NL2031958B1

NL2031958B1 - An ultraviolet light curable rosin resin, preparation method and application thereof

Info

Publication number: NL2031958B1
Application number: NL2031958A
Authority: NL
Inventors: Weng Liang; Xu Sheyang; Zeng Guangjian; Chen Jun
Original assignee: Guangxi Komo Co Ltd
Priority date: 2022-03-18
Filing date: 2022-05-23
Publication date: 2022-12-13
Also published as: CN114574104A; CN114574104B

Abstract

The invention discloses an ultraviolet light curable rosin resin, preparation method and application thereof, which relates to the field of rosin resin. The rosin is added to the alkyl phenolic resin, then hydrogenated under the action of a catalyst, and finally subjected to a ring-opening reaction with an epoxy resin with a free-radically polymerizable double bond to obtain the rosin resin. The raw material rosin belongs to natural renewable resources, has abundant sources, is environmentally friendly, and is simple to prepare. The rosin resin of the present application can be widely used in UV-curable inks, coatings and adhesives, especially in UV-curable inks, and can effectively solve the following problems: difficulty in deep curing, in non-absorbent materials (such as PP, PE, etc.) ) with low adhesion and extensive use of highly toxic irritating reactive monomer diluents.

Description

AN ULTRAVIOLET LIGHT CURABLE ROSIN RESIN, PREPARATION METHOD AND APPLICATION

THEREOF Technical Field The invention relates to the field of rosin resin, in particular to an ultraviolet light curable rosin resin, preparation method and application thereof. Background Art Rosin is a renewable resource with abundant reserves, and it is also an important chemical raw material, which is widely used in soap, paper, paint, ink, rubber, food, electrical and so on.

Because rosin contains carboxyl groups and double bonds, it can be modified by esterification, addition and other reactions. in addition, the two active centers in rosin can introduce the rosin skeleton into other materials. It also can impart some physical or chemical properties to the materials, such as anticorrosion properties, moisture resistance properties, and insulating properties. At the same time, the strong and rigid phenanthrene ring in rosin will obviously affect the properties of viscosity, film-forming, gloss and so on, and these properties play a key role in the use of ink.

Ultraviolet (UV) curing technology is photochemical reaction based on photosensitive resin, and there isn't solvent volatilizes in this reaction, so it is an energy-saving, environmentally friendly and efficient curing technology. With the continuous updating of technology, UV curing technology can be applied in more and more technical fields, which mainly include coatings, packaging and printing, adhesives, electronic information, biomedicine and so on. Especially in the field of packaging printing, the disadvantages caused by traditional solvent-based inks are avoided by using UV curing technology. As we all know, printing is an technology with serious organic pollution, because solvent-based inks for printing usually use volatile organic compounds such as benzene and alcohol as diluents. These organic substances are volatilized during the drying process of the ink, which will not only exacerbate the pollution of the environment, but also endanger human health. In recent years, with the enhancement of people's attention of environmental protection, the ultraviolet light curable ink have attracted more and more attention.

On the one hand, the ultraviolet light curable ink can reduce the emission of VOCs greatly, or even eliminate them. On the other hand, the curing speed of the ultraviolet light curable ink is faster than that of conventional solvent-based inks, which can be cured instantaneously, and can be produced continuously, improving work efficiency and reducing costs that caused by ink drying. In addition, the process of using the ultraviolet light curable ink does not need to dry the substrate, which saves energy and avoids the environmental pollution caused by the emission of organic substances, the reason is no organic solvent is used.

Chinese patent No. CN101070372A discloses a kind of epoxy-phenolic resin modified by rosin and its preparation method. The said epoxy-phenolic resin has the above structure, in which R represents H or nonyl, n=1, 2...10, Firstly the resin is melted in the preparation method, feeds phenol or nonylphenol, formaldehyde and ZnO or MgO catalyst under the protection of nitrogen, and then backflowing for some time, warming and vacuuming dehydrates to obtain the epoxy-phenolic resin modified by rosin. Epichlorohydrin and catalysts are added, reacting for some time, vacuuming distillates and feeding organic solvents to dissolve. Dropping alkali solution used in closed-loop or slowly feeds solid bases or metal oxides both fine grinded, reacting for some time, washing to neutral by water, then distillating and recovering the solution to obtain brown transparent epoxy resin products. The invention introduces ether bonds into the prepared epoxy resin, so that the resin has excellent electrical insulation performance and drug resistance, The resin also has multiple reactive epoxy rings, which improves crosslinking density, chemical resistance, and heat resistance after curing, so it can be used in electronic packaging, coatings, inks, and the like. However, there are double-bonded phenanthrene rings and saturated epoxy groups in the resin, so if it is used in light-curable inks, curing retardation will occur and large amounts of toxic reactive monomer diluents will be necessary.

Ak gh CH A A LOHR OH, | VOOr EH rh iik 9 TT ETT Toe Chinese patent No. CN107602768A discloses a modified rosin-based UV light curing resin.

