JP2017075110A - Agent for promoting polymerization of 2-cyanoacrylate monomer, and method for making fiber adhere to body hair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agent for promoting the polymerization of 2-cyanoacrylate monomer which can prevent the generation of formaldehyde.SOLUTION: The present invention provides an agent for promoting the polymerization of 2-cyanoacrylate monomer comprising at least diammonium hydrogen phosphate.SELECTED DRAWING: None

Description

  The present invention relates to a polymerization accelerator for promoting the polymerization of the monomer when, for example, a body hair such as eyelashes and an artificial fiber such as artificial eyelash are bonded with an adhesive containing a 2-cyanoacrylate monomer. The present invention relates to a method of bonding fibers to body hair with an adhesive containing a 2-cyanoacrylate monomer.

  The adhesive containing the 2-cyanoacrylate monomer is capable of firmly bonding the adherends to each other in a short time when the 2-cyanoacrylate monomer is polymerized by moisture in the air. For this reason, the adhesive containing a 2-cyanoacrylate monomer is widely used as a so-called instantaneous adhesive in fields such as industrial use, medical use, and home use. In recent years, an adhesive containing a 2-cyanoacrylate monomer has also been used for a so-called eyelash extension that bonds artificial eyelashes to eyelashes.

  In the treatment of eyelash extensions, the formaldehyde generated from the 2-cyanoacrylate monomer causes problems such as skin allergies and irritation to the eyes and throat. This problem is caused not only by eyelashes but also by formaldehyde when adhering artificial fibers to body hair such as eyebrows and hair.

  In view of such problems, as a technique for using an adhesive containing a 2-cyanoacrylate monomer (hereinafter, also referred to as 2-cyanoacrylate-based adhesive), after applying the adhesive to artificial eyelashes, A method of attaching artificial eyelashes to eyelashes while sucking volatile components that volatilize with a suction device is known (for example, Patent Document 1).

  However, when a 2-cyanoacrylate-based adhesive is used, the 2-cyanoacrylate monomer volatilizes, and formaldehyde is generated as described above by contact with moisture in the air or the like and decomposed. In this method, even if formaldehyde is sucked by the suction device as described above, the generation of formaldehyde itself cannot be prevented.

  On the other hand, a technique relating to a 2-cyanoacrylate adhesive containing a tertiary amine compound is known (for example, Patent Document 2). However, when the 2-cyanoacrylate adhesive described in Patent Document 2 is employed in, for example, eyelash extension treatment, it is considered that the treatment environment surrounding the patient and the practitioner is deteriorated due to an unpleasant odor peculiar to the amine compound.

  In addition, there has been filed a method for adhering an adhesive that reduces the amount of formaldehyde generated by applying a surface treatment agent such as water or an organic amide compound to the adhesive layer of a 2-cyanoacrylate adhesive (for example, patents). Reference 3). However, in the invention described in Patent Document 3, when water is used as the surface treatment agent, the contact of the water with the 2-cyanoacrylate monomer that volatilizes from the adhesive layer causes the generation of formaldehyde. Is not effective in reducing the amount of formaldehyde generated. Further, organic amide compounds which are other surface treatment agents are generally known as formaldehyde scavengers, but such scavengers trap generated formaldehyde and can suppress the occurrence of formaldehyde itself. It is not a thing.

  On the other hand, a formaldehyde scavenger containing a first ammonium phosphate and a second ammonium phosphate is known (for example, Patent Document 4). The formaldehyde scavenger described in Patent Document 4 is for capturing formaldehyde released from woody materials such as furniture, building materials, heat insulating materials, buffering agents, and heat insulating materials (see paragraph [0001]). However, the scavenger described in Patent Document 4 captures formaldehyde that has already been released from the wood material. Therefore, the scavenger described in Patent Document 4 does not suppress the occurrence of formaldehyde itself.

Japanese Patent Laying-Open No. 2015-105447 JP 2009-235115 A JP 2008-144060 A JP 2007-191575 A

  This invention makes it a subject to provide the polymerization accelerator of 2-cyanoacrylate monomer which can suppress generation | occurrence | production of formaldehyde in view of said problem. Another object of the present invention is to provide a method for bonding fibers to body hair, which can suppress the generation of formaldehyde.

  The polymerization accelerator for 2-cyanoacrylate monomer according to the present invention contains at least diammonium hydrogen phosphate. According to such a polymerization accelerator, since polymerization of the 2-cyanoacrylate monomer can be promoted by the diammonium hydrogen phosphate contained in the polymerization accelerator, formaldehyde is generated by a side reaction of the 2-cyanoacrylate monomer. Occurrence can be suppressed.

The method for adhering fibers to the body hair according to the present invention includes a step of applying an adhesive containing a 2-cyanoacrylate monomer to the fibers or the body hair of a subject, and in the presence of the polymerization accelerator, the 2-cyanoacrylate. A method of adhering fibers to body hair, comprising a step of promoting polymerization of monomers and adhering fibers to the body hair of the person to be treated with an adhesive containing the 2-cyanoacrylate monomer.
According to such a method, since polymerization of the 2-cyanoacrylate monomer can be promoted by the diammonium hydrogen phosphate contained in the polymerization accelerator, formaldehyde is generated by a side reaction of the 2-cyanoacrylate monomer. Can be suppressed. Moreover, as a result of suppressing generation | occurrence | production of formaldehyde, it can prevent that the skin allergy by formaldehyde generate | occur | produces in a to-be-treated person and a practitioner.

