JPH0129808B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymer latex for use in eyeliners that are excellent in water resistance, adhesion, writing feel, safety, and the like. Eyeliner is a beauty pigment that is widely loved by women as a cosmetic that accentuates the eyes and improves the impression of the eyes. There are various types of eyeliner,
It is known that eyeliners using polymer latex as a film-forming agent exhibit relatively well-balanced performance in terms of water resistance, adhesion, and writing feel. Manufactured and sold by the manufacturer. Unless limited to cosmetic applications, polymer latexes have conventionally been most commonly synthesized by a polymerization method known as emulsion polymerization, primarily using anionic emulsifiers such as sodium lauryl sulfate. It was hot. However, anionic emulsifiers, including sodium lauryl sulfate, are highly irritating to the skin, and their inclusion in cosmetics that are applied directly to the skin, such as eyeliners, is not desirable from a safety standpoint. JP-A-54-151139 discloses that a polymer latex for make-up cosmetics is polymerized in the coexistence of an anionic emulsifier and a nonionic emulsifier, and then the anionic emulsifier is removed by dialysis. It is being synthesized. However, this method involves removing the anionic emulsifier by dialysis, which is a complicated procedure, and it is a very difficult task to confirm how much anionic emulsifier has been removed. Become. It would be most convenient if the polymer latex could be polymerized using only a nonionic emulsifier.
Depending on the relationship between the monomer composition charged during polymerization and the combination of emulsifier, in many cases gel formation during polymerization may be significant, or the synthesized polymer latex may impair the properties of cosmetics. Often causes trouble. Therefore, as a result of intensive research, the present inventors found that 50-98% by weight of 2-ethylhexyl acrylate, 0.5-10% by weight of acrylic acid, 0.01-0.3 parts by weight of tetradecaethylene glycol dimethacrylate, and
A polymer latex containing 5 to 48% by weight of methyl acrylate and/or methyl methacrylate as the main monomer component is prepared using polyoxyethylene octyl phenyl ether or polyoxyethylene nonylphenyl ether with an HLB value of 8 to 17 as an emulsifier. When synthesized by emulsion polymerization, there is little gel formation during polymerization, and eyeliners using polymer latex synthesized by this method have excellent water resistance, adhesion, writing feel, etc. The inventors have discovered that such a manufacturing method is excellent as a method for manufacturing polymer latex for eyeliners, and have arrived at the present invention. That is, the present invention contains 50 to 98% by weight of 2-ethylhexyl acrylate, 0.5 to 10% by weight of acrylic acid,
Polyethylene glycol (degree of polymerization 9-14) 0.01-0.3% by weight of dimethacrylate and 5-48% by weight of acrylic ester and/or methacrylic ester whose side chain ester has 1 or 2 carbon atoms are used as main monomer components. , HLB value is 8~
This is a method for producing a polymer latex for eyeliner, which is characterized by carrying out emulsion polymerization using polyoxyethylene octyl phenyl ether or polyoxyethylene nonylphenyl ether of No. 17 as an emulsifier. The main monomer composition of the resin part of the polymer latex of the present invention is 50 to 98% by weight of 2-ethylhexyl acrylate, 0.5 to 10% by weight of acrylic acid,
Polyethylene glycol (degree of polymerization 9 to 14) dimethacrylate 0.01 to 0.3 parts by weight, and acrylic ester whose side chain ester has 1 to 2 carbon atoms and/or
or 5 to 48% by weight of methacrylic acid ester. 2-ethylhexyl acrylate has the function of improving the flexibility of the synthesized resin part in a dry state, and acrylic acid has the effect of increasing adhesive strength and water resistance. Polyethylene glycol dimethacrylate also has the effect of increasing adhesive strength, and from the viewpoint of flexibility of the dry resin part and gel formation during polymerization, polyethylene glycol dimethacrylate preferably has a polymerization degree of 9 to 14 in the polyethylene glycol chain.
Such polyethylene glycol dimethacrylates include nanoethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, undecaethylene glycol dimethacrylate, dodecaethylene glycol dimethacrylate, tridecaethylene glycol dimethacrylate, and tetradecaethylene glycol dimethacrylate. One can mention methacrylates. As the acrylic ester and/or methacrylic ester whose side chain ester has 1 to 2 carbon atoms, specifically, acrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid methyl ester, and methacrylic acid ethyl ester are used. By adding these ingredients, it becomes possible to balance the softness and hardness of the dry resin part, resulting in an eyeliner with excellent writing feel. In the present invention, when carrying out emulsion polymerization using such monomer components, as an emulsifier,
Polyoxyethylene octylphenyl ether or polyoxyethylene nonylphenyl ether having an HLB value of 8 to 17 is used. By using such a specific emulsifier during emulsion polymerization, gel formation is reduced, and the water resistance, adhesion, writing feel, etc. of the final eyeliner are significantly improved. . If the HLB value is less than 8 or more than 17, gel formation will increase, and the resulting eyeliner will have poor water resistance, adhesion, writing feel, etc., and is therefore unsuitable. In addition, the amount of emulsifier used during emulsion polymerization is preferably 0.5 to 3% by weight of the total amount. By using an amount within this range, gel formation will be reduced, and the resulting eyeliner will be water resistant. The adhesiveness, adhesion, writing feel, etc. are particularly excellent. The concentration of monomers charged during synthesis of polymer latex is preferably 20% to 40% by weight, and 25% by weight.
