CN110713763A

CN110713763A - Energy-curable acrylic resin composition and use thereof

Info

Publication number: CN110713763A
Application number: CN201810765950.1A
Authority: CN
Inventors: 钱晓春; 衡京; 胡春青; 翁云峰; 马丽君
Original assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Current assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date: 2018-07-12
Filing date: 2018-07-12
Publication date: 2020-01-21

Abstract

The invention provides an energy-curable acrylic resin composition and application thereof. The acrylic resin composition comprises resin, initiator and curable epoxy modified acrylic resin, wherein one or more oxetane groups are grafted on a branch chain of at least one repeating unit in the epoxy modified acrylic resin, and each oxetane group has a general formula (I)) A structure represented by the general formula (II) or the general formula (III). The energy-curable acrylic resin composition provided by the application has good flexibility, has high adhesive force and high curing film-forming speed for a coated substrate, and also has the advantages of not changing the existing production equipment, realizing low VOC (volatile organic compound) and even zero VOC (volatile organic compound) emission and the like.

Description

Energy-curable acrylic resin composition and use thereof

Technical Field

The invention relates to the field of energy-curable, in particular to an energy-curable acrylic resin composition and application thereof.

Background

Acrylic resin is a very important resin variety, has strong controllability of a synthesis process, and has excellent light resistance and weather resistance, so that the acrylic resin is very widely applied. From the product, the coating can be applied to the surface decoration of airplanes, automobiles, electric appliances, toys, furniture, buildings and the like. But with the increase of the use amount of the acrylic resin, more requirements are provided for the performance of the acrylic resin, for example, no pretreatment is performed on special substrates such as galvanized plates, magnesium aluminum alloy, glass and the like, and the coating prepared from the acrylic resin is required to have good adhesive force; when the acrylic resin is applied to car paint, the paint is required to have good hardness, scratch resistance and the like. However, the common acrylic resin is difficult to meet the requirements, the prior document provides epoxy modified acrylic resin prepared by introducing an oxirane functional group into a side chain, and the prepared epoxy modified acrylic resin has high adhesive force, yellowing resistance and good temperature and weather resistance. However, the properties such as hardness and adhesion cannot meet the requirements of high-grade car paint and high-grade glass baking paint, and therefore, the properties need to be further improved.

Because the application field of the acrylic resin belongs to the daily production and living field, and because people have stronger environmental awareness and more complaints about pollution are increased, the development of the acrylic resin composition with low VOC emission and environmental protection is imperative. At present, the water-soluble acrylic resin researched and developed has no pollution to the environment and meets the requirement of environmental protection. However, in order to produce a water-soluble acrylic resin, the proportion of the acidic monomer must be increased from the formulation, however, the amount of the monomer added to provide an acid value is increased, which results in a brittle coating film, poor flexibility and hardness, and a slow curing rate in most of the water-soluble acrylic resins, which are thermosetting. Another prior art patent provides a waterborne epoxy modified acrylic resin and its aqueous dispersion, which does not really realize zero VOC emission because the solvent usage of the solvent-based paint is reduced by half, and the adhesion of the paint film is deteriorated after the weather resistance test (such as high temperature and high humidity test) of the paint film.

Therefore, if the flexibility of the acrylic resin is improved, the adhesive force to a base material is improved, the curing time of a coating film is shortened on the premise of meeting the requirement of environmental protection, and the application range of the acrylic resin is greatly widened.

Disclosure of Invention

The invention mainly aims to provide an energy-curable acrylic resin composition and application thereof, and aims to solve the problems of poor flexibility and adhesion and long curing time of the existing coating.

In order to achieve the above object, according to one aspect of the present invention, there is provided an energy-curable acrylic resin composition comprising a resin, an initiator and a curable epoxy-modified acrylic resin, wherein one or more oxetane groups are grafted to a branch of at least one repeating unit in the epoxy-modified acrylic resin, and each oxetane group has a structure represented by general formula (i), general formula (ii) or general formula (iii):

wherein R is₁Is represented by C₁～C₄₀Linear or branched n-valent alkane of (1)Base, C₂～C₃₀N-valent alkenyl of, C₆～C₄₀N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, ester groups or

Substituted, R₁Any one of the hydrogen atoms in (a) may be substituted by alkyl, halogen or nitro;

R₂and R₄Each independently represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl of (C)₆～C₃₀Aryl of (A), R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

R₃and R₅Each independently represents C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₃₀Aryl of (A), R₃And R₅Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₃And R₅Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen, or nitro;

a represents C₁～C₂₀A straight or branched alkyl group of (A), any one of-CH₂-may be substituted by an oxygen atom or-COO-, any one of the hydrogen atoms of a may be substituted by alkyl, halogen or nitro;

m represents 3-valent C₁～C₂₀Wherein any one of M is-CH₂May be substituted by oxygen atoms, -COO-or

Any one hydrogen atom in M can be substituted by alkyl, halogen or nitro;

q represents C₁～C₂₀OfChain or branched alkylene, wherein any one of Q is-CH₂May be substituted by oxygen atoms, -COO-or

And any one hydrogen atom in Q can be substituted by alkyl, halogen or nitro,

n is an integer of 1 to 12.

Further, R₃And R₅Each independently represents

R₆Is represented by C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₃₀Aryl of (2), wherein R₆Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₆Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; r₇Represents C₁～C₂₀Linear or branched alkyl of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄Wherein R is₇And R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₇And R₈Wherein one or more hydrogen atoms are each independently substituted with alkyl, halogen, or nitro;

preferably, R₆Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₂₄Aryl of (2), wherein R₆Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₆Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; r₇Is represented by C₁～C₁₀Linear or branched alkyl of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₁₀Straight or branched alkyl of (2), C₃～C₁₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₁₂Wherein R is₇And R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₇And R₈Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

Further, R₁Is represented by C₁～C₃₀Linear or branched n-valent alkyl of (2), C₂～C₂₀N-valent alkenyl of, C₆～C₃₀N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

Substituted, R₁Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; preferably, R₁Is represented by C₁～C₁₅Linear or branched n-valent alkyl of (2), C₂～C₁₅N-valent alkenyl of, C₆～C₁₈N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

Substituted, R₁Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

Further, R₂And R₄Each independently represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄Aryl of (A), R₂Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; preferably, R₂And R₄Each independently represents hydrogen, halogen, nitro, C₁～C₁₀Straight or branched alkyl of (2), C₃～C₁₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₁₂Aryl of (A), R₂Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

Further, A represents C₁～C₁₅A straight or branched alkyl group of, any one of A-CH₂-may be substituted by an oxygen atom or-COO-, any one of the hydrogen atoms of a may be substituted by alkyl, halogen or nitro.

Further, M represents C having a valence of 3₁～C₁₅Straight or branched alkyl of (2), any one of M-CH₂May be substituted by oxygen atoms, -COO-or

Any one hydrogen atom in M may be substituted by alkyl, halogen or nitro.

Further, Q represents C₁～C₁₅Any one of-CH of (1) straight-chain or branched alkylene, Q₂May be substituted by oxygen atoms, -COO-or

Or, any one hydrogen atom in Q may be substituted by alkyl, halogen or nitro.

Further, n is an integer of 1 to 6.

Further, the energy-curable acrylic resin composition may further include an auxiliary agent.

Further, the auxiliary agent is selected from one or more of flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, colorants, stabilizers, release agents, antistatic agents, pigments, dyes, and flame retardants.

