JPH07133352A - Organopolysiloxane, hair-setting composition containing same, and setting method for hair using the same - Google Patents

Abstract

PURPOSE:To obtain a hair-setting compsn. improved in hair-setting capability and in keeping a hair set by reacting a specific organopolysiloxane with a poly(N-acylalkyleneimine) having reactive molecular ends. CONSTITUTION:An organopolysiloxane which has intra- and intermolecular, not covalently bonded crosslinks, does not undergo breakage nor plastic deformation at 0-15% elongation at 20 deg.C and a relative humidity of 65%, is solid at ordinary temp. and pressure, and is soluble or completely dispersible in water or a lower alcohol is produced by reacting an organopolysiloxane of formula I (R<1> is 1-22C satd. alkyl or phenyl; R<3> to R<5> are each R<2> or a group of one of formulas II-VII; p<1> is 100-4,000; and q<1> is 1-300) with a poly (N- acylalkyleneimine) having reactive terminal ends and obtd. by the ring-opening polymn. of a cyclic imino ether of formula VIII (R<1> is 1-22C alkyl, cycloalkyl, aralkyl, or aryl; and n is 2 or 3).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organopolysiloxane, a hair setting composition containing the same and a hair setting method using the same, and more particularly to excellent hair setting and holding properties, The present invention relates to a hair setting agent having a soft feeling of hair after setting and having good hair washability, an organopolysiloxane useful as an active ingredient thereof, and a hair setting method using the same.

[0002]

2. Description of the Related Art Hairstyles are made by different people, but in general, dry hair or towel-dried hair is coated with a hair setting agent, and the hair is shaped into a desired shape with a comb or a brush, or a desired shape is obtained. A method of drying with a dryer or natural drying while adjusting the shape is adopted. The hair setting agent used here is generally in the form of foam, spray, mist, lotion, cream or gel. Another method of making a hairstyle is to use a hair setting agent such as a spray or a mist on the hair having a desired shape with a curler and keep the hair as it is. In any case, in the hair setting agent,
A function that keeps the finished hairstyle for a long time is required.
It is required to have an excellent feel such as no stickiness or stickiness.

Conventional hair setting agents generally contain a film-forming set polymer. Examples of film-forming set polymers include polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, acrylic acid ester-methacrylic acid ester-acrylic acid copolymer, methyl vinyl ether-maleic anhydride copolymer, methacrylic acid ester (dialkylaminoethylmethacrylate and monochloromethane). Examples thereof include a bound product of acetic acid) and a copolymer.

Even when the above hair setting agent is used, the formed hairstyle is destroyed with the passage of time. Especially on a high-humidity day, the set lasts poorly.

The main cause of this set collapse is that the set polymer bonded between the hairs is deformed over time. Further, under high humidity, the polymer becomes plastic due to moisture absorption and easily deforms, which makes the set holding performance worse.

[0006] Therefore, conventionally, as the set polymer, one having a high elastic modulus which hardly causes deformation is generally used. However, the hair set by the set polymer having a high elastic modulus gives a hard and stiff feel, which is not preferable. Therefore, in general, hair feeler products are blended with various feel improvers for the purpose of improving the feel. Examples of the touch improver include silicone oil, modified silicone, oil and the like, all of which reduce the set-holding property. As described above, it is difficult to achieve both the set property and the feel. In addition, external forces such as wind and hands are another cause of collapse of the set. In general, a polymer having a high elastic modulus is fragile, and therefore a large external force causes the polymer film to break before deformation and set collapse.

In order to remedy these drawbacks, it is necessary to have a polymer which is flexible and exhibits rubber-elastic properties without plastic deformation. Examples of the polymer that does not cause plastic deformation include those having intramolecular / intermolecular crosslinks such as vulcanized rubber, but the crosslinked polymers generally have extremely low solubility in solvents such as water and alcohol. Not suitable for practical use. Further, JP-A-4-139116 discloses a hair setting agent containing a polymer obtained by reacting a polyalkylene oxide compound with a polyvalent carboxylic acid or diisocyanate. Although this polymer forms a flexible film, it is inferior in terms of the slippery feeling of hair and the like as compared with silicone derivatives and the like.

Attempts have been made to use silicone derivatives for the purpose of providing a good feel to the hair. For example, JP-A-61-158914 and JP-A-61-1612
Japanese Unexamined Patent Publication No. 14 discloses a hair cosmetic containing a partially crosslinked organic silicone resin. However, since the resin is cross-linked by a covalent bond, the solubility is extremely low and the hair washability is poor, so that the appearance of the hair is impaired.

Japanese Unexamined Patent Publication (Kokai) No. 4-261113 has a feature that it contains a silicone polymer having a crosslinkable functional group and a crosslinker, and forms crosslinks when exposed to the atmosphere to exhibit elastomeric properties. Hair protection compositions are disclosed. Crosslinking to some extent is necessary to provide the set-retaining property, but in the case of this composition, since the crosslinkage is due to a covalent bond, if the crosslinking is advanced to the extent that the set-retaining property is imparted, the hair washability becomes poor. Become. That is, there is a drawback that the hairstyle cannot be easily changed because the hair cannot be washed off by washing the hair.

JP-A-63-2918 discloses a hair styling foam containing a hydroxylated polyorganosiloxane emulsion capable of forming an elastomer. The silicone elastomer shown here is of the type described in U.S. Pat. No. 4,221,688 and is disclosed in the above-mentioned JP-A-4-261.
Similar to the one described in Japanese Patent Publication No. 113, it becomes an elastomer by covalent cross-linking and has the same drawbacks as described above.

Further, Japanese Patent Laid-Open No. 63-22010 discloses a hair styling composition comprising a hard silicone polymer and a volatile carrier. Examples of the polymer include filler-reinforced polydimethylpolysiloxane gums including those having terminal groups such as hydroxyl groups, crosslinked siloxanes such as organic substituted silicone elastomers, and those having terminal groups such as hydroxyl groups. And organic-substituted siloxane gums, resin-reinforced siloxanes and crosslinked siloxane polymers.

However, the organopolysiloxane having only a high molecular weight or containing a filler easily causes plastic deformation and does not have good settability. Those having an end group such as a hydroxyl group and capable of crosslinking with the filler are irreversible, and if the crosslinking proceeds until it has a set property, the solubility and the washability after application are extremely lowered. The organic substituted silicone elastomer is disclosed in the above-mentioned JP-A-63-2.
Similar to that described in U.S. Pat.
It is of the type described in Japanese Patent No. 1,688 and has the same drawbacks as described above.

Further, JP-A-60-68820, JP-A-2-276824 and JP-A-4-85334 disclose silicones modified with a sugar residue or poly (N-acylalkyleneimine). However, the silicones described here have a low molecular weight, are liquid at room temperature, or are brittle even if they are solid, and cannot be used for hair setting agents.

[0014]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to have excellent ability to set hair and its holding property, to give a good feeling that the hair after setting is soft and does not become stiff, and is easily washed off by washing hair. It is to provide a hair setting composition that can be used, a method of setting hair, and a novel organopolysiloxane that can be used for the same.

[0015]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of such circumstances, an organopolysiloxane having specific properties exhibits excellent set-holding properties and a soft touch, and also provides good hair wash. The present invention has been completed by finding out that it brings about the property.

That is, in the present invention, intramolecular and intermolecular crosslinks are caused by bonds other than covalent bonds, and no fracture or plastic deformation occurs at an elongation rate of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. , An organopolysiloxane is provided.

The present invention also provides a method for setting hair, which comprises applying a composition containing the organopolysiloxane to hair and then removing the solvent.

The present invention further provides a hair setting composition containing the organopolysiloxane.

The hair set according to the present invention retains a desired shape for a long period of time, is excellent in flexibility and does not become stiff.
Further, the shape can be easily released by ordinary hair washing.

The organopolysiloxane of the present invention has the property of causing intramolecular and intermolecular crosslinks by bonds other than covalent bonds. This property occurs in a solvent-free state or a highly concentrated solution. Since it is a non-covalent cross-link, the cross-link easily breaks in a dilute solution. The presence of this cross-link can be confirmed by observing with a transmission electron microscope (TEM) whether or not it has a microphase-separated structure.

