CN110669437A - Rosin modified resin, preparation method thereof and UV offset printing ink - Google Patents

Rosin modified resin, preparation method thereof and UV offset printing ink Download PDF

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Publication number
CN110669437A
CN110669437A CN201911005031.5A CN201911005031A CN110669437A CN 110669437 A CN110669437 A CN 110669437A CN 201911005031 A CN201911005031 A CN 201911005031A CN 110669437 A CN110669437 A CN 110669437A
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modified resin
rosin modified
acid
rosin
ink
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闭忠康
郭常州
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Guangdong Hao Hui New Material Co Ltd
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Guangdong Hao Hui New Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09FNATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04Chemical modification, e.g. esterification
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/08Printing inks based on natural resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses rosin modified resin, a preparation method thereof and UV offset printing ink. The rosin modified resin is prepared from the following raw materials in parts by weight: 100 parts of rosin modified resin base material; 2-5 parts of aluminum chelate. Compared with other types of resin, the rosin modified resin has the characteristics of high viscosity and low viscosity, so that good body bones are provided for the UV offset printing ink.

Description

Rosin modified resin, preparation method thereof and UV offset printing ink
Technical Field
The invention relates to the field of photocuring materials, in particular to rosin modified resin, a preparation method thereof and UV offset printing ink.
Background
The offset resin is a binder applied to preparing offset ink, and the proportion of the binder in an ink formula is the largest, so that various properties of the ink are determined. Polyester acrylate resin, modified epoxy resin and some inert resins are available in the market at present and can be used as main resin for ink. However, these types of resins have corresponding defects, wherein the polyester acrylate resin has the problems of general reactivity and serious ink flying, and the modified epoxy resin has the problems of serious influence on ink balance due to emulsification and the like. Therefore, the existing offset printing resin has corresponding defects, and the preparation of the ink with better performance is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a rosin modified resin, a preparation method thereof and a UV offset printing ink, and aims to solve the corresponding defects of the prior offset printing resin and limit the performance of the UV offset printing ink.
The rosin modified resin is prepared from the following raw materials in parts by weight:
100 parts of rosin modified resin base material;
2-5 parts of aluminum chelate.
The rosin modified resin comprises a rosin modified resin base material and is prepared from the following raw materials in parts by weight:
Figure BDA0002242486160000021
the rosin modified resin is characterized in that the conjugated polybasic acid is one or more of maleic acid and fumaric acid, and the conjugated polybasic anhydride is maleic anhydride.
The rosin modified resin is prepared by mixing the rosin modified resin and the polyol, wherein the polyol is one or more of neopentyl glycol, ethylene glycol, glycerol, trimethylolpropane and pentaerythritol.
The rosin modified resin is characterized in that the fatty acid is one or more of eleostearic acid, linoleic acid, soybean oleic acid, stearic acid and tall oil fatty acid.
The rosin modified resin is characterized in that the antioxidant is one or more of di-tert-butyl hydroquinone, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, dibutyl hydroxy toluene and trinonyl phenyl phosphite ester.
The rosin modified resin is prepared by mixing a rosin modified resin and a catalyst, wherein the catalyst is one or more of an organic tin catalyst, butyl titanate, p-methyl benzene sulfonic acid and methyl sulfonic acid.
The rosin modified resin is characterized in that the acrylate monomer is one or more of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate and glycerinated acrylate.
A method for producing the rosin-modified resin described above, comprising the steps of:
putting the molten rosin into a reaction kettle, and heating to 140-200 ℃;
adding conjugated polybasic acid and/or conjugated polybasic anhydride, polyol, fatty acid, antioxidant and catalyst, preserving heat for 20-40 minutes, and then heating to 250-290 ℃ for heat preservation;
adding an acrylate monomer and glycidyl methacrylate for reaction;
adding aluminum chelate to obtain the rosin modified resin.
A UV offset ink comprising the rosin-modified resin as described above.
Has the advantages that: the rosin modified resin can be used as a main resin of UV offset printing ink. Compared with other types of resin, the rosin modified resin has the characteristics of high viscosity and low viscosity, so that good body bones are provided for the UV offset printing ink.
Detailed Description
The invention provides rosin modified resin, a preparation method thereof and UV offset printing ink, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The rosin modified resin is prepared from the following raw materials in parts by weight:
100 parts of rosin modified resin base material;
2-5 parts of aluminum chelate.
