JPH044284A - Gel base - Google Patents

Abstract

PURPOSE:To obtain a gel base suitably useful as a cosmetic, aromatic, etc., consisting essentially of a copolymer comprising a specific (meth)acrylic ester, a specific oxyalkylene (meth)acrylic ester and a specific vinyl monomer. CONSTITUTION:The objective gel base consisting essentially of a copolymer comprising 15-85 wt.% (meth)acrylic ester shown by formula I (R<1> is H or meth yl; R<2> and R<3> are methyl or ethyl; A is 1-4C alkylene), (B) 0.1-20 wt.% oxyalkylene (meth)acrylic ester shown by formula II (n is 1-40 integer) and (C) 0-80 wt.% vinyl monomer shown by formula III (m is 3 or 4). The base can be blended with a cationic setting polymer, forms a flexible film after drying and has low content of impurities admixed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a gel base material. More specifically, the present invention relates to a gel base material that can be suitably used in cosmetics, fragrances, and the like.

[Prior Art] Research on gel base materials has been conducted for a long time, and the alkali neutralized salt of polyacrylic acid crosslinked polymer described in Japanese Patent Publication No. 82-4141 and Japanese Patent Application Laid-open No. 51-46586, etc. Gel base materials made of such materials are known as typical ones.

However, the gel base material has -〇〇〇 groups in the polymer chain, and part or all of the -COOe groups are Na0
HSKO) I, the base resin is an anionic polymer obtained by neutralizing with amines, etc.
It is difficult to add hair cosmetic materials such as cationic setting polymers to this. For example, when a cationic setting polymer containing a quaternary amine is added to the polymer chain, charge neutralization occurs between the anionic polymer and the cationic setting polymer, resulting in agglomeration, cloudiness, or bitterness. This may occur. Therefore, the only setting polymers that can be added are nonionic setting polymers such as polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer, and anionic setting polymers such as acrylic resin alkanolamine liquids. Also,
Aqueous cosmetics using the gel base form a hard film after drying, so when used as a hair cosmetic, for example, the film formed on the hair will peel off. Because a so-called flaking phenomenon occurs, there are limits to its use.

On the other hand, as a gel base material that forms a soft and flexible film after drying, it is known that a crosslinked base monomer containing an amino group is polymerized in an aqueous emulsion and the viscosity is increased by adjusting the p value. (Unexamined Japanese Patent Publication No. 57-1331
45), the crosslinked base monomer having an amino group is easily hydrolyzed, and if it is hydrolyzed, it is neutralized by an acid treatment performed later and a cationic group is introduced. Since anionic groups and cationic groups coexist in the same polymer molecular chain, a uniform cationic polymer may not be obtained.

In addition, in the gel base material, N as a starting material,
When N-dimethylaminoethyl methacrylate is used, a hydrolysis reaction occurs violently during the polymerization reaction, and the desired polymer cannot be obtained. In other words, this means that
This means that the aforementioned N,N-dimethylaminoethyl methacrylate, which is widely used industrially and is known to have excellent characteristics as a raw material for cosmetics, cannot be used, and the raw material monomer of the gel base material cannot be used. This shows that it is a very disadvantageous thing to make a choice. Furthermore, due to the nature of emulsion polymerization, there is a drawback that contamination with impurities such as surfactants cannot be avoided.

[Problems to be Solved by the Invention] In view of the above-mentioned prior art, the present inventors were able to blend a cationic setting polymer,
As a result of intensive research to create a gel base material that forms a flexible film after drying and contains a small amount of impurities, we have finally found a gel base material that satisfies all of the physical properties required for darkening.
This led to the completion of the present invention.

[Means for Solving the Problems] That is, the present invention has the general formula (I): (wherein, R1 is a hydrogen atom or a methyl group, R2 and R
(3 is a methyl group or an ethyl group, A is a linear or side chain alkylene group having 1 to 4 carbon atoms) 15 to 85% by weight of a (meth)acrylic acid ester, general formula (■) : 0.1 to 20% by weight of oxydialkylene di(meth)acrylic acid ester represented by (wherein R1 and A are the same as above, and n is an integer of 1 to 40) and general formula (I): The present invention relates to a gel base material mainly composed of a copolymer composed of 12C-CH (in the formula, 3 or 4) a monomer θ to 80ffi%.

