CN115304757A - Block type ink resin and preparation method thereof - Google Patents

Abstract

The invention discloses a block type ink resin and a preparation method thereof. The block type ink resin is obtained by esterification of dibasic acid (anhydride), dihydric alcohol, hydroxyl-terminated polyacrylate, and modified rosin resin. Due to the introduction of polyester, polyacrylate and modified rosin resin structures into the ink resin, the block type ink resin has a wide range of applicability to various plastic film substrates.

Description

A kind of block ink resin and preparation method thereof

technical field

The invention relates to the field of polymer chemistry, in particular to a block type ink resin.

Background technique

In recent years, the improvement of people's living standards has led to the rapid growth of the packaging industry. Since gravure printing occupies an important position in domestic plastic film printing, it has also promoted the continuous development of the composite ink technology and market for gravure printing. At present, ink resins for plastic gravure printing mainly include polyurethane system, vinyl chloride system, polyamide system, polyvinyl butyral system, nitrocellulose system, etc., but a single resin is often difficult to meet the various requirements of printing inks. Resin modification has always been an important aspect in the development of ink resins.

The composite ink prepared with polyacrylate as the ink binder is mainly suitable for printing on BOPP film substrates. Therefore, in order to expand the scope of application of this type of ink resin, many enterprises and scientific research institutes have actively carried out related research work. Patent CN102653595A discloses a preparation method of polyester-modified hydroxyl polyacrylate and a coating containing polyester-modified hydroxyl polyacrylate. The method prepares the resin through esterification reaction of hydroxyl polyester and hydroxyl polyacrylate containing anhydride. Patent CN101029122A discloses a preparation method and application of acrylate-modified polyester resin. The method first prepares the acrylate prepolymer with carboxyl groups, and then esterifies the prepolymer with dibasic acid and dibasic alcohol to prepare the resin.

Contents of the invention

The object of the present invention is to provide a block type ink resin.

The technical scheme provided by the invention is:

Firstly, hydroxyl-terminated polyacrylate is prepared, and then esterified with dibasic acid (anhydride), dibasic alcohol, modified rosin resin, etc. to synthesize block-type ink resin.

A kind of block type ink resin, this block type ink resin is made by following steps:

(1) Add the solvent into the reaction kettle, heat up to 75-90°C, and mix the mixture composed of (meth)acrylate, styrene monomer, active functional monomer, initiator and chain transfer agent for 2-5 hours Add it dropwise to the reaction kettle at a constant speed. After the dropwise addition is completed, continue to stir and react at this temperature for 5 to 8 hours, then drop it to room temperature, and discharge to obtain hydroxyl-terminated polyacrylate;

(2) Add dibasic acid (anhydride), dibasic alcohol, and catalyst into the reaction kettle, pass in nitrogen, raise the temperature to 140-150°C, start stirring reaction after all the raw materials are melted, and heat up to 180°C within 2-5 hours ℃, then raise the temperature to 220℃ at a rate of 10℃/hour, control the temperature at the top of the fractionation column at 100±1℃, and keep warm for the esterification reaction until the acid value is 10-30mgKOH/g, then lower the temperature to 120-130℃ During this period, add hydroxyl-terminated polyacrylate and modified rosin resin into the reaction kettle, heat up to 220°C within 1 to 2 hours, and keep warm until the acid value is lower than 3mgKOH/g, stop the reaction, cool down to room temperature, and leave The block type ink resin is prepared from the material.

Further, in step (1), the content of each component is as follows in weight percentage:

Solvent 30～70 wt%

(Meth)acrylate 10～35 wt%

Styrene monomer 15～30 wt%

Active functional monomer 1~15 wt%;

The dosage of the initiator is 0.5-10wt% of the total weight of the styrene monomer and the active functional monomer, and the dosage of the chain transfer agent is 10-50wt% of the weight of the initiator.

Further, the solvent described in step (1) is any one or more of ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl pentanone.

