JP7315930B2 - block copolymer - Google Patents

Description

The present invention relates to novel block copolymers.

In recent years, various surface modification techniques using polymer materials and the like have been investigated for the purpose of imparting antifouling properties, antifogging properties, dispersibility of inorganic particles and the like, modification of hair, and the like.

Patent Document 1 discloses antifogging properties and antistatic properties for various members containing at least a hydrophobic segment and a hydrophilic segment, the hydrophilic segment containing at least monomer units of a cationic monomer and an anionic monomer. A block polymer capable of imparting properties and the like is disclosed.

Patent Document 2 discloses a pigment dispersion containing a pigment, a liquid medium and a polymer dispersant, wherein the polymer dispersant is a block polymer represented by AB or ABC, and A The block and C block are polymer blocks composed of ethylenically unsaturated monomers having no amino group and hydroxyl group, and the B block is a polymer block composed of a monomer having a glycidyl group or an isocyanate group, through a glycidyl group or an isocyanate group. A pigment dispersion is disclosed which is a polymer block to which either one of an amino compound and a compound having a hydroxyl group is bound.

Patent Document 3 discloses a hair treatment composition containing a random copolymer having a silyl group to which at least one reactive functional group is bonded.

JP 2017-179112 A WO2010/016523 JP-A-11-302129

There are various demands for polymers used as surface treatment agents. For example, in the field of hair cosmetics, there has been a demand for polymers capable of continuously imparting properties such as slipperiness.

Accordingly, an object of the present invention is to provide a novel block copolymer that can be used as a surface treatment agent capable of imparting various properties in a sustained manner.

式１中、
Ｒ^１は、水素又はメチル基であり、
Ｒ^２及びＲ^３は、それぞれ独立に、炭素原子数１～６のアルキル基であり、
ｍは、１～６の整数であり、かつ
ｎは、５～７０の整数であり、

式２中、
Ｒ^１は、水素又はメチル基であり、
ｍは、１～６の整数であり、かつ
Ｒ^４は、それぞれ独立に、加水分解して架橋反応する官能基である。
〈態様２〉
前記式１のＲ^１及びＲ^２が、メチル基であり、Ｒ^３が、ブチル基であり、ｍが、１～３の整数であり、ｎが、１０～６０の整数であり、かつ
前記式２のＲ^１が、メチル基であり、Ｒ^４が、水素原子、アルコキシ基、ハロゲン原子、アシルオキシ基及びアミノ基から選択される少なくとも一種であり、ｍが、１～３の整数である、
態様１に記載のブロックコポリマー。
〈態様３〉
ブロックコポリマー中、前記式１の疎水性セグメントの割合が、１０～９０モル％であり、かつ、前記式２の親水性セグメントの割合が、５～７０モル％である、態様１又は２に記載のブロックコポリマー。
〈態様４〉
前記親水性セグメントが、下記式３のモノマーから構成されるモノマー単位をさらに有する、態様１～３の何れか一項に記載のブロックコポリマー：

式３中、
Ｒ^１は、水素又はメチル基であり、
ｍは、１～６の整数であり、かつ
Ｒ^５は、それぞれ独立に、炭素原子数１～６のアルキル基である。
〈態様５〉
ブロックコポリマー中、前記式３の親水性セグメントの割合が、７０モル％以下である、態様４に記載のブロックコポリマー。
〈態様６〉
式１のモノマーを用い、リビングラジカル重合法により疎水性セグメントを形成し、次いで、式２及び存在する場合は式３のモノマーを用い、リビングラジカル重合法により親水性セグメントを形成し、又は
式２及び存在する場合は式３のモノマーを用い、リビングラジカル重合法により親水性セグメントを形成し、次いで、式１のモノマーを用い、リビングラジカル重合法により疎水性セグメントを形成する、
態様１～５の何れか一項に記載のブロックコポリマーの製造方法。
〈態様７〉
リビングラジカル重合法が、ヨウ素化合物を開始化合物とし、かつ、リン化合物、窒素化合物又は酸素化合物を触媒とする重合法である、態様６に記載の方法。<Aspect 1>
A block copolymer having a hydrophobic segment and a hydrophilic segment,
The hydrophobic segment has a monomer unit composed of a monomer of formula 1 below,
The hydrophilic segment has a monomer unit composed of a monomer of formula 2 below,
Block copolymer:

In formula 1,
R ¹ is hydrogen or a methyl group,
R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms,
m is an integer from 1 to 6, and n is an integer from 5 to 70,

