CN112807246B - Ultraviolet-curing optically variable nail polish and preparation method thereof - Google Patents

Abstract

The invention provides an ultraviolet light curing optically variable nail polish, which comprises the following components: a:30-70 parts by weight of a UV-curable resin A; b:10-30 parts by weight of a UV-curable resin B; c:10-50 parts by weight of a diluent monomer; d:0.1 to 10 parts by weight of a photoinitiator; e:0.01-5 parts by weight of a polymerization inhibitor; f:0.01-5 parts by weight of a rheology modifier; g:0.1-15 parts by weight of optically variable pigments; h:0.1 to 10 parts by weight of a conventional pigment. The nail polish can enable the nail to be observed at different angles, presents different color effects, and has the effects of gorgeous color, high color saturation, simple operation, excellent adhesive force, high brightness, good durability and the like.

Description

A kind of UV-curable light-changing nail polish and preparation method thereof

technical field

The invention relates to the technical field of nail paints, in particular to an ultraviolet light-curable light-changing nail polish and a preparation method thereof.

Background technique

At present, the nail polishes used by people are divided into solvent-based nail polish, water-based nail polish and UV light-curable nail polish. Among them, light-curable nail polish has become one of the main products widely used in the nail art market today. Nail polish can not match the high gloss and colorful color, and it has better durability, easy operation and more convenience than conventional nail polish.

In order to make the nail polish more colorful, produce different decorative effects, and increase the color richness of the nail polish, color-changing nail polish came into being. The early color-changing nail polish mostly used the method of adding fluorescent dyes to the nail polish, which can produce fluorescent effects under the irradiation of ultraviolet light and other light sources.

Patent CN1231169A adopts the formula scheme of adding 0.5-1.5% color-changing pigment and 0.3-3.3% color material to form nail polish. The nail polish of this invention not only has the beautifying and protective effects of ordinary nail polish in general places, but also can change color in nightclubs, dance halls, karaoke, bars and other entertainment places equipped with ultraviolet light sources, and the color is gorgeous. However, the light produced by it is weak in a darker environment, and in bright places, this optical change effect is more difficult to show. In order to solve the above limitations and obtain more widely used nail polish, the patent document CN102631293A discloses a photosensitive color-changing nail polish made by using indoline spiropyran solution as a photochromic agent. On the nails, it is a color under ordinary weak light, and its photochromic agent will produce reversible discoloration under strong light such as sunlight, so that the nail polish will have a discoloration effect, and the original color will be restored after the strong light disappears, increasing interest and sex. However, its discoloration range is still relatively narrow, and the excitation light is ultraviolet light, and its discoloration effect cannot be displayed under strong and weak indoor light. Similar patents include CN103099741A, CN103690453A, CN106580725A, CN107325603A, etc., all of which use certain technologies to make the photochromic nail polish more vivid in color, faster in response, and suitable for more types of nail polish, but It is difficult for them to respond immediately, and it takes a certain amount of time.

Since then, a series of nail polish patents with both photosensitivity and temperature sensitivity have been produced. This type of nail polish is basically realized by adding reversible temperature-changing and reversible photochromic materials to the nail polish system at the same time. Such patents include: CN103735427A, CN105616182A, CN106924076A, CN109381372A. Although there are two environmental response factors introduced into the nail polish system, because environmental changes such as temperature and light change slowly over time, this type of nail polish cannot fundamentally achieve the visual effect that changes with the look. In order to solve the above problems, the patent document CN103126938A makes a kind of non-toxic nail polish by adding pearlescent powder, which integrates the characteristics of colorless, transparent and colored pearlescent nail polish. Oil. This kind of nail polish has a narrow range of color change, mostly gradient colors of the same color system, and the visual impact is not strong.

Contents of the invention

The technical problem to be solved by the present invention is to provide a UV-curable light-changing nail polish that can display different colors when viewed from different angles and a preparation method thereof, which has brilliant colors, high color saturation, and simple operation. , Excellent adhesion, high brightness, good durability and other effects.

A first aspect of the present invention provides a nail polish, comprising the following components:

A: 30-70 parts by weight, preferably the UV curable resin A of 35-65 parts by weight;

b: 10-30 parts by weight, preferably 15-25 parts by weight of UV curable resin B;

c: 10-50 parts by weight, preferably 15-45 parts by weight of the diluted monomer;

d: 0.1-10 parts by weight, preferably the photoinitiator of 1-5 parts by weight;

e: 0.01-5 parts by weight, preferably the polymerization inhibitor of 0.1-2 parts by weight;

f: 0.01-5 parts by weight, preferably 0.1-2 parts by weight of the rheology modifier;

g: 0.1-15 parts by weight, preferably 1-10 parts by weight of optically variable pigments;

h: 0.1-10 parts by weight, preferably 1-8 parts by weight of ordinary pigments.