The organopolysiloxane of the present invention is preferably solid at room temperature and atmospheric pressure (normally -10 to 40 ° C. and 1 atm). Further, it is desirable that it be soluble or completely dispersible in water or lower alcohol, that is, that the crosslink can be easily cleaved in water or lower alcohol. Here, the lower alcohol is preferably a C1 to C6 alcohol.

As the bond other than the covalent bond, a bond which is easily cleaved in water or a lower alcohol, for example, an ionic bond, a hydrogen bond, a hydrophobic interaction, a dipole-dipole interaction, a bond by Van der Waals attraction. Etc., but ionic bonds, hydrogen bonds and dipole-dipole interactions are preferred. The organopolysiloxane of the present invention has one or more functional groups that cause these bonds.

The organopolysiloxane of the present invention has an elongation rate of 0 to 0 at a temperature of 20 ° C. and a relative humidity of 65%.
It has the property of not breaking or plastically deforming in the range of 15%. It is known that a polymer usually recovers to its original shape when the deformation is small, but becomes difficult to recover when the deformation is large. Such deformation that does not return to the original shape is called plastic deformation. For hard and brittle polymers,
Some fracture before plastic deformation occurs. None of them can retain their original shape, and are unsuitable as hair set polymers. Therefore, the above-mentioned property of the organopolysiloxane of the present invention is so-called rubber elasticity and is extremely important for imparting a strong set holding force and improving the feel of hair after setting.

Whether or not the plastic deformation occurs in the elongation range of 0 to 15% can be confirmed by, for example, the following simple experiment. That is, the thickness is about 0.2 mm, the length is 20 mm,
Prepare a sample piece with a width of 5 mm, temperature 20 ℃, relative humidity 65%
While recording the stress-strain curve under the conditions of, the crosshead is stretched by 3 mm (15%) at a crosshead speed of 20 mm / min, and immediately thereafter, the crosshead is returned to the original position at the same speed. Ten minutes later, it was stretched again, and the stress-strain curve during the second stretch was 1
If you follow the same trajectory as the curve of the second time, it means that the recovery is complete and that no plastic deformation has occurred. In contrast,
When plastic deformation occurs, the stress has been delayed in the second extension because it has already been expanded in the first reciprocating motion, and as a result, the stress-strain curves do not follow the same locus.

The organopolysiloxane of the present invention undergoes intramolecular and intermolecular cross-linking by bonds other than covalent bonds, and has an elongation rate of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%.
Is not particularly limited as long as it does not cause breakage or plastic deformation within the range of, but in order to cause intramolecular and intermolecular cross-linking by other than covalent bond, some polar functional group at the terminal or side chain of the organopolysiloxane segment. Need to have. Examples of such polar functional groups include N-acylalkyleneimine and pyrrolidone in which a dipole-dipole interaction is generated, and those having a hydroxyl group such as saccharides and polyvinyl alcohol in a hydrogen bond-forming one, and poly Mono- or dialkyl (meth) acrylamide polymers having 1 to 4 carbon atoms such as (meth) acrylamide and polydimethylacrylamide, polydiethylacrylamide, poly-N-morpholine (meth) acrylamide,
Examples thereof include those having an amide group such as poly-N-vinylpyrrolidone, poly-N-vinylacetamide, and polyamino acid. In addition, as a substance that causes an ionic bond, betaine-based polymers such as carbobetaine, sulfobetaine and phosphobetaine, anionic monomers such as (meth) acrylic acid and N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylamino are used. Examples thereof include amphoteric ionomers such as copolymers of cationic monomers such as propyl (meth) acrylamide, and amine oxides.

Examples of the organopolysiloxane of the present invention include the following (A), (B), (C) and (D).

(A) The following general formula (1) is provided through an alkylene group containing a hetero atom to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment:

[0028]

[Chemical 4]

(In the formula, R ¹ is a hydrogen atom and has 1 to 22 carbon atoms.
Is an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and n is a number of 2 or 3), and is bonded to a poly (N-acylalkyleneimine).

In this organopolysiloxane (A), the weight ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is 98/2 to 40/60 (more preferably 94/6 to 6).
0/40) and a weight average molecular weight of 50,000 to 50
10,000 (more preferably 100,000 to 300,
000) is preferred. When the weight ratio of the organopolysiloxane segment to the poly (N-acylalkyleneimine) segment is greater than 98/2 or 4
When it is less than 0/60, or when the weight average molecular weight is 50,000.
When it is less than 0, breakage or plastic deformation is likely to occur before the elongation reaches 15%, while it is difficult to produce a resin having a weight average molecular weight of more than 500,000.

The alkylene group containing a hetero atom interposed in the bond between the organopolysiloxane segment and the poly (N-acylalkyleneimine) is an alkylene group containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms and having 2 carbon atoms. To 20 alkylene groups, and specific examples thereof include

[0032]

[Chemical 5]

And the like. Examples of the cycloalkyl group represented by R ¹ include those having 3 to 6 carbon atoms; examples of the aralkyl group include phenylalkyl and naphthylalkyl; and examples of the aryl group include phenyl and phenyl.
Examples thereof include naphthyl and alkyl-substituted phenyl.

The above-mentioned organopolysiloxane (A) is, for example, the following general formula (2);

[0035]

[Chemical 6]

(In the formula, R ² is the same or different and represents a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group,
R ³ and R ⁴ each represent the same group as R ² or the following formula

[0037]

[Chemical 7]

An organopolysiloxane represented by the formula ( ¹ ), R ⁵ represents a group represented by the above formula, p ¹ represents an integer of 100 to 4000, and q ¹ represents an integer of ¹ to 300). And the following general formula (3):

[0039]

[Chemical 8]

(In the formula, n represents a number of 2 or 3, and R ¹ has the same meaning as described above.) A terminal-reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic iminoether ) And are reacted with each other.

The ring-opening polymerization of the cyclic iminoether (3) is carried out by using a compound having a strong electrophilic reactivity, for example, a strong acid such as benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid. The methyl, ethyl, 3-propenyl, or benzyl ester of is used as an initiator. If, for example, a 2-substituted-2-oxazoline is used as the cyclic imino ether (3), poly (N-acylethyleneimine) (formula (1)
(Corresponding to n = 2), and using a 2-substituted-2-oxazine, poly (N-acylpropyleneimine)
(Corresponding to n = 3 in the formula (1)) is obtained.

The above poly (N-acylalkyleneimine)
The method for connecting the chain and the silicone chain includes ester formation reaction by condensation of carboxyl group and hydroxyl group; amide formation reaction by condensation of carboxyl group and amino group; halogenated alkyl group and primary, secondary or tertiary. A number of methods are used, such as a secondary, tertiary or quaternary ammonium forming reaction with a secondary amino group; an addition reaction of a Si-H group to a vinyl group; a β-hydroxyamine forming reaction between an epoxy group and an amino group. Although it is possible,
No. 824, No. 4-85334, No. 4
As disclosed in JP-A-85335, JP-A-4-96933 and the like, a terminally reactive poly (N-acylalkyleneimine) obtained by cationic ring-opening polymerization of a cyclic iminoether is represented by the formula (2). A method of reacting the represented organopolysiloxane, that is, a modified organopolysiloxane having a substituent on the side chain, is simple and effective.

(B) At least one of the silicon atoms at the terminal or side chain of the organopolysiloxane segment has the following general formula (4);

[0044]

[Chemical 9]

An organopolysiloxane in which the groups represented by the formula (in the formula, m represents an integer of 1 to 8) are bonded.

In this organopolysiloxane (B), the number of silicon atoms bonded to the group represented by the general formula (4) is 10 to 90% (more preferably 40 to 80%) of the total number of silicon atoms in the molecule. Yes, weight average molecular weight 50,000
0 to 300,000 (more preferably 100,000 to
200,000) is preferable.