In the step of adhering fibers to the body hair of the person to be treated, the polymerization accelerator can be present in the treatment environment by applying the polymerization accelerator to the outer surface of the body of the person to be treated.
If a polymerization accelerator is applied to the outer surface of the body of the person to be treated, diammonium hydrogen phosphate in the polymerization accelerator with respect to 2-cyanoacrylate monomer in the adhesive that adheres fibers to the body hair of the person to be treated Easily acts, and the polymerization of the 2-cyanoacrylate monomer is preferably promoted.

  The outer surface of the body of the person to be treated is, for example, body hair of the person to be treated, skin around the body hair, and tape attached to the skin around the body hair.

  Further, in the step of adhering fibers to the body hair of the person to be treated, the polymerization accelerator is present in the treatment environment by arranging the polymerization accelerator in a treatment room where the person to be treated is treated. Can do.

  As the body hair, for example, there are eyelashes, and as the fiber, for example, artificial eyelashes are used. When the above method is applied when artificial eyelashes are adhered to the eyelashes, not only the prevention of skin allergies to the patient and practitioner can be prevented by suppressing the generation of formaldehyde, but also the patient. And irritation to the eyes and throat of the practitioner can be prevented.

  The method for adhering fibers to body hair according to the present invention includes a step of applying an adhesive containing 2-cyanoacrylate monomer to fibers or body hair of a subject, and the polymerization accelerator according to claim 1 as the subject. Applying to the outer surface of the body to promote the polymerization of the 2-cyanoacrylate monomer and bonding the fibers to the body hair of the person to be treated by the adhesive.

  The above-described method includes a step of applying an adhesive containing a 2-cyanoacrylate monomer to a fiber or a human hair, and applying the polymerization accelerator according to claim 1 to the human hair. A step of promoting polymerization of the 2-cyanoacrylate monomer and adhering fibers to the body hair of the person to be treated by the adhesive.

  In the above method, the step of applying an adhesive containing a 2-cyanoacrylate monomer to the fiber or the hair of the subject, and the polymerization accelerator according to claim 1 in the treatment room in which the subject is treated. And a step of accelerating polymerization of the 2-cyanoacrylate monomer and adhering fibers to the body hair of the person to be treated by the adhesive.

  According to the present invention, generation of formaldehyde from the 2-cyanoacrylate monomer can be suppressed.

The graph which shows the correlation with the elapsed time after the dripping which dripped 2-cyanoacrylate adhesive agent in each aqueous solution of Test Example 3, and the generation amount of formaldehyde. The graph which shows the correlation of the elapsed time after installing the gel formulation of the test example 4 beside 2-cyanoacrylate adhesive, and the generation amount of formaldehyde. The graph which shows the correlation of the elapsed time after apply | coating the gel formulation and aqueous solution of Test Example 5 to a surgical tape, and dripping 2-cyanoacrylate adhesive in the part by which the surgical tape is not affixed, and the generation amount of formaldehyde. The graph which shows the correlation with the elapsed time after the application | coating which applied the aqueous solution of Test Example 6 to 2-cyanoacrylate adhesive, and the generation amount of formaldehyde.

  Below, one Embodiment of the polymerization accelerator (formaldehyde generation | occurrence | production inhibitor which suppresses that formaldehyde generate | occur | produces from a 2-cyanoacrylate monomer) based on this invention of 2-cyanoacrylate monomer is described.

  The polymerization accelerator for the 2-cyanoacrylate monomer of this embodiment contains at least diammonium hydrogen phosphate.

  In addition to the above-mentioned diammonium hydrogen phosphate, the polymerization accelerator of the present embodiment further includes water, thickeners, alcohols, fats and oils, surfactants, and other additives (pH buffer, preservative, oxidation Inhibitor) and the like.

  As said thickener, what is generally used as a cosmetic raw material is mentioned, for example. For example, as a thickener, guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, Glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, Carboxymethyl chitin, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxy vinyl polymer , (Hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurine ammonium / vinyl pyrrolidone) copolymer, (acryloyl dimethyl taurine ammonium beheneth-25 methacrylate) cross-polymer, (acryloyl dimethyl taurine ammonium / steales methacrylate-25 ) Crosspolymer, (acrylic acid / acryloyldimethyltaurine / dimethylacrylamide) crosspolymer, polyethylene glycol, bentonite and the like. These thickeners may be used alone or in combination of two or more.

  Examples of the alcohols include ethanol, 2-propanol, butanol, polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1, 2-pentanediol, 2,4-hexylene glycol, 1,2-hexanediol, 1,2-octanediol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol, etc. Is exemplified. These may be used alone or in combination of two or more.

  Examples of the oils and fats include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hardened coconut oil, and hardened Oil, molasses, hydrogenated castor oil, beeswax, candelilla wax, carnauba wax, botarou, lanolin, reduced lanolin, hard lanolin, jojoba oil, waxes, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, micro Hydrocarbons such as crystallin wax, higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, cetyl isooctanoate, isopropyl myristate, isostere Hexyldecyl phosphate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate , Synthetic ester oils such as glycerin tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentane erythritol tetra-2-ethylhexanoate, dimethylpolysiloxane, methyl Cyclic polysiloxanes such as chain polysiloxanes such as phenylpolysiloxane and diphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexanesiloxane Hexane, amino-modified polysiloxane, polyether-modified Porishirokin, alkyl-modified polysiloxanes, silicone oils modified polysiloxanes and fluorine-modified polysiloxane, and the like.