In the nail polish of the present invention, the UV curable resin A is a difunctional urethane acrylate oligomer, preferably, it is a product obtained by reaction comprising the following components, based on the total mass of raw materials:

Sa1: at least one diisocyanate added in an amount of 2-25wt%, preferably 10-20wt%;

Sa2: at least one polyether polyol, the number average molecular weight of which is 100-3000g/mol, preferably about 200-2000g/mol, and its addition amount is 40-90wt%, preferably 60-75wt%;

Sa3: at least one hydroxyalkyl (meth)acrylate, the addition amount is 2-30wt%, preferably 10-25wt%;

Sa4: at least one catalyst, its addition is 0.01-5wt%, preferably 0.1-0.5wt%;

In a specific embodiment, the preparation process of the UV curable resin A is as follows: first mix Sal, Sa2, and Sa4, and react at 60-90° C. for 1-5 hours to obtain a prepolymer terminated with isocyanate groups; then The obtained prepolymer is mixed with Sa3 for capping reaction. Preferably, the capping reaction temperature is 70-90° C., and the remaining NCO content of the UV curable resin A is controlled to be below 0.02%.

Preferably, said component Sa1 diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer and diisocyanate One or more of cyclohexylmethane diisocyanate, preferably one or more of dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

Preferably, said component Sa2 polyether polyol is polyethylene glycol glycol, polypropylene glycol glycol, polytetramethylene glycol glycol, polytetrahydrofuran ether glycol, polyethylene glycol-propylene glycol One or more, preferably polytetramethylene glycol diols and/or polypropylene glycol diols.

Preferably, said component Sa3 (meth)hydroxyalkyl acrylate is one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate, preferably Hydroxyethyl Acrylate.

Preferably, said component Sa4 catalyst includes but not limited to one or more of dibutyl tin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, preferably neodecanoic acid bismuth.

The UV curable resin B is a polyurethane acrylate oligomer with a functionality of 3-9, preferably, it is a product obtained by reaction comprising the following components, based on the total mass of raw materials:

Sb1: at least one diisocyanate added in an amount of 2-50 wt%, preferably 10-35 wt%;

Sb2: at least one polyether polyol with a number average molecular weight of 100-3000 g/mol, preferably a number average molecular weight of about 200-2000 g/mol, added in an amount of 40-90 wt%, preferably 50-75 wt%;

Sb3: at least one hydroxyalkyl (meth)acrylate, added in an amount of 5-30 wt%, preferably 10-25 wt%;

Sb4: at least one hydroxy-modified dimethylsiloxane, the addition amount is 0.5wt%-15%wt%, preferably 1-10wt%

Sb5: at least one catalyst, the added amount is 0.01-1 wt%, preferably 0.1-0.5 wt%.

In a specific embodiment, the preparation process of the UV curable resin B is as follows: first mix Sb1, Sb2, and Sb5, and react at 60-90° C. for 1-5 hours to obtain a prepolymer terminated with isocyanate groups; then The obtained prepolymer is subjected to a capping reaction with Sb3 and Sb4. Preferably, the temperature of the capping reaction is 70-90° C., and the remaining NCO content of the UV curable resin B is controlled to be below 0.02%. The obtained UV curable resin B is a urethane acrylate oligomer with a functionality of 3-9, and its functionality refers to the number of double bonds contained in a single cured resin B, and its functionality can be adjusted by those skilled in the art through Sb1 isocyanate The type or the type of Sb3, Sb4 end-capping monomers are adjusted.

Preferably, the component Sb1 diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer and diisocyanate One or more in cyclohexylmethane diisocyanate, preferably one or more in dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer and isophorone diisocyanate Various.

Preferably, said component Sb2 polyether polyol is polyethylene glycol glycol, polypropylene glycol glycol, polytetramethylene glycol glycol, polytetrahydrofuran ether glycol, polyethylene glycol-propylene glycol One or more, preferably polytetramethylene glycol.

Preferably, said component Sb3 (meth) hydroxyalkyl acrylate is hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol One or more of hexaacrylate, trimethylolpropane triacrylate and ethoxylated and propoxylated derivatives, pentaerythritol tetraacrylate, preferably pentaerythritol tetraacrylate and/or pentaerythritol triacrylate.