Further, the initiator is a cationic initiator; preferably, the cationic initiator is selected from one or more of diazonium salts, onium salts and organometallic complexes capable of forming strong acids upon application of an external energy source; more preferably, the cationic initiator is selected from the group consisting of diazonium fluoroborates, pyrazole diazonium inner salts, triptycene diazonium salts, diazoaminobenzenes, triarylsulfonium hexafluorophosphates, triarylsulfonium antimonates, 4' -dimethyldiphenyliodonium hexafluorophosphates, 4,4 '-dimethyldiphenyliodonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, bis (4-diphenylthiophenyl) sulfide dihexafluoroantimonate, 4-isobutylphenyl-4' -methylphenyliodionium hexafluorophosphate and 6-cumeneferrocenium hexafluorophosphate.

Furthermore, the content of the epoxy modified acrylic resin is 10-80 wt% in terms of weight percentage of the acrylic resin composition capable of being cured by energy; preferably, the content of the epoxy modified acrylic resin is 30-75 wt%.

Further, the resin composition may be cured by at least one of light, heat, or electron irradiation.

According to another aspect of the present invention, there is provided a use of an energy curable acrylic resin composition in the field of energy curing.

Further, the field of energy curable is the field of inks, coatings and adhesives.

By applying the technical scheme of the invention, after the epoxy modified acrylic resin is covalently grafted with oxetane on the branched chain of the acrylic resin, a coating film prepared from the curable epoxy modified acrylic resin composition containing the epoxy modified acrylic resin has good flexibility, higher adhesive force to a coated substrate and higher curing film-forming speed. In addition, as the main chain structure of the original acrylic resin is not influenced, compared with the original acrylic resin, the curing equipment is only added without changing the original equipment and the production flow of the product in the downstream application process, so the investment cost is lower, and the acrylic resin is more easily accepted and applied by the market. In addition, the epoxy modified acrylic resin has good compatibility with resin, initiator and the like, so that the using amount of a diluting solvent or an active monomer can be reduced or not used in the using process, the environmental conditions of the production and using processes of paint, printing ink, adhesive and the like are improved, and low VOC and even zero VOC emission can be realized. To sum up, the energy-curable acrylic resin composition provided by the application not only has good flexibility, has higher adhesive force and faster curing film-forming speed to a coated substrate, but also has the advantages of not changing the existing production equipment, realizing low VOC and even zero VOC emission and the like.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As described in the background, the prior art coatings suffer from poor flexibility and adhesion, and long cure times. In order to solve the above technical problems, the present application provides an energy-curable acrylic resin composition, which includes a resin, an initiator, and an energy-curable epoxy-modified acrylic resin, wherein one or more oxetane groups are grafted to a branch of at least one repeating unit in the epoxy-modified acrylic resin, and each oxetane group has a structure represented by general formula (i), general formula (ii), or general formula (iii):

wherein R is₁Is represented by C₁～C₄₀Linear or branched n-valent alkyl of (2), C₂～C₃₀N-valent alkenyl of, C₆～C₄₀N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

Substituted, R₁Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

R₂and R₄Each independently represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl of (C)₆～C₃₀Aryl of (2), wherein R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

R₃and R₅Each independently represents hydrogen or C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₃₀Aryl of (A), R₃And R₅Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₃And R₅Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

Any one hydrogen atom in M can be substituted by alkyl, halogen or nitro;

q represents C₁～C₂₀Linear or branched alkylene of (2), wherein any one of Q-CH₂May be substituted by oxygen atoms, -COO-or

Wherein any hydrogen atom in Q may be substituted by alkyl or halogenAnd n is an integer of 1-12.

In the energy-curable acrylic resin composition, after oxetane is covalently grafted on a branched chain of the acrylic resin by the epoxy modified acrylic resin, a coating film prepared from the curable epoxy modified acrylic resin composition containing the epoxy modified acrylic resin composition has good flexibility, high adhesion to a coated substrate and high curing film-forming speed. In addition, as the main chain structure of the original acrylic resin is not influenced, compared with the original acrylic resin, the curing equipment is only added without changing the original equipment and the production flow of the product in the downstream application process, so the investment cost is lower, and the acrylic resin is more easily accepted and applied by the market. In addition, the epoxy modified acrylic resin has good compatibility with resin, initiator, auxiliary agent and the like, so that the using amount of a diluting solvent or an active monomer can be reduced or not used in the using process, the environmental conditions of the production and using processes of paint, printing ink, adhesive and the like are improved, and low VOC and even zero VOC emission can be realized. To sum up, the energy-curable acrylic resin composition provided by the application not only has good flexibility, has higher adhesive force and faster curing film-forming speed to a coated substrate, but also has the advantages of not changing the existing production equipment, realizing low VOC and even zero VOC emission and the like.

It should be noted that the term "n-valent" in the term "n-valent alkyl" means that there are n substituents on the alkyl group, and similarly, "n-valent alkenyl" means that there are n substituents on the alkenyl group, and other expressions referring to the "n-valent group" in this application are interpreted in the same way.

Accordingly, "n" in formula (I) means R₁The number of substituents on the radical, e.g. R when n is 2₁The number of substituents on the group is 2.

The energy-curable acrylic resin composition with the structure has good flexibility, high adhesive force to a coated substrate and high curing film-forming speed, and simultaneously has the advantages of no change of the existing production equipment, realization of low VOC and even zero VOC emission and the like. In order to further improve the flexibility and adhesion of the coating formed by the coating, and further shorten the curing time, the substituent in the structure shown in the formula (I) can be further preferably selected, and specifically:

in a preferred embodiment, R₃And R₅Each independently represents hydrogen,

Wherein

R₆Is represented by C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₃₀Aryl of (2), wherein R₆Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₆Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; r₇Represents C₁～C₂₀Linear or branched alkyl of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄Wherein R is₇And R₈Any one of-CH₂-may be substituted by an oxygen atom or an ester group, R₇And R₈Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

Preferably, R₆Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₂₄Aryl of (2), wherein R₆Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₆Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; r₇Is represented by C₁～C₁₀Linear or branched alkyl of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₁₀Straight or branched alkyl of (2), C₃～C₁₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₁₂Wherein R is₇And R₈Any one of-CH₂-may be substituted by an oxygen atom or an ester group, R₇And R₈Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

In a preferred embodiment, R₁Is represented by C₁～C₃₀Linear or branched n-valent alkyl of (2), C₂～C₂₀N-valent alkenyl of, C₆～C₃₀N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-orSubstituted, R₁Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

More preferably, R₁Is represented by C₁～C₁₅Linear or branched n-valent alkyl of (2), C₂～C₁₅N-valent alkenyl of, C₆～C₁₈N-valent aryl of (A), R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

In a preferred embodiment, R₂And R₄Each independently represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄Aryl of (2), wherein R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

Preferably, R₂And R₄Are respectively independentAnd represents hydrogen, halogen, nitro, C₁～C₁₀Straight or branched alkyl of (2), C₃～C₁₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₁₂Aryl of (2), wherein R₂And R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, R₂And R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

In a preferred embodiment, A represents C₁～C₁₅A straight or branched alkyl group of (A), any one of-CH₂-may be substituted by an oxygen atom or-COO-, any one of the hydrogen atoms of a may be substituted by alkyl, halogen or nitro.

In a preferred embodiment, M represents a valence of 3C₁～C₁₅Straight or branched alkyl of (2), any one of M-CH₂May be substituted by oxygen atoms, -COO-or

Any one hydrogen atom in M may be substituted by alkyl, halogen or nitro.

In a preferred embodiment, Q each independently represents C₁～C₁₅Any one of-CH in Q, a straight or branched alkylene group of₂May be substituted by oxygen atoms, -COO-or

And any one hydrogen atom in Q can be substituted by alkyl, halogen or nitro.

In order to reduce the synthesis difficulty of the epoxy modified acrylic resin, n is preferably selected from an integer of 1-6.