[Function and Examples] As described above, the gel base material of the present invention has the formula (I)
: (wherein R1 and A are the same as above, n is an integer of 1 to 40) 0.1 to 20% of oxydialkylene di(meth)acrylic acid ester and general formula (I): 2C -CH (wherein, R1 is a hydrogen atom or a methyl group, R2 and R
(j is a methyl group or ethyl group, A is a linear or side chain alkylene group having 1 to 4 carbon atoms) 15 to 5% of (meth)acrylic acid ester (
The main material is a copolymer composed of θ to 80% of a vinyl monomer represented by the following formula (■): (in the formula, l represents 3 or 4).

The (meth)acrylic acid ester represented by formula (1,) above plays the role of imparting electrolytic ability to the copolymer by neutralizing it with an appropriate acid when the desired copolymer is obtained in the present invention. It is a component that has

Representative examples of such (meth)acrylic esters include:
For example, N,N-dimethylaminoethyl acrylate,
N,N-diethylaminoethyl acrylate, N,N-
Examples include dimethylaminoethyl methacrylate and N,N-diethylaminoethyl methacrylate, but the present invention is not limited to these examples. In addition, in this invention, the said (meth)acrylic ester is used individually or in mixture of 2 or more types.

The composition ratio of (meth)acrylic acid ester in the monomer constituting the copolymer is adjusted to be 15 to 85%, preferably 30 to BO%. It takes (meta)
If the composition ratio of the acrylic ester is less than 15%, the amount of the (meth)acrylic ester in the resulting copolymer that is neutralized by the acid will be too small, making it difficult to obtain sufficient gel hardness. It becomes difficult to change what you have,
Moreover, if it exceeds 80%, the flexibility of the film formed after the gel base material is dried will be lost.

The oxydialkylene di(meth)acrylic acid ester represented by the general formula (I) is a compound having two carbon-carbon unsaturated double bonds in one molecule, and crosslinks with other monomers. It has a role. Typical examples of such oxydialkylene di(meth)acrylic esters include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, etc., and the present invention It is not limited to only.

In addition, in this invention, the said oxydialkylene di(meth)acrylic acid ester is used 1 type, or 2 or more types mixed.

The composition ratio of oxydialkylene di(meth)acrylate in the monomers constituting the copolymer is 0.1.
The content is adjusted to 20%, preferably 1 to 10%. If the composition ratio of such oxyalkylene di(meth)acrylate ester is less than 0.1%, the strength of the resulting gel base material will be too low, making it impossible to increase the viscosity of the gel itself. Moreover, if it exceeds 20%, the viscosity of the gel itself increases, but fine aggregates may remain in the gel.

In addition, in the oxydialkylene di(meth)acrylic acid ester represented by the general formula (I), the formula +A-0+
The number n of parts represented by has a great effect on the physical properties of the gel base material obtained, and even when n is 1 to 40, a gel base material with physical properties suitable for practical use can be obtained. Generally, when used in cosmetics, the smaller n is,
Roughness tends to remain. Therefore, when the gel base material of the present invention is used as a gel base material for cosmetics, n is lO
It is preferable that it is 30.

The vinyl monomer represented by the above-mentioned formula circle is used as the remaining component of the (meth)acrylic ester and oxyalkylene di(meth)acrylic ester in the monomers constituting the copolymer. When such a vinyl monomer is used, flexibility, gloss, smoothness, etc. are exhibited in the film formed after the resulting gel base material is dried. Representative examples of the vinyl monomer include N-vinylpiperidone, N-vinylpyrrolidone, etc., but the present invention is not limited to these examples. In the present invention, the above monomers may be used alone or in combination of two or more.

The composition ratio of vinyl monomers in the monomers constituting the copolymer is adjusted to be 0 to 80%, preferably 20 to 60%. If the composition ratio of the vinyl monomer exceeds 80%, the gel strength of the resulting gel base material will be significantly reduced.