Preferably, the hydroxy-modified dimethylsiloxane of the component Sb4 is 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane, hydroxypropylpentamethyldisiloxane , one or more of 3-(3-hydroxypropyl) heptamethyltrisiloxane.

Preferably, the component Sb5 catalyst includes but not limited to one or more of dibutyl tin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, preferably neodecanoic acid bismuth.

In the nail polish of the present invention, the diluting monomer includes at least one of a monofunctional (meth)acrylate monomer, a difunctional (meth)acrylate monomer and a trifunctional (meth)acrylate monomer. species, further trimethylolpropane triacrylate, tripropylene glycol diacrylate, polydipentaerythritol hexaacrylate, isobornyl acrylate, and hydroxyethyl methacrylate, preferably hydroxyethyl methacrylate.

In the nail oil of the present invention, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethyl At least one of benzoyl-diphenylphosphine oxide and bis-2,6-difluoro-3-pyrrolephenyl titanocene, bistrimethylbenzoylphenylphosphine oxide, and isopropylthioflavone kind.

In the nail oil of the present invention, the polymerization inhibitor is hydroquinone, hydroquinone derivatives (such as 2-tert-butylcatechol, 2,5-di-tert-butylhydroquinone), three (N - at least one of nitroso-N-phenylhydroxylamine) aluminum salt and p-hydroxyanisole.

In the nail oil of the present invention, the rheology regulator is fumed silica, bentonite, polyamide waxes, castor oil derivatives (such as hydrogenated castor oil), polyhydroxycarboxylic acid amide solution (such as: RHEOBYK-405 , concentration 52%), at least one of modified urea solution (such as: RHEOBYK-410, concentration 52%), high molecular weight urea derivative solution (such as: RHEOBYK-415, concentration 30%), preferably modified urea ( RHEOBYK-410) solution.

In the composition of the present invention, the optically variable pigments are red-to-green light-change powder, green-to-magenta light-change powder, green-to-blue light-change powder, green-to-black light-change powder, gold-to-grey light-change powder, gold-change At least one of the green light-changing powder and the interference red pearl powder, the fineness of the powder is 2-25 microns.

Preferably, the optically variable pigments include one or more of the following:

1-8 parts by weight of red-to-green light-changing powder, 1-8 parts by weight of green-to-magenta light-changing powder, 1-8 parts by weight of green-to-blue color-changing powder, 1-8 parts by weight of green-to-black light-changing powder , 1-8 parts by weight of gold-colored gray light-changing powder, 1-8 parts by weight of gold-colored green light-changing powder; 0.5-3 parts by weight of interference red pearlescent powder;

In the nail polish of the present invention, the common pigment is at least one of UV special red, yellow, blue, white, black paste or toner.

The second aspect of the present invention provides the preparation method of the nail polish, comprising: stirring and mixing each component according to the proportion to a homogeneous state; preferably, adding a photoinitiator and a polymerization inhibitor to the diluting monomer, 200 Stir at -800r/min for 5-30min, dissolve and mix evenly; under the condition of stirring, add UV curable resin A and UV curable resin B, stir at 500-2000r/min for 20-30min until uniformly mixed, continue to add rheology The conditioner is stirred for 20-30 minutes until it is evenly mixed, then the optical variable pigment and ordinary pigment are added, stirred for 20-30 minutes until it is evenly mixed, filtered, and discharged to obtain the light-curable light-variable nail polish.

In the present invention, the nail polish adopts multi-layer interference optical film to realize the optical change effect, and the multi-layer optical film flake powder capable of optical interference is used as the dispersion material, which has specific spectral characteristics and is essentially an interference principle. Its reflection spectrum will change with the change of the incident angle; that is, as the observation angle changes, the optical variable pigment will show different colors. If the viewing angle is changed by 60 degrees, two distinctly different colors will appear. The first color can be observed under total reflection, in other words at a viewing angle of 90 degrees. Turning the viewing angle from 60 degrees to about 30 degrees, the first color disappears and the second color appears intensified. The different colors at different angles are the result of reflection, refraction and interference of light at the multilayer interface of the film. The degree of reflection and refraction depends on the wavelength of the light and the materials at the interface. For a fixed multilayer structure, the reflected light and the refracted light interfere, so that some wavelengths of the reflected light on the second surface add and some wavelengths cancel. As the viewing angle is changed, the interference conditions that produce a given color disappear, and then the interference conditions that produce a second color appear. The choice of material, number and thickness of layers determine the color pair. Any combination including the infrared part of the light is theoretically possible. For viewing by the human eye, highly contrasting color pairs such as magenta/green, green/magenta, gold/green, green/blue are preferred. Multilayer optical film flake powder is dispersed in nail polish matrix by UV curable resin and diluent monomer. When irradiated by ultraviolet light, the flake powder is fixed on the nail in a directional manner, and the visible light incident angles are 90 degrees and 30 degrees respectively, and the color can be visually changed (such as magenta/green, gold/green, green/blue, green/magenta) red, green/black, gold/grey, etc.).