In the above energy-curable acrylic resin composition, the method of chemically grafting one or more oxetane groups to a branch of one of the repeating units of the epoxy-modified acrylic resin is as follows: (1) carboxyl or hydroxyl groups on the acrylic resin and a compound containing oxetane and epoxy ethyl are subjected to ring opening reaction of epoxy ethyl to form hydroxyl, and the generated hydroxyl is terminated by acid anhydride, acyl halide, a compound containing epoxy ethyl, a compound containing oxetane or a compound containing double bonds; (2) carboxyl or hydroxyl groups of a comonomer of the acrylic resin and a compound containing oxetane and epoxy ethyl are subjected to ring opening reaction of epoxy ethyl to form hydroxyl, and the generated hydroxyl is capped by acid anhydride, acyl halide, a compound containing epoxy ethyl, a compound containing oxetane or a compound containing double bonds and then copolymerized with other olefinic monomers; (3) 3-hydroxymethyl-3-ethyl oxetane and methyl methacrylate are subjected to transesterification reaction and then copolymerized with other olefinic monomers.

In the chemical grafting method, the acrylic resin is copolymerized by acrylate or methacrylate and other olefinic monomers, wherein at least one of the acrylic and other olefinic monomers is a functional monomer containing hydroxyl or carboxyl. The hydroxyl group-containing functional monomer may be exemplified by: hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, allyl alcohol, cinnamyl alcohol, citronellol, 2-hexen-1-ol; the carboxyl group-containing functional monomer may be exemplified by: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate. Other olefinic monomers may be mentioned: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, acrylamide, glycidyl acrylate, dimethylaminopropyl acrylate, tetrahydrofuryl acrylate, fluoroalkyl acrylate, acrylonitrile or styrene, and can be the oxetane grafted olefinic monomer prepared according to the present invention.

In the chemical grafting method, the oxetane and epoxyethyl group-containing compound has a structure represented by general formula (IV) and/or general formula (V):

wherein R is₁、R₂、R₄A, M, Q and n have the same meanings as in formula (I) and formula (II).

Illustrative oxetane and oxiranyl containing compounds may be mentioned:

m is an integer of 1 to 30, preferably, m is an integer of 1 to 10; n is an integer of 1 to 10, preferably 1 to 5.

In the chemical grafting method, the acid halide has a structure represented by the general formula (VI).

Wherein R is₆Have the same definitions as above; x is a halogen atom.

Exemplary acid halides may be listed as: acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, n-valeryl chloride, isovaleryl chloride, trimethylacetyl chloride, tert-butylacetyl chloride, benzoyl chloride, cyclohexanoyl chloride, methacryloyl chloride, phthaloyl chloride, o-chloro-terephthaloyl chloride, biphenyldicarbonyl chloride, propionyl bromide, baccaproyl bromide, 2-bromooctanoyl bromide, p-bromophenylacetyl bromide, pivaloyl iodomethyl ester, acryloyl iodide.

In the chemical grafting method, the epoxyethyl group-containing compound has a structure represented by the general formula (VII).

Wherein R is₇Have the same definitions as above; x is a halogen atom.

Exemplary epoxyethyl-containing compounds include: epichlorohydrin, ethylene oxide chloride, butylene oxide chloride, 2- ((2-chloroethoxy) methyl) ethylene oxide, 2- ((2- (chloromethoxy) ethoxy) methyl) ethylene oxide, propylene oxide bromide, [ (1,1,2, 2-tetrafluoroethoxy) methyl ] ethylene oxide, 2-trifluoromethyl ethylene oxide.

In the chemical grafting method, the acid anhydride has a structure represented by the general formula (VIII).

Wherein R is₉、R₉' each is independently selected from C₁～C₆Linear or branched alkyl.

Illustratively, R₉、R₉' methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl are listed.

In the chemical grafting method, the oxetane-containing compound has a structure represented by the general formula (IX).

Wherein R is₇、R₈Have the same definitions as above; x is a halogen atom.

Exemplary oxetane-containing compounds may be listed: 2-methyl-2-iodomethyloxetane, 3-diiodomethyl-1-oxetane, 3-bromomethyl-3-methyl-1-oxetane, 3- (3-bromophenyl) oxetane, 3-bromophenyl-3-methyloxetane, 3-chloromethyl-3-methyloxetane, 3-bis (chloromethyl) oxetane, 3-fluoromethyl-3-chloromethyloxetane, 3-chloromethyl-3-iodomethyl-1-oxetane, 3-bromomethyl-3-chloromethyl-1-oxetane, 3-iodomethyloxetane, 3-iodooxetane, 3-iodomethyloxetane, and mixtures thereof, 3-bromomethyloxetane, 3-chlorooxetane, 3-iodomethyl-3-methyloxetane.

In the chemical grafting method, the double bond-containing compound has a structure represented by the general formula (X).

Wherein R is₇Have the same definitions as above; x is a halogen atom.

Illustrative examples of the double bond-containing compounds include: 3-chloropropene, 3-bromopropene, 3-chloromethoxy-1-propene, vinyl 2-chloroacetate, 6-chloro-3-methyl-1-hexene, 3-chloro-1-butene or 3-bromomethoxy-1-propene.

The energy-curable acrylic resin composition may include one or more resins selected from (modified) alkyd resins, (modified) phenolic resins, (modified) amino resins, (modified) polyester resins, (modified) acrylic resins, (modified) polyurethane resins, (modified) polyurea resins, (modified) fluorocarbon resins, (modified) silicone resins, and (modified) chlorinated polyolefin resins.

The modified resin refers to a modified resin obtained by modifying an existing resin (such as alkyd resin and phenolic resin) by a chemical or physical method (such as grafting or blending) in the prior art. The term "(modified) alkyd resin" denotes an alkyd resin or a modified alkyd resin, and similar terms are used in the same way to explain its meaning.

In a preferred embodiment, the epoxy-modified acrylic resin is present in an amount of 10 to 80 wt% based on the weight percent of the energy curable acrylic resin composition. The amount of the epoxy-modified acrylic resin used includes, but is not limited to, the above range, and the limitation thereof is advantageous for further improving the overall properties of a paint film formed by energy-curing the energy-curable acrylic resin composition. Preferably, the content of the epoxy modified acrylic resin is 30-75 wt%.

The energy-curable acrylic resin composition described above, wherein the resin composition is curable by at least one of light, heat or electron radiation. Preferably, the composition is cured by UV light. The UV light source may be a light source or radiation source made to emit light in the ultraviolet range (i.e. between 10nm and 420 nm), and may for example be selected from: fluorescent lamps, fluorescent black light lamps, short wave ultraviolet lamps, lasers, ultraviolet gas lasers, high power gas lasers (e.g., nitrogen lasers or excimer lasers), ultraviolet laser diodes, ultraviolet solid state lasers, electron beams, illuminators, monochromatic light sources, Light Emitting Diodes (LEDs), LED arrays, ultraviolet LEDs, gas discharge lamps, argon and deuterium lamps, Hg-Cd lamps, arc lamps, flash lamps, Xe or halogen lamps, or any other suitable light source.

In a preferred embodiment, the energy-curable acrylic resin composition further comprises an auxiliary. Such adjuvants include, but are not limited to, one or more of flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antimicrobials, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, colorants, stabilizers, release agents, antistatic agents, pigments, dyes, and flame retardants.

The initiator is a cationic initiator. Preferably, the cationic initiator is selected from one or more of diazonium salts, onium salts and organometallic complexes capable of forming strong acids upon application of an external energy source. More preferably, the cationic initiator includes, but is not limited to, diazonium fluoroborate, pyrazole diazonium inner salt, triptycene diazonium salt, diazoaminobenzene, triarylsulfonium hexafluorophosphate, triarylsulfonium antimonate, 4' -dimethyldiphenyliodonium hexafluorophosphate, 4,4 '-dimethyldiphenyliodonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, bis (4-diphenylthiophenyl) sulfide dihexafluoroantimonate, 4-isobutylphenyl-4' -methylphenyliodionium hexafluorophosphate and 6-cumeneferrocenium hexafluorophosphate.

