CN111875755B - Primer resin, preparation method thereof and nail polish primer - Google Patents

Primer resin, preparation method thereof and nail polish primer Download PDF

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CN111875755B
CN111875755B CN202010704336.1A CN202010704336A CN111875755B CN 111875755 B CN111875755 B CN 111875755B CN 202010704336 A CN202010704336 A CN 202010704336A CN 111875755 B CN111875755 B CN 111875755B
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primer
resin
parts
primer resin
esterification reaction
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CN111875755A (en
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李良君
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Zhuhai Zhanchen New Material Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C08F283/105Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
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    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00Manicure or pedicure preparations
    • A61Q3/02Nail coatings
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14Polycondensates modified by chemical after-treatment
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    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/1433Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461Unsaturated monoacids
    • C08G59/1466Acrylic or methacrylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
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Abstract

The application relates to the technical field of nail art, and provides a primer resin, a preparation method thereof and nail polish glue primer. The application provides a primer resin for first oil glue primer, primer resin's preparation raw materials includes: 15-25 parts of hydroxyl acrylate; 20-30 parts of acid anhydride; 30-50 parts of epoxy resin; 1-2 parts of organic dibasic acid; 10-15 parts of UV monomer; 0.5-1 part of catalyst; 0.1-0.3 part of polymerization inhibitor. The primer resin is used as the main resin of the primer of the nail polish, so that an adhesive film formed by curing the primer of the nail polish has good adhesive force and flexibility, the curing speed is high, and a good foundation is laid for implementing later-stage color glue and seal glue.

Description

Primer resin, preparation method thereof and nail polish primer
Technical Field
The application belongs to the technical field of nail art, and particularly relates to a primer resin and a preparation method thereof, and a nail polish primer.
Background
With the development of society, beauty of beauty lovers has gradually developed from the earliest face, skin, etc. to eyelash and nail. The nail polish has rich colors and a plurality of styles, and can fully show the individuality of the nail polish, so that the nail polish becomes more and more an ornament which is necessary for the daily use of the women who love beauty.
The existing nail polish mainly comprises solvent type nail polish, water-based nail polish, UV-LED nail polish glue and the like, and the solvent type nail polish and the water-based nail polish are gradually unsuitable for the fast-paced life at present and are finally eliminated due to the strong smell and the slow curing speed. The UV-LED nail polish glue has the advantages of no solvent, low irritation, low odor, fast curing, high gloss, easy molding and the like, and has become a new favorite in the nail art in recent years. The UV-LED nail polish glue is divided into three parts, namely a primer, a color glue and a seal glue, wherein the primer is used as a bottom layer, the adhesion force of the primer to nails and the flexibility of a glue film are often the key components of the nail polish glue, and the adhesion force and the flexibility of the primer depend on the performance of main resin. The primer of the traditional UV-LED methyl oil adhesive generally takes thermoplastic acrylate and a small amount of polyurethane acrylate as main resin, the curing speed is slow, and the formed adhesive film has poor adhesive force and low flexibility.
Disclosure of Invention
The application aims to provide primer resin, a preparation method thereof and nail polish primer, and aims to solve the problems of low adhesive force, low flexibility and the like of an adhesive film formed by the existing nail polish primer.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a primer resin for a nail polish primer, wherein the raw materials for preparing the primer resin comprise the following components in parts by weight:
Figure BDA0002594137490000021
in a second aspect, the present application provides a method for preparing a primer resin, comprising the steps of:
providing the preparation raw materials according to the primer resin: hydroxyl acrylate, anhydride, epoxy resin, organic dibasic acid, UV monomer, catalyst and polymerization inhibitor;
mixing the hydroxyl acrylate, the anhydride and the polymerization inhibitor, and carrying out a first esterification reaction to obtain a first product;
mixing the epoxy resin, the organic dibasic acid and a catalyst, and carrying out a second esterification reaction to obtain a second product;
mixing the second product and the first product to carry out a third esterification reaction to obtain a prepolymer;
and mixing the prepolymer and the UV monomer to obtain the primer resin.
In a third aspect, the present application provides a nail polish base coat comprising: the primer resin or the primer resin prepared by the preparation method.