Due to the size of the interference optical film and the interaction force between the material molecules, it is easy to agglomerate, making the nail polish unstable, prone to delamination, and internal unevenness. By introducing hydroxyl-modified dimethylsiloxane into the cured resin, it can be coupled with the interference optical shattered film, so that the interference optical shattered film can be uniformly dispersed in the cured resin, and finally achieve a stable arrangement. After curing Can form light change effect. Compared with adding silane coupling agent additives, methyl siloxane fixed on resin B can stabilize the interference optically variable pigments, and it is easier to form a stable and uniform arrangement of optically variable pigments during the curing process, resulting in obvious optically variable effects , Increase the visual impact of nail polish products.

In the present invention, the UV photocurable resin is divided into two types, and the physical properties of the cured nail polish can be controlled by adjusting and controlling the addition ratio thereof. The UV photocurable resin and diluted monomer in the nail polish form a cross-linked network structure after photocuring, which constitutes the main skeleton of the nail polish and provides physical properties such as gloss, hardness, and toughness for the cured nail polish. Due to the low power of UV curing nail lamps, the emitted ultraviolet energy is low, and the functionality of the irradiated nail polish composition to participate in the reaction is high or the functional groups need to have strong reactivity. Therefore, polyurethane acrylate and acrylic acid are selected. Esters are the main body of UV curable resins in the formula, and the carbon-oxygen double bonds connected to acrylates can reduce the minimum energy of free radicals generated by the double bonds, making it easier to carry out photocuring in a shorter time. Due to the high viscosity of UV curable resin, it is necessary to add diluting monomers to make it have good leveling and sagging performance before painting, and the rheology modifier also plays a role in adjusting the fluid properties of the system. Since the nail polish product will be exposed to external light when used, it may cause the nail polish to solidify in advance, so it is necessary to add a polymerization inhibitor to increase the storage time of the nail polish.

The beneficial effects of the present invention are:

The nail polish of the present invention can display different colors when viewed from different angles, and has the advantages of gorgeous colors, high color saturation, excellent adhesion, high brightness, and good durability.

detailed description

In order to better understand the solutions of the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention. Apparently, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

In following examples and comparative example, the source of main raw material is as follows:

IPDI(异佛尔酮二异氰酸酯，NCO含量约为37.8％，万华化学集团股份有限公司)；

IPDI (isophorone diisocyanate, NCO content is about 37.8%, Wanhua Chemical Group Co., Ltd.);

HDI(1,6-己二异氰酸酯，NCO含量约为50％，万华化学集团股份有限公司)；

HDI (1,6-hexamethylene diisocyanate, NCO content is about 50%, Wanhua Chemical Group Co., Ltd.);

PPG1000 (polypropylene glycol, Shandong Bluestar Co., Ltd.)

C2004(聚丙二醇二元醇，羟值270-290mgKOH/g，数均分子量≈1500g/mol，官能度为2，万华化学集团股份有限公司)

C2004 (polypropylene glycol diol, hydroxyl value 270-290mgKOH/g, number average molecular weight ≈1500g/mol, functionality 2, Wanhua Chemical Group Co., Ltd.)

PTMG (polytetrahydrofuran ether glycol, hydroxyl value 56mgKOH/g, number average molecular weight=2000, German BASF company)

HEA (hydroxyethyl acrylate, Shanghai Huayi Group Co., Ltd.)

PETA (pentaerythritol triacrylate, Yantai Houde Functional Polymer Materials Co., Ltd.)

HPSTS (Hydroxypropylpentamethyldisiloxane, Beijing Huawei Ruike Chemical Co., Ltd.)

8108: Organic bismuth catalyst (BiCAT organic bismuth catalyst, a leading company in the United States)

IBOA (isobornyl acrylate, diluted monomer, Shanghai Guangyi Chemical Co., Ltd.)

EO15TMPTA (PEG-15 trimethylolpropane triacrylate, diluted monomer, Shanghai Guangyi Chemical Co., Ltd.)