The application of the energy-curable epoxy modified acrylic resin in the field of energy curing. The coating formed by the energy-curable acrylic resin composition has good flexibility, high adhesive force to a coated substrate and high curing film-forming speed, and simultaneously has the advantages of not changing the existing production equipment, realizing low VOC and even zero VOC emission and the like.

Preferably, the energy curable areas are the ink, coating and adhesive areas. By way of example, the inks may be listed: relief, intaglio, lithographic and mesh inks; the coating materials include: building coatings, anticorrosive coatings, automotive coatings, dew-proof coatings, antirust coatings, waterproof coatings, moisture-retaining coatings, elastic coatings; the adhesive may be exemplified by: solvent-based adhesives, emulsion-based adhesives, reactive (thermal curing, UV curing, moisture curing) adhesives, hot melt adhesives, remoistenable adhesives, pressure-sensitive adhesives.

The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.

Preparation of (mono) epoxy modified acrylic resin

Preparation of starting materials 1-11:

raw material 1:

reaction: 58g (0.5mol) of 3-hydroxymethyl-3-ethyloxetane, 46g (0.5mol) of epichlorohydrin and 20g (0.5mol) of sodium hydroxide were added in this order to a three-necked flask and reacted at 40 ℃ for 12 hours, and the gas phase was followed until the 3-hydroxymethyl-3-ethyloxetane was completely reacted. After completion of the reaction, the reaction mixture was washed with water, extracted, and distilled under reduced pressure to obtain 86g of starting material 1.

Raw material 2:

reaction 1: 58g (0.5mol) of 3-hydroxymethyl-3-ethyloxetane, 4g (0.1mol) of sodium hydroxide and 100g of toluene were added in this order to a three-necked flask, stirred and heated to 80 ℃ and 86g (0.5mol) of starting material 1 was added dropwise thereto over 1.5 hours. The reaction was continued with stirring and the gas phase was followed until the 3-hydroxymethyl-3-ethyloxetane content no longer changed and heating was stopped. The pH of the reaction system was adjusted to neutral, filtered, washed with water, extracted, and distilled under reduced pressure to give 130g of a pale yellow viscous liquid compound 1.

Reaction 2: 144g (0.5mol) of Compound 1, 46g (0.5mol) of epichlorohydrin and 20g (0.5mol) of sodium hydroxide were charged in this order into a three-necked flask and reacted at 40 ℃ for 12 hours, and the gas phase was followed until Compound 1 was completely reacted. After the reaction, the reaction mixture was washed with water, extracted, and distilled under reduced pressure to obtain 155g of starting material 2.

The synthetic route is as follows:

referring to the preparation methods of the raw materials 1 and 2, 3-10 raw materials are prepared.

Preparation of epoxy modified acrylic resin:

example 1

Reaction 1: preparation of acrylic resin: carrying out copolymerization reaction by taking a methacrylic acid Monomer (MAA) and a methyl Methacrylate Monomer (MMA) as raw materials: a reaction flask was charged with 43g (0.5mol) of MAA and 200mL of propylene glycol monomethyl ether acetate and heated to 60 ℃ and then a mixture of MMA50g (0.5mol) and azobisisobutyronitrile (2.5 g, 3 wt%) was slowly added dropwise over a 0.5 hour period. After the reactant is added, the reaction is continued for 6 hours to prepare white polymer precipitate. The precipitate was filtered and dried to give 85g of MAA-MMA acrylic resin.

Reaction 2: in a three-necked flask, 100g (containing 0.5mol of carboxyl group) of MAA-MMA acrylic resin was charged, 500mL of toluene was added, and dissolved by heating at 70 ℃. After dissolution, 8g of triphenylphosphine and 170g (0.50mol) of raw material 2 were added, and after 8 hours of reaction, extraction and distillation under reduced pressure were carried out to obtain 250g of epoxy-modified acrylic resin.

Reaction 3: 100g (0.2mol of hydroxyl) epoxy modified acrylic resin, 21g (0.2mol) of isobutyryl chloride, 200mL of toluene and 10g of sodium hydroxide are sequentially added into a three-necked flask, and reacted at 40 ℃ for 12 hours, and after the reaction is finished, the mixture is washed, extracted and distilled under reduced pressure to obtain 110g of epoxy modified acrylic resin 1 with the weight-average molecular weight of 5 multiplied by 10⁴The molecular weight distribution index was 1.35, the acid value was 0.4mgKOH/g, and the epoxy equivalent was 263 g/mol.

The reaction process is as follows:

examples 1 to 1

Reaction 1: a three-necked flask was charged with 43g (0.5mol) of a methacrylic acid monomer, 200mL of toluene was added thereto, and the mixture was dissolved by heating at 70 ℃. After dissolution, 6.5g of triphenylphosphine and 2170 g (0.50mol) of the starting material were added, and after 8 hours of reaction, extraction and distillation under reduced pressure were carried out to obtain 200g of intermediate 1.

Reaction 2: 85g (0.2mol) of intermediate 1, 21g (0.2mol) of isobutyryl chloride, 200mL of toluene and 10g of sodium hydroxide were sequentially added to a three-necked flask, and reacted at 40 ℃ for 12 hours, and after the reaction was completed, the mixture was washed with water, extracted and distilled under reduced pressure to obtain 95g of intermediate 2.

Reaction 3: preparation of acrylic resin: 2245 g (0.5mol) of intermediate and 500mL of propylene glycol monomethyl ether acetate were charged into a reaction flask, and after previously heating to 60 ℃, MMA50g (0.5mol) and 9g (3 wt%) of azobisisobutyronitrile were mixed and slowly added dropwise to the reaction flask over a feed period of about 0.5 h. ReactantsAfter the addition, the reaction was continued for 6 hours, white polymer precipitates were generated, and 275g of epoxy-modified acrylic resin 1-1 having the same structure as epoxy-modified acrylic resin 1 and having a weight average molecular weight of about 2X 10 was obtained after filtration and drying⁴The molecular weight distribution was 1.50, the acid value was 0.4mgKOH/g, and the epoxy equivalent was 255 g/mol.

The reaction process is as follows:

example 2

Reaction 1: preparation of acrylic resin: carrying out copolymerization reaction by taking hydroxyethyl acrylate monomer (HEA) and methyl Methacrylate Monomer (MMA) as raw materials: after HEA53g (0.5mol) and 200mL of propylene glycol methyl ether acetate were added to the reaction flask and heated to 60 ℃. A mixture of MMA50g (0.5mol) and azobisisobutyronitrile (3 g, 3 wt%) was slowly added dropwise over a 0.5h feed time to the reaction flask. After the reactant is added, the reaction is continued for 6 hours, and white polymer precipitate is produced. The precipitate was filtered and dried to give 85g of HEA-MMA acrylic resin.

Reaction 2: 100g (containing 0.5mol of hydroxyl) HEA-MMA acrylic resin, 59g (0.5mol) of succinic acid, 5g of acidic cation exchange resin and 300mL of toluene are added into a three-necked flask, the materials are uniformly mixed and heated to start reaction, the reaction temperature is controlled at 120 ℃, and when the fractionated water is close to the theoretical water, the reaction is finished. The reaction system was washed with saturated brine, and then concentrated under reduced pressure and bubbled to obtain 130g of intermediate 3.

Reaction 3: in a three-necked flask, 100g (containing 0.3mol of carboxyl group) of intermediate 3 was charged, 200mL of toluene was added, and dissolved by heating at 70 ℃. After dissolution, 4.5g of triphenylphosphine and 52g (0.30mol) of raw material 1 were added, and after 8 hours of reaction, extraction and distillation under reduced pressure were carried out to obtain 130g of epoxy-modified acrylic resin.