  Examples of the surfactant include fatty acid soap (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkylsulfuric triethanolamine ether, stearyltrimethylammonium chloride, benzalkonium chloride, Cationic surfactants such as laurylamine oxide, imidazoline amphoteric surfactants (such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt), betaine surfactants (alkyl betaines, Amidobetaines, sulfobetaines, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (monostearic acid group) Serine etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), hydrogenated castor oil derivative, glycerin alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE Sorbit fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers ( POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl Nonionic interfaces such as ethers (POE / POP2-decyltetradecyl ether, etc.), tetronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), sucrose fatty acid esters, alkylglucosides, etc. And activators.

  Examples of the other additives include moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, and sodium lactate, and the surface may be treated, mica, talc, kaolin, synthetic phlogopite, calcium carbonate, magnesium carbonate, anhydrous Powders such as silicic acid (silica), aluminum oxide, barium sulfate, etc., surface may be treated, such as Bengala, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide Inorganic pigments, surface may be treated, pearl agents such as titanium mica, fish phosphorus foil, bismuth oxychloride, red 202, red 228, red 226, yellow 4 which may be raked No., Blue No. 404, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203 Organic dyes such as Blue No. 1, Green No. 201, Purple No. 201, Red No. 204, organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer, paraaminobenzoic acid UV absorber , Anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2'-hydroxy-5'-t-octylphenyl) benzo UV absorbers such as triazole, 4-methoxy-4'-t-butyldibenzoylmethane, lower alcohols such as ethanol and isopropanol, vitamin A or derivatives thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 Dioctanoate, vitamin B2 or its derivatives, vitamin B1 Vitamin B such as vitamin B15 or derivatives thereof, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, panthetin, pyrroloquinoline quinone, etc. Vitamins, fragrances and the like can be mentioned.

  The polymerization accelerator preferably contains 0.1 mass% or more and 40 mass% or less of diammonium hydrogen phosphate, and more preferably contains 1 mass% or more and 40 mass% or less. By containing 0.1 mass% or more of diammonium hydrogen phosphate, there is an advantage that generation of formaldehyde can be more sufficiently suppressed. By containing 40% by mass or less of diammonium hydrogen phosphate, there is an advantage that diammonium hydrogen phosphate is reliably dissolved in water.

  The polymerization accelerator usually contains water and diammonium hydrogen phosphate so that the mass ratio of water to diammonium hydrogen phosphate is 1.5 or more. In addition, as water, purified water, ion-exchange water, etc. can be used.

  The polymerization accelerator preferably contains 1% by mass or more of a thickener. The polymerization accelerator usually contains 5% by mass or less of a thickener. As the thickener, an (acryloyldimethyltaurine ammonium / vinyl pyrrolidone) copolymer is preferred.

  The polymerization accelerator is preferably in a gel state by containing a thickener. By being in the form of a gel, there is an advantage that the coating amount when the above polymerization accelerator is applied to a coating object can be easily adjusted.

  The polymerization accelerator is produced by a general method. Specifically, the polymerization accelerator can be produced, for example, by mixing water, diammonium hydrogen phosphate, a polyhydric alcohol, a thickener, and the like.

The 2-cyanoacrylate monomer that the polymerization accelerator of the present embodiment promotes polymerization has a molecular structure represented by the following general formula.
(In the formula, R represents a saturated or unsaturated hydrocarbon having 1 to 4 carbon atoms.)

  The 2-cyanoacrylate monomer is polymerized by moisture in the air and becomes a polymer. On the other hand, in an environment where water is excessively present, the 2-cyanoacrylate monomer promotes the side reaction instead of suppressing the polymerization reaction and generates formaldehyde. The polymerization accelerator can suppress a side reaction of the 2-cyanoacrylate monomer with diammonium hydrogen phosphate. Although it is not necessarily clear about the mechanism by which such a side reaction is suppressed, it is thought that diammonium hydrogen phosphate suppresses that 2-cyanoacrylate monomer volatilizes.

  For example, the polymerization accelerator of this embodiment is disposed and used in a chamber in which an adhesive containing a 2-cyanoacrylate monomer is used. Moreover, the polymerization accelerator of this embodiment is, for example, on a human outer surface (body hair or skin) when an adhesive containing a 2-cyanoacrylate monomer is applied to a fiber or a human body hair. Applied and used.

  Next, an embodiment of a method for bonding fibers to body hair according to the present invention will be described.

  The method for bonding fibers to the body hair of the present embodiment (hereinafter also simply referred to as the above-mentioned method) is a step of applying an adhesive containing 2-cyanoacrylate monomer to the fibers or body hair of the patient (hereinafter referred to as adhesive application). And the treatment with an adhesive containing the 2-cyanoacrylate monomer by promoting the polymerization of the 2-cyanoacrylate monomer in the presence of the polymerization accelerator containing at least diammonium hydrogen phosphate. And a step of bonding fibers to human body hair (hereinafter also referred to as a bonding step). The term “in the presence of a polymerization accelerator” includes being in the presence of a volatile component contained in the polymerization accelerator.