HEMA (Hydroxyethyl Methacrylate, Shanghai Huayi Group Co., Ltd.)

TPGDA (tripropylene glycol diacrylate, German BASF company)

TPO(2,4,6-三甲基苯甲酰基-二苯基氧化膦，光引发剂，德国BASF公司)

TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator, German BASF company)

819(双三甲基苯甲酰苯基膦氧化物，光引发剂，德国BASF公司)

819 (bistrimethylbenzoyl phenylphosphine oxide, photoinitiator, German BASF company)

184(1-羟基环己基苯基甲酮，光引发剂，德国BASF公司)

184 (1-hydroxycyclohexyl phenyl ketone, photoinitiator, German BASF company)

ITX(异丙基硫黄酮，光引发剂，德国BASF公司)

ITX (isopropylthioflavone, photoinitiator, German BASF company)

MEHQ (p-hydroxyanisole, polymerization inhibitor, Shanghai Aladdin Biochemical Technology Co., Ltd.)

RHEOBYK-405 (concentration 52%, polyhydroxycarboxylic acid amide solution, BYK Chemicals, Germany)

RHEOBYK-410 (concentration 52%, modified urea solution, BYK Chemicals, Germany)

RHEOBYK-415 (concentration 30%, high molecular weight urea derivative solution, BYK Chemicals, Germany)

Red-to-green light-changing pigment (light-changing pigment, Beijing Boda Green High-Tech Co., Ltd.)

Green-to-blue light-changing pigment (light-changing pigment, Beijing Boda Green High-Tech Co., Ltd.)

Gold gray light variable pigment (light variable pigment, Beijing Boda Green High-tech Co., Ltd.)

CI 77891 (UV white color paste, Swiss Clariant Chemical Co., Ltd.)

Preparation of UV curable resin A:

UV curable resin A-1:

Add 320g of polytetrahydrofuran ether diol into a four-necked flask equipped with mechanical stirring, a thermometer and a vacuum device, dehydrate at 112°C and a vacuum of 0.88MPa for 1.5h; cool down the dehydrated polytetrahydrofuran ether diol to 78°C, add 40g of isophorone diisocyanate and 0.5g of bismuth isooctanoate into a four-necked flask, control the temperature at 78°C, and after 2 hours of reaction, cool down to 72°C, add 23g of capping agent hydroxyethyl acrylate to In the four-necked flask, the temperature was controlled at 72°C, and the reaction was stopped when the NCO value dropped below 0.02%, to obtain UV curable resin A-1 with a functionality of 2.

UV curable resin A-2:

Add 270g of polypropylene glycol polyether diol into a four-necked flask equipped with mechanical stirring, a thermometer and a vacuum device, and dehydrate for 1 hour at 115°C and a vacuum of 0.82MPa; the dehydrated polypropylene glycol polyether diol Cool down to 76°C, add 45g of hexamethylene diisocyanate and 0.4g of bismuth neodecanoate into a four-neck flask, control the temperature at 76°C, react for 2 hours, cool down to 70°C, add 39g of capping agent methacrylic acid hydroxyl Ethyl ester was added into a four-necked flask, the temperature was controlled at 70°C, and the reaction was stopped when the NCO value dropped below 0.02%, to obtain UV curable resin A-2 with a functionality of 2.

UV curable resin A-3:

Add 270g of polypropylene glycol polyether diol into a four-necked flask equipped with mechanical stirring, a thermometer and a vacuum device, and dehydrate for 1 hour at 115°C with a vacuum of 0.86MPa; the dehydrated polypropylene glycol polyether diol Cool down to 74°C, add 60g of isophorone diisocyanate and 0.4g of bismuth neodecanoate into a four-neck flask, control the temperature at 74°C, react for 2 hours, cool down to 72°C, add 35g of blocking agent hydroxyethyl acrylate Put it into a four-neck flask, control the temperature at 72°C, wait until the NCO value drops below 0.02%, and stop the reaction to obtain UV curable resin A-3 with a functionality of 2.

UV curable resin B-1:

Add 320g of polytetrahydrofuran ether diol into a four-necked flask equipped with mechanical stirring, a thermometer and a vacuum device, dehydrate at 112°C and a vacuum of 0.88MPa for 1.5h; cool down the dehydrated polytetrahydrofuran ether diol To 78°C, add 110g of isophorone diisocyanate and 0.6g of bismuth isooctanoate into a four-neck flask, control the temperature at 78°C, and after 2 small tests, cool down to 72°C, add 80g of dipentaerythritol hexaacrylate and 12g Add hydroxypropylpentamethyldisiloxane into a four-necked flask, control the temperature at 72°C, wait until the NCO value drops below 0.02% to stop the reaction, and obtain UV curable resin B-1 with a functionality of about 7.