In formula 2,
R ¹ is hydrogen or a methyl group,
m is an integer of 1 to 6, and R ⁴ is each independently a functional group that hydrolyzes and undergoes cross-linking reaction.
<Aspect 2>
R ¹ and R ² in 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 R ¹ of 2 is a methyl group, R ⁴ is at least one selected from a hydrogen atom, an alkoxy group, a halogen atom, an acyloxy group and an amino group, and m is an integer of 1 to 3,
A block copolymer according to embodiment 1.
<Aspect 3>
Aspect 1 or 2, wherein the proportion of the hydrophobic segment of Formula 1 is 10 to 90 mol% and the proportion of the hydrophilic segment of Formula 2 is 5 to 70 mol% in the block copolymer. block copolymer.
<Aspect 4>
The block copolymer according to any one of aspects 1-3, wherein said hydrophilic segment further comprises a monomer unit composed of a monomer of formula 3:

In formula 3,
R ¹ is hydrogen or a methyl group,
m is an integer of 1 to 6, and each R ⁵ is independently an alkyl group having 1 to 6 carbon atoms.
<Aspect 5>
The block copolymer according to aspect 4, wherein the proportion of the hydrophilic segment of formula 3 in the block copolymer is 70 mol% or less.
<Aspect 6>
Using the monomers of formula 1 to form the hydrophobic segment by living radical polymerization methods, and then using the monomers of formula 2 and, if present, formula 3 to form the hydrophilic segments by living radical polymerization methods, or and, if present, using the monomer of formula 3 to form the hydrophilic segment by living radical polymerization, and then using the monomer of formula 1 to form the hydrophobic segment by living radical polymerization.
A method for producing a block copolymer according to any one of aspects 1-5.
<Aspect 7>
The method according to aspect 6, wherein the living radical polymerization method is a polymerization method using an iodine compound as an initiator compound and a phosphorus compound, a nitrogen compound, or an oxygen compound as a catalyst.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel block copolymer that can be used as a surface treatment agent capable of imparting various properties continuously.

FIG. 2 is a schematic diagram showing the modification mechanism of hair by the block copolymer of one embodiment of the present invention.

Embodiments of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the spirit 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 a monomer of formula 1 below, and the hydrophilic segment is a monomer of formula 2 below. It is a block copolymer having monomer units composed of

式１中、
Ｒ^１は、水素又はメチル基であり、
Ｒ^２及びＲ^３は、それぞれ独立に、炭素原子数１～６のアルキル基であり、
ｍは、１～６の整数であり、かつ
ｎは、５～７０の整数であり、

式２中、
Ｒ^１は、水素又はメチル基であり、
ｍは、１～６の整数であり、かつ
Ｒ^４は、それぞれ独立に、加水分解して架橋反応する官能基である。

In formula 1,
R ¹ is hydrogen or a methyl group,
R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms,
m is an integer from 1 to 6, and n is an integer from 5 to 70,

In formula 2,
R ¹ is hydrogen or a methyl group,
m is an integer of 1 to 6, and R ⁴ is each independently a functional group that hydrolyzes and undergoes cross-linking reaction.

Although not limited by the principle, the principle of action by which such block copolymers can continuously impart surface treatment performance is believed to be as follows.

For example, when a random copolymer is prepared from a hydrophobic monomer and a hydrophilic monomer, the copolymer has a hydrophobic site and a hydrophilic site randomly arranged in the copolymer, so the random copolymer as a whole , it exhibits an intermediate performance that is a mixture of hydrophobicity and hydrophilicity. On the other hand, in the case of a block copolymer, a hydrophobic segment made of a hydrophobic monomer and a hydrophilic segment made of a hydrophilic monomer are separately formed in the copolymer. It is possible to impart different parts with different properties such as.

The block copolymer of the present invention has a specific hydrophobic segment and a specific hydrophilic segment, and the hydrophilic segment among them adsorbs to the surface of the object to be surface-treated, as shown in FIG. to form a crosslinked structure at least between the copolymers. Copolymers having such a crosslinked structure tend to cling to objects, so it is believed that the copolymers are less likely to detach from the objects. In particular, when the object has hydroxyl groups on its surface, such as hair, the functional groups in the hydrophilic segment that hydrolyze and crosslink react with the hydroxyl groups on the surface of the hair and bond together. is considered to be more difficult to detach from the object.

In the case of random copolymers, since the cross-linking site and the hydrophobic site are arranged in close proximity at random, the hydrophobic site is simultaneously entangled with the object along with the formation of the cross-linked structure, resulting in It is considered that the performance based on the hydrophobic site cannot be fully exhibited on the object. On the other hand, the block copolymer of the present invention, as shown in FIG. I think that it can be fully demonstrated for the target object.