The rosin modified resin base material is a resin base material containing rosin or modified rosin. The rosin is carboxyl-containing rosin with a molecular formula of C19H29COOH. The aluminum chelate compound of the present invention is an organic aluminum type chelate compound such as aluminum oxide acylate, aluminum alkoxide and the like, and specifically the aluminum chelate compound can be di-sec-butoxy aluminum acetoacetate, di-iso-butoxy aluminum acetoacetate, n-butoxy aluminum, tert-butoxy aluminumOr the aluminum chelate complex may be directly a commercially available organic aluminum type complex X-110. The invention forms a thickening structure by the reaction of the aluminum chelate and carboxyl or hydroxyl in the rosin modified resin base material, so that the rosin modified resin has the characteristics of high viscosity and low viscosity.
The rosin modified resin can be used as a main resin of UV offset printing ink. Compared with other types of resin, the rosin modified resin has the characteristics of high viscosity and low viscosity, so that a good body skeleton is provided for the UV offset printing ink, and the UV offset printing ink has the comprehensive properties of good printing transferability, high gloss, low ink flying, low emulsification (good ink-water balance), excellent adhesion and the like.
In the rosin modified resin, the rosin modified resin base material comprises the following raw materials in parts by weight:
rosin, conjugated polybasic acid and/or conjugated polybasic anhydride, polyol, fatty acid and the like in the rosin modified resin base material can react with the aluminum chelate to form a thickening structure, so that the prepared rosin modified resin has more remarkable characteristics of high viscosity and low viscosity.
The structural formulas of the conjugated polybasic acid and the conjugated polybasic acid anhydride are molecular structures containing at least one carbonyl group connected to two ends of a carbon-carbon double bond. Specifically, the conjugate polybasic acid is one or more of maleic acid and fumaric acid, and the conjugate polybasic anhydride is maleic anhydride.
The polyhydric alcohol can be dihydric alcohol, trihydric alcohol and the like, and specifically, the polyhydric alcohol is one or more of neopentyl glycol, ethylene glycol, glycerol, trimethylolpropane and pentaerythritol.
The fatty acid is one or more of eleostearic acid, linoleic acid, soybean oleic acid, stearic acid and tall oil fatty acid.
The antioxidant is one or more of di-tert-butyl hydroquinone, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, dibutyl hydroxy toluene and trinonyl phenyl phosphite ester. The ditert-butylhydroquinone, DTBHQ for short, belongs to a non-toxic substance, and does not influence the physicochemical property of the resin; the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, which is 1010 for short, is white crystalline powder, has stable chemical properties, is not colored, is not polluted, is nontoxic, and is an excellent antioxidant; dibutyl hydroxy toluene, BHT for short, has high stability and strong oxidation resistance; the trisnonylphenyl phosphite ester is TNPP for short, and is a non-polluting heat-resistant antioxidant anti-aging agent.
The catalyst is one or more of organic tin catalyst, butyl titanate, p-methyl benzene sulfonic acid and methyl sulfonic acid.
The acrylate monomer can be monofunctional acrylate or multifunctional acrylate, and specifically, the acrylate monomer is one or more of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate (EM 2380 for short) and glycerinated acrylate (OTA-480 for short).
Further, the present invention provides a method for preparing the rosin modified resin, comprising the steps of:
A. putting the molten rosin into a reaction kettle, and heating to 140-200 ℃;
B. adding conjugated polybasic acid and/or conjugated polybasic anhydride, polyol, fatty acid, antioxidant and catalyst, preserving heat for 20-40 minutes, and then heating to 250-290 ℃ for heat preservation;
C. adding an acrylate monomer and glycidyl methacrylate for reaction;
D. adding aluminum chelate to obtain the rosin modified resin.
The reaction kettle is a reaction vessel for preparing the rosin modified resin, and other reaction vessels similar to the reaction kettle can be adopted by the technical personnel in the field. The invention adopts a step-by-step reaction method, namely, firstly, reacting rosin with conjugate polybasic acid and/or conjugate polybasic acid anhydride, polyalcohol and fatty acid to form a polymer with a certain molecular weight, then adding an acrylate monomer and glycidyl methacrylate for reaction to achieve the purpose of regulating and controlling the composition of the polymer in the rosin modified resin, obtaining the rosin modified resin with good comprehensive performance, and finally adding a certain amount of aluminum chelate to obtain the rosin modified resin with proper viscosity.