Further, the (meth)acrylate described in step (1) is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl acrylate, decyl acrylate, decaacrylate Dialkyl esters, cetyl (meth)acrylate, stearyl (meth)acrylate, phenyl acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Trimethylcyclohexyl, tert-butylcyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, Methoxyethyl (meth)acrylate, Ethoxymethyl acrylate, Propoxyethyl acrylate , butoxyethyl acrylate, ethoxypropyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-phenoxyethyl Any one or more of acrylates.

Further, the styrenic monomers described in step (1) are styrene, α-methylstyrene, p-methylstyrene, 4-acetoxystyrene, 3,4-dimethylstyrene, 2,4,6-Trimethylstyrene, p-ethylstyrene, 2,5-diethylstyrene, p-butylstyrene, m-tert-butylstyrene, p-benzylstyrene, o-methoxy Any one or more of phenylstyrene, p-methoxystyrene, 2,6-dimethoxystyrene, 2-methoxy-5-isopropylstyrene.

Further, the active functional monomers described in step (1) are (meth)acrylonitrile, N-methoxyethylmethacrylamide, N-butoxymethylmethacrylamide, (methyl) Dimethylaminomethylacrylate, Diethylaminomethyl(meth)acrylate, Dimethylaminoethyl(meth)acrylate, Diethylaminoethyl(meth)acrylate, Dipropylmethacrylate Any one or more of aminoethyl ester, dibutylaminoethyl methacrylate, dimethylaminopropyl (meth)acrylate, and diethylaminopropyl (meth)acrylate.

Further, the initiator described in step (1) is azobisisobutyronitrile, azobisisoheptanonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2 '-Dimethyl azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethyl valeronitrile), dimethyl 2,2'-azobis(2-methylpropionate), dibenzoyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, peroxide (2-Ethylhexanoic acid) tert-butyl ester, tert-butyl peroxyformate, tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, di-n-propyl peroxydicarbonate, Bis(2-ethoxy)ethyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, bis(3,5,5-trimethylhexanoyl peroxide), Any one or more of diacetyl peroxide.

Further, the chain transfer agent described in step (1) is β-mercaptoethanol, 3-mercaptopropanol, 3-mercapto-2-butanol, 3-mercapto-2-pentanol, 3-mercapto-2-methanol Any one or more of pentanol and 6-mercaptohexanol.

Further, in the step (2), by weight percentage, the content of each component is as follows:

Dibasic acid (anhydride) 15～35 wt%

Diol 10～30 wt%

Hydroxyl-terminated polyacrylate 10-35 wt%

Modified rosin resin 5-30 wt%;

The dosage of the catalyst is 0.01-0.5wt% of the total weight of the reactants.

Further, the dibasic acid (anhydride) in step (2) is oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid , terephthalic acid, phthalic acid (anhydride), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, isophthalic acid, maleic acid (anhydride), fumaric acid, 3, 3- Any one or more of dimethyl glutaric acid.

Further, the diol described in step (2) is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, methylpropanediol, neopentyl glycol, 2-ethyl-2- Any one or more of butyl-1,3-propanediol, 1,2-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol.

Further, the modified rosin resin in step (2) is any one or more of dihydroabietic, tetrahydroabietic, acrylpimaric acid, maleopimaric acid, and fumaric acid.

Further, the catalyst described in step (2) is dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, tributyltin oxide, dioctyltin oxide, tributyltin chloride, 2-ethyl tin Any one or more of lead hexylhexanoate, lead benzoate, lead naphthenate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, and iron octoate.

The block-type ink resin of the invention can effectively adapt to the printing of various plastic film substrates due to the combination of the characteristics of polyester, polyacrylate and modified rosin resin.

Detailed ways

The present invention is specifically described below through examples, which are only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. For those skilled in the art, on the premise of not departing from the scope and general concept of the present invention, various modifications and changes made according to the method of the present invention shall fall within the protection scope of the present invention.