UV curable resin B-2:

Add 240g of polypropylene glycol polyether diol into a four-necked flask equipped with mechanical stirring, a thermometer and a vacuum device, and dehydrate for 1 hour at 115°C with a vacuum of 0.82MPa; the dehydrated polypropylene glycol polyether diol Cool down to 76°C, add 126g of hexamethylene diisocyanate and 1.1g of bismuth neodecanoate into a four-neck flask, control the temperature at 76°C, react for 2 hours, cool down to 70°C, add 66g of pentaerythritol triacrylate and 6g of hydroxy Propylpentamethyldisiloxane was added into a four-neck flask, the temperature was controlled at 70°C, and the reaction was stopped when the NCO value dropped below 0.02%, to obtain UV curable resin B-2 with a functionality of about 8.

UV curable resin B-3:

Add 240g of polypropylene glycol polyether diol into a four-necked flask equipped with mechanical stirring, a thermometer and a vacuum device, and dehydrate for 1 hour at 115°C and a vacuum of 0.86MPa; the dehydrated polypropylene glycol polyether diol Cool down to 74°C, add 167g isophorone diisocyanate and 1.1g bismuth neodecanoate into a four-necked flask, control the temperature to 74°C, react for 2 hours, cool down to 72°C, add 66g pentaerythritol triacrylate and 6g1, Add 3-bis(3-hydroxyisobutyl)tetramethyldisiloxane into a four-necked flask, control the temperature at 72°C, and wait for the NCO value to drop below 0.02% to stop the reaction and obtain UV with a functionality of about 6. Cured Resin B-3.

Examples 1-6

The preparation of photocurable light-changing nail polish, formula is as shown in table 1 (weight part), and its preparation method comprises the following steps:

(1) Add the photoinitiator and polymerization inhibitor into the diluted monomer according to the ratio of ingredients, stir at 500r/min for 10min, dissolve and mix evenly;

(2) Under the condition of stirring, add UV curable resin A and UV curable resin B, stir at 1000r/min for 30min until uniformly mixed, continue to add rheology modifier, stir for 30min until uniformly mixed, then add optical variable pigment and Ordinary pigments, stirred for 30 minutes until uniformly mixed, filtered, and discharged to obtain the light-curable light-varying nail polish.

Table 1:

Comparative example 1

The composition is prepared by mixing 96.3 parts by weight of commercially available MissCandy small black sugar P13 transparent light-curable nail polish, 2.5 parts by weight of red-to-green light-change pigments, and 1.2 parts by weight of CI 77891 ordinary pigments.

Comparative example 2

According to the UV curing resin A-1 of 70 parts by weight, the HEMA of 20 parts by weight, the TPO of 6 parts by weight, the MEHQ of 0.05 parts by weight, the RHEOBYK-410 of 0.25 parts by weight, 2.5 parts by weight of red-to-green optically variable pigments, 1.2 parts by weight Parts of CI 77891 common pigments are formulated into compositions with reference to the examples.

A stability test

From the 1-8 ^# light-curable nail polish compositions obtained in Examples 1-6 and Comparative Examples 1 and 2, observe the morphology of the nail polish compositions stored at 25°C for 30 days and at 50°C for 7 days Filling, see Table 2.

Table 2:

It can be seen from Table 2 that Examples 1-5 can maintain stability no matter at 25°C or at 50°C. Due to the large particle size of the optically variable pigment, it is difficult for general nail polish resins to suspend it, so it is impossible to obtain a stable UV-curable optically variable nail polish product.

B performance index

A 36W special UV lamp for nail polish was used to irradiate the black glass plate coated with 0.1mm thick light-curable light-change nail polish for 2 minutes to obtain a UV-curable light-change nail polish coating, and its various technical indicators were tested, as shown in Table 3. Show.

Hardness testing method: refer to the national standard GB/T 6739 "Pencil Test Method for Paint Film Hardness", that is, use a sharp blade to cut off the xylem by 5mm to 6mm to expose the pencil core, but not damage it; take 400 mesh sandpaper, put the pencil Grind vertically on the sandpaper at an angle of 90°, and grind the tip of the pencil lead flat (at right angles); when the nib is ground into a flat surface, it can be used as a spare; The surface of the placed UV-cured nail polish sample is drawn 3 times in parallel at an angle of 45° to determine the hardness level of the paint film.