The above-described method includes, for example, a step of applying an adhesive containing a 2-cyanoacrylate monomer to a fiber or a human body hair, and applying the polymerization accelerator to the outer surface of the body of the user. And accelerating the polymerization of the 2-cyanoacrylate monomer and adhering fibers to the body hair of the person to be treated with the adhesive.
In the above-described method, for example, the step of applying an adhesive containing 2-cyanoacrylate monomer to fibers or body hair of a subject and the above-described polymerization accelerator to the body hair of the subject are performed as described in 2 above. -Promoting the polymerization of the cyanoacrylate monomer and adhering fibers to the body hair of the person to be treated by the adhesive.
In the above method, for example, a step of applying an adhesive containing a 2-cyanoacrylate monomer to fibers or body hair of a person to be treated, and the above polymerization accelerator are disposed in a treatment room in which the person to be treated is treated. And a step of promoting the polymerization of the 2-cyanoacrylate monomer to adhere fibers to the body hair of the person to be treated by the adhesive.
The above-described method is used, for example, in the treatment of eyelash extensions in which an artificial eyelash as a fiber is bonded to an eyelash as a body hair by an adhesive containing a 2-cyanoacrylate monomer.

  In the adhesive application step, the fiber is, for example, artificial eyelashes. As the fiber, other than artificial eyelashes can be used. The fiber is not particularly limited as long as it can be adhered to body hair, and examples thereof include artificial eyebrows, fibers for mascara, and hair wigs. Examples of the material of the fiber include polyamide (product name nylon), polypropylene, silk, and human hair.

  In the adhesive application step, the human hair of the human head such as eyelashes, eyebrows, and hair can be used as the body hair of the subject. The body hair is preferably eyelashes.

  In the adhesive application step, an adhesive containing a 2-cyanoacrylate monomer can be used, for example, in an eyelash extension treatment for making the eyelashes of a subject appear longer. In the eyelash extension treatment, an ethyl 2-cyanoacrylate monomer is preferably employed as the 2-cyanoacrylate monomer.

  The adhesive includes a 2-cyanoacrylate monomer as a main component, and further includes a thickener, a solvent, a plasticizer, a colorant, and the like depending on the purpose of use. The adhesive usually contains 70% by mass or more of 2-cyanoacrylate monomer.

  In the adhesion step, the polymerization accelerator can be present in the treatment environment by applying the polymerization accelerator to the outer surface of the body of the patient. In this case, the polymerization accelerator is applied to the outer surface of the body of the subject (such as the outer surface of the head). The outer surface of the body of the person to be treated is, for example, the body hair of the person to be treated, the skin around the body hair, and the tape outer surface attached to the skin around the body hair. In addition, for example, a polymerization accelerator can be applied to an adhesive containing the 2-cyanoacrylate monomer in a state of being attached to the body hair and fibers of the patient.

  For example, in the bonding step, the polymerization accelerator may be applied to the body hair, whereby the adhesive containing the 2-cyanoacrylate monomer applied to the body hair and the polymerization accelerator may be brought into contact with each other. The polymerization accelerator is not limited to body hair, and can be applied to the skin and used. The polymerization accelerator may be used by being applied onto a sheet-like material such as a tape attached to the skin.

  Examples of the skin include facial skin. Examples of facial skin include cheek skin and skin around eyes such as eyelids. In the eyelash extension treatment, it is preferable to apply a polymerization accelerator around the eyes such as eyelids.

In the bonding step, the polymerization accelerator can be present in the treatment environment by disposing the polymerization accelerator in a treatment room in which the subject is treated. For example, in the case of the eyelash extension treatment, the treatment room in which the person is treated is a treatment room in which the person is treated by the practitioner performing the eyelash extension treatment.
In this case, for example, a polymerization accelerator is placed in the vicinity of an adhesive containing a 2-cyanoacrylate monomer, and the adhesion process can be performed in a state where the polymerization accelerator is exposed to air. Formaldehyde can be generated from the 2-cyanoacrylate monomer in the adhesive, but since a polymerization accelerator containing diammonium hydrogen phosphate is placed in the vicinity of the adhesive, generation of formaldehyde can be suppressed. As a result, it is possible to prevent the occurrence of skin allergy and eye and throat irritation not only to the patient but also to the operator.

  In the bonding step, the fibers are usually bonded to the body hair so that the fiber extending direction and the body hair extending direction are the same direction. For example, the artificial eyelash fiber is bonded to the eyelashes so that the direction of eyelash extension is the same as the direction of extension of the artificial eyelash fiber as the fiber.

  The method of adhering fibers to the polymerization accelerator and body hair of this embodiment is as illustrated above, but is not limited to the above examples. Moreover, various forms employ | adopted in the method to adhere | attach a fiber on a general polymerization accelerator and body hair are employable in the range which does not impair the effect of this invention.

  In the above embodiment, the polymerization accelerator used at the time of so-called eyelash extension is described as an example. However, the polymerization accelerator of the present invention is used for indoor use of an adhesive containing a 2-cyanoacrylate monomer. May be. For example, it may be used for the purpose of suppressing the generation of formaldehyde in eyebrow extension treatment, model production, and the like.

  Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.

[Test Example 1]
A formaldehyde multi-monitor “FMM-MD” (manufactured by Shinei Technology Co., Ltd.) was previously placed in a desiccator and allowed to acclimatize for 1 hour, and then a commercially available 2-cyanoacrylate adhesive containing ethyl 2-cyanoacrylate (sales source: M & K) Co.) 0.1 g was put in a desiccator. The following aqueous solutions of Examples 1 and 2 and Comparative Examples 3 to 5 were dropped 0.3 g on the adhesive, and the amount of formaldehyde generated in the desiccator was measured every hour until 3 hours passed. .