The primer resin that this application first aspect provided, its preparation raw materials are by the hydroxyl acrylic ester of specific parts by weight ratio, the acid anhydride, epoxy, organic dibasic acid, the UV monomer, catalyst and polymerization inhibitor are constituteed, regard it as the main part resin of first oil glue primer, can make the glued membrane that first oil glue primer solidification formed have good adhesive force and pliability, lay good basis for the implementation of later stage colour glue and seal coat glue, and be favorable to improving first beautiful persistence, and simultaneously, because this main part resin does not have the solvent, the curing speed is fast, can implement next step molding rapidly after coating this primer, satisfy current consumer to the requirement of fast rhythm life.
According to the preparation method of the primer resin provided by the second aspect of the application, hydroxy acrylate, anhydride and a polymerization inhibitor are reacted to open the ring of the anhydride and perform esterification reaction with the hydroxy acrylate to form a first product containing a half ester intermediate with carboxyl, epoxy resin and organic dibasic acid are subjected to esterification reaction to introduce organic dibasic acid into a subsequently formed prepolymer to improve the flexibility of the primer film of the nail polish, then the first product and the second product are subjected to esterification reaction to form epoxy acrylate resin modified by the organic dibasic acid to serve as a prepolymer, and then the prepolymer and a UV monomer are mixed to prepare the primer resin. The primer glue film of the nail polish glue formed by the primer resin prepared by the method has good adhesive force and flexibility and high curing speed.
According to the nail polish primer provided by the third aspect of the application, the primer resin or the primer resin prepared by the preparation method is used as the main resin, no solvent is used, the curing speed is high, and the adhesive film formed by curing the primer resin has good adhesive force and flexibility.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, for example, "at least one of a, b, or c," or "at least one of a, b, and c," each of which may mean: a. b, c, a-b (i.e. a and b), a-c, b-c or a-b-c, wherein a, b and c can be respectively single or multiple.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first", "second", "third" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implicit indication of the number of technical features indicated, while features defined as "first", "second", "third" may explicitly or implicitly include one or more such features.
The embodiment of the application provides a primer resin for a nail polish primer, and the preparation raw materials of the primer resin comprise the following components in parts by weight:
Figure BDA0002594137490000041
the application embodiment provides a nail polish base glue, its preparation raw materials are by the hydroxyl acrylic ester of specific parts by weight ratio, the acid anhydride, epoxy, organic dibasic acid, the UV monomer, catalyst and polymerization inhibitor are constituteed, regard it as the main part resin of nail polish base glue, can make the glued membrane that the solidification of nail polish base glue formed have good adhesive force and pliability, lay good basis for the implementation of later stage colour glue and seal coat glue, and be favorable to improving beautiful first persistence, and simultaneously, because this main part resin does not have the solvent, the curing speed is fast, can implement molding on next step rapidly after coating this base glue, satisfy current consumer to the requirement of fast rhythm life.
Specifically, the hydroxyl acrylic acid ester is a type of acrylic acid monomer containing hydroxyl group, and can be selected from hydroxyl acrylic acid monomers which are conventional in the field. In some embodiments, the hydroxy acrylate is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. In specific examples, the hydroxy acrylate is 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts based on 100 parts by weight of the total raw materials for preparing the primer resin.
The acid anhydride may be selected from acid anhydrides conventional in the art, and in some embodiments, the acid anhydride is selected from at least one of phthalic anhydride, maleic anhydride, benzoic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. In specific embodiments, the acid anhydride is 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, or 30 parts, based on 100 parts by weight of the total raw materials for preparing the primer resin.
The epoxy resin can be selected from epoxy resins conventional in the art, and in some embodiments, the epoxy resin is selected from bisphenol A epoxy resins, which have good flexibility and economic price and can reduce production cost. In a further embodiment, the bisphenol a epoxy resin is selected from at least one of E12, E20, E42, E44, and E51. In specific embodiments, the epoxy resin is 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, or 40 parts, based on 100 parts by weight of the raw materials for preparing the primer resin.