Reaction 4: adding 100g (0.2mol of hydroxyl) epoxy modified acrylic resin, 18.5g (0.2mol) of epichlorohydrin, 200mL of toluene and 10g of sodium hydroxide into a three-necked flask in sequence, reacting at 40 ℃ for 12h, washing with water, extracting, and distilling under reduced pressure to obtain 110g of epoxy modified acrylic acidResin 2 having a weight average molecular weight of 1.5X 10⁵The molecular weight distribution index was 1.40, the acid value was 0.3mgKOH/g, and the epoxy equivalent was 304 g/mol.

The reaction process is as follows:

example 3

Reaction 1: preparation of acrylic resin: carrying out copolymerization reaction on hydroxyethyl acrylate monomer (HEA) and methyl Methacrylate Monomer (MMA): HEA53g (0.5mol) and 200mL of propylene glycol monomethyl ether acetate were charged into a reaction flask, preheated to 60 ℃, and then MMA50g (0.5mol) and azobisisobutyronitrile 3g (3 wt%) were mixed and slowly added dropwise into the reaction flask over a 0.5 hour feed period. After the reactant is added, the reaction is continued for 6 hours to prepare white polymer precipitate. The precipitate was filtered and dried to give 85g of HEA-MMA acrylic resin.

Reaction 2: 86g (containing 0.2mol of hydroxyl) HEA-MMA acrylic resin, 20g (0.2mol) of succinic anhydride, 3g of pyridine and 200mL of toluene are added into a three-necked flask, the mixture is uniformly mixed and heated to start reaction, the reaction temperature is controlled at 120 ℃, and the reaction is finished when the fractionated water is close to the theoretical water. The reaction system was washed with saturated brine, concentrated under reduced pressure and then bubbled, to obtain 85g of intermediate 4.

Reaction 3: in a three-necked flask, 105g (containing 0.2mol of carboxyl group) of intermediate 4 was charged, 200mL of toluene was added, and dissolved by heating at 70 ℃. After dissolution, 5g of triphenylphosphine and 68g (0.20mol) of raw material 2 were added, and after 8 hours of reaction, extraction and distillation under reduced pressure were carried out to obtain 150g of epoxy-modified acrylic resin.

Reaction 4: 140g (0.2mol hydroxyl group) epoxy modified acrylic resin, 30g (0.2mol)3- (bromomethyl) oxetane, 200mL toluene and 5g sodium hydroxide were sequentially added into a three-necked flask, reacted at 40 ℃ for 12 hours, and after the reaction was completed, washed with water, extracted and distilled under reduced pressure to obtain 150g epoxy modified acrylic resin 3 having a weight average molecular weight of 8X 10⁴The molecular weight distribution index was 2.05, the acid value was 0.6mgKOH/g, and the epoxy equivalent was 352 g/mol.

The reaction process is as follows:

example 4

Reaction 1: a three-necked flask was charged with 58g (0.4mol) of 4-hydroxybutylacrylate monomer, and 800mL of toluene was added and dissolved by heating at 70 ℃. After dissolution, 8.5g of sodium hydroxide and 3225 g (0.20mol) of the starting material were charged into the three-necked flask, and reacted for 8 hours, followed by extraction and distillation under reduced pressure to obtain 260g of intermediate 5.

Reaction 2: 200g (0.15mol) of intermediate 5, 28g (0.3mol) of epichlorohydrin, 500mL of toluene and 10g of sodium hydroxide were sequentially added to a three-necked flask, and reacted at 40 ℃ for 12 hours, and after the reaction was completed, water washing, extraction and distillation under reduced pressure were carried out to obtain 200g of intermediate 6.

Reaction 3: preparation of acrylic resin: 260g (0.2mol) of intermediate 6 and 500mL of propylene glycol monomethyl ether acetate were added to the reaction flask and heated to 60 ℃. Then MMA20g (0.2mol), 26g (0.2mol) of butyl acrylate monomer (BA) and 9g (3 wt%) of azobisisobutyronitrile were mixed and slowly added dropwise to the reaction flask over a feed period of 0.5 h. After the reactant is added, the reaction is continued for 6 hours to prepare white polymer precipitate. The precipitate was filtered and dried to give 275g of epoxy-modified acrylic resin 4 having a weight average molecular weight of 1X 10⁴The molecular weight distribution index was 2.00, the acid value was 0.8mgKOH/g, and the epoxy equivalent was 381 g/mol.

The reaction process is as follows:

example 5

Reaction 1: a three-necked flask was charged with 43g (0.5mol) of a methacrylic acid monomer, 200mL of toluene was added thereto, and the mixture was dissolved by heating at 70 ℃. After dissolution, 4g of triphenylphosphine and 186g (0.50mol) of the starting material were added, and after 8 hours of reaction, extraction and distillation under reduced pressure were carried out to obtain 110g of intermediate 7.

Reaction 2: 52g (0.2mol) of intermediate 7, 18g (0.2mol) of epichlorohydrin, 150mL of toluene and 5g of sodium hydroxide were sequentially added to a three-necked flask, and reacted at 40 ℃ for 12 hours, and after the reaction was completed, the intermediate 8 was washed with water, extracted and distilled under reduced pressure to obtain 55g of intermediate 8.

Reaction 3: in a three-necked flask, 65g (0.5mol) of hydroxyethyl acrylate (HEA) monomer was charged, 200mL of toluene was added, and dissolved by heating at 70 ℃. After dissolution, 4g of sodium hydroxide and 2186g (0.50mol) of the starting material were added to the solution, and after 8 hours of reaction, extraction and distillation under reduced pressure were carried out to obtain 140g of intermediate 9.

Reaction 4: 60g (0.2mol) of intermediate 9, 18g (0.2mol) of epichlorohydrin, 150mL of toluene and 5g of sodium hydroxide were sequentially added to a three-necked flask, and reacted at 40 ℃ for 12 hours, and after the reaction was completed, the intermediate 10 was washed with water, extracted and distilled under reduced pressure to obtain 65g of intermediate 10.

Reaction 5: preparation of acrylic resin: 63g (0.2mol) of intermediate 8 and 500mL of propylene glycol monomethyl ether acetate were charged into a reaction flask, and after previously heating to 60 ℃, MMA20g (0.2mol), intermediate 1072 g (0.2mol) and azobisisobutyronitrile 4.5g (3 wt%) were mixed and slowly dropped into the reaction flask over a feed period of about 0.5 hour. After the reactant is added, the reaction is continued for 6 hours, and white polymer precipitate is produced. The precipitate was filtered and dried to obtain 145g of epoxy-modified acrylic resin 5 having a weight average molecular weight of 5X 10⁴The molecular weight distribution index was 1.40, the acid value was 0.3mgKOH/g, and the epoxy equivalent was 205 g/mol.

The reaction process is as follows:

example 6

Reaction 1: HEA-MMA acrylic resin was prepared with reference to reaction 1 of example 3 above.

Reactions 2 to 4: referring to example 3 above, wherein raw material 2 was replaced with raw materials 4 to 10, respectively, epoxy-modified acrylic resins 6 to 12 were prepared, and the correspondence between the raw materials and the products is shown in table 1. The structural formulas of the epoxy modified acrylic resin 6 to 12 are as follows, wherein,

represents

TABLE 1

The structural formula of the prepared product is as follows:

epoxy-modified acrylic resin 6;

epoxy-modified acrylic resin 7;

epoxy-modified acrylic resin 8;

epoxy-modified acrylic resin 9;

(epoxy-modified acrylic resin 10);

epoxy-modified acrylic resin 11;

epoxy-modified acrylic resin 12.