Example 1

Preparation of block type ink resin:

(1) Add 45kg of ethyl acetate into the reaction kettle, heat up to 75°C, add 25kg of propyl methacrylate, 19kg of styrene, 8kg of N-butoxymethyl methacrylamide, 0.78kg of 2,2'-azo The mixed solution consisting of bis(2,4-dimethylvaleronitrile) and 0.156kg of 3-mercapto-2-butanol was added dropwise to the reaction kettle at a constant speed within 2 hours, and the stirring reaction was continued at this temperature after the dropwise addition was completed for 5 Hour, be down to room temperature, discharge and make hydroxyl-terminated polyacrylate;

(2) Add 18kg of adipic acid, 5kg of 1,3-propanediol, 7kg of 1,10-decanediol, and 0.155kg of stannous octoate into the reaction kettle, pass in nitrogen gas, raise the temperature to 140°C, and start the stirring reaction after all the raw materials are melted , raise the temperature to 180°C within 2 hours, then raise the temperature to 220°C at a rate of 10°C/hour, control the temperature at the top of the fractionation column at 100±1°C, keep warm for esterification reaction until the acid value is 15mgKOH/g, then lower the temperature To 120°C, add 20kg of hydroxyl-terminated polyacrylate and 12kg of tetrahydrorosin to the reactor, raise the temperature to 220°C within 1 hour, keep warm and esterify until the acid value is 2.9mgKOH/g, stop the reaction, and cool down to room temperature. The block type ink resin is obtained by discharging.

Example 2

Preparation of block type ink resin:

(1) Put 56kg of butyl acetate into the reaction kettle, heat up to 80°C, add 14kg of n-butyl acrylate, 16kg of nonyl acrylate, 24kg of 2,5-diethylstyrene, 11kg of dimethylaminopropyl methacrylate , 1.56kg of dibenzoyl peroxide, and 0.624kg of 3-mercapto-2-pentanol are added dropwise to the reaction kettle at a constant speed within 3 hours. To room temperature, discharging makes hydroxyl-terminated polyacrylate;

(2) Add 7kg of succinic acid, 18kg of sebacic acid, 16kg of dipropylene glycol, 6kg of 1,4-butanediol, and 0.115kg of dioctyltin oxide into the reaction kettle, pass in nitrogen, raise the temperature to 145°C, and wait for After all the raw materials are melted, start to stir and react, raise the temperature to 180°C within 3 hours, then raise the temperature to 220°C at a rate of 10°C/hour, control the temperature at the top of the fractionation column at 100±1°C, and keep warm for esterification reaction to acid value When the temperature is 21mgKOH/g, cool down to 125°C, add 20kg hydroxyl-terminated polyacrylate and 15kg propylene pimaric acid into the reactor, heat up to 220°C within 2 hours, and keep warm for esterification until the acid value is 1.8mgKOH/g. Stop the reaction, cool down to room temperature, and discharge to obtain block-type ink resin.

Example 3

Preparation of block type ink resin:

(1) Add 41kg of methyl ethyl ketone into the reaction kettle, raise the temperature to 85°C, add 10kg of methyl methacrylate, 9kg of tert-butyl acrylate, 22kg of o-methoxystyrene, 14kg of diethylaminopropyl acrylate, 1.76kg of tert- The mixed solution composed of pentyl hydroperoxide and 0.493kg of 6-mercaptohexanol was added dropwise to the reaction kettle at a uniform speed within 4 hours, and after the dropwise addition was completed, the stirring reaction was continued at this temperature for 7 hours, and the temperature was lowered to room temperature, and the material was discharged to obtain Hydroxyl-terminated polyacrylate;

(2) Add 23kg of suberic acid, 8kg of isophthalic acid, 9kg of 1,2-propanediol, 18kg of 1,2-cyclohexanedimethanol, and 0.41kg of tributyltin oxide into the reaction kettle, blow in nitrogen, and raise the temperature to 143 ℃, start stirring reaction after all the raw materials are melted, raise the temperature to 180°C within 5 hours, then raise the temperature to 220°C at a rate of 10°C/hour, control the temperature at the top of the fractionating column at 100±1°C, and keep warm for the esterification reaction When the acid value is 14mgKOH/g, lower the temperature to 126°C, add 19kg of hydroxyl-terminated polyacrylate and 22kg of fumopimaric acid into the reactor, heat up to 220°C within 1.5 hours, and keep warm for esterification until the acid value is 2.7mgKOH /g, stop the reaction, cool down to room temperature, and discharge to obtain block type ink resin.