First, maleopimaric anhydride reacts with aliphatic diamine to form bismaleipimaric acid bisamide, and then reacts with glycidyl acrylate or glycidyl methacrylate under the action of a polymerization inhibitor and a ring-opening agent, in an organic solvent. and using quaternary ammonium salt as a catalyst to obtain the modified rosin-based UV light-curable resin. Firstly, the resin has high strength due to the introduction of polar groups such as carboxyl and hydroxyl groups, plus a rigid phenanthrene ring of rosin, in the resin, thereby ensuring that the ink is stable when used. Secondly, the introduction of aliphatic diamine increases the flexibility of the resin, thereby enhancing the adhesion on non-polar materials such as PP and PE. Thirdly, the usage of irritant reactive monomer diluent is reduced because the polymerizable double bond is introduced through the epoxy ring-opening reaction, which is green and environmentally friendly. However, the phenanthrene rings in the resin still contain double bonds, so in the subsequent UV curing step, the double bonds have a tendency to self-polymerize, which results in a large planar structure and prevents the resin from effectively dispersing in the ink, which ultimately affects the degree of UV curing and causes hardening obstacles. In addition, the flexible diamine group in the resin is too short and directly connected to the main chain of the molecule through amidation reaction, resulting in the restricted movement of its flexible aliphatic chain, which affects its compatibility with PP and PE, thereby reducing its adhesion on PP and PE.

Chinese patent No, CN108250409A discloses an active energy ray-curable resin modified by diallyl phthalate. The resin is obtained by the following steps: the free radical polymerization of aromatic unsaturated derivatives and acrylate derivatives firstly, then the ring-opening reaction of reserved carboxyl and saturated aromatic epoxy, and the last is the esterification reaction with phthalic anhydride. According to the invention, hydroxyl and carboxyl groups are introduced into the active energy ray-curable resin, and the good compatibility between diallyl phthalate and polyfunctional acrylic reactive monomer diluent is retained. When it is used in printing inks, the properties such as curing, solvent resistance, and gloss are the same as or even better than conventional inks. However, the invention does not describe whether the resin can be used on non-absorbent materials, so we have no way of knowing its properties such as adhesion on non-absorbent materials. Moreover, there is no single double bond available for polymerization in the resin, and the invention does not describe the use of monofunctional acrylic {ester) reactive diluents and difunctional acrylic (ester) reactive diluents, so the application effect cannot be known. Although it has good performance in the multifunctional dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate reactive monomer diluents, the mass proportion of these two reactive monomer diluents in the ink formulation More than 40%, even nearly 80%, which is not conducive to cost saving and environmental protection, because too many toxic reactive monomer diluents are used.

Chinese patent No.

CN109071785A discloses a rosin-modified active energy ray hardening type resin and a manufacturing method thereof.

The resin is obtained through the following steps: after the D-A addition reaction of rosin and unsaturated acid (anhydride), the ratio of alcohol and acid is designed, and the acid (or acid anhydride) is subjected to polycondensation reaction with alcohol containing more than two hydroxyl groups.

The resin has higher molecular weight and linear density.

Since it is based on an aliphatic polybasic acid anhydride structure, it significantly improves the adhesion of the phthalic anhydride-based structural unit in patent CN108250409A.

The resin has both flexible aliphatic hydrocarbon groups and rigid aromatic groups, so it has good compatibility with non-absorbent materials such as PP and PE, and can be used in non-absorbent materials to optimize performance, especially solvent resistance , gloss, abrasion resistance and adhesion.

However, the resin introduces a rosin-based phenanthrene ring containing a large number of double bonds, which leads to a hardening hindrance during curing, so the degree of hardening and the strength of the light film are affected.

In addition, the resin also requires the use of large amounts of toxic reactive monomer diluents.

Chinese patent No.

CN109476940A discloses a resin for active energy ray-curable inks.

The resin has a polyester structure similar to patent CN109071785A.

The difference is that stabilized rosin (such as disproportionated rosin, hydrogenated rosin) is used in the resin product in patent CN109071785A.

This product uses unsaturated acid {anhydride} as the acid for esterification, and does not undergo D-A addition reaction with rosin.

The unsaturated acid (anhydride) is matched with other acids (anhydrides), and then undergoes a polycondensation reaction with an alcohol containing two or more hydroxyl groups to obtain the resin product.

This product has both high molecular weight, linear density, flexible aliphatic hydrocarbon group, rigid aromatic group and good performance on non-absorbent materials{PP, PE) of the resin described in patent CN109071785A, especially solvent resistance, gloss, wear resistance sex and tightness on non-absorbent materials.

At the same time, the resin achieves strong hardening depth and light film strength when cured because it eliminates a large number of double bonds in the rosin phenanthrene ring.

However, the molecular structure of the resin also lacks a single polymerizable double bond, so the resin must be used with a large amount of reactive toxic monomer diluents to solve the problems of curing speed and curing efficiency, which results in the use of a large amount of reactive Disadvantages of monomeric diluents.

At present, ultraviolet light curable rosin resins mainly have the following problems: low adhesion on non-absorbent substrates, the existence of double bonds in the molecular ring 5 structure that hinder ink hardening, and the need for a large number of irritating and toxic reactive monomer diluents.

These problems limit the application of UV curing technology.

Therefore, it is very necessary to invent a UV-curable resin with good performance, which has the characteristics of strong adhesion, deep hardening, fast cross-linking speed and less reactive monomer diluent on non-absorbing substrates.

It can broaden the application range of UV-curable resin and enhance its application value.

Summary of the Invention In view of the shortcomings of the prior art, the present invention provides an ultraviolet light curable rosin resin, preparation method and application thereof.

The high performance ultraviolet light curable rosin resin is obtained through the following steps: firstly, the rosin containing double bonds is subjected to an addition reaction with an alkyl phenolic resin; Free radical polymerization of epoxy resins with a single double bond undergoes a ring-opening reaction.