When the weight average molecular weight of the organopolysiloxane (B) is less than 50,000, breakage or plastic deformation tends to occur before the elongation reaches 15%, and the weight average molecular weight exceeds 300,000. Is
Difficult to manufacture. When the number of silicon atoms bonded to the group represented by the general formula (2) is less than 10% of the total number of silicon atoms in the molecule, sufficient crosslinking is not brought about, so that the organopolysiloxane (B) is elongated. When the ratio reaches 15%, breakage or plastic deformation is likely to occur, and when it exceeds 90%, it is difficult to develop a good feel characteristic of silicone.

Such an organopolysiloxane (B)
Is, for example, an organohydrogenpolysiloxane represented by the following general formula (5) is used as a precursor,
It can be synthesized by a so-called hydrosilylation reaction in which this is reacted with N-alkylenepyrrolidone represented by the following general formula (6). This hydrosilylation reaction is carried out at room temperature to 100 ° C. using a halogen solvent such as dichloromethane, chloroform, or 1,2-dichloroethane, or an aliphatic ether such as tetrahydrofuran, diisopropyl ether, or dibutyl ether as a reaction solvent. At, a transition metal complex such as platinum chloride can be used as a catalyst.

[0049]

[Chemical 10]

(In the formula, p ² represents an integer of 30 to 3,000, q ² represents an integer of 60 to 1,500, and R ² and R
³ , R ⁴ and m are as defined above. )

Japanese Unexamined Patent Publication (Kokai) No. 5-32784 discloses a siloxane compound similar to the organopolysiloxane (B) and a method for producing the same, but the molecular weight of the siloxane compound is not particularly described, and ,
Neither is it disclosed about an elastomeric property that does not cause fracture or plastic deformation until the elongation reaches 15%. In addition, the examples also show that the molecular weight is low and the elongation rate is 1.
Only compounds that cause fracture or plastic deformation by 5% are mentioned.

(C) An organopolysiloxane in which a sugar-derived residue is bonded to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment.

In this organopolysiloxane (C), examples of the sugar-derived residue include sugar lactone amide alkyl groups (groups in which a sugar lactone compound and an aminoalkyl group are amide-bonded). The organopolysiloxane (C) has a silicone chain of 40 to 97% by weight (more preferably 50 to 85% by weight) and a weight average molecular weight of 50,000 to 500,000 (more preferably 1
It is preferably from 0,000 to 300,000). If the silicone chain is less than 40% by weight, it tends to be broken or plastically deformed until the elongation reaches 15% and it is difficult to exhibit rubber elasticity. On the other hand, if it exceeds 97% by weight, crosslinking is not sufficient and a paste form is formed. After all, it becomes difficult to show rubber elasticity. If the weight average molecular weight is less than 50,000, breakage or plastic deformation is likely to occur before the elongation reaches 15%, and if the weight average molecular weight exceeds 500,000, it is difficult to manufacture.

The organopolysiloxane (C) is, for example, an amide bond obtained by reacting an organopolysiloxane having at least one aminoalkyl group with a sugar lactone compound (an aldonic acid or uronic acid intramolecularly dehydrated and cyclized). Is produced.

As the aminoalkyl group, an aminoalkyl group having 1 to 20 carbon atoms, particularly an aminoalkyl group having 1 to 8 carbon atoms is preferable. Examples of the lactone compound obtained by intramolecular cyclization of aldonic acid or uronic acid include D-glucose, D-galactose, D-allose, D-aldose, D-mannose, D-gulose, D-idose and D.
Lactones of aldonic acid derived from reducing monosaccharides such as talose; aldonic acid lactones derived from reducing disaccharides such as maltose, cellobiose, lactose, xylobiose, isomaltose, nigerose, kojibiose; maltotriose, vanose, Aldonic acid lactones derived from reducing trisaccharides such as isomalttriose; aldonic acid lactones derived from reducing oligosaccharides of tetrasaccharides or more; D
Examples include lactones of uronic acids such as glucuronic acid, L-iduronic acid, and mannuronic acid. These can be used in the reaction either alone or as a mixture.

The reaction between the organopolysiloxane precursor having an aminoalkyl group and the sugar lactone is preferably carried out by using a sugar lactone in an amount of 1.0 to 1.3 times the mol of the amino group of the organopolysiloxane precursor in a solvent. It can be achieved by mixing in a solution and stirring the solution at a solution concentration of 5 to 30% by weight under reflux for 3 to 20 hours. As the solvent used at this time, lower alcohols such as methanol, ethanol, 1-propanol and 2-propanol are suitable.

(D) The following general formula (7) is provided via an alkylene group containing a hetero atom in at least one of the silicon atoms at the terminal or side chain of the organopolysiloxane segment.

[0058]

[Chemical 11]

(In the formula, R ⁶ is a hydrogen atom and has 1 to 22 carbon atoms.
Represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group of
Represents a number of 1 to 5), and is an organopolysiloxane in which poly (N-propylenecarbobetaine) consisting of repeating units is bound.

In this organopolysiloxane (D), the weight ratio of the organopolysiloxane segment to the poly (N-propylenecarbobetaine) segment is 98/2 to 40/60 (more preferably 90/1).
0-60 / 40) and a weight average molecular weight of 50,000
~ 500,000 (more preferably 100,000 to 3)
It is preferably 0,000). When the weight ratio of the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment is greater than 98/2,
Or when it is less than 40/60, or when the weight average molecular weight is 5
When it is less than 10,000, breakage or plastic deformation is likely to occur before the elongation reaches 15%, while it is difficult to produce a resin having a weight average molecular weight of more than 500,000.

As the alkylene group containing a hetero atom which is present in the bond between the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment, a nitrogen atom, an oxygen atom and / or a sulfur atom may be contained in an amount of 1 to 3
Examples include alkylene groups having 2 to 20 carbon atoms, and specific examples thereof include:

[0062]

[Chemical 12]

And the like. Examples of the cycloalkyl group represented by R ⁶ include those having 3 to 6 carbon atoms; examples of the aralkyl group include phenylalkyl and naphthylalkyl; and examples of the aryl group include phenyl and phenyl.
Examples thereof include naphthyl and alkyl-substituted phenyl.

The above-mentioned organopolysiloxane (D) includes the organopolysiloxane represented by the above formula (2) and the following formula (8);

[0065]

[Chemical 13]

(In the formula, R ⁶ is the same as above) The end-reactive poly (N
-Propylene imine) to react with poly (N-
Propylene imine) is bonded to produce an organopolysiloxane. By further reacting this with sodium chloroacetate, β-propiolactone, γ-butyrolactone, and ε-caprolactone, an organopolysiloxane (D) having poly (N-propylenecarbobetaine) bonded thereto is produced.

As still another production method, the obtained poly (N-propyleneimine) is bonded to the organopolysiloxane to be quaternized with an alkyl halide having 1 to 22 carbon atoms, a cycloalkyl halide, an aryl halide or the like. After the reaction, a hydrolysis reaction of an alkoxycarbonylethyl group or an alkoxycarbonylmethyl group is performed under basic conditions to produce an organopolysiloxane (D) having poly (N-propylenecarbobetaine) bound thereto. To be done.

Here, the ring-opening polymerization of cyclic amine is carried out by compounds such as Lewis acid, protic acid, alkylating agent, for example, triethyloxonium tetrafluoroborate, benzyl chloride, benzyl bromide, benzyl iodide, methyl bromide, Methyl iodide, ethyl bromide, ethyl iodide, dimethyl sulfate, diethyl sulfate, trifluoromethane sulfonic acid, methyl trifluoromethane sulfonate, ethyl trifluoromethane sulfonate, benzene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, p -Toluenesulfonic acid, p-toluenesulfonic acid methyl, p-
It is carried out using ethyl toluene sulfonate or the like as an initiator. If, for example, N-substituted-azetidine is used as the cyclic amine, poly (N-substituted-propylenecarbobetaine) can be obtained.

Further, as a solvent used for ring-opening polymerization of cyclic amine and production of the copolymer of the present invention, acetic acid esters such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran. , Ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, nitrile solvents such as acetonitrile and benzonitrile, non-solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide. A protic polar solvent can be used.