The polymerization of the (meth)acrylic acid ester, ethyl oxydialkylene di(meth)acrylate, and tonyl monomer is carried out in a non-aqueous solvent under heating in an atmosphere of an inert gas such as nitrogen gas.

In the present invention, the reason why the polymerization reaction is carried out in a non-aqueous solvent under an inert gas atmosphere is to prevent the ester groups present in the monomer or the formed copolymer from being hydrolyzed.

The non-aqueous solvent may be, for example, methanol, ethanol, isopropanol, acetone, chloroform, acetic acid, etc., in order to suppress the formation of a homopolymer due to the difference in reactivity of each monomer and obtain a uniform copolymer. Ethyl, benzene, toluene, xylene, etc. are used. Among these solvents, ethanol and benzene are particularly preferred.

The ethanol may be ethanol with a purity of 95% by volume or more, and more preferably ethanol with a purity of 99% by volume or more. In addition, when the gel base material of the present invention is used for cosmetics or the like, it is preferable to use ethanol because benzene and the like are harmful.

When using a solvent, a reaction device that can complete polymerization while kneading is required in order to improve the kneading state. When a general stirrer for solution polymerization is used as such a reaction device, the concentration of the total amount of monomers is 30%.
Polymerization can be completed by the following.

The polymerization reaction is preferably carried out under heating at 50 to 100°C, and is generally carried out at the reflux temperature of the volatile solvent used in the reaction.

The time required for the polymerization reaction is usually 10 hours or more. Note that the polymerization reaction can be arbitrarily completed when the amount of remaining monomer becomes 10% or less. The amount of the remaining monomer can be determined, for example, by adding oxaline to a double bond by a known method such as the PSDB method and measuring the amount of double bond gold.

Note that a polymerization catalyst may be used in the polymerization reaction.

Such polymerization catalysts include, for example, 2.2°-azobisisobutyronitrile, 2.2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2
, 2°-azobisisobutyre), 2.2°-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, diisopropyl purge carbonate, t-
Examples include butyl perisobutyrate. The type of heavy metal catalyst varies depending on the boiling point of the solvent used; for example, when using ethanol or benzene,
2,2-Azobisisobutyronitrile is the most preferred because it is easy to handle. The amount of the polymerization catalyst used is 0.05 to 3%, preferably 0.1 to 1%, based on the total weight of the monomers.

At the initial stage of the polymerization reaction, the polymerization reaction solution exhibits the same appearance as in normal solution polymerization, but as the polymerization reaction progresses, the crosslinking reaction progresses and a copolymer begins to be produced. The generated gel-like copolymer is sheared by stirring and is further polymerized while being kneaded. If the kneading at this stage is insufficient, the resulting gel base material may have lumps or uneven viscosity.

Since the produced copolymer is not stirred as is done during so-called solution polymerization, it is thought that static polymerization is proceeding. Note that the produced copolymer can be solvent-substituted in water or a water-alcohol mixed solvent, if necessary, and turned into a slurry-like dispersion using a high-speed stirrer such as a mixer homogenizer.

If the kneading is insufficient, it is likely that lumps or uneven viscosity will occur when the mixture is neutralized later using an appropriate acid, so it is preferable to thoroughly stir the mixture.

A gel can be obtained from the gel base material of the present invention thus obtained by adjusting the content of the gel base material to a desired viscosity at 2% or less.

When preparing a gel using the gel base material, mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid, citric acid, lactic acid, amino acids, succinic acid, and malic acid are used as neutralizing agents. It is preferable to dilute the gel base material with water to 2% or less and then neutralize it.

Next, the gel base material of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 In a three-necked flask equipped with a thermometer, reflux tube and nitrogen introduction tube, 120 g of N,N-dimethylaminoethyl methacrylate and 1 dimethacrylate of polyoxyethylene were added.
8 g and N-vinylpyrrolidone 180 g 5
A 20% ethanol solution was prepared and degassed by stirring under a nitrogen stream for 2 hours while refluxing at 80°C.