The addition reaction of rosin and alkyl phenolic resin makes the non-polar alkyl side chain of phenolic resin connected to the resin, which can be better compatible with non-absorbent materials such as PP and PE, so after photocuring to form a film, the resin obtains strong adhesion on the surface of these non-absorbent materials.

The removal of the double bond in the phenanthrene ring after the hydrogenation reaction can effectively solve the hindrance of late hardening.

The introduction of a radically polymerizable single double bond enables self-polymerization during photocuring, which can replace the polymerization function of reactive monomer diluents, thereby effectively reducing the use of reactive monomer diluents.

In order to achieve the above objective, The technical solution of the present invention is as follows: The present invention provides a rosin resin, and the structural formula of the rosin resin is shown in formula (1):

OH ‚coox xOOC. _ ĳ ( 0 CH, ,C ° ’ Tl. me " n (Ho Wherein, in the formula (1), R is alkyl group of the phenolic resin. X is residue of epoxy resin, and the residue of epoxy resin bears a free-radically polymerizable single double bond. n refers to the degree of polymerization of the alkylphenolic resin, and the degree of polymerization is an integer in the range of 1-10.

Furthermore, the alkyl group of the phenolic resin is selected from aliphatic hydrocarbon groups, the residue of the epoxy resin contains a free-radically polymerizable straight chain containing a single double bond.

Furthermore, the alkyl group of the phenolic resin is selected from at least one of tert-butyl, tert-amyl, octyl, nonyl and dodecyl. Preferably, the alkyl group of the phenolic resin is selected from at least one of tert-butyl, octyl and nonyl. More preferably, the alkyl group of the phenolic resin is tert-butyl. The residue of epoxy resin is selected from at least one of residue of allyl glycidyl ether and residue of glycidyl methacrylate. Preferably, the residue of epoxy resin is residue of allyl glycidyl ether.

The application also provides a preparation method of the rosin resin, comprising the following steps: (1) Heating rosin to melting, adding phenolic resin, and reacting to obtain material 1; (2) Dissolving and heating the material 1 obtained in the step (1), adding a catalyst, introducing hydrogen to generate a hydrogenation reaction, and filtering to obtain a material 2; (3) Adding polymerization inhibitor and ring-opening agent to the material 2 obtained in step (2), heating up, dropwise adding free-radically polymerizable epoxy resin with a single double bond, reacting, adding antioxidant and cooling to obtain the rosin resin.

Furthermore, in step (1), the rosin is at least one of gum rosin, wood rosin and tall oil rosin.

Preferably, the rosin is gum rosin, and the gum rosin is at least one of rosin of pinus massoniana, slash pine rosin and rosin of pinus kesiya. Preferably, the gum rosin is rosin of pinus massoniana.

Furthermore, in step (2), the solvent of the hydrogenation reaction is at least one of pinane,

hydrogenated turpentine, and No. 200 solvent oil. Preferably, the solvent is pinnae.

Furthermore, in step (2), the catalyst is a supported catalyst, and the catalysts are prepared by supporting precious metals on carrier. Wherein, the precious metal is at least one of palladium, nickel and rhodium, preferably, the precious metal is at least one of palladium and nickel. The carrier is at least one of activated carbon, SiO2, Al203 and SiO2-Al203. The consumption of the catalyst is 1-3% of rosin weight. Preferably, the consumption of the catalyst is 1.5-2.5% of rosin weight. The hydrogen pressure of the hydrogenation reaction is 6-12Mpa, preferably 8-10Mpa.

Furthermore, in step (3), the polymerization inhibitor is at least one of phenols, quinones and aromatic nitro compounds. The phenols are at least one of 4-methoxyphenol, hydroquinone, catechol, p-tert-butylcatechol, and biphenol. The quinones are at least one of naphthoguinone, 1,4-benzoquinone and phenanthreneguinone. The aromatic nitro compound is at least one of dinitrobenzene and trinitrotoluene. Preferably, the polymerization inhibitor is at least one of 4-methoxyphenol and naphthoquinone. The dosage of the polymerization inhibitor is 0.5-2.5%0 of the weight of the rosin, preferably 1-2%0.

Furthermore, in step (3), the ring-opening agent is at least one of organic base and inorganic base, the organic base is at least one of triethylamine, diphenylamine, and triphenylamine, and the inorganic base is at least one of NaOH, KOH, and LIOH. Preferably, the ring-opening agent is at least one of triethylamine and diphenylamine. The dosage of the ring-opening agent is 1-3%o of the weight of the rosin, preferably 1.5-2.5%s..

Furthermore, in step (3), the free-radically polymerizable epoxy resin with a single double bond is at least one of allyl glycidyl ether and glycidyl methacrylate.