Gloss test method: use a 100μm wet film maker to scrape the sample on a clean black glass plate, and cure it by ultraviolet light, and then use a gloss meter to test the gloss of the nail polish.

Variable-angle optical change detection method: Use a 100 μm wet film maker to scrape a nail polish sample on a clean black glass plate, and cure it by ultraviolet light. Then use the visual method to observe within the range of 0° to 90° between the line of sight and the nail polish sample, and evaluate the degree of color change.

table 3:

From the results of the performance test and the senses after use, it can be seen that after curing, Example 1, Example 2, Example 3, Example 4, Example 5, and Example 6 can make the nails shiny and durable, Different colors can be displayed at different angles.

Claims (16)

1. An ultraviolet curing optically variable nail polish comprises the following components:

(a) 30-70 parts by weight of UV curing resin A; the UV curing resin A is a bifunctional urethane acrylate compound which is a product obtained by reacting the following components based on the mass of raw materials:

sa1:2 to 25 weight percent of at least one diisocyanate;

sa2:40-90wt% of at least one polyether polyol having a number average molecular weight of 100-3000g/mol;

sa3:2-30wt% of at least one hydroxyalkyl (meth) acrylate;

sa4:0.01 to 5wt% of at least one catalyst;

the preparation process of the UV curing resin A comprises the following steps: firstly, sa1, sa2 and Sa4 are mixed and react to obtain a prepolymer capped with isocyanate groups; then mixing the obtained prepolymer with Sa3 for end-capping reaction, and controlling the residual NCO content of U V cured resin A to be less than 0.02%;

(b) 10-30 parts by weight of UV curing resin B; the UV curing resin B is a multifunctional urethane acrylate compound with the functionality of 3-9, and is a product obtained by reacting the following components based on the mass of raw materials:

sb1:2 to 50wt% of at least one diisocyanate;

sb2:40-90wt% of at least one polyether polyol having a number average molecular weight of 100-3000g/mol;

sb3:5-30wt% of at least one hydroxyalkyl (meth) acrylate;

sb4: 0.5-15% by weight of at least one hydroxy-modified dimethylsiloxane;

sb5:0.01 to 1wt% of at least one catalyst;

the preparation process of the UV curing resin B comprises the following steps: mixing Sb1, sb2 and Sb5, and reacting to obtain a prepolymer terminated by isocyanate groups; then carrying out end-capping reaction on the obtained prepolymer, sb3 and Sb4, and controlling the residual NCO content of the UV curing resin B to be below 0.02%;

(c) 10-50 parts by weight of a diluent monomer;

(d) 0.1 to 10 parts by weight of a photoinitiator;

(e) 0.01-5 parts by weight of polymerization inhibitor;

(f) 0.01-5 parts by weight of a rheology modifier;

(g) 0.1 to 15 parts by weight of optically variable pigments; the optically variable pigment is at least one of red-to-green-light variable powder, green-to-magenta-light variable powder, green-to-blue-to-black-to-grey-to-light variable powder, gold-to-green-to-light variable powder and interference red pearl powder, the powder fineness of the optically variable pigment is 2-25 micrometers, and the optically variable pigment is produced by Beijing Baddaglin high-tech limited;

(h) 0.1 to 10 weight portions of common pigment.

2. Nail varnish according to claim 1, characterized in that it comprises the following ingredients:

(a) 35-65 parts by weight of UV curing resin A;

(b) 15-25 parts by weight of UV curing resin B;

(c) 15-45 parts by weight of a diluent monomer;

(d) 1-5 parts by weight of a photoinitiator;

(e) 0.1-2 parts by weight of polymerization inhibitor;

(f) 0.1-2 parts by weight of a rheology modifier;

(g) 1-10 parts by weight of optically variable pigment;

(h) 1-8 parts of common pigment.

3. Nail varnish according to claim 1, characterised in that (a) UV-curable resin A is a product obtained by reaction of the following components, based on the raw material mass:

sa1: 10-20wt% of at least one diisocyanate;

sa2: 60-75wt% of at least one polyether polyol having a number average molecular weight of 200-2000g/mol;

sa3: 10-25wt% of at least one hydroxyalkyl (meth) acrylate;

sa4: 0.1 to 0.5wt% of at least one catalyst.

4. The nail polish of claim 1 or 3, wherein the component Sa1 diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate trimer and dicyclohexylmethane diisocyanate;

the polyether polyol of the component Sa2 is one or more of polyethylene glycol dihydric alcohol, polypropylene glycol dihydric alcohol, polytetramethylene glycol dihydric alcohol, polytetrahydrofuran ether dihydric alcohol and polyethylene glycol-propylene glycol;

the component Sa3 hydroxyalkyl (meth) acrylate is one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.