The organic diacid is a flexible molecule, and the organic diacid is used as one of raw materials, so that a flexible chain segment can be introduced into resin, and the flexibility of the primer glue film is improved. Preferably, the organic dibasic acid is selected from organic dibasic acids with the carbon number of more than 5, and the organic dibasic acids can effectively improve the overall flexibility of the adhesive film. In some embodiments, the organic diacid is selected from at least one of adipic acid, suberic acid, sebacic acid, and lauric acid. In specific embodiments, the organic dibasic acid is 1 part, 1.3 parts, 1.5 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts, based on 100 parts of the total weight of the raw materials for preparing the primer resin.
The UV monomer may be selected from UV monomers conventional in the art, and in some embodiments, the UV monomer is selected from at least one of IBOA (chinese name isobornyl acrylate), TPGDA (chinese name tripropylene glycol diacrylate), DPGDA (chinese name dipropylene glycol diacrylate), HDDA (chinese name hexanediol diacrylate), and NPGDA (chinese name neopentyl glycol diacrylate). In specific embodiments, the UV monomer is 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts, based on 100 parts by weight of the total raw materials for preparing the primer resin.
The catalyst is used for promoting the esterification reaction of the epoxy resin and the organic dibasic acid and promoting the esterification reaction of the epoxy resin and the acrylate monomer or the acrylate polymer. In some embodiments, the catalyst is selected from at least one of triethylamine, benzyltriethylammonium chloride, triphenylphosphine, and N, N-dimethylbenzylamine. In specific embodiments, the catalyst is 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part, based on 100 parts of the total weight of the raw materials for preparing the primer resin.
The polymerization inhibitor is used to prevent the hydroxyacrylate and the anhydride from self-polymerizing during the esterification reaction, and in some embodiments, the polymerization inhibitor is selected from at least one of p-hydroxyanisole, hydroquinone, phenothiazine, and methylhydroquinone. In specific embodiments, the polymerization inhibitor is 0.1 part, 0.2 part or 0.3 part based on 100 parts by weight of the total raw materials for preparing the primer resin.
The primer resin provided by the embodiment of the application is mainly used for the nail polish primer, and endows the nail polish primer adhesive film with good adhesive force and flexibility. In the practical application process, the primer resin and the initiator are mixed to form the nail polish primer. The nail polish gel primer is coated on the surface of a nail, and then is irradiated and cured under an ultraviolet lamp to form a gel film.
The type and the amount of the initiator can refer to the conventional operation in the field, so that the primer resin can be cured into a film under ultraviolet light. In some embodiments, the initiator is selected from at least one of 184, 1173, TPO, ITX, and BP. In some embodiments, the weight ratio of initiator to primer resin is (1-5): 100.
Based on the raw material formula of the nail polish primer, the embodiment of the application also provides a preparation method of the primer resin.
Correspondingly, the preparation method of the primer resin comprises the following steps:
s01, providing preparation raw materials according to the primer resin: hydroxyl acrylate, anhydride, epoxy resin, organic dibasic acid, UV monomer, catalyst and polymerization inhibitor;
s02, mixing the hydroxyl acrylic ester, the anhydride and the polymerization inhibitor, and carrying out a first esterification reaction to obtain a first product;
s03, mixing the epoxy resin, the organic dibasic acid and a catalyst, and carrying out a second esterification reaction to obtain a second product;
s04, mixing the second product with the first product, and carrying out a third esterification reaction to obtain a prepolymer;
s05, mixing the prepolymer with the UV monomer to obtain the primer resin.
According to the preparation method of the methyl oil adhesive base glue, the hydroxyl acrylate, the acid anhydride and the polymerization inhibitor are reacted to enable the acid anhydride to be subjected to ring opening and to be subjected to esterification with the hydroxyl acrylate to form a first product containing a half ester intermediate with carboxyl, the epoxy resin and the organic dibasic acid are subjected to esterification to introduce the organic dibasic acid into a subsequently formed prepolymer to improve the flexibility of the methyl oil adhesive base glue film, then the first product and the second product are subjected to esterification to form the epoxy acrylate resin modified by the organic dibasic acid to serve as a prepolymer, and the prepolymer and the UV monomer are mixed to obtain the base glue resin. The nail polish glue primer glue film formed by the primer resin prepared by the method has good adhesive force and flexibility and high curing speed.