In the preparation method of the rosin modified resin, before the step C, the acid value of a product in the reaction kettle is detected, and when the acid value of the first intermediate product in the reaction kettle is 40-60mgKOH/g, the step C can be carried out. Before the step D, detecting the acid value of the second intermediate product in the reaction kettle, and performing the subsequent step D when the acid value of the product in the reaction kettle is less than or equal to 5 mgKOH/g. The invention determines whether the corresponding step is finished or not by controlling the acid value of the intermediate product in the reaction process.
Further, the invention also provides a UV offset printing ink, which comprises the rosin modified resin. The UV offset printing ink adopts the rosin modified resin as a main resin. The UV offset printing ink disclosed by the invention has the comprehensive properties of good printing transferability, high gloss, low ink flying, low emulsification (good ink balance), excellent adhesion and the like.
Specifically, the UV offset printing ink is prepared from the following raw material components in parts by weight:
the main resin is the rosin modified resin; the active diluent is trimethylolpropane triacrylate (TMPTA), and the viscosity of the formula is adjusted; the initiator is a UV initiator, such as a ketone photoinitiator, and specifically can be one or more of 907 (commercially available), ITX (commercially available) and TPO (commercially available); the filler is talcum powder used as a filler of the UV offset printing ink, and the talcum powder is 8000 meshes of talcum powder; the pigment is one or more of pigment red, titanium dioxide, benzidine yellow, phthalocyanine blue and carbon black.
Further, the present invention also provides a method for preparing the UV offset ink as described above, comprising:
uniformly mixing the components according to a UV offset printing ink formula to obtain ink paste;
and grinding the mixed ink paste on a three-roller machine for 4-5 times, and detecting the fineness of the ink paste by using a fineness plate to be less than 10 micrometers to obtain the UV offset printing ink.
The technical solution of the present invention will be described below by specific examples.
Example 1
Preparation of rosin modified resin
1. The formula of the rosin modified resin base material comprises the following raw materials:
Figure BDA0002242486160000071
the preparation method of the rosin modified resin comprises the following steps:
putting rosin in a molten state into a reaction kettle, and heating to 170 ℃;
<2> adding raw materials of maleic acid, neopentyl glycol, eleostearic acid, DTBHQ and butyl titanate;
after the temperature is kept for 30 minutes, the temperature is increased to 260 ℃ for heat preservation;
<4> the acid value was measured by sampling and was 51mgKOH/g, and after passing, the temperature was lowered after 1 hour of vacuum treatment.
And (5) adding trimethylolpropane triacrylate, dropwise adding glycidyl methacrylate, and keeping the temperature at 120 ℃ for reaction until the acid value is less than or equal to 5mgKOH/g to obtain the rosin modified resin base material.
2. The formula of the rosin modified resin comprises the following raw materials:
100g of rosin modified resin base material,
commercially available aluminum chelate X-1105 g.
According to the formula, rosin modified resin is used for enabling a rosin modified resin base material to react with a commercially available aluminum chelate X-110 to form a thickening structure, and the method comprises the following steps:
putting the rosin modified resin base material into a reaction kettle, and heating to 130 ℃;
dripping the aluminum chelate solution at the temperature of 120 ℃ under the stirring condition;
heating to 150 ℃, and keeping the temperature for 1 h;
and <2> cooling after sampling and determining qualification.
Secondly, UV offset printing ink is prepared, and the formula composition of the UV offset printing ink is shown in table 1.
TABLE 1 UV offset ink composition raw materials
Ink formulation Red colour Yellow colour Blue color White colour Black color
Main body resin (g) 50 52 50 35 52
TMPTA(g) 18 18 18 10 18
907/ITX/TPO(g) 4/2/1 6/1/0 6/1/0 2/1/2 8/1/0
8000 mesh talcum powder (g) 5 5 5 5 5
Pigment Red (57:1) L5B01(g) 20 \ \ \ \
Titanium dioxide RDIS (g) \ \ \ 45 \
Carbon black MA-11(g) \ \ \ \ 12
BiphenylamineYellow 1138(g) \ 16 \ \ \
15DT7072 phthalocyanine blue (g) \ \ 18 \ \
24000 dispersing agent (g) 1 1 1 1 1
Total amount (g) 101 101 101 101 97
Note: in Table 1, "\" indicates that the corresponding component content is 0.