Example 4

Preparation of block type ink resin:

(1) Add 62kg of cyclohexanone into the reactor, heat up to 90°C, add 5kg of ethyl methacrylate, 12kg of dodecyl acrylate, 17kg of 2,4,6-trimethylstyrene, 6kg of methacrylic acid The mixed solution composed of dimethylaminoethyl ester, 3kg di-n-propyl peroxydicarbonate, and 0.54kg 3-mercaptopropanol was added dropwise to the reaction kettle at a uniform speed within 5 hours, and the stirring reaction was continued at this temperature after the dropwise addition was completed. 8 hours, down to room temperature, discharging to obtain hydroxyl-terminated polyacrylate;

(2) Add 14kg of azelaic acid, 9kg3, 3-dimethylglutaric acid, 9kg of diethylene glycol, 15kg of methylpropanediol, and 0.374kg of cobalt benzoate into the reaction kettle, feed nitrogen, and raise the temperature to 150 ℃, start stirring reaction after all the raw materials are melted, raise the temperature to 180 ℃ within 3.5 hours, then raise the temperature to 220 ℃ at a speed of 10 ℃/hour, control the temperature at the top of the fractionating column at 100±1 ℃, keep warm for esterification reaction When the acid value is 24mgKOH/g, lower the temperature to 128°C, add 15kg hydroxyl-terminated polyacrylate and 25kg maleopimaric acid to the reactor, heat up to 220°C within 2 hours, and keep warm for esterification until the acid value is 1.1mgKOH /g, stop the reaction, cool down to room temperature, and discharge to obtain block type ink resin.

Example 5

Preparation of block type ink resin:

(1) Add 58kg of methylpentyl ketone into the reaction kettle, raise the temperature to 90°C, add 12kg of methyl methacrylate, 14kg of benzyl acrylate, 26kg of 2,6-dimethoxystyrene, 6kg of diethylaminomethacrylate The mixed solution composed of ethyl ester, 1.972kg tert-butyl peroxyformate and 0.513kg β-mercaptoethanol was added dropwise to the reaction kettle at a constant speed within 5 hours. , discharging to obtain hydroxyl-terminated polyacrylate;

(2) Add 10kg of glutaric acid, 17kg of fumaric acid, 8kg of ethylene glycol, 11kg of 1,8-octanediol, and 0.072kg of lead naphthenate into the reaction kettle, pass in nitrogen, raise the temperature to 142°C, and wait until the raw materials are all After melting, start to stir and react, raise the temperature to 180°C within 4 hours, then raise the temperature to 220°C at a rate of 10°C/hour, control the temperature at the top of the fractionating column at 100±1°C, and keep warm for esterification reaction until the acid value is 27mgKOH /g, lower the temperature to 126°C, add 25kg of hydroxyl-terminated polyacrylate and 9kg of propylene pimaric acid to the reactor, heat up to 220°C within 1 hour, and stop the reaction when the acid value is 2.1mgKOH/g for esterification , down to room temperature, and discharged to obtain a block-type ink resin.

Example 6

Ink preparation:

Use the block type ink resin that embodiment 1,2,3,4 and 5 make respectively to prepare the composite ink for gravure printing, process is as follows: 33kg block type ink resin, 1.6kg polyketone resin, 30kg ethyl acetate Put ester, 6kg butyl acetate, 29kg titanium dioxide, 2kg BYK-191 dispersant, 1kg polyethylene wax and 1.5kg fumed silica into the container, stir for 30 minutes with a high-speed disperser, take out the material and send it to a sand mill Sanding is carried out in the machine, and when the fineness is lower than 10 microns, the material is discharged and filtered to obtain a composite ink for gravure printing. The test indexes of the prepared composite ink for gravure printing are shown in Table 1.