Example 1
As shown in Table 1, 10 parts by mass of diammonium hydrogen phosphate and 90 parts by mass of water were mixed to prepare a polymerization accelerator (aqueous solution) so that the concentration of diammonium hydrogen phosphate was 10% by mass.

(Example 2)
As shown in Table 1, 5 parts by mass of diammonium hydrogen phosphate and 95 parts by mass of water were mixed to prepare a polymerization accelerator (aqueous solution) so that the concentration of diammonium hydrogen phosphate was 5% by mass.

(Comparative Example 3)
As shown in Table 1, 10 parts by mass of ammonium dihydrogen phosphate and 90 parts by mass of water were mixed to prepare an aqueous solution so that the concentration of ammonium dihydrogen phosphate was 10% by mass.

(Comparative Example 4)
As shown in Table 1, 10 parts by mass of urea and 90 parts by mass of water were mixed to prepare an aqueous solution so that the concentration of urea was 10% by mass.

(Comparative Example 5)
As shown in Table 1, 10 parts by mass of triethanolamine and 90 parts by mass of water were mixed to prepare an aqueous solution so that the concentration of triethanolamine was 10% by mass.

(Comparative Example 1)
As Comparative Example 1, the amount of formaldehyde generated when nothing was dropped on the 2-cyanoacrylate adhesive was measured.

(Comparative Example 2)
As Comparative Example 2, the amount of formaldehyde generated when 0.3 g of water was dropped on a 2-cyanoacrylate adhesive was measured.

  Table 2 shows the measurement results of the amount of formaldehyde generated in Examples 1 and 2 and Comparative Examples 1 to 5.

As is clear from Table 2, in Comparative Examples 1 to 5, generation of formaldehyde was observed in all cases. In particular, the amount of formaldehyde generated after 2 hours and 3 hours in Comparative Examples 1 to 3 was large.
On the other hand, when the polymerization accelerator of Example 1 was added dropwise, no formaldehyde was observed until 3 hours had passed immediately after the addition. Moreover, when the polymerization accelerator of Example 2 was dropped, although the generation of formaldehyde was slightly observed, the generation amount was significantly smaller than those of Comparative Examples 1-5. From these facts, it was found that the polymerization accelerator containing diammonium hydrogen phosphate has an excellent effect of suppressing generation of formaldehyde.

[Test Example 2]
Instead of the aqueous solution of Test Example 1, the following gel preparations of Examples 3 and 4 and Comparative Examples 6 to 9 were prepared. In the same manner as in Test Example 1, the amount of formaldehyde generated was measured using a formaldehyde multi-monitor “FMM-MD” (manufactured by Shinei Technology Co., Ltd.). Specifically, simultaneously with placing the formaldehyde multi-monitor “FMM-MD” in the desiccator, 50 g of the gel preparations of Examples 3 and 4 and Comparative Examples 6 to 9 were placed in the desiccator. After allowing to stand for 1 hour for acclimatization of formaldehyde multi-monitor, the 2-cyanoacrylate adhesive used in Test Example 1 is put into a desiccator, and formaldehyde in the desiccator is passed every hour until 3 hours have passed. The generation amount of was measured.

(Example 3)
As shown in Table 3, 1 part by mass of diammonium hydrogen phosphate and 2.5 parts by mass of “(acryloyldimethyltauronium ammonium / vinylpyrrolidone) copolymer” [Aristoflex AVC (manufactured by Clariant Japan Co., Ltd.)] as a thickener Then, 96.5 parts by mass of water was mixed, and a polymerization accelerator (gel preparation) was prepared so that the concentration of diammonium hydrogen phosphate was 1% by mass.

Example 4
As shown in Table 3, 0.5 parts by mass of diammonium hydrogen phosphate, 2.5 parts by mass of Aristoflex AVC, and 97 parts by mass of water were mixed, and the concentration of diammonium hydrogen phosphate was 0.5% by mass. Thus, a polymerization accelerator (gel preparation) was prepared.

(Comparative Example 6)
As shown in Table 3, a gel preparation was prepared by mixing 2.5 parts by weight of Aristoflex AVC and 97.5 parts by weight of water. This gel formulation does not contain diammonium hydrogen phosphate.

(Comparative Example 7)
As shown in Table 3, 1 part by mass of ammonium dihydrogen phosphate, 2.5 parts by mass of Aristoflex AVC, and 96.5 parts by mass of water are mixed so that the concentration of ammonium dihydrogen phosphate becomes 1% by mass. A gel formulation was prepared.

(Comparative Example 8)
As shown in Table 3, 1 part by mass of urea, 2.5 parts by mass of Aristoflex AVC, and 96.5 parts by mass of water were mixed to prepare a gel preparation so that the concentration of urea was 1% by mass.

(Comparative Example 9)
As shown in Table 3, 1 part by mass of triethanolamine, 2.5 parts by mass of Aristoflex AVC, and 96.5 parts by mass of water are mixed so that the concentration of triethanolamine is 1% by mass. Was prepared.

  Table 4 shows the measurement results of the amount of formaldehyde generated in Examples 3 and 4 and Comparative Examples 6 to 9.