The main resins in table 1 are rosin modified resin, modified epoxy resin HE 3219 (commercially available), and polyester resin HT7379 (commercially available) prepared in this example, and the monomer TMPTA is changxing EM 231; the 8000-mesh talcum powder is used for filling ink; the pigment red (57:1) is Crainen L5B 01; the titanium dioxide is Finland RDI-S provided by Heshi wall chemical industry; benzidine yellow 1138 provides Yuhong pigment; 15DT7072 phthalocyanine blue Fulitt organic phthalocyanine blue provided by Kjeldahl chemical; the dispersing agent is Luborun 24000, and improves the wetting and dispersing effects of the resin.
The preparation method of the UV offset printing ink for each color comprises the following specific steps:
the components were mixed uniformly according to the formulation shown in table 1;
and grinding the mixed ink paste for 5 times on a three-roller machine, and detecting the fineness of the ink paste by using a fineness plate to be less than 10um to obtain the UV offset printing ink.
Thirdly, evaluating the prepared UV offset printing ink
Substrate material: coated paper, PVC, PET, silver card paper.
The ultraviolet radiation curing conditions are as follows:
lamp tube type: a high-pressure mercury lamp;
lamp tube output power: more than or equal to 30 KW;
energy of the lamp tube: 100 to 1000J/cm2
Equipment: offset printing color developing instrument, ink emulsifying instrument, viscosity instrument, 60-degree inclined glass plate and Rayleigh viscosity instrument.
Construction viscosity: 8 to 12.
Coating thickness: 3 to 5 μm.
Performance testing of the UV offset inks of various colors prepared in this example
The UV offset inks of the respective colors prepared in this example were tested for ink fluidity, gloss, emulsion rate, viscosity Poise, adhesion property, and curing property by a conventional test method in the art, and the test results are shown in tables 2, 3, 4, 5, and 6.
In the embodiment, the ink flying performance is measured by using the adhesion instrument to operate, the ink layer is split, when ink drops fly off the ink roller and enter the air, the ink sticking condition of the white paper on the beam of the ink adhesion instrument is observed, specifically, after the ink adhesion instrument is started for one minute, a piece of white paper is placed on the beam, the white paper is taken down after the beam continues rotating for 1 minute, whether the white paper has ink or not is observed, and the ink flying degree is judged according to the amount of the ink stuck on the white paper.
TABLE 2 white UV offset ink test results
Example-white color Rosin modified resin HE3219 HT7379
Fluidity/cm 40 30 35
Gloss of 75 66 60
Degree of emulsification/%) 23 35 34
Viscosity of 9 14 13
Viscosity Poise 950 983 901
Silver card paper-attachment 5B 5B- 5B
PVC adhesion 5B- 0B 5B-
PET-attachment 4B 0B 3B
Curing 4 5 3
Ink mist 5 4 3
TABLE 3 yellow UV offset ink test results
Example yellow color Rosin modified resin HE3219 HT7379
Fluidity/cm 35 15 20
Gloss of 70 61 55
Degree of emulsification/%) 25 34 35
Viscosity of 8 13 12
Viscosity Poise 890 912 900
Silver card paper-attachment 5B 5B 5B
PVC adhesion 5B- 0B 5B-
PET-attachment 5B- 0B 4B
Curing 4- 4 3
Ink mist 5 3 3-
TABLE 4 test results for Red UV offset ink
Example Red color Rosin modified resin HE3219 HT7379
Fluidity/cm 36 20 27
Gloss of 80 71 72
Degree of emulsification/%) 26 33 36
Viscosity of 10 15 14
Viscosity Poise 953 971 964
Silver card paper-attachment 5B 5B 5B
PVC adhesion 5B- 0B 5B-
PET-attachment 5B- 0B 4B
Curing 4 4+ 4-
Ink mist 5 3 3-
TABLE 5 Red UV offset ink test results
Example blue color Rosin modified resin HE3219 HT7379
Fluidity/cm 30 13 15
Gloss of 66 54 57
Degree of emulsification/%) 27.5 34.3 35.7
Viscosity of 8.2 12.6 13.4
Viscosity Poise 933 951 938
Silver card paper-attachment 5B 5B 5B
PVC adhesion 5B- 0B 5B-
PET-attachment 5B- 0B 4B
Curing 4- 4 3
Ink mist 5- 3- 2
TABLE 6 test results for black UV offset ink
example-Black color Rosin modified resin HE3219 HT7379
Fluidity/cm 32 21 22
Gloss of 68 61 58
Degree of emulsification/%) 24.6 32.9 34.4
Viscosity of 9.3 12.5 12.7
Viscosity Poise 911 923 920
Silver card paper-attachment 5B 5B- 5B
PVC adhesion 4B 0B 3B
PET-attachment 3B 0B 2B
Curing 3 4 2
Ink mist 4 2 2-
Note: the cured and ink-flying scores in tables 2 to 6 were 1 to 5, and the larger the score, the better the corresponding performance.