Furthermore, in step (3), the antioxidant is at least one of phosphonate, thiomethylol acid, paraformaldehyde, sulfide and hindered phenol. The phosphonate, the thiomethylol acid, the paraformaldehyde, the sulfide and the hindered phenol are not limitedly selected from compounds known in the art. Specifically, the phosphonate includes but is not limited to at least one of diethyl benzylphosphonate, diethyl 1,4-dihydroxynaphthalen-2-yl-2-phosphonate and dibutyl 2-hydroxybenzene phosphonate. The sulfide includes but is not limited to at least one of sodium sulfide, potassium sulfide, magnesium sulfide, and zinc sulfide, and the hindered phenol includes but is not limited to at least one of CHEMNOX 1010, CHEMNOX 1076 and CHEMNOX

3114. Preferably, the antioxidant is hindered phenol. The dosage of antioxidant is 0.5-3.5%0 of the rosin weight, preferably 1-2%.. In some specific embodiments, the preparation method of the rosin resin comprises the following steps: (1) Pulverizing the rosin, melting, heating up at a constant speed, adding phenolic resin in batches, keeping the temperature and reacting, and obtaining material 1; (2) Dissolving the material 1 obtained in step {1) in a saturated solvent, heating up, adding a catalyst, introducing hydrogen to pressurize, reacting, filtering, and removing the solvent to obtain material 2; (3) Adding the polymerization inhibitor and the ring-opening agent to the material 2 obtained in step (2), heating up, adding the free-radically polymerizable epoxy resin with a single double bond drop by drop, keeping the temperature and reacting, vacuumizing, adding the antioxidant, and cooling to obtain the resin.

Furthermore, in step {1}, the rosin is at least one of gum rosin, wood rosin and tall oil rosin.

The gum rosin is at least one of rosin of pinus massoniana, slash pine rosin and rosin of pinus kesiya.

Preferably, the rosin is gum rosin.

More preferably, the gum rosin is rosin of pinus massoniana.

Furthermore, in step (1), the heating is a uniform heating, and the heating time is controlled to 2-3h.

Furthermore, in step (1), the meaning of the keeping the temperature is to keep at 220-260°C, preferably 230-250°C.

Furthermore, in step {1}, the time for the keeping the temperature is controlled at 3-6 h, preferably 4-5 h.

Furthermore, in step (2), the temperature for the heating up is 210-230°C.

Furthermore, in step (3), the temperature for the heating up is 200-220°C.

Furthermore, in step (3), the time for the keeping the temperature is controlled at 3-5 h.

Furthermore. the rosin resin or the rosin resin obtained by the preparation method is used in inks, coatings and adhesives.

Compared with the prior art, the present invention has the following beneficial effects: (1) The invention provides a high-performance ultraviolet light curable rosin resin, the raw material rosin used in the resin is a natural renewable resource, and the source is abundant and environmentally friendly. The resin can be widely used in industrial products, such as inks, coatings and adhesives, and it can play an excellent tackifying effect.

(2) The ultraviolet light curable rosin resin can not only significantly enhance the hardening depth in photo-curable inks, coatings and adhesives and the adhesion strength on non-absorbent materials (such as PP, PE, etc.), but also significantly reduce the dosage of toxic reactive monomer diluents.

(3) The ultraviolet light curable rosin resin is added with an antioxidant in the later stage of preparation, which can prevent the resin from being oxidized by residual oxygen in the later stage of the reaction, thereby preventing the resin from reacting with oxygen in the later storage process. This not only protects the color of the product during the preparation process, but also effectively reduces the performance change caused by the oxidation of the product during storage.

Brief description of the drawing FIG.1 UV-Vis spectrum of the intermediate product of the addition reaction of rosin of pinus massoniana, p-tert-butylphenol formaldehyde resin (BPF), rosin of pinus massoniana and BPF in Example 1, wherein, 1 represents rosin of pinus massoniana, 2 represents BPF, and 3 represents the intermediate product of the addition reaction of rosin of pinus massoniana and BPF.

FIG.2 UV-Vis spectra of the intermediate product of the addition reaction of rosin of pinus massoniana and BPF, the raw material allyl glycidyl ether (AGE) and the rosin resin product 1 in Example 1, wherein 3 represents the intermediate product of the addition reaction of rosin of pinus massoniana and BPF, 4 represents AGE, 5 represents rosin resin product 1.

FIG.3 Infrared spectra of the intermediate product of the addition reaction of rosin of pinus massoniana, p-tert-butylphenol formaldehyde resin (BPF), rosin of pinus massoniana and BPF in Example 1, wherein, 1 represents rosin of pinus massoniana, 2 represents BPF, and 3 represents the intermediate product of the addition reaction of rosin of pinus massoniana and BPF.

FIG.4 Infrared spectra of the intermediate product of the addition reaction of rosin of pinus massoniana and BPF, the raw material allyl glycidyl ether (AGE) and the rosin resin product 1 in Example 1, wherein 3 represents the intermediate product of the addition reaction of rosin of pinus massoniana and BPF, 4 represents AGE, 5 represents rosin resin product 1.

Description of Embodiments it should be noted that the raw materials used in the present invention are all common commercially available products, and their sources are not specifically limited.

Examples Different values of parameters in the embodiments will constitute different embodiments, and the parameters such as A, B,C, D, E, F, G, T1, T2, T3, t1, t2, t3, P are shown in the Table 1. Table 2 shows the specific types of raw materials and the physical properties of the ultraviolet light curable rosin resin.

A preparation method of high-performance ultraviolet light curable rosin resin, comprising the following steps: (1) Pulverizing the rosin of mass A, melting, heating up at a constant speed, the time of the heating up is ti. Adding phenolic resin of mass B in batches, keeping the temperature and reacting, the temperature is Ti and the time of the keeping the, temperature is t2, obtaining material 1.

(2) Dissolving the material 1 obtained in step (1) in a saturated solvent, heating up to a temperature of T2, adding a catalyst of mass C, introducing hydrogen to pressurize, the hydrogen pressure is P. Reacting, filtering, and removing the solvent to obtain material 2.