Particularly preferred is % by weight to 35% by weight. Polymerization temperature is 40
C. to 80.degree. C. is preferred, and 50.degree. C. to 65.degree. C. is particularly preferred. The polymerization initiator is preferably a redox type one,
Examples include combinations of ammonium persulfate and sodium bisulfite, and potassium persulfate and sodium bisulfite. However, if the polymerization temperature is high, e.g.
Ammonium persulfate at a polymerization temperature of 80°C;
Alternatively, sufficient polymerization can be carried out using an initiator consisting only of potassium persulfate. When the polymer latex synthesized by this method is incorporated into an eyeliner formulation, other eyeliner components used together can be arbitrarily selected from known materials conventionally used for eyeliners. That is, examples of pigments include carbon black, ultramarine blue, red No. 202, red No. 226, yellow No. 205,
Examples include patterns. Furthermore, extender pigments such as kaolin, titanium oxide, zinc white, barium sulfate, talc, and magnesium carbonate can also be used.
These additives are said to have the effect of enhancing the elegance of eyeliner and improving its volume. Thus, according to the manufacturing method of the present invention, the eyeliner finally obtained has excellent water resistance, writing feel, adhesion, etc., and also has a low amount of gel generated during emulsion polymerization, and therefore the present invention The manufacturing method is excellent. The present invention will be explained in more detail below using Examples. Example 1 70 parts by weight of water containing 1.05 parts by weight of nonionic emulsifier polyoxyethylene (added mole number 10) octyl phenyl ether with HLB value of 11.5 was stirred in a nitrogen stream while maintaining the temperature at 57°C, and then 2- 90% by weight of ethylhexyl acrylate, 2.5% by weight of acrylic acid, 7.4% by weight of methyl methacrylate, tetradecaethylene glycol dimethacrylate
10 to 30 parts by weight of a monomer mixture with a composition of 0.1% by weight
At the same time, 0.15 parts by weight of a 6% by weight aqueous ammonium persulfate solution and 0.15 parts by weight of a 6% by weight aqueous sodium bisulfite solution were added. After continuing the reaction for 20 minutes and adjusting the reaction temperature to 60°C, the remaining monomer mixture with the above composition was 90% and 6% by weight.
1.35 parts by weight of an aqueous ammonium persulfate solution and 1.35 parts by weight of a 6% by weight sodium bisulfite aqueous solution were added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for 2 hours, and after cooling, it was briefly filtered through gauze to obtain a polymer latex. The amount of gel produced during polymerization was about 1.4 parts by weight, and the resin content of the resulting polymer latex was about 30% by weight. The obtained polymer latex was concentrated under reduced pressure using a rotary evaporator, and then neutralized with a 6% by weight aqueous solution of caustic soda to give a resin concentration of 45% by weight and pH.
6.0 polymer latex. Using this polymer latex, an eyeliner was manufactured according to the following formulation. (Formulation) Polymer latex 40 parts by weight Carbon black 45 Polyoxyethylene stearylamide
0.3 〃 Polyoxyethylene nonyl phenyl ether
0.6 〃 Kaolin 15 〃 Propylene glycol 10.8 〃 Synthetic clay 0.2 〃 Carboxymethylcellulose 0.2 〃 Water 28.4 〃 The results of the organoleptic test using the eyeliner prepared with this formulation were good as shown in Table 1. All evaluations of the eyeliner according to the present invention were conducted by sensory tests. The writing quality (easiness of application, ease of line formation, repellency, smudging, flexibility) was determined through a sensory test when the product was applied to the rim of the eye, and the scratch resistance was determined by applying it to the back of the hand and then rubbing it with your fingers. The ease of removal was measured. Water resistance was also determined by how easily it could be removed when rubbed in water after being applied to the back of the hand. Example 2 Example except that the nonionic emulsifier polyoxyethylene (number of added moles: 10) octyl phenyl ether with an HLB value of 11.5 was replaced with the nonionic emulsifier polyoxyethylene (number of added moles: 15) octyl phenyl ether with an HLB value of 13.5. Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in exactly the same manner as in Example 1. the result,
The amount of gel produced during polymerization was 0.8 parts by weight, and the results of the eyeliner sensory test were good as shown in Table 1. Example 3 Example except that the nonionic emulsifier polyoxyethylene (number of added moles: 10) with an HLB value of 11.5 and octyl phenyl ether were changed from the nonionic emulsifier polyoxyethylene (number of added moles: 30) with an HLB value of 17.0. Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in exactly the same manner as in Example 1. As a result, the amount of gel produced during polymerization was about 1.4 parts by weight, and the results of the eyeliner sensory test were good as shown in Table 1. Example 4 Example except that the nonionic emulsifier polyoxyethylene (number of added moles: 10) octyl phenyl ether with an HLB value of 11.5 was replaced with the nonionic emulsifier polyoxyethylene (number of added moles: 5) nonylphenyl ether with an HLB value of 8.0. Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in exactly the same manner as in Example 1. As a result, the amount of gel formed during polymerization was about 0.8 parts by weight, and the results of the eyeliner sensory test were good as shown in Table 1. Example 5 Example except that the nonionic emulsifier polyoxyethylene (additional mole number 10) octyl phenyl ether with an HLB value of 11.5 was replaced with the nonionic emulsifier polyoxyethylene (additional mole number 10) nonylphenyl ether with an HLB value of 16.5. Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in exactly the same manner as in Example 1. As a result, the amount of gel produced during polymerization was 0.6 parts by weight, and the results of the eyeliner sensory test were good as shown in Table 1. Example 6 The nonionic emulsifier polyoxyethylene (number of added moles: 10) octyl phenyl ether with an HLB value of 11.5 was replaced with the nonionic emulsifier polyoxyethylene (number of added moles: 15) octyl phenyl ether with an HLB value of 13.5, and 2-ethylhexyl acrylate 90
2% by weight, 7.4% by weight of methyl methacrylate
- Example 1 except that 57.4% by weight of ethylhexyl acrylate and 40% by weight of methyl acrylate were used.
Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in the same manner as described above. As a result, the amount of gel produced during polymerization was 1.3
The results of the sensory test of the eyeliner were good as shown in Table 1. Example 7 The nonionic emulsifier polyoxyethylene (number of added moles: 10) with an HLB value of 11.5 was changed to the nonionic emulsifier polyoxyethylene (number of added moles: 10) nonylphenyl ether with an HLB value of 16.5, and 2-ethylhexyl 90% by weight of acrylate, 7.4% by weight of methyl methacrylate in 2-
Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in exactly the same manner as in Example 1, except that 57.4% by weight of ethylhexyl acrylate and 40% by weight of methyl acrylate were used. As a result, the amount of gel produced during polymerization was 1.4 parts by weight, and the results of the eyeliner sensory test are shown in Table 1.
It was as good as expected. Comparative Example 1 Example except that the nonionic emulsifier polyoxyethylene (additional mole number 10) octyl phenyl ether with HLB value 11.5 was changed to nonionic emulsifier polyoxyethylene (additional mole number 3) octyl phenyl ether with HLB value 6.0. Polymer latex synthesis, eyeliner production, and eyeliner sensory testing were carried out in exactly the same manner as in Example 1. As a result, the amount of gel produced during polymerization was extremely large at 3.0 parts by weight, and the eyeliner's sensory test results, as shown in Table 1, showed some drawbacks in terms of water resistance and writing feel. Comparative Example 2 Same as Example 1 except that the nonionic emulsifier polyoxyethylene (number of added moles: 10) octyl phenyl ether with HLB value of 11.5 was changed to polyoxyethylene (number of added moles: 2) nonylphenyl ether with HLB value of 4.5. Similarly, synthesis of polymer latex,
Manufacture of eyeliner and sensory test of eyeliner were conducted. As a result, the amount of gel produced during polymerization was
The amount was extremely large at 3.5 parts by weight, and the results of the eyeliner sensory test were somewhat defective as shown in Table 1. Comparative Example 3 A polymer latex was prepared in exactly the same manner as in Example 1 except that the nonionic emulsifier polyoxyethylene (additional mole number 10) octyl phenyl ether with an HLB value of 11.5 was changed to polyoxyethylene nonylphenyl ether with an HLB value of 18.9. synthesis, production of eyeliner, and sensory testing of eyeliner. As a result, the amount of gel formed during polymerization was extremely large at 8.0 parts by weight, and the results of the sensory test of the eyeliner also showed some defects as shown in Table 1. Comparative Example 4 Polymer latex was synthesized in exactly the same manner as in Example 1, except that the nonionic emulsifier polyoxyethylene (additional mole number 10) octyl phenyl ether with an HLB value of 11.5 was changed to polyoxyethylene lauryl ether with an HLB value of 15.5. , manufacturing of eyeliner, and sensory testing of eyeliner.
As a result, the amount of gel produced during polymerization was as large as 3.0 parts by weight. Comparative Example 5 A polymer latte was prepared in the same manner as in Example 1 except that the nonionic emulsifier polyoxyethylene (additional mole number 10) octyl phenyl ether with an HLB value of 11.5 was replaced with polyoxyethylene sorbitan monolaurate with an HLB value of 16.7. Synthesis of Tuxus, production of eyeliner, and sensory test of eyeliner were performed. As a result, the amount of gel produced during polymerization was 12.0 parts by weight, which was extremely large.

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Claims (1)

[Claims] 1 50-98% by weight of 2-ethylhexyl acrylate, 0.5-10% by weight of acrylic acid, 0.01-0.3% by weight of tetradecaethylene glycol dimethacrylate, and 5-48% by weight of methyl acrylate and/or methyl methacrylate as main monomer components. 1. A method for producing a polymer latex for eyeliner, which comprises carrying out emulsion polymerization using polyoxyethylene octylphenyl ether or polyoxyethylene nonylphenyl ether having an HLB value of 8 to 17 as an emulsifier.