Compared with other types of resin, the rosin modified resin prepared by the invention has the characteristics of high viscosity and low viscosity through ink performance test, and is a good UV offset printing ink skeleton. The UV offset printing ink skeleton prepared by the invention has the comprehensive properties of good printing transferability, high gloss, low ink flying, low emulsification (good ink balance), excellent adhesion and the like.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. The rosin modified resin is characterized by being prepared from the following raw materials in parts by weight:
100 parts of rosin modified resin base material;
2-5 parts of aluminum chelate.
2. The rosin modified resin according to claim 1, wherein the rosin modified resin base material is prepared from the following raw materials in parts by weight:
Figure FDA0002242486150000011
3. the rosin modified resin according to claim 2, wherein the conjugated polybasic acid is one or more of maleic acid and fumaric acid, and the conjugated polybasic acid anhydride is maleic anhydride.
4. The rosin modified resin according to claim 2, wherein the polyol is one or more of neopentyl glycol, ethylene glycol, glycerol, trimethylolpropane, and pentaerythritol.
5. The rosin modified resin of claim 2, wherein the fatty acid is one or more of eleostearic acid, linoleic acid, soya oleic acid, stearic acid, tall oil fatty acid.
6. The rosin modified resin of claim 2, wherein the antioxidant is one or more of di-tert-butylhydroquinone, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dibutylhydroxytoluene, and trisnonylphenyl phosphite.
7. The rosin modified resin according to claim 2, wherein the catalyst is one or more of an organotin catalyst, butyl titanate, p-toluenesulfonic acid, and methanesulfonic acid.
8. The rosin modified resin according to claim 2, wherein the acrylate monomer is one or more selected from trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and glycerated acrylate.
9. A method of preparing the rosin-modified resin according to claim 2, comprising the steps of:
putting the molten rosin into a reaction kettle, and heating to 140-200 ℃;
adding conjugated polybasic acid and/or conjugated polybasic anhydride, polyol, fatty acid, antioxidant and catalyst, preserving heat for 20-40 minutes, and then heating to 250-290 ℃ for heat preservation;
adding an acrylate monomer and glycidyl methacrylate for reaction;
adding aluminum chelate to obtain the rosin modified resin.
10. A UV offset ink comprising the rosin-modified resin according to any one of claims 1 to 8.
CN201911005031.5A 2019-10-22 2019-10-22 Rosin modified resin, preparation method thereof and UV offset printing ink Pending CN110669437A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN111647303A (en) * 2020-06-30 2020-09-11 湖南科茂林化有限公司 Phenolic-free rosin ester resin for offset printing ink and preparation method thereof
CN113416492A (en) * 2021-07-13 2021-09-21 桂林兴松林化有限责任公司 Production process of rosin modified resin for hot melt adhesive production
CN115029068A (en) * 2022-06-20 2022-09-09 广东科茂林产化工股份有限公司 Rosin-based ultraviolet curing resin, application, printing ink and preparation method thereof

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CN105838141A (en) * 2016-06-06 2016-08-10 上海飞亚油墨有限公司 Rosin and fatty acid modified polyacrylate resin for UV (ultraviolet) offset ink and preparation method of rosin and fatty acid modified polyacrylate resin
CN108219676A (en) * 2016-12-22 2018-06-29 谭海剑 A kind of special modified rosin resin, preparation method and its application

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US20070232786A1 (en) * 2001-01-05 2007-10-04 Sun Chemical Corporation Acrylated maleic-modified rosin ester and method of preparation
CN105838141A (en) * 2016-06-06 2016-08-10 上海飞亚油墨有限公司 Rosin and fatty acid modified polyacrylate resin for UV (ultraviolet) offset ink and preparation method of rosin and fatty acid modified polyacrylate resin
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111647303A (en) * 2020-06-30 2020-09-11 湖南科茂林化有限公司 Phenolic-free rosin ester resin for offset printing ink and preparation method thereof
CN113416492A (en) * 2021-07-13 2021-09-21 桂林兴松林化有限责任公司 Production process of rosin modified resin for hot melt adhesive production
CN115029068A (en) * 2022-06-20 2022-09-09 广东科茂林产化工股份有限公司 Rosin-based ultraviolet curing resin, application, printing ink and preparation method thereof

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Application publication date: 20200110