Example 7

Reaction 1: preparation of acrylic resin: carrying out copolymerization reaction on an acrylic monomer (AA), a methacrylic Monomer (MAA) and a hydroxyethyl acrylate monomer (HEA): reaction procedure reaction 1 according to example 4-1, AA-MAA-HEA acrylic resin was obtained.

Reactions 2 to 4: referring to reactions 2 to 4 of example 2, an epoxy-modified acrylic resin 13 having a weight average molecular weight of 3X 10 was obtained⁴The molecular weight distribution index was 1.40, and the acid value was 0.3 mgKOH/g.

The reaction process is as follows:

example 8

Reaction 1: adding 58g (0.5mol) of 3-hydroxymethyl-3-ethyl oxetane, 50g (0.5mol) of methyl methacrylate and 200mL of toluene into a four-neck flask provided with a stirring device, a thermometer, a rectifying tower and a water distribution device, heating and refluxing to remove water in the system, cooling to about 60 ℃, adding 2.5g of tetraethyl titanate, heating and refluxing to react, adjusting the reflux ratio to take out methanol generated by the reaction, stopping the reaction when the temperature of the top of the rectifying tower rises to 110 ℃, cooling to 70 ℃, adding 10g of water, stirring for 1h, filtering while hot, and distilling the filtrate under reduced pressure to obtain 75g of an intermediate 11.

Reaction 2: preparation of acrylic resin: after the intermediate 1192 g (0.5mol) and 200mL of propylene glycol monomethyl ether acetate were charged into a reaction flask, which was preheated to 60 ℃, MMA50g (0.5mol) and azobisisobutyronitrile 5g (3 wt%) were mixed and slowly added dropwise to the reaction flask over a 0.5 hour feed period. After the reactant is added, the reaction is continued for 6 hours to prepare white polymer precipitate. The precipitate was filtered and dried to obtain 130g of epoxy-modified acrylic resin 14 having a weight average molecular weight of 3.5X 10⁴Molecule(s)The weight distribution index was 1.15, the acid value was 0.2mgKOH/g, and the epoxy equivalent was 300 g/mol.

The reaction process is as follows:

preparation of (di) curable epoxy-modified acrylic resin composition

Example 9

The curable epoxy-modified acrylic resin composition of the present invention comprises: 75 parts by weight of epoxy-modified acrylic resin 4 (molecular weight 1X 10)⁴Viscosity of 2000cps, acid value of 0.8mgKOH/g), 25 parts by weight of a polyester resin (manufactured by SK, commercial number: ES900), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, product number: BYK-333), 6 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976).

Example 10

The curable epoxy-modified acrylic resin composition of the present invention comprises: 30 parts by weight of epoxy-modified acrylic resin 4 (molecular weight 1X 10)⁴Viscosity of 2000cps, acid value of 0.8mgKOH/g), 60 parts by weight of polyester resin (SK is manufactured, product number: ES900), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, product number: BYK-333), 6 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976).

Example 11

The curable epoxy-modified acrylic resin composition of the present invention comprises: 60 parts by weight of epoxy-modified acrylic resin 4 (molecular weight 1X 10)⁴Viscosity of 2000cps, acid value of 0.8mgKOH/g), 30 parts by weight of a polyester resin (manufactured by SK, commercial number: ES900), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, product number: BYK-333), 6 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976).

Example 12

The curable epoxy-modified acrylic resin composition of the present invention comprises: 60 parts by weight of epoxy-modified acrylic resin 4A quantum of 1X 10⁴Viscosity of 2000cps, acid value of 0.8mgKOH/g), 30 parts by weight of a polyester resin (manufactured by SK, commercial number: ES900), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, product number: BYK-333), 2 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976) cured using Electron Beam (EB).

Example 13

The curable epoxy-modified acrylic resin composition of the present invention comprises: 60 parts by weight of epoxy-modified acrylic resin 4 (molecular weight 1X 10)⁴Viscosity of 2000cps, acid value of 0.8mgKOH/g), 30 parts by weight of a polyester resin (manufactured by SK, commercial number: ES900), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, product number: BYK-333), 6 parts by weight of a thermal initiator (strong manufacturer, commercial code: TR-TAG-50101).

Example 14

The curable epoxy-modified acrylic resin composition of the present invention comprises: 60 parts by weight of epoxy-modified acrylic resin 4 (molecular weight 1X 10)⁴Viscosity of 2000cps, acid value of 0.8mgKOH/g), 30 parts by weight of alkyd resin (manufactured by Youzhou, Fangxin chemical materials Co., Ltd., product number: FX-1270B), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, commercial code: BYK-333), 6 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976).

Example 15

The curable epoxy-modified acrylic resin composition of the present invention comprises: 60 parts by weight of epoxy-modified acrylic resin 1 (molecular weight: 5X 10)⁴Viscosity of 3000cps, acid value of 0.4mgKOH/g), 30 parts by weight of alkyd resin (manufactured by Youzhou, Fangxin chemical materials Co., Ltd., product number: FX-1270B), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, commercial code: BYK-333), 6 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976).

Example 16

The curable epoxy-modified acrylic resin composition of the present invention comprises: 60 parts by weight of epoxy-modified acrylic resin 14 (molecular weight: 3.5X 10)⁴Viscosity of 2000cps, acid value of 0.2mgKOH/g), 30 parts by weight of alkyd resin (manufactured by Youzhou, Fangxin chemical materials Co., Ltd., product number: FX-1270B), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, commercial code: BYK-333), 6 parts by weight of a photoinitiator (triarylsulfonium salt, manufactured by currase, commercial code: easipi 6976).

Comparative example 1

Comparative example composition components included: 60 parts by weight of acrylic resin (reaction 1 in preparation reference example 1, molecular weight 4.8X 10⁴Viscosity of 3500cps, acid value of 5mgKOH/g), 30 parts by weight of a polyester resin (manufactured by SK, commercial number: ES900), 15 parts by weight of a diluent (methyl ethyl ketone), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, trade number: BYK-333).

Comparative example 2

Comparative example composition components included: 60 parts by weight of acrylic resin (reaction 1 in preparation reference example 1, molecular weight 4.8X 10⁴Viscosity of 3500cps, acid value of 5mgKOH/g), 30 parts by weight of alkyd resin (manufactured by Changzhou, Fangxin chemical materials Co., Ltd., product number: FX-1270B), 15 parts by weight of a diluent (methyl ethyl ketone), 4 parts by weight of an auxiliary agent (leveling agent, manufactured by BYK, commercial code: BYK-333).

The contents of the main components of the above examples 9 to 16 and comparative examples 1 to 2 are shown in Table 2 (parts by weight).

TABLE 2

Performance testing

The curable epoxy-modified acrylic resin compositions shown in table 2 were subjected to performance evaluation tests after film formation.

The operation is as follows:

the sample preparation method comprises the following steps: the curable epoxy-modified acrylic resin compositions shown in table 2 were dispersed at high speed for 30min and mixed well.

The tinplate is used as a base material, the tinplate is polished by sand paper to remove oil stains on the tinplate, the tinplate is cleaned by deionized water, dried and sprayed, the thickness of the coating is 25 +/-5 mu m, and the performance of the tinplate is tested after the tinplate is completely cured.

The test method comprises the following steps:

(1) and (3) hardness testing: referring to the national standard GB/T6739-86, a set of drawing pencils with hardness of 6B-6H was prepared, and the pencil hardness of the coating film was measured manually. The coated sheet was placed horizontally on a table, held at a 45 ° angle with the pencil, and pushed hard at a uniform rate for about 1cm against the coated surface, leaving a scratch on the coated film. And repeatedly scratching 5 times on pencils with the same hardness mark, and if 2 or more times are not scratched to the bottom plate of the sample plate, replacing the pencils with the hardness larger by one mark until the coating is found to be scratched by 2 or more times. The pencil hardness smaller than the pencil hardness is the pencil hardness of the coating film, and the test results are shown in table 3.