(3} Adding the polymerization inhibitor of mass D and the ring-opening agent of mass E to the material 2 obtained in step (2), heating up to a temperature of T3, adding the free-radically polymerizable epoxy resin with a single double bond of mass F drop by drop, keeping the temperature and reacting, the time of keeping the temperature is t3, vacuumizing, adding the antioxidant of mass G, cooling to obtain the resin.

Table 1. Par Para am Para | Para | Para | Para Para | Para Para | Param | Param Param Param | Para Exam | mete ete mete | meter | mete | met mete | met meter | eter | eter eter eter | meter ples r r r p r er r er t(h) | Big) | TC) Ta{°C) T3(°C) | Fg) Alg) ta Clg) | (Mpa) | Dig) | Eg) tlg) | Gig) h) om [on | 7 [sees | + | = [om [or | [on] = [om

Exam

300 2.5 179 230 45 210 4.5 10 0.45 210 132.8 3 0.3 ple2 Exam

300 3 165 250 5 230 7.5 0.3 0.75 220 104.9 5 ple3 Exam

300 2.5 111.5 230 4.5 210 0.45 | 0.75 210 103.6 4 pled Exam

300 3 2235 250 5 230 7.5 220 132.8 5 0.45 ple5 Exam

300 2 125.9 240 4 220 4.5 10 0.45 | 0.45 200 105.8 3 0.3 ple6 Exam

300 2.5 158.5 230 4.5 210 0.3 0.45 210 131 4 ple? Exam

300 3 137.2 250 5 230 7.5 0.75 220 104.3 5 0.45 ple8 Exam

300 2.5 182 240 4 210 4.5 10 0.45 210 121.8 3 pled Exam

300 2 138.5 230 45 220 0.3 0.45 200 118.7 4 0.3 ple10 Exam

300 2.5 112.2 250 4.5 210 1.5 0.45 210 102.6 4 0.45 ple11 Exam

300 3 115.7 240 5 230 4.5 4 0.75 210 135.2 5 0.3 ple12 Exam

300 2 122.9 230 4 230 10 0.15 220 131.4 3 ple1i3 Exam

300 2.5 134.5 275 4 220 0.45 200 108 4 0.45 ple14 Exam

300 3 2235 250 5 230 7.5 180 132.8 5 0.45 ple15

Table 2. Examples Types and | Types and | Types and | Types and | Types and | Types and Types and proportions of | proportion | proportions proportions of | proportions of | proportions proportions | the phenolic | s of the | of the | the the epoxy resin of the of the rosin | resin catalyst polymerizatio | ring-opening antioxidant n inhibitor agent Examplel p-tert-butylph rosin of enol 4-methoxyph allyl glycidyl pinus palladium triethylamine 1010 formaldehyde enol ether (AGE) massoniana resin (BPF) Example2 rosin of p-octylphenol glycidyl 4-methoxyph pinus formaldehyde | palladium diphenylamine methacrylate 1076 enol massoniana | resin (OPF) (GMA Example3 p-nonylphenol rosin of naphthoquino formaldehyde nickel diphenylamine AGE 3114 pinus kesiya ne resin (NPF) Example4 p-tert-amylphe (triethylamin (1010/1076) slash pine nol naphthoquino | e/diphenylamin nickel AGE Mass ratio rosin formaldehyde ne e) Mass ratio is1:1 resin (APF) is1:1 Examples {4-methoxy p-dodecylphen i palladiu (triethylamin rosin of phenol / (1010/1076) ol m / nickel) e/diphenylamin pinus naphthoquino GMA Mass ratio formaldehyde | Mass ratio e) Mass ratio massoniana ne Mass ratio is1:2 resin (DPF) is1:1 is2:1 isl:1 Example6 {rosin of (palladiu pinus (1010/3114) m / nickel) | 4-methoxyph massoniana BPF triethylamine AGE Mass ratio Mass ratio enol / rosin of is1:1 is2:1 pinus kesiya > Mass ratio is 1:1 Example? (rosin of pinus massoniana (triethylamin (1076/3114) / rosin of naphthoquino | e/diphenylamin OPF nickel GMA Mass ratio pinus ne e) Mass ratio is1:1 kesiya) is1:1 Mass ratio is 1:1 Example8 {rosin of {4-methoxy {triethylamin pinus kesiya phenol / (NPF/APF)Mas e/diphenylamin / slash pine palladium | naphthoguino AGE 1076 s ratio is3:2 e) Mass ratio rosin) Mass ne ) Mass ratio is1:1 ratio is 2:1 is1:1 Example9 {4-methoxy Cpalladiu rosin of phenol / {1010/1076/ (BPF/DPF)Mas | m / nickel) CAGE/GMA) pinus naphthoguino | diphenylamine 3114)Mass s ratio is1:1 Mass ratio Mass ratio is1:1 massoniana ne Mass ratio ratio ís1:1:1 is1:1 is2:1 Example {rosin of pinus massoniana (triethylamin {BPF/OPF) (1010/1076) / rosin of 4-methoxyph | e/diphenylamin CAGE/GMA) Mass ratio is palladium Mass ratio pinus kesiya enol e) Mass ratio Mass ratio is1:1 1:1 is1:1 / slash pine is1:1 rosin) Mass ratio ís 1:1:1