In the step S01, the hydroxy acrylate, the anhydride, the epoxy resin, the organic dibasic acid, the UV monomer, the catalyst and the polymerization inhibitor are selected by referring to the above technical scheme of the primer resin, and the two have the same kind, amount and effect.
In step S02, the hydroxyl acrylate, the anhydride and the polymerization inhibitor are mixed, so that the components are uniformly mixed, and the subsequent first esterification reaction is facilitated. Specific methods of mixing may be according to conventional techniques in the art, such as by mechanical stirring.
In the process of carrying out the first esterification reaction, the acid anhydride is subjected to ring opening and esterification reaction with the hydroxyl acrylate, so that the formed first product contains a half-ester intermediate with carboxyl, and meanwhile, the polymerization inhibitor inhibits partial hydroxyl acrylate and partial acid anhydride from forming by-products by self polymerization in the reaction process, so that the yield of the target product is improved.
In order to ensure that the first esterification reaction is mainly an esterification reaction between an anhydride and a hydroxy acrylate, the applicant further optimized the reaction conditions to increase the yield of the target product. In some embodiments, the step of performing the first esterification reaction is performed at 110 ℃ to 120 ℃ for 2 to 3 hours.
In step S03, the specific method for mixing the epoxy resin, the organic dibasic acid and the catalyst can be determined by the conventional techniques in the art, such as mechanical stirring.
In the process of carrying out the second esterification reaction, under the action of a catalyst, part of the epoxy resin is subjected to ring opening and esterification reaction with the organic dibasic acid, so that the second product contains the epoxy resin oligomer modified by the organic dibasic acid.
In order to increase the yield of the desired product, the Applicant has further optimized the reaction conditions. In some embodiments, in the step of performing the second esterification reaction, the reaction is performed at 100 ℃ to 110 ℃ until the acid value is less than or equal to 1mg KOH/g.
In step S04, the second product and the first product are mixed to form a reaction system synthesis prepolymer. Because the first product contains the hydroxyl acrylate which does not participate in the first esterification reaction and the half ester intermediate with the carboxyl, and the second product contains the epoxy resin which does not participate in the second esterification reaction, the epoxy resin oligomer modified by the organic dibasic acid and the catalyst, in the process of carrying out the third esterification reaction, the epoxy resin and the epoxy acrylate oligomer modified by the organic dibasic acid are esterified with the hydroxyl acrylate and the half ester intermediate under the action of the catalyst to form the modified epoxy acrylate prepolymer. The organic diacid is a flexible molecule, and the organic diacid flexible chain segment is introduced into the prepolymer, so that the flexibility of the primer resin can be improved to a certain extent, and the flexibility of the adhesive film is improved.
In order to increase the yield of the desired product, the Applicant has further optimized the reaction conditions. In some embodiments, in the step of performing the third esterification reaction, the reaction is performed at 110 ℃ to 120 ℃ until the acid value is less than or equal to 5mg KOH/g.
Specific methods for mixing the second product and the first product can be found by techniques conventional in the art, such as mechanical stirring.
In step S05, the prepolymer and the UV monomer are mixed to uniformly mix the prepolymer and the UV monomer, and the specific method can refer to the conventional technology in the art, for example, mechanical stirring. In some embodiments, the step of compounding the prepolymer with the UV monomer is performed at 80 ℃ to 100 ℃.
Based on the above technical scheme, this application embodiment still provides a first polish base adhesive, includes: the primer resin or the primer resin prepared by the preparation method.
The primer resin or the primer resin prepared by the preparation method is used as the main body resin, no solvent is used, the curing speed is high, and the adhesive film formed by curing the primer resin has good adhesive force and flexibility.
The practice of the present invention is illustrated by the following examples.
Example 1
The embodiment prepares the primer resin for the UV-LED nail polish primer, and the specific steps comprise:
(1) Stock preparation
The raw materials for preparing the primer resin comprise the following components:
Figure BDA0002594137490000091
(2) At normal temperature, adding hydroxyethyl acrylate, maleic anhydride and p-hydroxyanisole in a reaction kettle according to a certain amount, stirring, heating to 120 ℃, and reacting for 2 hours to obtain a first product for later use;
(3) At normal temperature, adding epoxy resin E20, adipic acid and triethylamine into a reaction kettle according to the amount, stirring and heating to 105 ℃ for reaction until the acid value in the reaction liquid is less than or equal to 1mg KOH/g, then adding the first product prepared in the step (2), reacting at 110 ℃ until the acid value is less than or equal to 5mg KOH/g, then cooling to 100 ℃, adding TPGDA solution according to the dosage, and stirring uniformly.