《Block Copolymer》
In the block copolymer of the present invention, the proportion of the hydrophobic segment of Formula 1 in the copolymer is set to 10 mol% or more, 15 mol% or more, or 20 mol% or more in consideration of the performance expression based on the hydrophobic segment. can be 90 mol % or less, 80 mol % or less, or 70 mol % or less. Considering the adsorption to the object, the formation of the crosslinked structure, etc., the proportion of the hydrophilic segment in Formula 2 can be 5 mol% or more, 10 mol% or more, or 15 mol% or more. It can be 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. ,000 to 50,000, more preferably 5,000 to 20,000. Also, the molecular weight distribution, which is the ratio of the number average molecular weight to the weight average molecular weight, can be in the range of 1.05 to 5.0, preferably in the range of 1.05 to 3.0.

疎水性セグメントのモノマー単位を構成し、コポリマーを適用する対象物に対し、滑り性、撥水性等の性能を付与することができる。特に、対象物が毛髪である場合には、滑り性、速乾性等の性能を向上させることができる。<Hydrophobic segment>
(monomer of formula 1)
The monomer of Formula 1 below is

It constitutes the monomer unit of the hydrophobic segment and can impart properties such as slipperiness and water repellency to the object to which the copolymer is applied. In particular, when the object is hair, performances such as slipperiness and quick drying can be improved.

In Formula 1, R ¹ is hydrogen or a methyl group, R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 to 6, and , n is an integer from 5 to 70. From the viewpoint of the expression of performance such as slipperiness and quick-drying properties, R ¹ and R ² in Formula 1 are preferably methyl groups, R ³ is preferably a butyl group, and m is 1. n is preferably an integer of 1 to 3, preferably an integer of 10 to 60, more preferably an integer of 20 to 60, and particularly preferably an integer of 20 to 50. Here, the (CH ₂ ) _m moiety in Formula 1 may be linear or branched, but preferably linear.

親水性セグメントのモノマー単位を構成し、対象物の表面に吸着して加水分解し、少なくともコポリマー相互間で架橋構造を形成する。<Hydrophilic segment>
(monomer of formula 2)
The monomer of Formula 2 below is

It constitutes the monomer unit of the hydrophilic segment, adsorbs to the surface of the object and hydrolyzes to form a crosslinked structure at least between the copolymers.

In Formula 2, R ¹ is hydrogen or a methyl group, m is an integer of 1 to 6, and R ⁴ is each independently a functional group that hydrolyzes and undergoes cross-linking reaction. From the viewpoint of adsorbability to a target, formation of a crosslinked structure, etc., R ¹ in Formula 2 is preferably a methyl group, and R ⁴ is a hydrogen atom, an alkoxy group, a halogen atom, an acyloxy group, and an amino group. Among them, it is preferably at least one selected from, more preferably a methoxy group or an ethoxy group, and m is preferably an integer of 1 to 3. Here, the (CH ₂ ) _m moiety in Formula 2 may be linear or branched, but preferably linear.

から構成されるモノマー単位をさらに有していてもよい。係るモノマー単位は、Ｎ^＋にイオン化して毛髪等の対象物に吸着し易くなるため、ブロックコポリマーが対象物に対して配向し易くなる。<Arbitrary monomer>
The hydrophilic segment of the present invention is a monomer of formula 3 below

It may further have a monomer unit composed of. Such a monomer unit is ionized into N ⁺ and easily adsorbed to an object such as hair, so that the block copolymer is easily oriented with respect to the object.

In Formula 3, R ¹ is hydrogen or a methyl group, m is an integer of 1 to 6, and each R ⁵ is independently an alkyl group having 1 to 6 carbon atoms. R ¹ and R ⁵ are preferably methyl groups, and m is preferably an integer of 1 to 3, from the viewpoint of adsorbability to a target. Here, the (CH ₂ ) _m moiety in Formula 3 may be linear or branched, but preferably linear.

In the block copolymer, the proportion of the hydrophilic segment represented by formula 3 can be 70 mol % or less, 60 mol % or less, or 50 mol % or less from the viewpoint of adsorption to the object.

The block copolymer of the present invention may further have monomer units composed of monomers other than the above formulas 1 to 3 as long as the effects of the present invention are not impaired. The proportion of such monomer units can be in the range of 30 mol % or less, 20 mol % or less, 10 mol % or less, or 5 mol % or less of the total amount of constituent monomer units. Examples of such monomers include acrylamide, methacrylamide, methylacrylamide, methylmethacrylamide, dimethylmethacrylamide, ethylacrylamide, ethylmethacrylamide, diethylmethacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, ε-caprolactam, and vinyl alcohol. , maleic anhydride, diallyldimethylammonium chloride, alkyl acrylate, alkyl methacrylate, N,N'-dimethylacrylamide, styrene, and the like.