As is clear from Table 4, in all of Comparative Examples 6 to 9, the generation of formaldehyde was observed, and the amount of formaldehyde generated after 3 hours in Comparative Examples 7 and 8 was particularly large.
On the other hand, when the polymerization accelerator (gel preparation) of Example 3 was used, no formaldehyde was observed until 3 hours had elapsed. In addition, when the polymerization accelerator (gel preparation) of Example 4 was dropped, although the generation of formaldehyde was slightly observed, the generation amount was remarkably small as compared with Comparative Examples 6-9. From these facts, it was found that a formaldehyde generation suppressing effect excellent in a polymerization accelerator (gel preparation) containing diammonium hydrogen phosphate was recognized.

[Test Example 3]
The following aqueous solutions (1) to (6) were prepared, and the amount of formaldehyde generated when 2-cyanoacrylate adhesive was dropped into each aqueous solution was measured. The amount of formaldehyde generated was measured using HPLC. That is, 50 ml of the prepared aqueous solution of (1) to (6) was taken, and 0.2 g of the adhesive was added dropwise thereto and stirred well. This was allowed to stand in a 25 ° C. water bath, and a part of which was sampled with time was filtered through a 0.45 μ membrane filter to obtain a sample solution. 1 ml of a solution prepared by dissolving 0.01 g of 2,4-dinitrophenylhydrazine in 9.8 g of phosphoric acid and purified water to make a total volume of 50 ml is added to 1 ml of each of the above sample solutions, and is allowed to stand for 30 minutes after stirring. It was set as the sample solution for HPLC.

(1) Water (2) Aqueous solution containing 1% by weight urea and 1% by weight tripotassium phosphate (3) Aqueous solution containing 1% by weight urea (4) 1% by weight urea and 1% by weight dihydrogen phosphate An aqueous solution containing ammonium (5) An aqueous solution containing 1% by mass urea and 1% by mass diammonium hydrogen phosphate (6) An aqueous solution containing 1% by mass diammonium hydrogen phosphate

The result of Test Example 3 is shown in the graph of FIG. As apparent from FIG. 1, when the 2-cyanoacrylate adhesive was dropped into the water of (1), 382 ppm of formaldehyde was generated immediately after the dropping, and the amount of formaldehyde generated was 589 ppm after 10 minutes. , Increased to 754 ppm after 30 minutes and increased to 807 ppm after 60 minutes. When the 2-cyanoacrylate adhesive was dropped into the aqueous solution (2), the amount of formaldehyde generated immediately after dropping was 101 ppm, increased to 483 ppm after 10 minutes, 703 ppm after 60 minutes, and 60 minutes. Later it increased to 885 ppm.
When the 2-cyanoacrylate adhesive was dropped into the aqueous solution (3), the amount of formaldehyde generated immediately after dropping was 205 ppm, 240 ppm after 10 minutes, 269 ppm after 60 minutes, and 60 minutes. Later it was 294 ppm. When the 2-cyanoacrylate adhesive was dropped into the aqueous solution of (4), the amount of formaldehyde generated immediately after dropping was 251 ppm, 239 ppm after 10 minutes, 249 ppm after 30 minutes, 60 minutes Later it was 255 ppm.
In contrast, for the aqueous solutions of (5) and (6) containing diammonium hydrogen phosphate, almost no formaldehyde was observed immediately after the 2-cyanoacrylate adhesive was dropped, and after 60 minutes. Was 22 ppm or less.

  As is clear from the above test results, the amount of formaldehyde generated when 2-cyanoacrylate adhesive was dropped into an aqueous solution containing diammonium hydrogen phosphate was the amount of water in (1) or (2) to (4). The amount of formaldehyde generated when the 2-cyanoacrylate adhesive is dropped into the aqueous solution is significantly lower. It was recognized that the aqueous solution containing diammonium hydrogen phosphate has the effect of promoting the polymerization of the 2-cyanoacrylate monomer of the 2-cyanoacrylate adhesive to suppress the generation of formaldehyde.

[Test Example 4]
A formaldehyde generation suppression test using a gel preparation was performed. A gel preparation containing 4% by mass of diammonium hydrogen phosphate and a gel preparation containing “graft polymerized polymer” {formaldehyde capturing product, trade name G-MAQ (manufactured by Grafton Laboratories)} are placed in a desiccator. The amount of formaldehyde generated when 0.075 g of 2-cyanoacrylate adhesive was dropped beside each gel preparation was measured. As a control for this test, the amount of formaldehyde generated when 0.075 g of 2-cyanoacrylate adhesive was dropped into a desiccator without placing the gel preparation was also measured.
The amount of formaldehyde generated is measured using a formaldehyde multi-monitor “FMM-MD” (manufactured by Shinei Technology Co., Ltd.) in the same manner as in Test Example 1 above, and the amount of formaldehyde generated after the elapse of 200 minutes is measured every 30 minutes. It was measured.

The result of Test Example 4 is shown in the graph of FIG. As is clear from FIG. 2, in the control, 30 ppb after dropping 2-cyanoacrylate adhesive, 33 ppb after 60 minutes, 67 ppb after 60 minutes, 85 ppb after 90 minutes, 96 ppb after 120 minutes, and 96 minutes after 150 minutes. It continued to increase to 105 ppb. The amount of formaldehyde generated after 30 minutes when the 2-cyanoacrylate adhesive was dropped alongside the gel preparation containing the graft polymer was 21 ppb, 61 ppb after 60 minutes, 78 ppb after 90 minutes, 120 minutes. After and after 150 minutes, it became 96 ppb and 97 ppb and continued to increase.
On the other hand, when 2-cyanoacrylate-based adhesive is dropped by the side of a gel preparation containing diammonium hydrogen phosphate, the amount of formaldehyde generated is from 30 minutes to 200 minutes later, It did not exceed 10 ppb.

