was good. C: Out of 20, 6 to 11 answered that the smoothness was good. D: Out of 20, 0 to 5 answered that the smoothness was good.

(Quick-drying evaluation) 20 professional functional inspectors conducted a functional evaluation of quick-drying. As an evaluation method, the hair after shampoo and hair conditioner were immersed in water for 1 minute immediately after preparation and repeated 30 times, taken out, dried with a towel and placed in the atmosphere for 10 minutes, and then the hair was dried Questionnaire survey of the degree and evaluation according to the following criteria. The results are shown in Table 1.

A: Of the 20 people, 16 or more answered dry. B: Among the 20 people, 12 to 15 answered dry. C: Out of 20, 6 to 11 answered dry. D: Out of 20, 0 to 5 answered dry.

[Table 1]

<Result> It is clearly confirmed from Table 1 that the cosmetics containing the block copolymers of Examples 1 to 5 can provide smoothness continuously compared with the cosmetics containing the random copolymers of Comparative Examples 1 to 2. In addition, it can be seen that as the n-number of the monomer of Formula 1 or the ratio of the monomer unit of Formula 1 increases, quick-drying property can be continuously given.

In this embodiment, although hair is used as the object of applying the block copolymer, it is not limited to hair. For example, as long as the surface is hydrophilic, the hydrophilicity of the block copolymer can be easily predicted The segments are aligned on the surface of the object, and the hydrophobic segments are aligned on the outside of the object. Therefore, as long as it is based on the present example, it is possible to easily presume that such an object can continue to impart various characteristics based on the hydrophobic segment in the same manner.

1‧‧‧ block copolymer 2‧‧‧hydrophobic segment 3‧‧‧Hydrophilic segment 4‧‧‧Adsorbable monomer unit 5‧‧‧Crosslinking reactive monomer unit 6‧‧‧hair

FIG. 1 is a schematic diagram showing a mechanism for modifying hair using a block copolymer according to an embodiment of the present invention.

1‧‧‧ block copolymer

2‧‧‧hydrophobic segment

3‧‧‧Hydrophilic segment

4‧‧‧Adsorbable monomer unit

5‧‧‧Crosslinking reactive monomer unit

6‧‧‧hair

Claims (7)

A block copolymer having a hydrophobic segment and a hydrophilic segment, the hydrophobic segment has a monomer unit composed of a monomer of the following formula 1, and the hydrophilic segment has the following Monomer unit composed of monomer of formula 2: [Chem 1]

... Formula 1 In Formula 1, 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2]

… Formula 2 In Formula 2, R ¹ is hydrogen or methyl, m is an integer from 1 to 6, and R ^{4 is} independently a functional group for hydrolysis crosslinking reaction. The block copolymer according to claim 1, wherein R ¹ and R ² of the above formula 1 are methyl groups, R ³ is a butyl group, m is an integer of 1 to 3, n is an integer of 10 to 60, and the above formula 2 R ¹ is a methyl group, R ⁴ is at least one selected from a hydrogen atom, an alkoxy group, a halogen atom, an oxy group and an amine group, and m is an integer of 1 to 3. The block copolymer according to claim 1 or 2, wherein in the block copolymer, the ratio of the hydrophobic segment of the above formula 1 is 10 to 90 mol %, and the ratio of the hydrophilic segment of the above formula 2 is 5 ~70 mol%. The block copolymer according to any one of claims 1 to 3, wherein the above-mentioned hydrophilic segment further has a monomer unit composed of a monomer of formula 3 below: [化3]

... Formula 3 In Formula 3, R ¹ is hydrogen or methyl, m is an integer of 1 to 6, and R ^{5 is} independently an alkyl group having 1 to 6 carbon atoms. The block copolymer according to claim 4, wherein the ratio of the hydrophilic segment in the above formula 3 in the block copolymer is 70 mol% or less. A method for manufacturing a block copolymer according to any one of claims 1 to 5, which uses the monomer of formula 1 and forms a hydrophobic segment by a living radical polymerization method, and then uses formula 2 and the existing In this case, use the monomer of formula 3 and form a hydrophilic segment by living radical polymerization, or Using Formula 2 and, when present, using the monomer of Formula 3 and forming a hydrophilic segment by living radical polymerization, and then using the monomer of Formula 1 and forming a hydrophobic segment by living radical polymerization . The method according to claim 6, 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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