TT [el TT Example naphthoguino tall oil rosin OPF rhodium triphenylamine GMA 1010 12 ne Example ‘ palladiu {triphenylami 13 m / nickel} | naphthoquino AGE/GMA) tall oil rosin NPF ne / LOH) 1010 Mass ratio ne Mass ratio is1:1 Mass ratio is1:1 is1:1 Example ‘ palladiu rosin of (1010/1076) 14 m / nickel} | 4-methoxyph pinus BPF triethylamine AGE Mass ratio Mass ratio enol massoniana is1:1 is1:1 Example i palladiu {4-methoxy (triethylamin 15 rosin of m/ phenol / (1010/1076) e/diphenylamin pinus DPF rhodium) naphthoquino GMA Mass ratio e) Mass ratio massoniana Mass ratio | ne)Mass ratio is1:2 is1:1 is1:1 isl:1 Test example The structure characterization of the rosin resin prepared by example 1-15 and the measuring method of relevant index are as follows: Ultraviolet spectrum: UV-2550 double-beam ultraviolet-visible spectrophotometer (Shimadzu, Japan) was used to analyze the sample, the scanning range was 190nm-380nm, the scanning accuracy was 1nm, and the sample was dissolved in ethyl acetate.

Infrared spectrum: FTIR-8400S Fourier Transform Infrared Spectrometer (Shimadzu, Japan) was used to measure the sample, KBr tablet or liquid model method was used to measure the sample, and the measured wavenumber range was 4000-400cm-1.

Color: Measure with reference to GB/T 1722-1992 "Method for Determination of Color of Varnishes, Clear Oils and Diluents". In the present invention, unless otherwise specified, the measured colors are all liquid colors {that is, the resin is dissolved in toluene of equal quality and detected Gardner color scale), the test results are shown in Table 3.

Softening point: Refer to GB/T 8146-2003 "Rosin Test Method" to measure, the test results are shown in Table 3.

Coating preparation: Weigh a certain amount of resin and put it in a container. Add a certain amount of active diluent butyl acrylate BA {the mass ratio of resin and diluent is 3:1) and an appropriate amount of photoinitiator {the amount of photoinitiator is 3% of the mass of resin and BA). Use ultrasound to disperse it and make it fully dissolved and stirred evenly for use. Then use a wire rod coater (10 um) to uniformly coat the prepared standby solution on the polypropylene (PP) film. Placed under a UV lamp (1kW, the distance from the coating is 21cm) until it is completely dried and cured, and its performance is measured. The test results are shown in Table 4.

Curing time: Refer to the national standard GB 1728-79 "Determination of Drying Time of Paint Film and Putty Film" to test the surface drying method-B method finger touch method. The specific steps are as follows: touch the surface of the paint film with your fingers, if you feel the paint film sticky but unpainted sticking to the hand, the surface is considered dry. Use a stopwatch for timing, each group of samples is measured three times, and the average value is taken, and the test results are shown in Table 4.

Water resistance: Test according to GB/T 1733-93 A method immersion test method: Add distilled water or deionized water to a beaker, put three test plates in it at room temperature, and immerse each sample in water for two weeks. Observe the changes of the coating (whether there is loss of gloss, whitening, bubbles, falling off, etc.), and the test results are shown in Table

4.

Acid and alkali resistance and solvent resistance: Test according to GB 9274-1988 method, choose method A (immersion method): 2/3 of each group of three test plates are immersed in 10% sulfuric acid aqueous solution at room temperature. Immerse in 10% NaOH aqueous solution and xylene for two weeks, observe and record the changes of the coating (whether there is Joss of gloss, whitening, bubbles, peeling, etc.), the test results are shown in Table 4.

Hardness: The hardness of the cured film is tested according to the manual method (B method) in GB/T6739-1996: the Zhonghua brand pencil is pushed on the coating at a 45° angle for 1cm at a speed of 1cm/s. Press the pencil with the same hardness for 5 times. If there are two or more scratches or cracks, write down the pencil hardness model of the last pencil of this model. Otherwise, change to the previous model and continue to measure until scratches or cracks appear. The test range is 4B-6H. The test results are shown in Table 4.

Adhesion: Test according to GB/T 9286-1998 and cut by hand.

Place the specimen on a hard, flat surface to prevent it from being damaged or twisted during the experiment.

Use a Octagonal knife perpendicular to the sample and apply force, move at a constant speed and make the Octagonal knife cut through the coating but do not scratch the substrate.

In the same way, make it perpendicular to the original cutting line.

Use a small brush to gently sweep back and forth along the diagonal line, observe whether the coating falls off, and stick it on the cutting grid line with 3M tape, rub it hard to make the tape tightly bonded to the surface of the sample.

Pull the tape at a constant speed of 0.5-1.0s at a 60° angle as much as possible, and check the damage of the coating with a magnifying glass.

Grading reference for results: Grade 0, the cutting edge is smooth, and no grid falls off.

Grade 1, the grid is damaged, but the damaged area is No more than 5%. Grade 2, grid damage, the area is greater than 5% and less than 15%. Grade 3, grid damage, the area is greater than 15% and less than 35%. Grade 4, the grid is damaged, the area is greater than 35% and less than 65%. The test results are shown in Table 4. Tensile test: Refer to GB/T 1040.3-2006 for testing.

The samples were cast into thin sheets in a mold and were tested on a CMT 5104 microcomputer-controlled electronic universal testing machine to measure its tensile strength and elongation at break.

The experimental temperature was room temperature, the humidity was 40%, the gauge length of the sample was 25 mm, the width of the sample was 6 mm, and the tensile rate was 5 mm/min.

The test results are shown in Table 4. Table 3. ew ew ew |e we ewe ew em ews

To further confirm the prepared high-performance ultraviolet light curable rosin resin, ultraviolet visible spectrum (UV-vis) was used to characterize this type of resin.