Table 1 The various detection indexes of the prepared ink

。

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The above test results are tested according to the QB/T2024-2012 standard.

Comparative example 1

(1) Add 13kg of glutaric acid, 10kg of sebacic acid, 9kg of ethylene glycol, 15kg of neopentyl glycol, and 0.12kg of tributyltin chloride into the reaction kettle, feed in nitrogen, raise the temperature to 150°C, and wait until the raw materials are all After melting, start to stir the reaction, raise the temperature to 180°C within 3.5 hours, then raise the temperature to 220°C at a rate of 10°C/hour, control the temperature at the top of the fractionation column at 100±1°C, and keep warm for esterification reaction until the acid value is 2mgKOH /g, lower the temperature and discharge to obtain the ink resin.

(2) Take 33kg of ink resin prepared above, 1.6kg of polyketone resin, 30kg of ethyl acetate, 6kg of butyl acetate, 29kg of titanium dioxide, 2kg of BYK-191 dispersant, 1kg of polyethylene wax and 1.5kg of fumed silica In the container, after stirring with a high-speed disperser for 30 minutes, take out the material, send it to a sand mill for sand grinding, and discharge it when the fineness is less than 10 microns, and filter to obtain a composite ink for gravure printing. The detection indexes of the composite ink for gravure printing are shown in Table 2.

Table 2

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The above test results are tested according to the QB/T2024-2012 standard.

It should be noted that at last: above each embodiment is only in order to illustrate technical scheme of the present invention, and is not intended to limit; Although the present invention has been described in detail with reference to foregoing each embodiment, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. range.

Claims (13)