5. The nail polish of claim 4, wherein the component Sa1 diisocyanate is one or more of dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate;

the polyether polyol of the component Sa2 is polytetramethylene glycol diol;

the hydroxyalkyl ester of the component Sa3 (methyl) acrylate is hydroxyethyl acrylate.

6. The nail polish of claim 1, wherein (B) the UV-curable resin B is a product obtained by reacting the following components, based on the mass of raw materials:

sb1:10 to 35 weight percent of at least one diisocyanate;

sb2:50-75wt% of at least one polyether polyol having a number average molecular weight of 200-2000g/mol;

sb3:10-25wt% of at least one hydroxyalkyl (meth) acrylate;

sb4:1-10wt% of at least one hydroxy-modified dimethylsiloxane;

sb5:0.1 to 0.5wt% of at least one catalyst.

7. The nail polish of claim 1 or 6, wherein the component Sb1 diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate trimer and dicyclohexylmethane diisocyanate;

the Sb2 polyether glycol is one or more of polyethylene glycol dihydric alcohol, polypropylene glycol dihydric alcohol, polytetramethylene glycol dihydric alcohol, polytetrahydrofuran ether dihydric alcohol and polyethylene glycol-propylene glycol;

the component Sb3 (methyl) acrylic acid hydroxyalkyl ester is one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethoxylated and propoxylated derivatives and pentaerythritol tetraacrylate;

the component Sb4 hydroxyl modified dimethyl siloxane is one or more of 1,3-bis (3-hydroxy isobutyl) tetramethyl disiloxane, hydroxypropyl pentamethyl disiloxane and 3- (3-hydroxypropyl) heptamethyl trisiloxane.

8. The nail polish of claim 7, wherein the component Sb1 diisocyanate is one or more of dicyclohexylmethane diisocyanate, hexamethylene diisocyanate trimer and isophorone diisocyanate;

the Sb2 polyether polyol is polybutylene glycol diol and/or polypropylene glycol diol;

the component Sb3 hydroxyalkyl (methyl) acrylate is pentaerythritol tetraacrylate and/or pentaerythritol triacrylate.

9. The nail polish of claim 1 or 2, wherein said (c) diluent monomer comprises at least one monomer selected from the group consisting of a monofunctional (meth) acrylate monomer, a difunctional (meth) acrylate monomer, and a trifunctional (meth) acrylate monomer.

10. The nail polish of claim 9, wherein said diluent monomer (c) comprises at least one of trimethylolpropane triacrylate, tripropylene glycol diacrylate, polydipentaerythritol hexaacrylate, isobornyl acrylate, and hydroxyethyl methacrylate.

11. The nail polish of claim 10, wherein said diluent monomer of (c) is hydroxyethyl methacrylate.

12. The nail polish of claim 1 or 2, wherein said photoinitiator (d) is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis 2,6-difluoro-3-pyrrol-ylphenyltitanocene, bis-trimethylbenzoylphenylphosphine oxide, isopropylthioflavone.

13. The nail polish of claim 1 or 2, wherein (f) the rheology modifier is at least one of fumed silica, bentonite, polyamide waxes, castor oil derivatives, polyhydroxycarboxylic acid amide solutions, modified urea solutions, high molecular weight urea derivative solutions.

14. The nail polish of claim 13, wherein said rheology modifier of (f) is a modified urea solution.

15. Nail varnish according to claim 1, characterised in that the optically variable pigments comprise one or more of the following: 1-8 parts of red-to-green light variable powder, 1-8 parts of green-to-magenta light variable powder, 1-8 parts of green-to-blue color variable powder, 1-8 parts of green-to-black light variable powder, 1-8 parts of gold-to-gray light variable powder and 1-8 parts of gold-to-green light variable powder; 0.5-3 parts by weight of interference red pearl powder.

16. A process for the preparation of nail varnish according to any one of claims 1 to 15, comprising: adding a photoinitiator and a polymerization inhibitor into a diluent monomer, stirring, dissolving and mixing uniformly; under the condition of stirring, adding UV curing resin A and UV curing resin B, stirring until the mixture is uniformly mixed, adding a rheological regulator, stirring until the mixture is uniformly mixed, adding optically variable pigment and common pigment, stirring until the mixture is uniformly mixed, filtering and discharging to obtain the optically cured optically variable nail polish.