Next, 2,2°-azobisisobutyronitrile 0.9
g was added to a three-necked flask and polymerization was initiated at 80'C. After 3 hours from the start of polymerization, the reaction solution became gel-like.
As the polymerization progressed further, a uniform slurry solution was obtained.

The reaction was completed in about 10 hours, and the concentration was adjusted with ethanol to obtain a gel base material (20% polymer slurry ethanol solution). The viscosity of the obtained gel base material was measured at 20° C. using a BH type viscometer oven cup rotor 1lkL6 and found to be 8830 cP. In addition, the measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C62,92, H8,75, NIo, 49
(%) Measured values: C63,12, H9,OO, N10.
22 (%) Next, add water to the gel base material obtained and
% polymer slurry aqueous solution, the pH was adjusted to 6.4 using lactic acid as a neutralizing agent, and the mixture was sufficiently kneaded with a homogenizer to obtain a gel. The physical properties of the resulting gel, such as texture, appearance, and flexibility of the formed film, were examined based on the following methods. The results are shown in Table 1.

(Approximately 2 ml of the textured gel was rubbed between fingers to examine the texture and evaluated based on the following evaluation criteria.

(Evaluation criteria) ◎: Smooth and light texture O: Slightly rough texture Δ: Somewhat rough The evaluation was conducted based on the evaluation criteria.

(Evaluation criteria) ◎: No contamination of impurities is observed. O: Very little contamination of impurities is observed. Δ: Contamination of impurities is slightly observed. A coating film with a thickness of 10 mm was formed on a vinyl chloride film using a bar coater, and the film was formed by air drying for 3 hours.The state of the formed film was examined when the vinyl chloride film was randomly folded.
Evaluation was made based on the following evaluation criteria.

(Evaluation criteria) ◎: No change observed.

○: Very slight peeling is observed.

ΔD Partial peeling is observed.

×: Complete peeling is observed.

Example 2 A 20% benzene solution consisting of 270 g of N,N-dimethylaminoethyl methacrylate and 48 g of polyoxyethylene dimethacrylate was prepared in a three-necked flask equipped with a thermometer, a reflux tube, and a nitrogen introduction tube, and the solution was heated to 80°C.
The mixture was degassed by stirring for 2 hours under a nitrogen gas stream.

Next, 2,2°-azobisisobutyronitrile 0.9
was added, and polymerization was carried out at 80°C.

Thirty minutes after the start of polymerization, the reaction solution became gel-like, and as the polymerization progressed, it became a uniform slurry solution.

After completing the reaction in about 10 hours, distilled water
g was added thereto, and benzene was distilled off under a reduced pressure of 300 to 100 sHg at 50 to 70°C, and when the benzene odor disappeared, distilled water was added to obtain a gel base material (20% polymer slurry aqueous solution).

The viscosity of the obtained gel base material was measured in the same manner as in Example 1 and found to be 50 cP (20° C.).

In addition, the results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated value: C60,28, )19.50, H7,5B
(%) Measured values: C60,51, H9,134, H
7.69 (%) Next, a gel was prepared in the same manner as in Example 1 using the gel base material obtained, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 3 Polymerization was carried out in the same manner as in Example 1, except that benzene was used as the solvent instead of ethanol to prepare a 20% benzene solution, and a uniform polymer slurry benzene solution was obtained.

Distilled water 120% to the obtained polymer slurry benzene solution
Add 0g, 300-100100l at 50-70℃
Benzene was distilled off under reduced pressure, and when the benzene odor disappeared, distilled water was added to prepare a gel base material (20% polymer slurry aqueous solution).

The viscosity of the obtained gel base material was measured in the same manner as in Example 1, and was found to be 33,500 cP (2 (1°C)).

The results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C82,92, H8,75, NIo, 49
(%) Measured value: C63,02,118,93, NlO
, 33 (%) Example 1 using the gel base material obtained next.
A gel was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 4 720 g of the 20% polymer slurry ethanol solution obtained in Example 1 was distilled off at 50 to 70°C under a reduced pressure of 300 to 100 @ Hg, and distilled water was added to prepare the gel base (
A 20% water-ethanol solution of polymer slurry was obtained.