<Method for producing block copolymer>
The block copolymer of the present invention can be obtained by a known living radical polymerization method. For example, using the monomer of formula 1 above, the hydrophobic segment is formed by a living radical polymerization method, and then using the monomer of formula 2 and, if present, the monomer of formula 3 is used to form a hydrophilic segment by a living radical polymerization method. block copolymers can be obtained. Alternatively, the monomers of formula 2 and, if present, formula 3 are used to form the hydrophilic segment by living radical polymerization, and then the monomer of formula 1 is used to form the hydrophobic segment by living radical polymerization to block Copolymers can be obtained.

The living radical polymerization method is a method in which a catalyst, a chain transfer agent, or the like is added to a conventional radical polymerization method to control the reactivity of the terminal active radicals, thereby allowing the polymerization to proceed in a pseudo-living manner. The molecular weight distribution can be narrowed compared to ordinary radical polymerization, and the molecular weight can be controlled. As the known living radical polymerization method, specifically, the living radical polymerization method using a nonmetallic catalyst disclosed in International Publication No. 2010/016523, etc., the metal complex disclosed in International Publication No. 96/030421, etc. ATRP method by addition, TEMPO method of introducing thermally dissociable groups disclosed in U.S. Pat. RAFT polymerization method, Chem. Iniferter method with a photo-thermally dissociable group disclosed in Express 5 (10), 801 (1990) and the like can be mentioned.

Among them, the living radical polymerization method using a non-metallic catalyst is preferable because it is inexpensive and has less burden on the environment. Such polymerization methods are carried out using, for example, the various monomers, initiator compounds, catalysts, radical polymerization initiators and optionally polymerization solvents described above.

で表されるヨウ素化合物を用いることが好ましい。(starting compound)
As a starting compound, the following formula 4

It is preferable to use an iodine compound represented by.

The iodine atom in such starting compounds is bound to a secondary or tertiary carbon atom, and X, Y and Z may be the same or different, hydrogen, hydrocarbon groups, halogen groups, cyano groups, It is preferably selected from alkoxycarbonyl, aryloxycarbonyl, acyloxy, allyloxy, alkoxy, alkylcarbonyl and allylcarbonyl groups.

Considering the dissociation 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 cannot be hydrogen atoms. Specific examples of X, Y and Z are given below, but are not limited thereto.

Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups. Specifically, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-methylpropyl, t-butyl, pentyl, dodecyl; alkenyl groups containing a bond; alkynyl groups containing a triple bond such as acetylene, methylacetylene; aryl groups such as phenyl, naphthyl, methylphenyl, ethylphenyl, propylphenyl, dodecylphenyl, biphenyl, including pyridinyl, Aryl groups, which can also contain heterocycles such as imidazolinyl; arylalkyl groups such as phenylmethyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl; and the like.

A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

Alkoxycarbonyl or aryloxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propylcarbonyl, cyclohexylcarbonyl, benzyloxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl and the like.

Acyloxy or aryloxy groups include acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, naphthylcarboxyoxy and the like.

Alkoxy groups include methoxy, ethoxy, methoxyethoxy, phenoxyethoxy, and the like.

Alkylcarbonyl or allylcarbonyl groups include methylcarbonyl, ethylcarbonyl, phenylcarbonyl and the like.

Preferred specific examples of starting compounds include 1-iodo-1-phenylethane, 2-iodo-2-cyanopropane, 2-iodo-2-cyano-4-methylpentane and the like.

Also, in such polymerization methods, the molecular weight of the copolymer can be controlled by the amount of the starting compound. By setting the number of moles of the monomer with respect to the number of moles of the starting compound, it is possible to control the desired molecular weight or the size of the molecular weight. The molar ratio between the starting compound and the monomer is not particularly limited, and can be appropriately determined according to the required molecular weight and the like. For example, 500 moles of a monomer with a molecular weight of 100 can be polymerized using 1 mole of the starting compound to provide a theoretical molecular weight of 1 x 100 x 500 = 50,000.

(catalyst)
As the catalyst, iodine in the starting compound or a non-metallic compound that becomes a radical capable of abstracting iodine at the terminal of the polymer, such as a phosphorus compound, a nitrogen compound, or an oxygen compound having such properties can be used.