(2) And (3) testing the adhesive force: according to the national standard GB/T9286-1998, a scribing knife is used for cutting 6 parallel cuts on the coating film, and the whole depth of the coating film is cut through; then, the same 6 passes were cut perpendicularly to the former to form a plurality of small squares, and then, a translucent pressure-sensitive adhesive tape having a width of 25mm was attached to the whole of the cut-mark divisions, the tape was pulled hard, and the number of stages of the adhesion of the coating film was determined in comparison with the standard, and the test results are shown in Table 3.

(3) Flexibility test: according to the national standard GB1731, the composition is coated on PET, after curing, the paint film surface faces upwards, a test sample is tightly pressed on a mandrel with the required diameter and is bent around the mandrel, and after bending, two thumbs are symmetrical to the central line of the mandrel. The paint film is observed with eyes or a 4-time magnifying glass to see whether the paint film has the damage phenomena of reticulate patterns, cracks, peeling and the like, the flexibility of the paint film is expressed by the minimum diameter of the mandrel rod of which the sample plate is bent on the mandrel rods with different diameters without causing the damage of the paint film, the smaller the diameter of the mandrel rod is, the better the flexibility is, and the test result is shown in table 3.

(4) And (3) testing curing time:

examples curing operations: spraying the composition on tinplate to obtain a sample with a thickness of 200 μm, irradiating the sample with ultraviolet light at room temperature, wherein the ultraviolet light wavelength is 3, the irradiation time is the initial time of the sample, the reaction completion time is the time of the sample surface complete curing, and the difference between the two times is the time required by the sample complete curing65nm, and the light irradiation intensity is 20mw/cm²The complete curing is regarded as complete curing when the surface of the cured film is touched by a finger and no fingerprint mark is left on the surface. When the sample was cured by thermal radiation, the temperature was 120 ℃. When the sample is cured by electron beam radiation, the electron beam energy is less than 300 KeV.

Comparative example curing operation: the composition was sprayed on tin plate to prepare a sample having a thickness of 200 μm, and the curing time of the composition was measured and the sample was left in a conventional laboratory environment to be naturally dried, and the surface of the cured film was judged to have been completely cured without any fingerprint mark by touching the surface with a finger. The test results are shown in Table 3.

(5) VOC testing: weighing 0.2g of sample, coating the sample on a weighed aluminum plate, and weighing; solidifying the aluminum plate coated with the sample, cooling the solidified sample for 15min at room temperature, and weighing; the cured and cooled sample was placed in a vented oven at 110 ℃ for 1h to dry, the sample was placed in a desiccator to cool to room temperature and weighed, and the test results are shown in table 3.

Process volatiles of 100[ (B-C)/(B-a) ]; potential volatiles of 100[ (C-D)/(B-a) ];

total volatiles% + processing volatiles + latent volatiles%,

wherein: a-weight of aluminum plate, g; b-weight of sample and aluminum plate, g;

c-weight of sample and aluminum plate after sample curing, g; d-weight of sample and aluminum plate after curing after heating, g.

TABLE 3

As shown in Table 3, the epoxy modified acrylic resin composition has better adhesive force, high hardness, excellent flexibility and high curing rate, and the epoxy modified acrylic resin used in the invention has good compatibility with other components in a formula system, so that no solvent or active monomer is added in the application process, the real zero VOC emission can be realized, and the commercial application prospect is wide.

Application of (III) curable epoxy modified acrylic resin in fields of printing ink, coating and adhesive

Example 17< energy curable coating >

Acrylic resin (reaction 1 in preparation reference example 1, molecular weight 4.8X 10⁴3500cps in viscosity and 5mgKOH/g in acid value), epoxy-modified acrylic resin 1, and a photoinitiator (triarylsulfonium salt, manufactured by currase, product number: easepi6976) is added into a stirring tank, stirred at normal temperature and high speed until the mixture is uniformly mixed, then titanium dioxide is added and stirred for 4 hours, then a macromolecular dispersant (German BYK110 dispersant) is added and stirred for 2 hours, and the mixture is uniformly mixed and filtered to prepare the energy curable coating.

The contents of the components of the above examples and comparative examples are shown in Table 4 (parts by weight).

TABLE 4

Components	Examples	Comparative example
			Epoxy-modified acrylic resin 1	40	0
Acrylic resin	20	60
			Polymeric dispersant	5	5
Photoinitiator	10	10
			Titanium white powder	20	20
Solvent(s)	0	15

The energy curable coatings prepared in the above examples and comparative examples were uniformly coated on the surface of a metal substrate (cold rolled steel sheet, galvanized steel sheet or silicon steel sheet), and the coated metal substrate was placed in a Dymax curing apparatus and cured with a medium pressure mercury lamp for 60s (3.3J/cm)²UVA), and the cured product was subjected to the performance test in the same manner as above, and the test results are shown in table 5.

TABLE 5

Sample (I)	Adhesion force	Hardness of	VOC emission (%)
				Examples	Level 0	4H	0
ComparisonExample (b)	4 stage	2H	18

As can be seen from Table 5 above, the energy curable coating provided by the present invention has high hardness, good adhesion, and no VOC emissions.

Example 18< energy curable ink >

Polyester resin (manufactured by SK, product number: ES900), epoxy-modified acrylic resin 2 or acrylic resin (manufactured by BASF Co., Ltd., product number: Joncryl 678) and photoinitiator (triarylsulfonium salt, manufactured by CUREASE, product number: Easepi6976) were added to a stirring tank under a non-light condition, stirred at a high speed at normal temperature until mixed uniformly, then added with a filler (diatomaceous earth) and stirred for 4 hours, then added with an auxiliary agent (German BYK381), stirred for 2 hours, ground uniformly, and then filtered of insoluble matter with a polytetrafluoroethylene filter having a pore size of 0.45 μm to obtain a curable ink.

The contents of the components of the above examples and comparative examples are shown in Table 6 (parts by weight).

TABLE 6

Components	Examples	Comparative example
			Epoxy modified acrylic resin 2	40	0
Acrylic resin	0	40
			Polyester resin	20	20
Photoinitiator	10	10
			Auxiliary agent	5	5
Filler material	20	20
			Solvent(s)	0	15

The energy curable inks obtained in the above examples and comparative examples were uniformly coated on PET, which was then placed in a Dymax curing apparatus and cured for 60s (3.3J/cm) with a medium pressure mercury lamp²UVA), and the cured product was subjected to the performance test in the same manner as above, and the test results are shown in table 7.

TABLE 7

Sample (I)	Adhesion force	Flexibility (mm)	VOC emission (%)
				Examples	Level 0	2.0	0
Comparative example	4 stage	2.5	18

As can be seen from Table 7 above, the energy curable ink provided by the present invention has good adhesion, good flexibility, and no VOC emissions.

Example 19< energy curable Adhesives >

Adding phenolic resin (purchased from DKSH company of Switzerland, with the product number of 2402), epoxy modified acrylic resin 3 or acrylic resin (purchased from Pasteur, Inc., with the product number of Joncryl 678) and photoinitiator (triarylsulfonium salt, manufactured by CURREASE, with the product number of Easepi6976) into a stirring tank, stirring at high speed at normal temperature until the mixture is uniformly mixed, then adding filler (talcum powder) and stirring for 4h, then adding auxiliary agent (silane coupling agent), stirring for 2h, grinding uniformly and defoaming to prepare the energy-curable adhesive.

The component contents of the above examples and comparative examples are shown in Table 8 (parts by weight).