The viscosity of the obtained gel base material was measured in the same manner as in Example 1 and found to be 8250 cP (20°C).

The measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C82,92, HJl, 75, NlO,
49 (%) Measured value: C62,77, H8,8B, N
1O, 31 (%) Next, a gel was prepared in the same manner as in Example 1 using the gel base material obtained, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

As is clear from the results of Examples 1 and 4, it can be seen that the viscosity of the gel base material obtained is greater when a water-ethanol mixed solvent is used than when ethanol is used as the solvent.

Example 5 In Example 1, polyoxyethylene dimethacrylate 18. 3. Ethylene glycol dimethacrylate.
A gel base material was obtained in the same manner as in Example 1 except that the weight was changed to 75 g.

The viscosity of the obtained gel base material was measured in the same manner as in Example 1 and found to be 1000 cP (20''C).

The measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C63,33, H8,73, NlO,99C
%) Measured value: C63,01,f(li,52,N1
0.7g (%) Next, a gel was prepared in the same manner as in Example 1 using the gel base material obtained, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 6 N,N-dimethylaminoethyl acrylate was placed in a three-necked flask equipped with a thermometer, reflux tube, and nitrogen introduction tube.
120g, polyoxyethylene dimethacrylate 45
20% consisting of g and 180 g of N-vinylpyrrolidone
An ethanol solution was prepared and degassed by stirring under a nitrogen stream for 2 hours while refluxing at 80°C.

Next, 2,2°-azobisisobutyronitrile 0.9
g was added to a three-necked flask, and polymerization was started at 80°C. After 15 minutes from the start of polymerization, the reaction solution became gel-like.
As the polymerization progressed further, a uniform slurry solution was obtained.

The reaction was completed in about 10 hours, and the concentration was adjusted with ethanol to obtain a gel base material (20% polymer slurry ethanol solution).

The viscosity of the obtained gel base material was measured in the same manner as in Example 1 and found to be 1000 cP (20''C).The measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated value: CB2. [i5, H8, 87, NIo, 92
(%) Measured values: C62,61, H8,97, N10
．． 99 (%) Next, a gel was prepared in the same manner as in Example 1 using the obtained gel base material, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

From the results of Example 1 and Example 6, in the (meth)acrylic ester represented by the general formula (I), when R1 is a methyl group (Example 6), it is more favorable than when R1 is a hydrogen atom (Example 6). It can be seen that the gel base obtained in Example 1) has a higher viscosity.

Example 7 A gel base material was prepared in the same manner as in Example 1 except that 120 tr of N,N-dimethylaminoethyl methacrylate was replaced with 120 g of N,N-dimethylaminopropyl methacrylate.

The viscosity of the obtained gel base material was examined in the same manner as in Example 1 and found to be 5860 cP (20°C).

In addition, the measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C83,68, H8,89, NIo, 21
(%) Measured values: C63,74, H8,97, NlO,
29 (%) Next, using the obtained gel base material, Example 1
A gel was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

From the results of Example 1 and Example 7, in the (meth)acrylic ester represented by the general formula (1), when A is a methylene group (Example 1), it is better to use a propylene group (Example 1). It can be seen that the viscosity of the gel base material obtained in Example 7) is lower.

Example 8 A gel base material was prepared in the same manner as in Example 1 except that 18 g of polyoxyethylene (9) dimethacrylate was used instead of 18 g of polyoxyethylene dimethacrylate.

The viscosity of the obtained gel base material was examined in the same manner as in Example 1, and was found to be 5050 eP (20° C.).

In addition, the measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C62.99, H8.73, N10.5
(%) Measured values: C82.98, H8.91, N11.
0 (%) Next, using the obtained gel base material, a shiso gel was prepared in the same manner as in Example 1, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

From the results of Example 1, Example 5, and Example 8, it can be seen that when n is 1 in the oxydialkylene di(meth)acrylic acid ester represented by formula [1] (Example 5
), as is clear from comparing the case where n is 9 (Example 8) and the case where n is 23 (Example 1), n
It can be seen that as the number increases, the viscosity of the gel base material obtained increases.