Examples of phosphorus compounds include, but are not limited to, phosphorus halides containing iodine atoms, phosphite compounds, phosphinate compounds, and the like. Nitrogen compounds include imide compounds, hydantoins, Barbituric acids, cyanuric acids, etc., and oxygen compounds include phenolic compounds, iodooxyphenyl compounds, vitamins, and the like. These can be used alone or in combination of two or more.

Specifically, phosphorus compounds include phosphorus halides containing iodine atoms, phosphite compounds, and phosphinate compounds, such as dichloroiodrine, dibromoiodrine, phosphorus triiodide, dimethylphosphite, Diethylphosphite, dibutylphosphite, di(perfluoroethyl)phosphinate, diphenylphosphite, dibenzylphosphite, bis(2-ethylhexyl)phosphite, bis(2,2,2-trifluoroethyl)phosphite , diallyl phosphite, ethylene phosphite, ethyl phenyl phosphinate, phenyl phenyl phosphinate, ethyl methyl phosphinate, phenyl methyl phosphinate and the like.

Examples of nitrogen compounds include imides such as succinimide, 2,2-dimethylsuccinimide, α,α-dimethyl-β-methylsuccinimide, 3-ethyl-3-methyl-2,5-pyrrolidinedione, cis-1, 2,3,6-tetrahydrophthalimide, α-methyl-α-propylsuccinimide, 5-methylhexahydroisoindole-1,3-dione, 2-phenylsuccinimide, α-methyl-α-phenylsuccinimide, 2,3- diacetoxysuccinimide, maleimide, phthalimide, 4-methylphthalimide, N-chlorophthalimide, N-bromophthalimide, N-bromophthalimide, 4-nitrophthalimide, 2,3-naphthalenecarboximide, pyromellitic diimide, 5-bromoisoindole -1,3-dione, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide and the like. Hydantoins include hydantoin, 1-methylhydantoin, 5,5-dimethylhydantoin, 5-phenylhydantoin, 1,3-diaiodo-5,5-dimethylhydantoin and the like. Barbituric acids include barbituric acid, 5-methylbarbituric acid, 5,5-diethylbarbituric acid, 5-isopropylbarbituric acid, 5,5-dibutylbarbituric acid, thiobarbituric acid, and the like. Cyanuric acids include cyanuric acid, N-methylcyanuric acid, triiodocyanuric acid and the like.

Examples of oxygen compounds include phenolic compounds that are phenolic hydroxyl groups having a hydroxyl group in an aromatic ring, iodooxyphenyl compounds that are iodides of phenolic hydroxyl groups, and vitamins. Examples of phenols include phenol, hydroquinone, 4-methoxyphenol, 4-t-butylphenol, 4-t-butyl-2-methylphenol, 2-t-butyl-4-methylphenol, catechol, resorcinol, 2,6-di-t-butyl-4-methyl Polymers obtained by polymerizing phenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-di-t-butyl-4-methoxyphenol, 4-hydroxystyrene, or polymer fine particles supporting hydroxyphenyl groups thereof, Examples thereof include monomers having a phenolic hydroxyl group such as 3,5-di-t-butyl-4-hydroxyphenylethyl methacrylate. Since these are added to the ethylenically unsaturated monomers as polymerization inhibitors, the effects can also be exhibited by using the commercially available ethylenically unsaturated monomers as they are without purification. The iodooxyphenyl compounds include thymol iodide and the like, and the vitamins include vitamin C, vitamin E and the like.

The amount of the catalyst used is generally less than the number of moles of the radical polymerization initiator, and can be arbitrarily determined in consideration of the polymerization control state and the like.

(Radical polymerization initiator)
As the radical polymerization initiator, conventionally known ones can be used without particular limitation, but for example, organic peroxides or azo compounds can be used. Specifically, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate , t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butyl peroxy)hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, isobutyl peroxide, 3 , 3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)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), and the like.

From the viewpoint of polymerizability, etc., the radical polymerization initiator can be used in the range of 0.001 mol times or more, 0.002 mol times or more, or 0.005 mol times or more with respect to the number of moles of the monomer, Moreover, it can be used in the range of 0.1 mol times or less, 0.05 mol times or less, or 0.01 mol times or less.