1. a block type ink resin, is characterized in that, this block type ink resin is made by following steps: (1) Add the solvent into the reaction kettle, heat up to 75-90°C, and mix the mixture composed of (meth)acrylate, styrene monomer, active functional monomer, initiator and chain transfer agent for 2-5 hours Add it dropwise to the reaction kettle at a constant speed. After the dropwise addition is completed, continue to stir and react at this temperature for 5 to 8 hours, then drop it to room temperature, and discharge to obtain hydroxyl-terminated polyacrylate; (2) Add dibasic acid (anhydride), dibasic alcohol, and catalyst into the reaction kettle, pass in nitrogen, raise the temperature to 140-150°C, start stirring reaction after all the raw materials are melted, and heat up to 180°C within 2-5 hours ℃, then raise the temperature to 220℃ at a rate of 10℃/hour, control the temperature at the top of the fractionation column at 100±1℃, and keep warm for the esterification reaction until the acid value is 10-30mgKOH/g, then lower the temperature to 120-130℃ During this period, add hydroxyl-terminated polyacrylate and modified rosin resin into the reaction kettle, heat up to 220°C within 1 to 2 hours, and keep warm until the acid value is lower than 3mgKOH/g, stop the reaction, cool down to room temperature, and leave The block type ink resin is prepared from the material. 2. The block type ink resin according to claim 1, characterized in that, in step (1), the content of each component is as follows in weight percentage: Solvent 30～70 wt% (Meth)acrylate 10～35 wt% Styrene monomer 15～30 wt% Active functional monomer 1~15 wt%; The dosage of the initiator is 0.5-10wt% of the total weight of the styrene monomer and the active functional monomer, and the dosage of the chain transfer agent is 10-50wt% of the weight of the initiator. 3. The block ink resin according to claim 1 or 2, characterized in that the solvent in step (1) is any one of ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl pentanone one or more species. 4. The block-type ink resin according to claim 1, characterized in that, the (meth)acrylate described in step (1) is methyl (meth)acrylate, ethyl (meth)acrylate, ( Propyl (meth)acrylate, Isopropyl (meth)acrylate, n-Butyl (meth)acrylate, Isobutyl (meth)acrylate, Tert-Butyl (meth)acrylate, (Meth)acrylate-2 - Ethylhexyl, nonyl acrylate, decyl acrylate, lauryl acrylate, cetyl (meth)acrylate, octadecyl (meth)acrylate, phenyl acrylate, benzyl (meth)acrylate ester, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, methoxyl (meth)acrylate ethyl ester, ethoxymethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2 Any one or more of -ethoxyethoxy)ethylacrylate and 2-phenoxyethylacrylate. 5. The block-type ink resin according to claim 1, characterized in that, the styrenic monomers described in step (1) are styrene, α-methylstyrene, p-methylstyrene, 4- Acetoxystyrene, 3,4-dimethylstyrene, 2,4,6-trimethylstyrene, p-ethylstyrene, 2,5-diethylstyrene, p-butylstyrene, m-tert-butylstyrene, p-benzylstyrene, o-methoxystyrene, p-methoxystyrene, 2,6-dimethoxystyrene, 2-methoxy-5-isopropylbenzene Any one or more of ethylene. 6. The block-type ink resin according to claim 1, characterized in that the active functional monomer in step (1) is (meth)acrylonitrile, N-methoxyethyl methacrylamide, N-butoxymethylmethacrylamide, dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth)acrylate base) diethylaminoethyl acrylate, dipropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, dimethylaminopropyl (meth)acrylate, diethyl (meth)acrylate Any one or more of aminopropyl esters. 7. The block type ink resin according to claim 1, characterized in that the initiator in step (1) is azobisisobutyronitrile, azobisisoheptanonitrile, 2,2'-azo Bis(2,4-Dimethylvaleronitrile), 2,2'-Dimethyl azobisisobutyrate, 4,4'-Azobis(4-cyanovaleric acid), 2,2'- Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate) dimethyl ester, dibenzoyl peroxide, benzene peroxide tert-butyl formate, diisopropyl peroxydicarbonate, tert-butyl peroxy(2-ethylhexanoate), tert-butyl peroxyformate, tert-butyl hydroperoxide, tert-amyl hydroperoxide, iso Propylbenzene hydroperoxide, di-n-propyl peroxydicarbonate, di(2-ethoxy)ethyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, peroxydicarbonate Any one or more of bis(3,5,5-trimethylhexanoyl) oxide and diacetyl peroxide. 8. The block ink resin according to claim 1, characterized in that the chain transfer agent in step (1) is β-mercaptoethanol, 3-mercaptopropanol, 3-mercapto-2-butanol, Any one or more of 3-mercapto-2-pentanol, 3-mercapto-2-methylpentanol, and 6-mercaptohexanol. 9. The block type ink resin according to claim 1, characterized in that, in the step (2), the content of each component is as follows in weight percentage: Dibasic acid (anhydride) 15～35 wt% Diol 10～30 wt% Hydroxyl-terminated polyacrylate 10-35 wt% Modified rosin resin 5-30 wt%; The dosage of the catalyst is 0.01-0.5wt% of the total weight of the reactants. 10. The block ink resin according to claim 1, characterized in that the dibasic acid (anhydride) in step (2) is oxalic acid, succinic acid, glutaric acid, adipic acid, octane Diacid, azelaic acid, sebacic acid, undecanedioic acid, terephthalic acid, phthalic acid (anhydride), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, isophthalic acid , maleic acid (anhydride), fumaric acid, 3,3-dimethylglutaric acid in any one or more. 11. The block-type ink resin according to claim 1, characterized in that the dihydric alcohol in step (2) is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol Diol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, Any one or more of methylpropanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol kind. 12. The block type ink resin according to claim 1, characterized in that the modified rosin resin in step (2) is dihydroabietic, tetrahydroabietic, acrylpimaric acid, maleopimaric acid, fumaric acid Any one or more of pimaric acid. 13. The block type ink resin according to claim 1, characterized in that the catalyst described in step (2) is dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, tributyltin oxide, Dioctyltin oxide, tributyltin chloride, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, iron octoate any one or more.