The test results of it, the comparative raw materials rosin, alkyl phenolic resin and epoxy resin are shown in Figure 1 and Figure 2. Due to the similarity in structure, the resin product 1 of Example 1, raw material rosin of pinus massoniana, p-tert-butylphenol formaldehyde resin {BPF} and allyl glycidyl ether (AGE) were selected for testing and analysis.

Figure 1 shows that after reaction with rosin of pinus massoniana, the strong characteristic absorption peak at 289 nm assigned to p-tert-butylphenol formaldehyde resin (BPF) is blue-shifted to 285 nm.

This indicated that the strongly electron-withdrawing carboxyl group played a role in reducing color after rosin of pinus massoniana was added to the BPF chain.

The strong characteristic absorption peak at 259nm attributed to rosin of pinus massoniana is red-shifted to 261nm after reacting with BPF.

This indicates that the electron-donating methylene and ether bonds on BPF play an auxiliary role.

In addition, as can be seen from the figure, the characteristic absorption peak at 273 nm attributed to BPF disappeared after the reaction with rosin of pinus massoniana.

To sum up, it shows that rosin of pinus massoniana reacts with BPF to successfully synthesize modified BPF intermediate products based on rosin of pinus massoniana.

Rosin of pinus massoniana-based modified BPF intermediates were hydrogenated and then subjected to a ring-opening reaction with allyl glycidyl ether (AGE). It can be seen from Figure 2 that the characteristic absorption peak at 261 nm attributed to the intermediate product is red-shifted to 263 nm due to the AGE assisted color effect of the electron-donating group.

However, compared with the intermediate product, an obvious characteristic absorption peak appeared at 278 nm after the hydrogenation reaction.

At the same time, the characteristic absorption peak of AGE at 255nm disappeared after reacting with the intermediate product after hydrogenation, which indicated that this kind of high-performance UV-curable rosin resin was successfully synthesized.

To further confirm the prepared high-performance ultraviolet light curable rosin resin, fourier transform infrared spectroscopy (FTIR) was used to characterize this type of resin.

The test results of it, the comparative raw materials rosin, alkyl phenolic resin and epoxy resin are shown in Figure 3 and Figure 4. Due to the similarity in structure, the resin product 1 of Example 1, raw material rosin of pinus massoniana, p-tert-butylphenol formaldehyde resin (BPF) and allyl glycidyl ether (AGE) were selected for testing and analysis.

Figure 3 shows that the characteristic absorption peak of the hydroxyl group of p-tert-butylphenol formaldehyde resin (BPF) at 3368 cm? is greatly weakened after the addition reaction.

At the same time, the characteristic absorption peak of 1200cm™ belonging to the ether bond appeared, which indicated that rosin of pinus massoniana was successfully added to BPF to generate the BPF intermediate product modified with rosin of pinus massoniana.

Figure 4 shows that after the hydrogenated rosin of pinus massoniana-modified BPF intermediate reacts with AGE, the characteristic absorption peak of hydroxyl at 3440 cm-1 reappeared, while the characteristic absorption peak of the carboxyl group attributable to the intermediate product at 1695 cm? is red-shifted to the characteristic absorption peak of the ester group at 1725 cm, the characteristic absorption peak at 1645 cm’? attributed to the double bond of AGE is clearly displayed in Figure 4, which indicated that the double bond of AGE was retained after the ring-opening reaction.

To sum up, after the addition reaction of rosin of pinus massoniana and alkyl phenolic resin BPF, it is hydrogenated, and then undergoes a ring-opening reaction with epoxy resin AGE to generate a high-performance ultraviolet light curable rosin resin as shown in formula (1). Since the structures and characterizations of the resins of other examples are similar to those of the products in the above-mentioned example 1, they will not be repeated here.

The test results in Table 3 show that, according to the preparation method of the present invention, a light-colored high-performance ultraviolet light curable rosin resin with a suitable softening point is successfully synthesized.

In addition, the resin prepared in the example was fully mixed with a certain proportion of butyl acrylate (BA), and then cured by ultraviolet light irradiation to form a film under the action of a photoinitiator.

The test results of its performance indicators are shown in Table 4. Table 4.

examples exa exa exa exa exa exa exa exa exa exa exa exa exa exa exa mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl | mpl el e2 e3 e4 e5 e6 e7 e8 e9 eld | ell el2 e13 eld | e15 Light curing

2.2 2.5 3.7 3.2 3.5 2.8 3.4 3.6 3.7 7.8 9.5 4.7 5.6 4.2 time (sJ Water no no no no no no no no no no no no no no no resistance cha cha cha cha cha cha cha cha cha cha cha cha cha cha cha (24h) nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge Acid resistance no no no no no no no no no no no no no no no (10% cha cha cha cha cha cha cha cha cha cha cha cha cha cha cha H2SO4 nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge solution, 2 weeks) Alkali whit whit resistance no no no no no no no no no no no no ish, no ish, (10%Na0H | cha cha cha cha cha cha cha cha cha cha cha cha | bub | cha | bub solution. 2 | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge bly, nge | bly, weeks) dull dull Solvent no no no no no no no no no no no no no no no resistance cha cha cha cha cha cha cha cha cha cha cha cha cha cha cha {Xylene, 2 nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge | nge weeks EE EE EE EE | we | mwa | a EN Gra Gra Gra Gra Gra Gra Gra Gra Gra Gra Gra Gra Gra Gra Gra adhesion de de deO | deO | de | de 0 deQ | deQ | deO deQ | de2 | de2 | de3 | de2 | de3 0-1 0-1 este | 108] 86 | as [102 7s [ss 83 | 87 | 78 | 91 18 [1635 | 22 | 2s |