As the method for connecting the poly (N-propyleneimine) chain and the silicone chain, the same method as the method for connecting the poly (N-acylalkyleneimine) chain and the silicone chain can be used.

Japanese Patent Publication No. 63-16418 discloses a siloxane having a betaine group similar to the organopolysiloxane formed by binding the poly (N-propylenecarbobetaine) and a method for producing the same. The molecular weight of the siloxane compound is limited to a low range, and the elastomeric property that does not cause fracture or plastic deformation by the elongation rate of 15% is not disclosed.

Hair is set using the organopolysiloxane of the present invention by applying a composition containing the organopolysiloxane to the hair and then removing the solvent.

Here, the compounding amount of the organopolysiloxane in the composition containing the organopolysiloxane is
0.05 to 20% by weight is preferable, and 0.1 to 10% by weight is particularly preferable.

In this composition, as ingredients other than the above,
Most components such as water, solvents such as C1-C6 alcohol, surfactants, oils, polyhydric alcohols, various medicinal agents, preservatives, and fragrances that are usually applied to hair setting agents have their respective purposes, uses, and dosage forms. Etc. are appropriately selected and blended.
For example, as the surfactant, a linear or branched alkylbenzene sulfonate, an alkyl or alkenyl ether sulfate added with ethylene oxide and / or propylene oxide, an olefin sulfonate, an alkane sulfonate, a saturated or unsaturated fatty acid salt, Alkyl or alkenyl ether carboxylic acid salts added with ethylene oxide and / or propylene oxide, α-sulfo fatty acid salt esters, amino acid type surfactants, phosphoric acid ester type surfactants, sulfosuccinic acid type surfactants, sulfonic acid type amphoteric Surfactants, betaine type amphoteric surfactants, alkylamine oxides, cationic surfactants such as straight chain and / or branched chain alkyl or alkenyl quaternary ammonium salts, polyoxyalkylene alkyl or alkenyl ethers, Polyoxyalkylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts, esters of polyhydric alcohols and fatty acids, esters of sorbitol and fatty acids, esters of sucrose with fatty acids, ethers of higher alcohols and sugar are used. The content of the surfactant in this composition is preferably 0 to 10% by weight, and particularly preferably 0 to 5% by weight. Examples of the oil component include higher fatty acids such as stearic acid, higher alcohols such as cetanol, cholesterol, vaseline, cholesteryl isostearate, solid fats such as sphingolipids, squalene, jojoba oil, and other liquid fats such as silicone derivatives. . Examples of the polyhydric alcohol include glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polyglycerin and sorbitol.
Solvents other than water and ethanol include benzyl alcohol, 2-benzyloxyethanol, N-alkylpyrrolidone, diethylene glycol monoethyl ether and the like. Other ingredients include pearling agents, fragrances,
Dyes, ultraviolet absorbers, antioxidants, triclosan, fungicides such as trichlorocarban, dipotassium glycyrrhizinate, anti-inflammatory agents such as tocopherol acetate, zinc pyrithione, antidandruff agents such as octopirox, methylparaben,
Preservatives such as butyl paraben, pH adjusting agents such as lactic acid and citric acid, etc. can be optionally added within a range that does not impair the effects of the present invention. Of these components, it is desirable to blend water and a C1-C6 alcohol, and optionally blend other components.

This composition can be prepared into various dosage forms, such as sprays, mists, gels, lotions, tonics, blowing agents, creams, and post-foaming gels, according to a conventional method. When it is an aerosol, it contains volatile hydrocarbons such as butane, isobutane, pentane, and isopentane, halogenated hydrocarbons such as dichlorofluoromethane and dichlorotetrafluoroethane, and propellant gases such as dimethyl ether, carbon dioxide, nitrogen, and air. Can be made.

When a film-forming polymer is added to this composition, the holding power of the set is further improved, and the smooth feel of the hair is improved.

The film-forming polymer used here includes those shown in the following (1) to (8).

(1) Polyvinylpyrrolidone type polymer compound Polyvinylpyrrolidone As commercially available products, rubiscol K12, K30 (above BAS
F company), PVP K15, K30 (above GAF company)
And so on. Polyvinylpyrrolidone / vinyl acetate copolymer As a commercial product, Rubiscol VA28, VA73 (above B
ASF), PVP / VA E-735, S-630
(These are manufactured by GAF). Polyvinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer As a commercial product, Rubiscol VAP343 (manufactured by BASF) and the like can be mentioned. Polyvinylpyrrolidone / alkylaminoacrylate copolymer Commercially available products include Rubiflex (manufactured by BASF) and copolymers 845, 937, 958 (manufactured by GAF). Polyvinylpyrrolidone / acrylate / (meth) acrylic acid copolymer As a commercial item, Rubiflex VBM35 (manufactured by BASF) and the like can be mentioned. Polyvinylpyrrolidone / alkylamino acrylate /
Vinyl caprolactam copolymer As a commercially available product, copolymer VC-713 (manufactured by GAF) and the like can be mentioned.

(2) Acidic vinyl ether polymer compound Methyl vinyl ether / maleic anhydride alkyl half ester copolymer Gantrez ES-225, ES-42 as a commercial product
5, SP-215 (all manufactured by GAF) and the like.

(3) Acidic polyvinyl acetate polymer compound Vinyl acetate / crotonic acid copolymer Examples of commercially available products include Resin 28-1310 (manufactured by National Starch) and Rubyset CA66 (manufactured by BASF). Vinyl acetate / crotonic acid / vinyl neodecanoate copolymer As a commercial item, resin 28-2930 (manufactured by National Starch) and the like can be mentioned. Vinyl acetate / crotonic acid / vinyl propionate copolymer Commercially available products include Rubiset CAP (manufactured by BASF).

(4) Acidic acrylic polymer compound (meth) acrylic acid / (meth) acrylic acid ester copolymer As a commercially available product, plus size L53P (Kyoso Chemical Co., Ltd.)
Manufactured by Mitsubishi Yuka Co., Ltd., and the like. Acrylic acid / alkyl acrylate / alkyl acrylamide copolymer As commercially available products, Ultrahold 8 (manufactured by BASF), Amphomer V-42 (manufactured by National Starch) and the like can be mentioned.

(5) Amphoteric acrylic polymer (meth) acrylethyl betaine / (meth) acrylic acid alkyl ester copolymer For example, N-methacryloyloxyethyl N, N-dimethylammonium α-N-methylcarboxybetaine and ( Examples thereof include copolymers with (meth) acrylic acid alkyl ester, and as commercially available products, Yucaformer M-75, SM
(Above, manufactured by Mitsubishi Petrochemical Co., Ltd.) and the like. Alkyl acrylate / butylaminoethyl methacrylate / octylamide acrylic acid copolymer, for example, octylacrylamide / acrylate / butylaminoethylmethacrylate copolymer,
Examples of commercially available products include UNFORMER 28-4910 (manufactured by National Starch).

(6) Basic acrylic polymer compound Acrylamide / acrylic ester quaternary copolymers, such as those described in JP-A-2-180911.

(7) Cellulose Derivative Cationic Cellulose Derivative Commercially available products include Cellcoat H-100 and L-200 (National Starch).

(8) Chitin / chitosan derivative Hydroxypropyl chitosan. [Examples of commercially available products include Chitofilmer (manufactured by Ichimaru Falcos). ] Carboxymethyl chitin, carboxymethyl chitosan,
Salts of chitosan with monoacids such as pyrrolidonecarboxylic acid, lactic acid and glycolic acid or diacids such as adipic acid and succinic acid. [As commercial products, Kitemer PC (pyrrolidone carboxylate), Kitemer L (lactate) (above, manufactured by Union Carbide)]

Among these film-forming polymers, (meth)
A film-forming polymer selected from acrylic acid-based polymers, amphoteric acrylic-based polymers, polyvinylpyrrolidone-based polymers and polymers having a sugar skeleton is particularly preferable. The amount of these film-forming polymers added to the above composition is 0.05-
20% by weight is preferable, and 0.1 to 10% by weight is particularly preferable.