(Polymerization solvent)
A polymerization solvent can be used if desired. As such a polymerization solvent, a solvent that does not exhibit reactivity with the functional groups of the monomers is appropriately selected. Hydrocarbon solvents such as, but not limited to, hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, cumene; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Alcohol solvents such as hexanol, benzyl alcohol, cyclohexanol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, butyl Hydroxyl group-containing glycol ethers such as carbitol, butyltriethylene glycol and methyldipropylene glycol; glycol solvents such as diglyme, triglyme, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl ether acetate and diethylene glycol monobutyl ether acetate; diethyl Ether solvents such as ether, dimethyl ether, dipropyl ether, methyl cyclopropyl ether, tetrahydrofuran, dioxane, and anisole; ketone solvents such as dimethyl ketone, diethyl ketone, ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, isophorone, and acetophenone; acetic acid ester solvents such as methyl, ethyl acetate, butyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, caprolactone, methyl lactate, ethyl lactate; halogen solvents such as chloroform, dichloromethane, dichloroethane, o-dichlorobenzene; Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam; dimethylsulfoxide, sulfolane, tetramethylurea, ethylene carbonate, propylene carbonate, dimethyl carbonate , diethyl carbonate, nitromethane, acetonitrile, nitrobenzene, dioctyl phthalate, and the like.

(polymerization temperature)
The polymerization temperature is appropriately adjusted depending on the half-life of the radical polymerization initiator, and is not particularly limited. .

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

(Polymerization atmosphere)
The polymerization atmosphere is not particularly limited, and the polymerization may be carried out as it is under an air atmosphere. You can do it under ambient conditions. Impurities may be removed from the various materials used by distillation, activated carbon, alumina, or the like, but commercially available products may be used as they are. Moreover, the polymerization may be carried out under light shielding, or may be carried out in a transparent container such as glass.

《Applications of block copolymers》
The block copolymer of the present invention can be used, for example, as a surface treatment agent. Objects to which such a surface treatment agent can be applied are not particularly limited, but for example, objects having a hydrophilic surface, among which inorganic particles having hydroxyl groups on the surface and hair are preferred, and hair is particularly preferred. preferable. Such hydroxyl groups on the surface of the object can react with the functional groups of the hydrophilic segments on the surface of the object to form strong bonds. Although not intended to limit the present invention, hair cosmetics using the block copolymer of the present invention will be specifically described below.

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

(solvent)
When the hair cosmetic is a non-aqueous composition, solvents include aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, ether solvents, and aliphatic mono- to tetrahydric alcohols having 1 to 4 carbon atoms. alcohol-based solvents, such as ethyl cellosolve and butyl cellosolve, dioxane, methyl acetate, diformamide, and the like. Among them, aliphatic mono- to dihydric alcohols such as methanol, ethanol, isopropanol and propylene glycol are preferred, and ethanol and isopropanol are more preferred from the viewpoint of safety.

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

(Combination amount)
The blending amount of the block copolymer in the hair cosmetic is not particularly limited. 50% by mass or less, 25% by mass or less, or 10% by mass or less, and preferably in the range of 0.5% by mass to 3% by mass.

(dosage form)
The dosage form of the hair cosmetic is not particularly limited, and any form may be used as long as the effects of the present invention can be exhibited. Examples thereof include liquid, milky lotion, cream, gel, mist, spray, aerosol, and mousse.

(Optional component)
Various ingredients can be appropriately blended in the hair cosmetic as long as the effects of the present invention are not affected. Examples of various components include additive components that can be usually blended in cosmetics, such as liquid fats and oils, solid fats and oils, waxes, oils such as higher fatty acids, rosehip oil, and camellia oil, higher alcohols, anionic surfactants, and cationic surfactants. Active agents, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, film-forming agents such as siliconized polysaccharides, sequestering agents, lower alcohols, polyhydric alcohols, various extracts Liquids, sugars, amino acids, organic amines, polymer emulsions, chelating agents, UV absorbers, pH adjusters, skin nutrients, royal jelly extracts, vitamins, pharmaceuticals, quasi-drugs, water-soluble agents applicable to cosmetics, etc. Antioxidants, buffering agents, preservatives, antioxidizing aids, propellants, organic powders, pigments, dyes, dyes, fragrances, water, acid components, alkali components and the like can be mentioned. Here, water, acid and alkali are preferably prepared separately from the block copolymer.

<Hair treatment method>
As a method for treating hair with a hair cosmetic, the cosmetic is applied to the hair, and the functional groups that hydrolyze and crosslink in the block copolymer contained in the cosmetic are crosslinked with each other at least on the hair surface. be. Cross-linking methods include, for example, methods utilizing reactions with water, acids or alkalis, reactions with heat, and the like. Specifically, after applying the hair cosmetic to the hair using a known means such as coating, the hair is hydrolyzed by contacting the hair with water, steam, acid, or alkali, or by heating. There is also a method of cross-linking by Alternatively, the hair cosmetic may be applied to hair pretreated with water, acid or alkali for hydrolysis and cross-linking.