Strength (Mpa) pe ee

45.3 | 483 | 51.5 | 46.7 | 56.3 | 47.2 | 50.7 | 49.1 | 54.6 | 48.6 | 25.3 | 22.5 | 30.5 | 31.7 | 36.3 at break (%) The ultraviolet light curable rosin resin prepared in Examples 1-10 was mixed with a certain proportion of butyl acrylate (BA) sufficiently. Then it was cured into a film by UV-irradiation under the action of photoinitiator. Tested it and found that although the amount of reactive monomer diluent (BA) used {less than 25% of the total mass of the UV-curable material) was far less than the amount disclosed in the current data, the prepared UV-curable coating film has excellent performance. It has short light curing time (no more than 4s), high coating hardness (HB~2H), strong adhesion on non-absorbent material PP (0-1~0), and mechanical properties of the coating film Excellent (including high tensile strength and elongation at break).

In addition, the coating film made of the photocurable resin also has excellent water resistance, acid or alkali resistance and solvent resistance. The rosin resins prepared in Examples 11-15 are not fully hydrogenated, partially decomposed at high temperature or epoxy ring-opening is not complete. This leads to the film-forming products formed by mixing them with BA in the same proportion and cured by ultraviolet light have the following conditions: longer curing time, poorer alkali resistance, softer film hardness, poorer adhesion on non-absorbent material PP, and weaker mechanical properties.

Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than limiting the protection scope of the present invention. Simple modifications or equivalent substitutions made by those of ordinary skill in the art to the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention.

Claims

CONCLUSION

A resin-resin having a resin-resin structural formula as shown in formula (1):

OH ,LCOOX XOOC. _ CH, ,C Oo Oo Fr PTY

R n Formula {|} where in the formula (I) R is an alkyl group of the phenolic resin, X is an epoxy resin residue, and the epoxy resin residue bears a polymerizable single double bond free radical, n represents the degree of polymerization of alkylphenol resin and the degree of polymerization is an integer from 1-10.

The rosin-resin according to claim 1, wherein the alkyl group of the phenolic resin is selected from an aliphatic hydrocarbon group, preferably the alkyl group of the phenolic resin is selected from at least one of tertbutyl, tert-amyl, octyl, nonyl, dodecyl ; the epoxy resin residue contains a polymerizable free radical straight chain containing a single double bond, preferably the epoxy resin residue is selected from at least one allyl glycidyl ether residue and glycidyl residue.

A method for preparing the resin-resin according to claims or 2 comprising the steps of: {1) heating resin until it melts, and reacting to obtain a material 1; (2) dissolving and heating the material 1 obtained in step (1), adding a catalyst, introducing hydrogen to generate a hydrogenation, and filtering to obtain a material 2; (3) Add to the material obtained in step (2) of a polymerization inhibitor and heat ring-opening agent, and add a radical-free single double bond polymerizable epoxy resin dropwise, react, add antioxidant, and cool to make the resin-resin to obtain.

The method of claim 3, wherein in step (1), the rosin-resin is at least one of gum rosin, wood rosin and tall oil rosin, the gum rosin is at least one of Masson pine rosin, wetland rosin and Simao rosin.

The method according to claim 3, wherein the solvent of the hydrogenation reaction mentioned in step (2) contains at least one of pine krine, hydrogenated turpentine and Nr. 200 are solvent oil; the catalyst is a supported catalyst, and the catalyst is obtained by loading the noble metal onto a support, the noble metal is at least one of palladium, nickel and rhodium; the carrier is at least one of activated carbon, SiO2, Al203 and SiO2-Al203; the consumption by the catalyst is 1-3% of the total weight of resin; the hydrogen pressure in the hydrogenation reaction is 6-12Mpa.

The method of claim 3, wherein in step (3) the polymerization inhibitor is at least one of phenolic, quinone and aromatic nitro compounds; the phenol is at least one of 4-methoxyphenol, hydroquinone, catechol, p-tert-butylcatechol and biphenol to be; the quinone is at least one of naphthoquinone, 1,4-benzoquinone and phenanthrenequinone; the aromatic nitro compound is at least one of dinitrobenzene and trinitrotoluene; the dosage of the polymerization inhibitor is 0.5-2.5% of the total weight of resin.

The method of claim 3, wherein the ring opening agent of step {3} is at least one of organic base and inorganic base, the organic base is at least one of triethylamine, diphenylamine and triphenylamine, and the inorganic base is at least one of sodium hydroxide , potassium hydroxide and lithium hydroxide; the dosage of the ring-opening agent is 1-3% of the total weight of resin.

The method of claim 3, wherein the radical-free polymerizable single double bond epoxy resin mentioned in step (3) is at least one of allyl glycidyl ether and methacrylate glycidyl.

The method of claim 3, wherein said antioxidant in step (3) is at least one of phosphonate, thiohydroxymethyl acid, paraformaldehyde, sulfide and hindered phenol; the dosage of the antioxidant is 0.5-3.5% of the total weight of resin.

The rosin-resin according to claims 1 or 2 or rosin-resin obtained by the method according to any of claims 3-9 is used in inks, coatings, and adhesives.