The means for applying these compositions to the hair differs depending on the above-mentioned dosage form, but usually spraying or the like, application by hand, or a combination of the two are performed. Also,
Removal of the solvent after coating is preferably performed by natural drying, heating, or the like. In order to set the hair in a desired shape, it is desirable to shape the hair after application and before drying. For shaping, a method using a brush or a curler is usually used.

[0088]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following examples, the content of the silicone segment is a value obtained from quantitative analysis of Si element by plasma emission analysis, and the weight average molecular weight is from gel permeation liquid chromatography using chloroform as a developing solvent. The calculated polystyrene equivalent weight average molecular weight.

Synthesis Example 1 Organopolysiloxane A-1 21.4 g (0.139 mol) of diethyl sulfate and 331 g (3.33 mol) of 2-ethyl-2-oxazoline were dissolved in 700 g of dehydrated ethyl acetate, and a nitrogen atmosphere was prepared. The mixture was heated under reflux for 5 hours to synthesize a terminal-reactive poly (N-propionylethyleneimine). Here, side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,00
0, amine equivalent 4,840 (560 g, 0.116 g mol in terms of amino group) in 50% ethyl acetate was added all at once, and the mixture was heated under reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (885 g, yield 97).
%). The weight average molecular weight was 109,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Comparative Synthetic Example 1 Organopolysiloxane a 21.4 g (0.139 mol) of diethyl sulfate and 331 g (3.33 mol) of 2-ethyl-2-oxazoline were dissolved in 700 g of dehydrated ethyl acetate, and the mixture was dissolved in a nitrogen atmosphere. The mixture was heated under reflux for 5 hours to synthesize terminally reactive poly (N-propionylethyleneimine). Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 24,000,
Amine equivalent 4,810 (560 g)
116 g mol) of 50% ethyl acetate solution was added all at once, and the mixture was heated under reflux for 10 hours. The reaction mixture was concentrated under reduced pressure,
N-propionylethyleneimine-dimethylsiloxane copolymer is a pale yellow rubbery solid (867 g, yield 95%).
Got as. The weight average molecular weight was 25,800.
Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 2 Organopolysiloxane A-2 30.6 g (0.199 mol) of diethyl sulfate and 945 g (9.53 mol) of 2-ethyl-2-oxazoline were dissolved in 1,950 g of dehydrated ethyl acetate, Under nitrogen atmosphere 8
The mixture was heated under reflux for a period of time to synthesize terminally reactive poly (N-propionylethyleneimine). Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 110,0
00, amine equivalent 4,840) (800 g, 0.165 g mol in terms of amino group) in 50% ethyl acetate was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (1,720 g, yield 97%). Weight average molecular weight is 122,000
Met. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 3 Organopolysiloxane A-3: 3.56 g (0.0230 mol) of diethyl sulfate and 27.5 g (0.277 mol) of 2-ethyl-2-oxazoline.
Was dissolved in 60 g of dehydrated ethyl acetate, and the solution was placed under a nitrogen atmosphere.
The mixture was heated under reflux for a period of time to synthesize terminally reactive poly (N-propionylethyleneimine). Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 110,0
00, amine equivalent 20,800) (400 g (0.0192 g mol as an amino group)) in 50% ethyl acetate was added all at once, and the mixture was heated under reflux for 8 hours. The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (428 g, yield 9
9%). The weight average molecular weight was 115,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 4 Organopolysiloxane A-4 3.75 g (0.0244 mol) of diethyl sulfate and 58.6 g (0.591 mol) of 2-ethyl-2-oxazoline.
Was dissolved in 125 g of dehydrated ethyl acetate and heated under reflux in a nitrogen atmosphere for 5 hours to synthesize terminally reactive poly (N-propionylethyleneimine). Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 110,
000, amine equivalent 9,840) (200 g, 0.0203 mol of amino group) in 50% ethyl acetate was added all at once, and the mixture was heated under reflux for 8 hours. The reaction mixture was concentrated under reduced pressure to give an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (257 g, yield 98).
%). Silicone segment content is 76
%, And the weight average molecular weight was 118,000. Also,
As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 5 Organopolysiloxane A-5 29.7 g (0.193 mol) of diethyl sulfate and 153 g (1.54 mol) of 2-ethyl-2-oxazoline were dissolved in 370 g of dehydrated ethyl acetate, and a nitrogen atmosphere was prepared. The mixture was heated under reflux for 3 hours to synthesize end-reactive poly (N-propionylethyleneimine). Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 90,000,
Amine equivalent weight 1,870) 300 g (converted to amino group to 0.
160 mol) of 50% ethyl acetate solution is added all at once,
The mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure and N-
A propionylethyleneimine-dimethylsiloxane copolymer was obtained as a pale yellow rubbery solid (468 g, yield 97%). The content of the silicone segment was 61%, and the weight average molecular weight was 102,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 6 Organopolysiloxane A-6 3.75 g (0.0243 mol) of diethyl sulfate and 49.8 g (0.585 mol) of 2-ethyl-2-oxazoline.
Was dissolved in 107 g of dehydrated chloroform and heated under reflux for 5 hours in a nitrogen atmosphere to synthesize terminal-reactive poly (N-acetylethyleneimine). Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 110,0
00, amine equivalent 9,840) (400 g, 0.0407 mol of amino group) in 50% ethyl acetate was added all at once, and the mixture was heated under reflux for 13 hours. The reaction mixture was concentrated under reduced pressure to give an N-acetylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (444 g, yield 98%).
Got as. Silicone segment content is 88%,
The weight average molecular weight was 137,000. Further, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

Synthesis Example 7 Organopolysiloxane B-1 500 g of methyl hydrogen polysiloxane (SiH
2.91 mol, weight average molecular weight 100,000,
While adding 2.0 g of a 5% isopropyl alcohol solution of chloroplatinic acid to SiH equivalent 172) and stirring under a nitrogen atmosphere, N- (3-propenyl) pyrrolidone 382 was added thereto.
g (3.06 mol) was added dropwise at such a rate that the temperature in the system did not exceed 60 ° C. After the dropping, keep the system at 65 ° C,
The stirring was continued for another 3 hours, and the temperature was returned to room temperature. To this, 3,530 g of ethanol was added to make a uniform solution, 10 g of activated carbon powder was further added, the mixture was stirred at room temperature for 30 minutes, and then the activated carbon was filtered off. The obtained solution was concentrated under reduced pressure, ethanol and unreacted N- (3-propenyl) pyrrolidone were distilled off, and 847 g (yield 98%) of methylpolysiloxane having an alkylpyrrolidone group in its side chain was colorless. Obtained as a transparent gummy solid. The weight average molecular weight was 155,000. In addition, Si-H stretching vibration absorption (2125 cm ^-1 ) was not found in the FT-IR spectrum.

Comparative Synthesis Example 2 Organopolysiloxane b Methylhydrogenpolysiloxane 500 g (SiH
2.97 mol, weight average molecular weight 4,300, Si
To H equivalent 168), 2.0 g of a 5% isopropyl alcohol solution of chloroplatinic acid was added and stirred under a nitrogen atmosphere while N- (3-propenyl) pyrrolidone (390 g) was added thereto.
(3.12 mol) was added dropwise at such a rate that the temperature in the system did not exceed 60 ° C. After the dropwise addition was completed, the temperature inside the system was kept at 65 ° C., and stirring was continued for another 3 hours to return to room temperature. To this, add 3,600 g of ethanol to make a uniform solution, and then add activated carbon powder 1
After adding 0 g and stirring at room temperature for 30 minutes, activated carbon was filtered off. The resulting solution was concentrated under reduced pressure to remove ethanol and unreacted N- (3-propenyl) pyrrolidone,
819 g (yield 94%) of methylpolysiloxane having an alkylpyrrolidone group in the side chain was obtained as a colorless transparent rubber-like solid. The weight average molecular weight was 7,100. Also,
No Si-H stretching vibration absorption (2125 cm ^-1 ) was found in the FT-IR spectrum.