Example 9 Same as Example 1 except that the amount of N,N-dimethylaminoethyl methacrylate used was changed from 120 g to Bof, and the amount of N-vinylpyrrolidone was changed from 180 g to 240 g. A gel base material was prepared in the same manner.

The viscosity of the obtained gel base material was examined in the same manner as in Example 1 and found to be 100 cP (20°C). In addition, the measurement results of elemental analysis are as follows.

(Measurement results of elemental analysis) Calculated values: C83.63, H8.4g, N11.19
(%) Measured values: C63,71, H8,25, NlO
, 94 (%) Next, a gel was prepared in the same manner as in Example 1 using the obtained gel base material, and the physical properties of the gel were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 When polymerization was started in the same manner as in Example 5, except that cyclohexane was used instead of ethanol, precipitation of a powdery polymer began in about 1 hour, and precipitation was completed in about 10 hours. Ta.

Next, add 1200 g of distilled water and heat at 50 to 30℃ for 30 minutes.
Cyclohexane was distilled off under reduced pressure of 0 to loOms+Hg, and when the cyclohexane odor disappeared, a gel base material (20% polymer slurry aqueous solution) was prepared with distilled water.

The viscosity of the gel base material obtained was measured in the same manner as in Example 1, and was found to be 50 cP (20°C).
After diluting the mixture to 50%, neutralization was attempted, but the result was a sol-like fluid liquid that could not be used.

Margin below E] Table 1 (Note) Content of gel base material = 2%, neutralizing agent: lactic acid, pH:
6.4 Experimental Example 1 Water was added to the gel base material (20% polymer slurry ethanol solution) obtained in Example 1 to make a 2% polymer slurry solution, and various neutralizing agents were added to adjust the pH and viscosity (at 20°C). ) was investigated. The viscometer used was a BH type viscometer oven cup rotor type 5. The results are shown in FIG. In Figure 1, (1) is lactic acid, (
2) shows the relationship between pH and viscosity when using phosphoric acid, (3) using malic acid, and (4) using succinic acid.

From the results shown in FIG. 1, it can be seen that the pH value at which the viscosity of the gel base reaches its maximum differs depending on the type of neutralizing agent.

Experimental Example 2 Each gel base material obtained in Examples 1 to 9 was heated at 105°C, lOs.
After drying for 12 hours under reduced pressure of mHg, analysis by IR spectrum was performed. As a result, almost the same spectra were obtained in all Examples.

As an example, the IR spectrum of the gel base material obtained in Example 1 is shown in FIG. Note that IR-460 (manufactured by Shimadzu Corporation) was used as an analytical instrument for the measurement.

Experimental Example 3 10g of each gel base material obtained in Examples 1 to 9 at 105°C
After drying under reduced pressure of mHg for 12 hours, gravithermal analysis was conducted using TG-8110 and TG-DTA manufactured by Rigaku Denki Building at a heating rate of 5° C./min and a temperature range of 50 to 450° C. As a result, almost the same spectra were obtained in all Examples.

- As an example, the measurement results for the gel base material obtained in Example 1 are shown below.

(Endothermic peak) 290°C (DTA) No other peak was observed below 30°C (1°C).

Experimental Example 4 Each gel base material obtained in Examples 1 to 9 was heated at 105°C, IO-
After drying under reduced pressure of 10 g for 12 hours, pyrolysis gas chromatography was used as a thermal decomposition device, JHP-3S (decomposition temperature: 445°C, decomposition time: 6 seconds) manufactured by Nippon Analytical Industry Co., Ltd. cm Shimadzu GC7AG (Column: Ov10114msφ3mm
, Temperature = 70-220°C1 Temperature rising rate: 8°C/min, Detector: FID, Injection temperature: 200°C, Nitrogen gas flow rate: 1kg/cJ, Hydrogen gas flow rate'0.
8 kg/cd, air flow rate 0.9 kg/cj). As a result, almost the same spectra were obtained in all the examples.