A method of mixing the hair cosmetic with water, acid or alkali and applying the mixture immediately is also conceivable, but it is preferable to apply the hair cosmetic and water, acid or alkali separately to the hair. The reaction with water, acid or alkali proceeds normally at room temperature, but may be accelerated by heating. If the progress of the cross-linking reaction is allowed to be slow, natural cross-linking can be carried out only by moisture in the atmosphere. In any case, tools such as a brush, a comb, and a brush can be used as necessary for uniform application and treatment.

Acids and alkalis used in the hair treatment method are not particularly limited as long as they are capable of promoting the reaction of the functional groups that hydrolyze and crosslink in the block copolymer, and organic or inorganic acids or alkalis are used. be able to. These acids and alkalis may be used alone or in combination of two or more, and may be a mixture with water.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, the compounding amount is shown in parts by mass.

<<Examples 1 to 5 and Comparative Examples 1 to 2>>
<Synthesis of copolymer>
(Copolymer 1)
25 parts by mass of the monomer of formula 1 below, 0.167 parts by mass of iodine, and 0.3 parts by mass of 2,2'-azobis(isobutyronitrile) were placed in a reaction vessel equipped with a stirrer, a backflow condenser, a thermometer, and a nitrogen inlet tube. and 0.082 parts by mass of N-iodosuccinimide, and polymerized at 60° C. for 2 hours while bubbling nitrogen to prepare a hydrophobic segment.

式１中、Ｒ^１及びＲ^２はメチル基、Ｒ^３はブチル基であり、ｍは３であり、かつ、ｎは１０である。

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

Subsequently, 11.7 parts by mass of a monomer of the following formula 2 and 6.4 parts by mass of a monomer of the following formula 3 are added, and further polymerized at the same temperature for 2 hours to form a hydrophilic block portion to form a hydrophobic block. A block copolymer with a segment and a hydrophilic segment was obtained. When the molar ratio of the resulting block copolymer is converted from the amount of each monomer raw material used, the ratio of the monomer units of formula 1 is about 49.4 mol%, and the ratio of the monomer units of formula 2 is about 25. .2 mol %, and the proportion of monomer units of Formula 3 above was about 25.4 mol %.

式２中、Ｒ^１はメチル基であり、ｍは３であり、かつ、Ｒ^４はエトキシ基であり、

式３中、Ｒ^１及びＲ^５はメチル基であり、ｍは２である。

wherein R ¹ is a methyl group, m is 3, and R ⁴ is an ethoxy group;

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

(Copolymer 2)
Copolymer 1 in the same manner as for copolymer 1 except that the amount of each monomer added was 30 parts by mass of the monomer of formula 1, 21 parts by mass of the monomer of formula 2, and 0 parts by mass of the monomer of formula 3. A block copolymer of Polymer 2 was made.

(Copolymer 3)
The n of the monomer of formula 1 was changed to 60, and the amount of each monomer added was 45 parts by mass of the monomer of formula 1, 3.5 parts by mass of the monomer of formula 2, and monomer 1 of formula 3 A block copolymer of Copolymer 3 was prepared in the same manner as Copolymer 1, except that the content was 9 parts by mass.

(Copolymer 4)
The n of the monomer of formula 1 was changed to 30, and the amount of each monomer added was 45 parts by mass of the monomer of formula 1, 5.5 parts by mass of the monomer of formula 2, and 0 of the monomer of formula 3. A block copolymer of Copolymer 4 was produced in the same manner as Copolymer 1 except that the amount was set to parts by mass.

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

(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, 6.3 parts by mass of the monomer of formula 3 above, and 0.0082 parts by mass of N-iodosuccinimide was charged and polymerized at 60° C. for 2 hours while bubbling nitrogen to prepare a random copolymer.

(Copolymer 7)
8.0 g (27 mmol) of 3-methacryloxypropyltriethoxysilane and 4.0 g (40 mmol) of methyl methacrylate were dissolved in 100 ml of ethanol, heated with stirring at 70° C. for 1 hour under a stream of nitrogen, and then added with 0.0 g of potassium persulfate. 05 g was added and allowed to react overnight to complete the copolymerization reaction. The reaction solution 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. The precipitate was collected to obtain the intended random copolymer. In the resulting random copolymer, the proportion of 3-methacryloxypropyltriethoxysilane monomer units corresponding to y was 40.3 mol %, and the proportion of methyl methacrylate monomer units was 59.7 mol %.

<Method for preparing cosmetics and evaluation samples>
3 parts by mass of each of copolymers 1 to 7 were sampled and dissolved in 97 parts by mass of ethanol, and the solution was filled in spray containers to prepare cosmetics.