Synthesis Example 8 Organopolysiloxane C-1 γ-aminopropyl-modified dimethylpolysiloxane 2 having an amine equivalent of 406 and a weight average molecular weight of 36,000.
00 g (0.493 mol in terms of amino group), maltobionolactone 201 g (0.591 mol), and ethanol 800 g were mixed, and the mixture was heated under reflux for 9 hours with vigorous stirring under a nitrogen atmosphere. 1,000 g of hexane was added dropwise to this solution with vigorous stirring at room temperature. The precipitate formed was filtered off and the filtrate was concentrated under reduced pressure to give dimethylpolysiloxane containing sugar-derived residues as a colorless transparent elastic solid.
42 g (yield 93%) was obtained. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained. The silicone segment content was 54%.

Synthesis Example 9 Organopolysiloxane C-2 Amine equivalent is 996 and weight average molecular weight is 108,000.
Of γ-aminopropyl-modified dimethylpolysiloxane (0.201 mol in terms of amino group), 39.3 g of δ-gluconolactone (0.221 mol), and 200 g of methanol were mixed and stirred vigorously under a nitrogen atmosphere. While heating and refluxing for 8 hours. This solution was diluted 3-fold with methanol and added dropwise to 10 liters of water that was vigorously stirred at room temperature. Stirring was stopped, the precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 204 g (yield 86%) of a sugar-derived residue-containing dimethylpolysiloxane as a colorless transparent elastic solid.
As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained. The silicone segment content was 86%.

Synthesis Example 10 Organopolysiloxane C-3 Amine equivalent is 9,940, and weight average molecular weight is 128,0.
200 g of γ-aminopropyl-modified dimethylpolysiloxane (0.0201 mol as an amino group), 8.22 g (0.0241 mol) of maltobionolactone,
And 300 g of ethanol were mixed, and the mixture was heated under reflux under a nitrogen atmosphere for 9 hours with vigorous stirring. This solution was diluted 2.5 times with ethanol and added dropwise to 10 liters of water with vigorous stirring at room temperature. The stirring was stopped, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 206 g of dimethylpolysiloxane containing a residue derived from sugar as a colorless transparent elastic solid (yield 9
2%) was obtained. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained. The silicone segment content is 97%
Met.

Comparative Synthesis Example 3 Organopolysiloxane c 50 g of 6-amino-4-azahexyl-modified dimethylpolysiloxane (KF393, manufactured by Shin-Etsu Chemical Co., Ltd.) having an amine equivalent of 360 and a weight average molecular weight of 3,800.
(0.0694 mol of primary amino group), glucono-
6 g of a mixture of 13 g of delta-lactone and 200 ml of methanol
Reflux for hours. Methanol was distilled off under reduced pressure, and the residue was dissolved in water. Then, the aqueous solution of the reaction mixture was put into a cellophane tube for dialysis, and unreacted glucono-δ-
Gluconic acid derived from the lactone was removed. Further, by freeze-drying, 60 g of 6-gluconamide-4-azahexyl-modified organopolysiloxane c was obtained as a white solid.
(Yield 95%) was obtained. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained. Further, the content rate of the silicone segment was 70%.

Synthesis Example 11 Organopolysiloxane D-1 30.6 g (0.198 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 1498.2 g
(9.53 mol) was dissolved in 3,058 g of dehydrated ethyl acetate and heated under reflux for 15 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 800 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 4,840)
A 50% ethyl acetate solution (0.165 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 9
5%). This reaction product was added to methanol 5,0
Dispersed in 00 g, and sodium chloroacetate 1665.6 g
(14.3 mol) was added, and the mixture was reacted under heating under reflux for 24 hours. The reaction solution was cooled to room temperature and sodium chloride was filtered off. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 12 Organopolysiloxane D-2 3.56 g (0.023 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 43.5 g (0.
(277 mol) was dissolved in 94.2 g of dehydrated ethyl acetate and heated under reflux for 6 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 400 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 20,800)
A 50% ethyl acetate solution (0.0192 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (425 g, yield 95).
%). The reaction product was treated with methanol
0 g and dispersed in sodium chloroacetate 46.6 g (0.
4 mol) was added, and the mixture was reacted under heating under reflux for 24 hours.
The reaction solution was cooled to room temperature and sodium chloride was filtered off. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 13 Organopolysiloxane D-3 30.6 g (0.198 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 1498.2 g
(9.53 mol) was dissolved in 3,058 g of dehydrated ethyl acetate and heated under reflux for 15 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 800 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 4,840)
A 50% ethyl acetate solution (0.165 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 9
5%). The obtained reaction mixture was dissolved in 5,000 g of diethyl ether to give β-propiolactone 82.
4 g (11.4 mol) was added at room temperature, and the mixture was reacted overnight at room temperature. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 14 Organopolysiloxane D-4 3.56 g (0.023 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 43.5 g (0.
(277 mol) was dissolved in 94.2 g of dehydrated ethyl acetate and heated under reflux for 6 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 400 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 20,800)
A 50% ethyl acetate solution (0.0192 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (425 g, yield 95).
%). The obtained reaction mixture was dissolved in 1,000 g of diethyl ether, and β-propiolactone 23.
95 g (0.332 mol) was added at room temperature, and the mixture was reacted overnight at room temperature. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 15 Organopolysiloxane D-5 triethyloxonium tetrafluoroborate 37.
6 g (0.198 mol) and 1- (2-carboethoxyethyl) azetidine 1498.2 g (9.53 mol) were dissolved in dehydrated tetrahydrofuran (3,058 g), heated under reflux in a nitrogen atmosphere for 15 hours, and subjected to terminal reactivity. Poly (N-propyleneimine) was synthesized. Here, side chain primary aminopropyl modified polydimethylsiloxane (molecular weight 110,
000, amine equivalent 4,840) 800 g (0.165 g mol in terms of amino group) in 50% tetrahydrofuran was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 95).
%). The obtained reaction mixture was dissolved in 5,000 g of diethyl ether, and γ-butyrolactone 981.
4 g (11.4 mol) was added at room temperature, and the mixture was reacted overnight at room temperature. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 16 Organopolysiloxane D-6 3.45 g (0.023) of trifluoromethanesulfonic acid
Mol) and 4-3.5 g (0.277 mol) of 1- (2-carboethoxyethyl) azetidine were dissolved in 94.2 g of dehydrated diisopropyl ether, heated under reflux for 6 hours in a nitrogen atmosphere, and reacted with poly (N- Propyleneimine) was synthesized. Here, 400 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 20,800) (0.0192 as an amino group)
(g mol) of 50% diisopropyl ether solution was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (425 g, yield 95%).
The obtained reaction mixture was dissolved in 1,000 g of diethyl ether, 37.9 g (0.332 mol) of ε-caprolactone was added at room temperature, and the mixture was reacted overnight at room temperature. The obtained solution was concentrated under reduced pressure, and N-propylenecarbobetaine-
A dimethylsiloxane copolymer was obtained as a pale yellow solid.

Synthesis Example 17 Organopolysiloxane D-7 30.6 g (0.198 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 1498.2 g
(9.53 mol) was dissolved in 3,058 g of dehydrated ethyl acetate and heated under reflux for 15 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 800 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 4,840)
A 50% ethyl acetate solution (0.165 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 9
5%). The resulting reaction mixture was added to acetone 5,
Dissolved in 000 g, 1246.2 g of ethyl bromide (11.
44 mol) was added, and the mixture was reacted under heating under reflux for 24 hours.
The reaction mixture was concentrated under reduced pressure, dispersed in 5,000 g of methanol, and 5,000 g of 2N potassium hydroxide methanol solution was added.
Was added and the mixture was heated at 80 ° C. for 6 hours. The obtained solution was concentrated under reduced pressure, dissolved in chloroform, washed with water, and then concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 18 Organopolysiloxane D-8 3.56 g (0.023 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 43.5 g (0.
(277 mol) was dissolved in 94.2 g of dehydrated ethyl acetate and heated under reflux for 6 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 400 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 20,800)
A 50% ethyl acetate solution (0.0192 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (425 g, yield 95).
%). The reaction mixture obtained was added with acetone 1,0
It was dissolved in 00 g, 25.2 g (0.231 mol) of ethyl bromide was added, and the mixture was reacted under heating under reflux for 24 hours. The reaction mixture was concentrated under reduced pressure, dispersed in 1,000 g of methanol,
Add 150 g of 2N potassium hydroxide methanol solution,
Heating was performed at 80 ° C. for 6 hours. The resulting solution was concentrated under reduced pressure, dissolved in chloroform, washed with water, and concentrated under reduced pressure.
An N-propylenecarbobetaine-dimethylsiloxane copolymer was obtained as a pale yellow solid.