TABLE 8

Components	Examples	Comparative example
			Epoxy modified acrylic resin 3	40	0
Acrylic resin	0	40
			Phenolic resin	20	20
Photoinitiator	10	10
			Silane coupling agent	5	5
Filler material	20	20
			Solvent(s)	0	15

The energy curable adhesives prepared in the above examples and comparative examples were uniformly coated on PET, which was then placed in a Dymax curing apparatus and cured for 60s (3.3J/cm) with a medium pressure mercury lamp²UVA) and curing, and then carrying out performance test on the cured product, wherein the adhesive force test method is the same as the above method, the tensile shear strength is tested according to GB/T7124-2008, and the test results are shown in Table 9.

TABLE 9

As can be seen from the above Table 9, the energy curable adhesive provided by the invention has good adhesion, strong tensile shear force and no VOC emission.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An energy-curable acrylic resin composition, comprising a resin, an initiator and a curable epoxy-modified acrylic resin, wherein one or more oxetane groups are grafted to a branch of at least one repeating unit in the epoxy-modified acrylic resin, and each oxetane group has a structure represented by general formula (I), general formula (II) or general formula (III):

wherein, R is₁Is represented by C₁～C₄₀Linear or branched n-valent alkyl of (2), C₂～C₃₀N-valent alkenyl of, C₆～C₄₀N-valent aryl of (A), said R₁Any one of-CH₂May be substituted by oxygen atoms, ester groups or

Substituted, said R₁Any one of the hydrogen atoms in (a) may be substituted by alkyl, halogen or nitro;

the R is₂And said R₄Each independently represents hydrogen, halogen, nitro, C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₅Alkenyl of (C)₆～C₃₀Aryl of (a), said R₂And said R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₂And said R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

the R is₃And said R₅Each independently represents C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₃₀Aryl of (a), said R₃And said R₅Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₃And said R₅Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen, or nitro;

a represents C₁～C₂₀A straight or branched alkyl group of (A), any one of the groups-CH₂-may be substituted by an oxygen atom or-COO-, any one of the hydrogen atoms of a may be substituted by alkyl, halogen or nitro;

said M represents a valence of 3C₁～C₂₀Wherein any one of said M is-CH₂May be substituted by oxygen atoms, -COO-or

Wherein any one hydrogen atom in M may be substituted by alkyl, halogen or nitro;

q represents C₁～C₂₀Wherein any one of said Q is-CH₂May be substituted by oxygen atoms, -COO-or

Any one hydrogen atom in the Q can be substituted by alkyl, halogen or nitro,

and n is an integer of 1-12.

2. The energy-curable acrylic resin composition according to claim 1, wherein R is₃And said R₅Each independently represent

The R is₆Is represented by C₁～C₃₀Straight or branched alkyl of (2), C₃～C₃₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₃₀Wherein said R is₆Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₆Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; the R is₇Represents C₁～C₂₀Linear or branched alkyl of (a); the R is₈Represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄Wherein R is₇And said R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₇And said R₈Wherein one or more hydrogen atoms are each independently substituted with alkyl, halogen, or nitro;

preferably, said R is₆Is represented by C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₆～C₂₄Wherein said R is₆Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₆Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro; the R is₇Is represented by C₁～C₁₀Linear or branched alkyl of (a); r₈Represents hydrogen, halogen, nitro, C₁～C₁₀Straight or branched alkyl of (2), C₃～C₁₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₁₂Wherein R is₇And said R₈Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₇And said R₈Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

3. The energy-curable acrylic resin composition according to claim 1, wherein R is₁Is represented by C₁～C₃₀Linear or branched n-valent alkyl of (2), C₂～C₂₀N-valent alkenyl of, C₆～C₃₀N-valent aryl of (A), said R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-or

Substituted, said R₁Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

preferably, said R is₁Is represented by C₁～C₁₅Linear or branched n-valent alkyl of (2), C₂～C₁₅N-valent alkenyl of, C₆～C₁₈N-valent aryl of (A), said R₁Any one of-CH₂May be substituted by oxygen atoms, -COO-orSubstituted, said R₁Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

4. The energy-curable acrylic resin composition according to claim 1, wherein R is₂And said R₄Each independently represents hydrogen, halogen, nitro, C₁～C₂₀Straight or branched alkyl of (2), C₃～C₂₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₂₄Aryl of (a), said R₂And said R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₂And said R₄Any one of the hydrogen atoms in (b) may be substituted by alkyl, halogen or nitro;

preferably, said R is₂And said R₄Each independently represents hydrogen, halogen, nitro, C₁～C₁₀Straight or branched alkyl of (2), C₃～C₁₀Cycloalkyl or substituted cycloalkyl of (A), C₂～C₁₀Alkenyl of (C)₆～C₁₂Aryl of (a), said R₂And said R₄Any one of-CH₂-may be substituted by an oxygen atom or-COO-, said R₂And said R₄Any one of the hydrogen atoms in (b) may be substituted with alkyl, halogen or nitro.

5. The energy-curable acrylic resin composition according to claim 1, wherein A represents C₁～C₁₅A straight or branched alkyl group of (A), any one of the groups-CH₂-may be substituted by an oxygen atom or-COO-, any one of the hydrogen atoms of a may be substituted by alkyl, halogen or nitro.

6. The energy-curable acrylic resin composition according to claim 1, wherein M represents C having a valence of 3₁～C₁₅A straight or branched alkyl group of (1), any one of said M-CH₂May be substituted by oxygen atoms, -COO-orIs substituted byAnd any one hydrogen atom in the M can be substituted by alkyl, halogen or nitro.

7. The energy-curable acrylic resin composition according to claim 1, wherein Q represents C₁～C₁₅Any one of said Q-CH, a straight or branched alkylene group of (1)₂May be substituted by oxygen atoms, -COO-or

Or any one hydrogen atom in the Q can be substituted by alkyl, halogen or nitro.

8. The energy curable acrylic resin composition according to claim 1, wherein n is an integer of 1 to 6.

9. The energy curable acrylic resin composition according to any one of claims 1 to 8, wherein said energy curable acrylic resin composition further comprises an auxiliary agent.

10. The energy-curable acrylic resin composition according to claim 9, wherein the auxiliary agent is selected from one or more of flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, colorants, stabilizers, release agents, antistatic agents, pigments, dyes, and flame retardants.

11. The energy curable acrylic resin composition according to any one of claims 1 to 10, wherein the initiator is a cationic initiator;

preferably, the cationic initiator is selected from one or more of diazonium salts, onium salts and organometallic complexes capable of forming strong acids upon application of an external energy source;

more preferably, the cationic initiator is selected from the group consisting of diazonium fluoroborate, pyrazole diazonium inner salt, triptycene diazonium salt, diazoaminobenzene, triarylsulfonium hexafluorophosphate, triarylsulfonium antimonate, 4' -dimethyldiphenyliodonium hexafluorophosphate, 4,4 '-dimethyldiphenyliodonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 4-octyloxydiphenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluorophosphate, bis (4-diphenylthiophenyl) sulfide dihexafluoroantimonate, 4-isobutylphenyl-4' -methylphenyliodionium hexafluorophosphate and 6-cumeneferrocenium hexafluorophosphate.

12. The energy curable acrylic resin composition according to any one of claims 1 to 8, wherein the epoxy-modified acrylic resin is contained in an amount of 10 to 80 wt% based on the weight percentage of the energy curable acrylic resin composition;

preferably, the content of the epoxy modified acrylic resin is 30-75 wt%.

13. The energy curable acrylic resin composition according to any one of claims 1 to 12, wherein the resin composition is curable by at least one of light, heat or electron radiation.

14. Use of the energy curable acrylic resin composition according to any one of claims 1 to 13 in the field of energy curing.

15. Use of the energy curable acrylic resin composition according to claim 14 in the field of energy curable, characterized in that the field of energy curable is the fields of inks, coatings and adhesives.