As an example, a gas chromatogram of the gel base material obtained in Example 1 is shown in FIG.

Formulation Example 1 After adding 82 g of ion-exchanged water to 5 g of the gel base material (20% polymer slurry ethanol solution) obtained in Example 1 and dispersing it, 3 g of lo% lactic acid aqueous solution was added to adjust the pH to 6.
7 and stirred using a high speed mixer to obtain a homogeneous gel.

Next, HCP-1 (diethyl vinyl pyrrolidone-N
, N-dimethylaminoethyl methacrylic acid copolymer, manufactured by Osaka Organic Chemical Industry ■, trade name), and further kneaded with a high-speed stirring mixer until it became a smooth, cream-like transparent shell. ting shell was prepared.

The physical properties of the resulting hair setting gel, such as hair washing properties and setting power, were examined according to the methods shown below.

The results are shown in Table 2.

(Hair washability) 3 g of setting gel was evenly applied by hand to 2 g of hair with a length of 25 cm, and dried with warm air at 40° C. for 60 minutes. This hair was washed with a 0.5% commercially available hair wash at 30°C (
The setting gel was immersed in hot water containing shampoo, stirred, and the state of removal of the setting gel per unit time was examined, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) ◎: Hair can be completely washed away without sliminess within 30 minutes.

◯: Hair can be completely removed without slimy within 40 minutes.

Δ: Slightly slimy after 40 minutes and some remains.

×: Even after 40 minutes or more, the slime remains and cannot be removed by washing the hair.

(Setting power) 3 g of setting gel was evenly applied by hand to 2 g of hair with a length of 2501 mm. The hair was wrapped in a curler with an outer diameter of 1.2 cm and dried with warm air at 40°C for 60 minutes.The hair was then removed from the curler and hung vertically in an atmosphere at a temperature of 30°C and a relative humidity of 80%. The length immediately after (jet
) and the length (92) after being left for 1 hour were measured, and the curl retention was calculated from the following formula.

[Curl Retention] -25-Love2X100(%)2
5-t+ Note that the larger the curl retention, the greater the setting force, and in the present invention, curl retention of 60% or more satisfies the acceptance criteria.

Formulation Example 2 In Formulation Example 1, the gel base material obtained in Example 1 (20
A hair setting gel was prepared in the same manner as in Formulation Example 1, except that the gel base obtained in Example 3 (20% polymer slurry aqueous solution) was used instead of the 20% polymer slurry ethanol solution).

The physical properties of the resulting hair setting gel were investigated in the same manner as in Formulation Example 1. The results are shown in Table 2.

Table 2 As is clear from the results shown in Table 2, the hair setting gel using the gel base material of the present invention has excellent hair washing properties and setting power.

[Effects of the Invention] The gel base material of the present invention has good compatibility with cationic polymers as well as nonionic polymers commonly used as setting polymers, so it can be used as a gel base for hair cosmetics, for example. It can be used in a wide range of applications.

Furthermore, since the gel base material of the present invention is composed of a vinyl monomer such as N-vinyl lactam, it forms a highly flexible coating film on hair, etc., and has an excellent setting effect. It is something that plays.

FIG. 3 is a gas chromatogram of the gel base material obtained in Example 1 of the present invention.

Claims (1)

[Claims] 1 General formula (I): ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R^1 is a hydrogen atom or a methyl group, R^2 and R^3 are each methyl or ethyl group, A represents an alkylene group having a linear or side chain and having 1 to 4 carbon atoms) (meth)acrylic acid ester 15-8
5% by weight, General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^1 and A are the same as above, n represents an integer from 1 to 40) Oxyalkylene di(meth)
Acrylic acid ester 0.1-20% by weight and general formula (III): ▲Mathematical formula, chemical formula, table, etc. ▼(III) (In the formula, m indicates 3 or 4) Vinyl monomer 0-80 A gel base material whose main material is a copolymer consisting of % by weight.