  As is apparent from the above test results, the amount of formaldehyde generated when a gel preparation containing diammonium hydrogen phosphate is placed next to the 2-cyanoacrylate adhesive is controlled and gel containing other components. It was significantly less than when the preparation was placed beside the 2-cyanoacrylate adhesive. It was recognized that the gel preparation containing diammonium hydrogen phosphate has the effect of promoting the polymerization of the 2-cyanoacrylate monomer of the 2-cyanoacrylate adhesive and suppressing the generation of formaldehyde.

[Test Example 5]
As a condition assumed during the eyelash extension treatment, a formaldehyde generation suppression test was performed when a gel preparation containing diammonium hydrogen phosphate and an aqueous solution were applied on a surgical tape to be applied around the eyelashes. Gel formulations and aqueous solutions containing 4% by mass and 1% by mass of diammonium hydrogen phosphate, respectively, were prepared. A surgical tape to be applied around the eyelashes in the eyelash extension treatment is applied to a plastic plate, and each gel preparation or aqueous solution is applied on the plastic plate. Further, a 2-cyanoacrylate adhesive is applied to the plastic plate where the surgical tape is not applied. The amount of formaldehyde generated was measured when the plastic plate in which 0.025 g was dropped was placed in a desiccator. As a control for this test, nothing was applied to the surgical tape, and the amount of formaldehyde generated when 0.025 g of 2-cyanoacrylate adhesive was dropped into a desiccator was also measured.
The amount of formaldehyde generated is measured using a formaldehyde multi-monitor “FMM-MD” (manufactured by Shinei Technology Co., Ltd.) in the same manner as in Test Example 1 above, and the amount of formaldehyde generated after 120 minutes elapses every 30 minutes. It was measured.

The result of Test Example 5 is shown in the graph of FIG. As is clear from FIG. 3, in the case of the control, it continued to increase to 3 ppb after 30 minutes, 35 ppb after 60 minutes, 64 ppb after 90 minutes, and 85 ppb after 120 minutes.
On the other hand, when an aqueous solution containing diammonium hydrogen phosphate was applied on the surgical tape, it was 6 ppb after 30 minutes, 25 ppb after 60 minutes, 30 ppb and 31 ppb after 90 minutes and 120 minutes. The amount of formaldehyde generated was less than in the case of the control.
When the gel preparation containing diammonium hydrogen phosphate was applied on surgical tape, formaldehyde was not generated after 30 minutes and 60 minutes. 14 ppb of formaldehyde was generated after 90 minutes and 21 ppb of formaldehyde after 120 minutes, but the amount generated was remarkably smaller than that of the above control. In addition, the amount of formaldehyde generated was small as compared with the case where an aqueous solution containing diammonium hydrogen phosphate was applied on the surgical tape.

  As is apparent from the above test results, the amount of formaldehyde generated when a gel preparation containing diammonium hydrogen phosphate and an aqueous solution were applied on surgical tape was smaller than that of the control. In particular, the formaldehyde generation suppression effect when a gel preparation containing diammonium hydrogen phosphate was applied on a surgical tape was excellent.

[Test Example 6]
As a condition assuming after eyelash extension treatment, 0.025 g of 2-cyanoacrylate adhesive (glue) was dropped on a plastic plate and left outside the desiccator for 1 hour to cure the 2-cyanoacrylate adhesive. Later, a formaldehyde generation suppression test was performed when an aqueous solution containing diammonium hydrogen phosphate was applied to the 2-cyanoacrylate adhesive. An aqueous solution containing 1% by mass of diammonium hydrogen phosphate was prepared. An aqueous solution containing diammonium hydrogen phosphate was applied to a 2-cyanoacrylate adhesive that was allowed to stand for 1 hour, and the amount of formaldehyde generated when placed in a desiccator was measured. As a control for this test, an aqueous solution containing diammonium hydrogen phosphate was not applied, and 0.025 g of 2-cyanoacrylate adhesive was dropped on a plastic plate, and then left outside a desiccator for 1 hour to give 2-cyano. The amount of formaldehyde generated when only the plastic plate on which the acrylate adhesive was cured was placed in a desiccator was also measured.
The amount of formaldehyde generated is measured using a formaldehyde multi-monitor “FMM-MD” (manufactured by Shinei Technology Co., Ltd.) in the same manner as in Test Example 1 above, and the amount of formaldehyde generated after 120 minutes elapses every 30 minutes. It was measured.

The result of Test Example 6 is shown in the graph of FIG. As apparent from FIG. 4, in the case of the control, the amount of formaldehyde generated was 6 ppb after 30 minutes, 20 ppb after 60 minutes, 33 ppb after 90 minutes, and 35 ppb after 120 minutes, and continued to increase.
In contrast, when an aqueous solution containing diammonium hydrogen phosphate was applied to a 2-cyanoacrylate adhesive that was allowed to stand for 1 hour, formaldehyde was not generated after 30 minutes and 60 minutes. It was 3 ppb after 90 minutes and 1 ppb after 120 minutes. The amount of formaldehyde generated hardly increased and was smaller than that of the above control.