Synthesis Example 19 Organopolysiloxane D-9 30.6 g (0.199 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 1498.2
(9.53 mol) was dissolved in 3,058 g of dehydrated ethyl acetate and heated under reflux for 15 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 800 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 4,840)
A 50% ethyl acetate solution (0.165 g mol as an amino group) was added all at once, and the mixture was heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 9
5%). The resulting reaction mixture was added to acetone 5,
Dissolve in 000 g and hexyl bromide 1888.5 g (1
(1.44 mol) was added, and the mixture was reacted for 24 hours while heating under reflux. The reaction mixture was concentrated under reduced pressure and methanol 5,000 g
And 2N potassium hydroxide in methanol solution 5,000
0 g was added, and heating was performed at 80 ° C. for 6 hours. The obtained solution was concentrated under reduced pressure, dissolved in chloroform, washed with water, and then concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 20 Organopolysiloxane D-10 3.56 g (0.023 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 43.5 g (0.
(277 mol) was dissolved in 94.2 g of dehydrated ethyl acetate and heated under reflux for 6 hours in a nitrogen atmosphere to synthesize a terminal-reactive poly (N-propyleneimine). 400 g of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000, amine equivalent: 20,800)
A 50% ethyl acetate solution (0.0192 g mol as an amino group) was added all at once and heated under reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (425 g, yield 95).
%). The reaction mixture obtained was added with acetone 1,0
Dissolve in 00g and hexyl bromide 38.1g (0.231
Mol) was added, and the mixture was reacted for 24 hours while heating under reflux. The reaction mixture was concentrated under reduced pressure, dispersed in 1,000 g of methanol, 150 g of 2N potassium hydroxide methanol solution was added, and the mixture was heated at 80 ° C. for 6 hours. The obtained solution was concentrated under reduced pressure, dissolved in chloroform, washed with water, and then concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Reference Example 1 Organopolysiloxanes of the present invention obtained in Synthesis Examples 1 to 20, organopolysiloxanes having a low molecular weight obtained in Comparative Synthesis Examples 1 to 3, and coating physical properties of the following commercially available set polymers d and e. Was measured by the following method. The results are also shown. d: Mitsubishi Yuka Co., Ltd., Yukaformer M-75 e: GAF, GANTREZ ES 225

(Evaluation method) Each polymer was made into a 10% ethanol solution, and ethanol was allowed to spontaneously evaporate to a thickness of about 0.2.
Films of ~ 0.3 mm were prepared. A test piece is cut out from this, and a sample with a length of 20 mm and a width of 5 mm is measured at a temperature of 20.
It was attached to Tensilon installed in a room at ℃ and relative humidity of 65%. While recording the stress-strain curve, the crosshead was stretched 3 mm at a crosshead speed of 20 mm / min and immediately thereafter the crosshead was returned to its original position at the same speed. Ten minutes later it was stretched again and the stress-strain curve during the second stretch was recorded.

(Results) In all of the organopolysiloxanes of the present invention, it was found that the stress-strain curves were overlapped twice and that they were not plastically deformed by the first elongation. In the case of the commercial set polymer d, the organopolysiloxanes a, b and c obtained in Comparative Synthesis Examples 1 to 3 broke during the first elongation.
In the case of the commercially available set polymer e, it was found that the stress-strain curves at the first time and the second time follow different trajectories, and plastic deformation occurs at the first elongation. Further, as a result of observing the film formed of the organopolysiloxane of the present invention with a transmission electron microscope (TEM), all had a microphase-separated structure and a crosslinked structure.

Reference Example 2 The solubility of the organopolysiloxane of the present invention obtained in the above Synthesis Examples 1 to 20 in ethanol and a 20% aqueous ethanol solution was examined. Semi-transparent and uniformly dispersed. On the other hand, room temperature curable silicone elastomer S manufactured by Shin-Etsu Chemical Co., Ltd.
Neither H9585 nor silicone elastomer KE-10 (covalent bond cross-linking type) dissolved or dispersed at the same concentration.

Examples 1 to 6 and Comparative Examples 1 to 5 Organopolysiloxanes of the present invention obtained in Synthesis Examples 1 to 3, 7, 8 and 11, organopolysiloxanes a and b obtained in Comparative Synthesis Examples 1 to 3 and c and the commercial polymers d and e
Was used to prepare a hair set mist whose composition is shown in Table 1. Hair was treated with the obtained mist and tested for the following evaluation items. The results are also shown in Table 1.

(A) Set holding property A hair bundle having a length of 18 cm and a weight of 1.5 g was wetted with water, towel-dried, 2 g of mist was applied, wound on a rod having a diameter of 2 cm, and then naturally dried. After drying, the curled hair was removed from the rod. This is a high humidity box (20 ℃, 98%
RH) for 30 minutes, the curl elongation was observed, and the set retention was judged according to the following criteria. (Evaluation Criteria) A: Very good compared to uncoated hair. ◯: Better than uncoated hair. Δ: Same as uncoated hair X: Worse than uncoated hair.

(B) Sensory evaluation A hair bundle having a length of 18 cm and a weight of 10 g was wetted with water, towel-dried, coated with 2 g of mist, wound on a rod having a diameter of 2 cm, and then naturally dried. About this, five expert panelists evaluated the feeling according to the following criteria. (Evaluation Criteria) A: Very good compared to uncoated hair. ◯: Better than uncoated hair. Δ: Same as uncoated hair X: Worse than uncoated hair. XX: Very worse than uncoated hair.

(C) Curling elasticity Set retention (A) As in the test, curls are formed in the hair bundle,
The elasticity of curls was evaluated by 5 expert panelists according to the following criteria. (Evaluation Criteria) A: More elastic than uncoated hair. ◯: Slightly more elastic than uncoated hair. Δ: Same as uncoated hair X: Rigid and stiffer than uncoated hair.

[0120]

[Table 1]

As is clear from the results shown in Table 1, all the products of the present invention were superior in set retainability, feel and curl elasticity as compared with the comparative product. In addition,
The product of the present invention provided good hair washability. Although not shown in Table 1, the above-mentioned Synthesis Examples 4 to 6, 9, 1
The organopolysiloxanes of the present invention obtained in Nos. 0 and 12 to 20 also exhibited excellent set-holding properties, and the hair after setting had good feel and elasticity.

Example 7 A mist having the composition shown in Table 2 below was prepared by a conventional method using the organopolysiloxane of the present invention and the film-forming polymer. The obtained mist was applied to the hair, and the set holding power and the slipperiness were evaluated by the following test methods according to the following criteria. The results are also shown in Table 2.

(Set holding power test) A hair bundle having a length of 18 cm and a weight of 1.5 g was wetted with water, towel-dried, 2 g of mist was applied, and the hair was wound on a rod having a diameter of 2 cm and naturally dried. After drying, the rod was removed from the curled hair. This was hung in a constant temperature box (20 ° C., 98% RH) for 30 minutes, the curl elongation was observed, and the set holding power was evaluated according to the following criteria. (Evaluation Criteria) A: Very good. ○: Good. Δ: Normal X: Somewhat bad. XX: Bad.

(Slidability test) Length 18 cm, weight 10 g
Wet a bunch of hair with water, towel dry, then mist 0.2 g
Was applied and naturally dried. The slip property was evaluated according to the following criteria. (Evaluation Criteria) A: Very good. ○: Good. Δ: Normal X: Somewhat bad. XX: Bad.

[0125]

[Table 2]

As is clear from the results shown in Table 2, the product of the present invention is superior to the comparative product in set holding power and slipperiness. Further, although not shown in Table 2, the compositions obtained by blending the organopolysiloxanes obtained in Synthesis Examples 1 to 5, 11 and 13 to 20 and the amphoteric polymer also have excellent set holding power, It imparted good smoothness to the hair.