Example 2
The embodiment prepares the primer resin for the UV-LED nail polish primer, and the specific steps comprise:
(1) Stock preparation
The raw materials for preparing the primer resin comprise the following components:
Figure BDA0002594137490000092
Figure BDA0002594137490000101
(2) At normal temperature, putting hydroxyethyl acrylate, phthalic anhydride and hydroquinone into a reaction kettle according to the measurement, stirring, heating to 110 ℃, and reacting for 3 hours to obtain a first product for later use;
(3) And (3) at normal temperature, adding epoxy resin E51, adipic acid and triethylamine into a reaction kettle according to the amount, stirring and heating to 110 ℃ for reaction until the acid value of the reaction liquid is less than or equal to 1mg KOH/g, then adding the first product prepared in the step (2), reacting at 108 ℃ until the acid value is less than or equal to 5mg KOH/g, then cooling to 100 ℃, adding a DPGDA solution according to the dosage, and uniformly stirring.
Example 3
The embodiment prepares the primer resin for the UV-LED nail polish primer, and the specific steps comprise:
(1) Stock preparation
The raw materials for preparing the primer resin comprise the following components:
Figure BDA0002594137490000102
(2) At normal temperature, putting hydroxyethyl acrylate, phthalic anhydride and p-hydroxyanisole into a reaction kettle according to a certain amount, stirring, heating to 115 ℃ and reacting for 1.5 hours to obtain a first product for later use;
(3) At normal temperature, adding epoxy resin E20, suberic acid and benzyltriethylammonium chloride in a reaction kettle according to the amount, stirring and heating to 100 ℃ for reaction until the acid value of the reaction solution is less than or equal to 1mg KOH/g, then adding the first product prepared in the step (2), reacting at 120 ℃ until the acid value is less than or equal to 5mg KOH/g, then cooling to 100 ℃, adding TPGDA solution according to the dosage, and uniformly stirring.
Example 4
The embodiment prepares the primer resin for the UV-LED nail polish primer, and the specific steps comprise:
(1) Stock preparation
The raw materials for preparing the primer resin comprise the following components:
Figure BDA0002594137490000111
(2) At normal temperature, putting hydroxypropyl acrylate, tetrahydrophthalic anhydride and methyl hydroquinone into a reaction kettle according to the measurement, stirring, heating to 120 ℃ and reacting for 2 hours to obtain a first product for later use;
(3) And (3) at normal temperature, adding epoxy resin E12, sebacic acid and triphenylphosphine into a reaction kettle according to the measurement, stirring and heating to 103 ℃ for reaction until the acid value of the reaction liquid is less than or equal to 1mg KOH/g, then adding the first product prepared in the step (2), reacting at 120 ℃ until the acid value is less than or equal to 5mg KOH/g, then cooling to 100 ℃, adding HDDA solution according to the dosage, and uniformly stirring.
The primer resins obtained in examples 1 to 4 were taken, and the viscosity and acid value of each primer resin were measured, respectively, and the appearance thereof was observed, and the results are shown in Table 1.
TABLE 1
Sample (I) Appearance of the product Viscosity (60 ℃ C.) Acid value
Example 1 Water white transparent liquid 25000 ≤5
Example 2 Water white transparent liquid 30000 ≤5
Example 3 Water white transparent liquid 35000 ≤5
Example 4 Water white transparent liquid 28000 ≤5
The primer resins obtained in examples 1-4 were taken and mixed with an initiator to form a nail polish primer. The nail polish adhesive primer is coated on the surface of a nail, and then is irradiated under an ultraviolet lamp for curing to form an adhesive film.
Respectively testing the performances of the adhesive films such as hardness, adhesive force, flexibility and the like, wherein the hardness test is a pencil hardness test and refers to the standard GB/T6739-2006; the adhesion test uses 3M adhesive tape, white lattice test, reference standard GB/T9286-1998.