[Test Example 7]
Prepare a mixed aqueous solution of formaldehyde / diammonium hydrogenphosphate having a formaldehyde concentration of 100 ppm and diammonium hydrogenphosphate concentrations of 0.1 mass%, 0.01 mass%, and 0.001 mass%, respectively, and let it come to room temperature for 2 hours. After standing, the formaldehyde concentration was measured. The measurement was performed by HPLC as in Test Example 3. In any case, the measured formaldehyde concentration value was 99-100 ppm. From this, it was found that formaldehyde was not captured by diammonium hydrogen phosphate.

[Test Example 8]
Ethyl 2-cyanoacrylate monomer was dropped onto the glass plate. When left as it was, a whitening phenomenon occurred around the dropped droplet. The whitening phenomenon is considered to be caused by the polymerization of the volatilized monomer around the droplet. On the other hand, when an ethyl 2-cyanoacrylate monomer was dropped on a glass plate that had been coated with a 1% by weight aqueous diammonium hydrogen phosphate solution and then dried, no whitening phenomenon occurred. It is thought that monomer volatilization was suppressed by the aqueous diammonium hydrogen phosphate solution.

[Test Example 9]
A safety test using a human patch test of an aqueous diammonium hydrogen phosphate solution was performed. An aqueous solution of 12 mass% diammonium hydrogen phosphate (food additive, Junsei Chemical Co., Ltd.) was applied to the back skin of 26 humans (patients such as dermatitis) for 48 hours, and the irritation to human skin was examined. A filter paper having a diameter of 8 mm to which 0.01 mL of an aqueous diammonium hydrogen phosphate solution was dropped was placed in a fin chamber, and used as a test substance. The test substance was affixed to the upper back of the subject for 48 hours, the skin reaction was observed twice after 30 to 60 minutes and 24 hours after removal of the adherence according to Japanese criteria, and the determination was scored. The skin irritation of each test solution was determined from the score, and this was classified into three stages as follows to evaluate safety.
○: Skin irritation index is 15 or less
Δ: Skin irritation index greater than 15 and 30 or less
X: Skin irritation index exceeding 30 When the above skin irritation index is 30 or less (◯ and Δ), it is evaluated that irritation to human skin is low, and when exceeding 30 (x), irritation to human skin is high It was evaluated.

[Test Example 10]
An eye mucosa irritation test of diammonium hydrogen phosphate was conducted. A test based on an alternative evaluation test for eye mucosal irritation by the STE method using SIRC cells (hereinafter referred to as the STE test) was performed. Using. The determination was made based on the classification criteria of the STE test, classifying ocular mucosa irritation, and the determination was made according to the following criteria.
○: STE rank is 1
Δ: STE rank is 2
×: STE rank is 3
When the STE rank was 1 (◯), it was evaluated that eye irritation was low, and when it was 2 or more (Δ and ×), it was evaluated that eye irritation was high.

  Table 5 shows the test results of Test Examples 9 and 10.

  The polymerization accelerator for 2-cyanoacrylate monomer of the present invention is suitably used for suppressing generation of formaldehyde in an eyelash extension treatment in which fibers such as artificial eyelashes are bonded to body hair such as eyelashes. The The polymerization accelerator for the 2-cyanoacrylate monomer of the present invention is suitably used as a formaldehyde generation inhibitor that suppresses the generation of formaldehyde from the 2-cyanoacrylate monomer.

Claims (9)

  A polymerization accelerator for 2-cyanoacrylate monomer containing at least diammonium hydrogen phosphate.   A step of applying an adhesive containing 2-cyanoacrylate monomer to fibers or body hair of a subject, and in the presence of the polymerization accelerator according to claim 1, the polymerization of the 2-cyanoacrylate monomer is promoted to Adhering the fibers to the body hair of the person to be treated with an adhesive.   In the step of adhering fibers to the body hair of the person to be treated, the polymerization accelerator is present in a treatment environment by applying the polymerization accelerator to an outer surface of the body of the person to be treated. The method for adhering fibers to body hair as described.   The outer surface of the body of the person to be treated is a body hair of the person to be treated, skin around the body hair, and tape attached to the skin around the body hair. How to bond.   3. In the step of adhering fibers to the body hair of the person to be treated, the polymerization accelerator is present in a treatment environment by disposing the polymerization accelerator in a treatment room where the person to be treated is treated. A method for adhering fibers to body hair as described in 1.   The method for bonding fibers to body hair according to any one of claims 2 to 5, wherein the body hair is eyelashes and the fibers are artificial eyelashes.   The step of applying an adhesive containing 2-cyanoacrylate monomer to the fiber or the hair of the subject, and applying the polymerization accelerator according to claim 1 to the outer surface of the body of the subject, A method for adhering fibers to body hair, comprising: promoting polymerization of cyanoacrylate monomer and adhering fibers to the body hair of the subject using the adhesive.   The step of applying an adhesive containing 2-cyanoacrylate monomer to fibers or the body hair of a subject, and applying the polymerization accelerator according to claim 1 to the body hair of the subject, thereby the 2-cyanoacrylate. A method of adhering fibers to body hair, comprising the step of promoting polymerization of monomers and adhering fibers to the body hair of the subject using the adhesive.   A step of applying an adhesive containing 2-cyanoacrylate monomer to the fiber or the body hair of the subject, and by placing the polymerization accelerator according to claim 1 in a treatment room in which the subject is treated, Promoting the polymerization of the 2-cyanoacrylate monomer and adhering the fibers to the body hair of the person to be treated with the adhesive, and bonding the fibers to the body hair.