Subsequently, the hair was immersed in a wetting liquid containing citric acid for 5 minutes, then the hair was removed from the wetting liquid, and about 0.5 g of a cosmetic was spray-coated on the hair. The hair was blended through a comb, left in the air for 5 minutes, and then dried with a hair dryer. Then, a hair iron at 180° C. was applied to the hair for 15 seconds, and shampoo and conditioner were applied to prepare an evaluation sample.

<Evaluation method>
(Slipperiness evaluation)
A sensory evaluation of slipperiness was conducted by 20 expert panels. As an evaluation method, a questionnaire was given to the hair to which no cosmetic was applied, the hair immediately after preparation and the hair to which the shampoo and the conditioner were applied 30 times each, and the slipperiness was evaluated according to the following criteria. Table 1 shows the results.

A: 16 or more out of 20 people answered that the slipperiness was good.
B: 12 to 15 out of 20 people answered that the slipperiness was good.
C: 6 to 11 out of 20 people answered that the slipperiness was good.
D: 0 to 5 persons out of 20 persons answered that the slip property was good.

(Quick-drying evaluation)
A sensory evaluation of the quick-drying properties was conducted by 20 expert panels. As an evaluation method, the hair immediately after preparation and after repeated shampooing and conditioning 30 times each was immersed in water for 1 minute, taken out, dried with a towel, left in the atmosphere for 10 minutes, and then a questionnaire was given on the dryness of the hair. was performed and evaluated according to the following criteria. Table 1 shows the results.

A: 16 or more out of 20 people answered that it was dry.
B: 12 to 15 out of 20 answered that it was dry.
C: 6 to 11 out of 20 people answered that it was dry.
D: 0 to 5 persons out of 20 persons answered that it was dry.

<result>
As is clear from Table 1, it was confirmed that the cosmetics containing the block copolymers of Examples 1 to 5 could provide more slipperiness in a sustained manner than the cosmetics containing the random copolymers of Comparative Examples 1 and 2. did it. It was also found that as the number n of the monomers of Formula 1 or the ratio of the monomer units of Formula 1 increases, quick-drying properties can be continuously imparted.

In this example, hair was used as an object to which the block copolymer was applied. oriented and the hydrophobic segment oriented on the outside of the object can be easily predicted. Therefore, based on this example, it can be easily presumed that various properties based on the hydrophobic segment can be continuously imparted to such an object as well.

1 block copolymer 2 hydrophobic segment 3 hydrophilic segment 4 adsorptive monomer unit 5 cross-linking reactive monomer unit 6 hair

Claims (5)

A block copolymer having a hydrophobic segment and a hydrophilic segment,
The hydrophobic segment has a monomer unit composed of a monomer of formula 1 below,
The hydrophilic segment has a monomer unit composed of a monomer of the following formula 2 and a monomer unit composed of a monomer of the following formula 3 ,
Block copolymer:
In formula 1,
R ¹ is hydrogen or a methyl group,
R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms,
m is an integer from 1 to 6, and n is an integer from 5 to 70,
In formula 2,
R ¹ is hydrogen or a methyl group,
m is an integer of 1 to 6, and R ⁴ is each independently at least one selected from a hydrogen atom, an alkoxy group, a halogen atom, an acyloxy group and an amino group ,
In formula 3,
R ¹ is hydrogen or a methyl group,
m is an integer from 1 to 6, and
Each R ⁵ is independently an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² in 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 R ¹ of 2 is a methyl group and m is an integer of 1 to 3;
The block copolymer of claim 1. In the block copolymer, the proportion of the hydrophobic segment of formula 1 is 10 to 90 mol% , the proportion of the hydrophilic segment of formula 2 is 5 to 70 mol%, and the proportion of formula 3 is 3. The block copolymer according to claim 1 or 2 , wherein the proportion of hydrophilic segments is 70 mol% or less . Using the monomer of Formula 1 to form a hydrophobic segment by a living radical polymerization method, then using the monomers of Formulas 2 and 3 to form a hydrophilic segment by a living radical polymerization method, or Using the monomer of Formula 3 to form a hydrophilic segment by a living radical polymerization method, and then using the monomer of Formula 1 to form a hydrophobic segment by a living radical polymerization method.
A method for producing the block copolymer according to any one of claims 1 to 3 . 5. The method according to claim 4 , wherein the living radical polymerization method is a polymerization method using an iodine compound as an initiator compound and a phosphorus compound, a nitrogen compound or an oxygen compound as a catalyst.

Images