The test results are shown in table 2, which shows that the primer adhesive film formed by the primer resin provided in the examples of the present application has good adhesion and flexibility.
TABLE 2
Sample(s) Hardness of Adhesion force Flexibility of the film
Example 1 F 5B Can not be cracked when folded
Example 2 F 5B Can not be cracked when folded
Example 3 F 5B Is folded in half without cracking
Example 4 F 5B Can not be cracked when folded
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (11)

1. The primer resin is characterized by being used for a nail polish primer, and the primer resin is prepared from the following raw materials in parts by weight:
15-25 parts of hydroxyl acrylate;
20-30 parts of acid anhydride;
30-50 parts of epoxy resin;
1-2 parts of organic dibasic acid;
10-15 parts of UV monomer;
0.5-1 part of catalyst;
0.1-0.3 part of polymerization inhibitor;
wherein the preparation steps of the primer resin comprise:
mixing the hydroxyl acrylate, the anhydride and the polymerization inhibitor, and carrying out a first esterification reaction to obtain a first product; in the step of carrying out the first esterification reaction, the reaction is carried out for 2 to 3 hours at the temperature of between 110 and 120 ℃;
mixing the epoxy resin, the organic dibasic acid and a catalyst, and carrying out a second esterification reaction to obtain a second product; in the step of carrying out the second esterification reaction, the reaction is carried out at 100-110 ℃ until the acid value is less than or equal to 1mg KOH/g;
mixing the second product and the first product to carry out a third esterification reaction to obtain a prepolymer; in the step of carrying out the third esterification reaction, the reaction is carried out at 110-120 ℃ until the acid value is less than or equal to 5mg KOH/g;
and mixing the prepolymer with the UV monomer to obtain the primer resin.
2. The primer resin of claim 1, wherein the organic diacid is selected from at least one of adipic acid, suberic acid, sebacic acid, and lauric acid.
3. The primer resin of claim 1, wherein the epoxy resin is selected from bisphenol a type epoxy resins.
4. The primer resin of claim 1, wherein the hydroxy acrylate is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; and/or
The anhydride is at least one of phthalic anhydride, maleic anhydride, benzoic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
5. The primer resin of any one of claims 1-4, wherein the UV monomer is selected from at least one of IBOA, TPGDA, DPGDA, HDDA and NPGDA; and/or
The catalyst is selected from at least one of triethylamine, benzyltriethylammonium chloride, triphenylphosphine and N, N-dimethylbenzylamine; and/or
The polymerization inhibitor is at least one selected from p-hydroxyanisole, hydroquinone, phenothiazine and methyl hydroquinone.
6. The preparation method of the primer resin is characterized by comprising the following steps:
the primer resin according to any one of claims 1 to 5 provides a preparation raw material: hydroxyl acrylate, anhydride, epoxy resin, organic dibasic acid, UV monomer, catalyst and polymerization inhibitor;
mixing the hydroxyl acrylate, the anhydride and the polymerization inhibitor, and carrying out a first esterification reaction to obtain a first product;
mixing the epoxy resin, the organic dibasic acid and a catalyst, and carrying out a second esterification reaction to obtain a second product;
mixing the second product and the first product to carry out a third esterification reaction to obtain a prepolymer;
and mixing the prepolymer with the UV monomer to obtain the primer resin.
7. The method of claim 6, wherein the first esterification reaction is carried out at 110 ℃ to 120 ℃ for 2 to 3 hours.
8. The method of claim 6, wherein in the step of performing the second esterification reaction, the reaction is performed at 100 ℃ to 110 ℃ until the acid value is less than or equal to 1mg KOH/g.
9. The method of claim 6, wherein in the step of performing the third esterification reaction, the reaction is performed at 110 ℃ to 120 ℃ until the acid value is less than or equal to 5mg KOH/g.
10. A nail polish base adhesive is characterized by comprising: the primer resin according to any one of claims 1 to 5 or the primer resin produced by the production method according to any one of claims 6 to 9.
11. A primer resin, wherein the primer resin is produced by the production method according to any one of claims 6 to 9.
CN202010704336.1A 2020-07-21 2020-07-21 Primer resin, preparation method thereof and nail polish primer Active CN111875755B (en)

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