Example 8 A foaming agent was prepared by mixing the following components.

[0128]

(Table 3) (Components) (wt%) Organopolysiloxane A-1 3.0 Coconut oil fatty acid diethanolamide 0.5 Ethanol 20.0 Fragrance Trace amount Purified water Residual liquefied petroleum gas 10.0 Total 100.0

Example 9 A foaming agent was prepared by mixing the following components.

[0130]

[Table 4] (Components) (wt%) Organopolysiloxane A-3 1.0 Commercially available set polymer (GANTREZ ES 225 manufactured by GAF) 2.0 Cetyltrimethylammonium chloride solution (25%) 0.5 Ethanol 15.0 Fragrance Trace amount Purified water Residual liquid petroleum gas 10.0 Total 100.0

The foam agents obtained in Examples 8 and 9 above all exhibited excellent set-holding property, touch and curl elasticity.

Example 10 A mist agent was prepared by mixing the following components.

[0133]

[Table 5] (Components) (% by weight) Organopolysiloxane A-1 2.0 Ethanol 30.0 Fragrance Micro- purified water Fuel gauge 100.0

Example 11 A set lotion for hair was prepared by mixing the following ingredients.

[0135]

[Table 6] (Components) (wt%) Organopolysiloxane A-1 1.0 Ethanol Remaining amount Perfume Micro purified water 10.0 Total 100.0

Example 12 A hair spray was prepared by mixing the following ingredients.

[0137]

[Table 7] (Component) (wt%) Organopolysiloxane B-1 5.0 Ethanol Remaining amount Fragrance Liquefied petroleum gas 50.0 Total 100.0

Example 13 A blowing agent having the composition shown below was prepared by a conventional method.

[0139]

[Table 8] (Components) (wt%) Organopolysiloxane C-1 0.5 Amphoteric polymer ("Yukaformer M-75") 0.5 Perfume Trace ethanol 30.0 Purified water Qty 100.0

Example 14 A foaming agent having the composition shown below was prepared by a conventional method.

[0141]

[Table 9] (Components) (wt%) Organopolysiloxane C-1 1.0 Chitin liquid (manufactured by Ichimaru Falcos) 5.0 Nonionic surfactant ("Softanol 90" manufactured by Nippon Shokubai Co., Ltd.) 1.0 Perfume Trace amount of purified water Residual liquefied petroleum gas 10.0 Total 100.0

Example 15 A hair spray having the composition shown below was prepared by a conventional method.

[0143]

[Table 10] (Components) (wt%) Organopolysiloxane C-3 1.5 Nonionic polymer ("Luviskol VA37" manufactured by BASF) 5.0 Fragrance trace amount Ethanol Residual liquefied petroleum gas 50.0 Total 100.0

Example 16 A set lotion for hair having the composition shown below was prepared by a conventional method.

[0145]

[Table 11] (Component) (wt%) Organopolysiloxane C-2 1.0 Amphoteric polymer ("Yukaformer M-75") 2.0 Ethanol remaining amount Purified water 10.0 Fragrance Micrometer 100.0

Each of the hair setting agents obtained in Examples 10 to 16 is excellent in set holding power and slipperiness, and is good in natural luster, smoothness, suppleness, combability, etc. It did not interfere with sex.

Example 17 A foaming agent was obtained by mixing the following components.

[0148]

[Table 12] (Components) (wt%) Organopolysiloxane D-1 3.0 Polyoxyethylene (9) tetradecyl ether 0.5 Ethanol 10.0 Perfume 0.10 Purified water Residual liquefied petroleum gas 10.0 100.0 in total

Example 18 A hair spray was obtained by mixing the following components.

[0150]

[Table 13] (Components) (wt%) Organopolysiloxane D-5 3.0 Squalane 0.1 Methylphenylpolysiloxane (KF-53 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 Perfume 0.10 Ethanol Remaining Liquefied Petroleum Gas 25.0 Dimethyl ether 25.0 Total 100.0

Example 19 A foaming agent was obtained by mixing the following components.

[0152]

[Table 14] (Component) (wt%) Organopolysiloxane D-8 1.0 Commercially available set polymer (GANTREZ ES-225 manufactured by GAF) 1.5 Polyoxyethylene (9) tetradecyl ether 0.5 Ethanol 10. 0 Fragrance 0.10 Purified water Residual liquid petroleum gas 10.0 Total 100.0

The hair setting agents obtained in Examples 17 to 19 have an excellent set-holding ability, give a good feel and curl elasticity to the hair, and do not impair the washability. It was

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 5-229921 (32) Priority date Hei 5 (1993) September 16 (33) Priority claim country Japan (JP) (72) Inventor Takashi Ito 2-9-6-303 Hokukitakata, Ichikawa City, Chiba Prefecture Parkheim Takizawa (72) Inventor Yoko Sato 4-7-10 Takaido Higashi, Suginami-ku, Tokyo 206 (72) Inventor Takahisa Kure Tokyo 3-16-1-307 Higashisuna, Koto-ku (72) Inventor Katsuhiko Hayashifuji 180-1-302 Nainaka, Hainan City, Wakayama Prefecture

Claims (16)

[Claims] 1. An organopolysiloxane which undergoes intra- and inter-molecular cross-linking by a bond other than a covalent bond and which does not break or plastically deform at an elongation rate of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. 2. The organopolysiloxane according to claim 1, which is a solid at room temperature and pressure and can be dissolved or completely dispersed in water or a lower alcohol. 3. An organopolysiloxane segment having a heteroatom-containing alkylene group at least at one of the silicon atoms at the terminal or side chain of the organopolysiloxane segment, the following general formula (1); (In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and n represents a number of 2 or 3). The organopolysiloxane according to claim 1, which is formed by bonding N-acylalkyleneimine). 4. The blending weight ratio of the organopolysiloxane segment and the poly (N-acylalkyleneimine) segment is 98/2 to 40/60, and the weight average molecular weight is 50,000 to 500,000. Item 3. The organopolysiloxane according to item 3. 5. An organopolysiloxane segment having at least one silicon atom at the terminal or side chain thereof represented by the following general formula (4); The organopolysiloxane according to claim 1, wherein a group represented by the formula (wherein, m is an integer of 1 to 8) is bonded. 6. The number of silicon atoms bonded to the group represented by the general formula (4) is 10 to 90% of the total number of silicon atoms in the molecule, and the weight average molecular weight is 50,000 to 300,000. The described organopolysiloxane. 7. The organopolysiloxane according to claim 1, wherein a sugar-derived residue is bonded to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment. 8. The organopolysiloxane according to claim 7, wherein the sugar-derived residue is a sugar lactone amide alkyl group. 9. The organopolysiloxane according to claim 7, wherein the silicone chain is present in an amount of 40 to 97% by weight and the weight average molecular weight is 50,000 to 500,000. 10. An organopolysiloxane segment having a alkylene group containing a hetero atom in at least one of silicon atoms at a terminal or a side chain of the organopolysiloxane segment, the following general formula (7); (Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, and r represents a number of 1 to 5) Poly (N
-Propylenecarbobetaine) is bonded to the organopolysiloxane according to claim 1. 11. A weight average of the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment in a weight ratio of 98/2 to 40/60 (more preferably 90/10 to 60/40). Molecular weight is 5
The organopolysiloxane according to claim 10, which has an amount of from 50,000 to 500,000. 12. An organopolysiloxane which undergoes intramolecular and intermolecular cross-linking by a bond other than a covalent bond and which does not break or plastically deform at an elongation rate of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. A method for setting hair, which comprises applying the composition containing the composition to hair and then removing the solvent. 13. The setting method according to claim 12, wherein the composition further contains a film-forming polymer. 14. The setting method according to claim 12, wherein the solvent is removed at room temperature or under heating. 15. An organopolysiloxane which causes intra- and inter-molecular cross-linking by a bond other than a covalent bond and does not break or plastically deform at an elongation rate of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. A hair setting agent composition. 16. The composition according to claim 15, which further comprises a film-forming polymer.