CN106752738B - A kind of biodegradable ultraviolet cured gloss oil and preparation method thereof - Google Patents
A kind of biodegradable ultraviolet cured gloss oil and preparation method thereof Download PDFInfo
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- CN106752738B CN106752738B CN201611046242.XA CN201611046242A CN106752738B CN 106752738 B CN106752738 B CN 106752738B CN 201611046242 A CN201611046242 A CN 201611046242A CN 106752738 B CN106752738 B CN 106752738B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of biodegradable ultraviolet cured gloss oils, are composed of the following raw materials in parts by weight: biodegradable light-cured resin 20~70, reactive diluent 15~55, photoinitiator 1~8, polymerization inhibitor 0.1~5, surfactant 0.5~6, defoaming agent 1~8.Wherein, the biodegradable light-cured resin is composed of the following raw materials in parts by weight: polyhydroxyalkanoate 30~180, photo-curable polymer 20~190, modifying agent 30~100, polymerization inhibitor 0.1~5, catalyst 0.5~10.What the present invention designed carries out biodegradable ultraviolet cured gloss oil, can be degraded to carbon dioxide (CO in a natural environment2) and water (H2O); realize the zero-emission of waste; the feature of environmental protection is had more than common oil polish; the problems such as ultraviolet-curing paint scrap concrete difficulty, the increasingly strict environmental protection policy faced and the petroleum base prices of raw materials rise steadily can effectively be solved; positive impetus is played in the sustainable development for promoting photocureable coating to environmental protection.
Description
Technical field
The invention belongs to printing technologies, and in particular to a kind of biodegradable ultraviolet cured gloss oil and its system
Preparation Method.
Background technique
It is the irradiation by ultraviolet light that ultraviolet light, which solidifies cardinal principle, causes the chain reaction of unsaturated group in oil polish,
So that whole system is crosslinked solidification, solid-state is changed by liquid.The technology mainly has the advantage that (1) curing materials not
Using organic solvent, without VOC emission, environmental protection characteristic is significant；(2) curing rate is fast, and reaction can be realized in zero point several seconds,
Solidification crosslinking；(3) the film layer glossiness formed after solidifying is high, and resistance is good.Due to these outstanding features, ultraviolet light solidifies skill
Art has obtained great application in printing industry, is widely used in and prepares various ink, separation layer, oil polish or bottoming oil etc.,
Especially on the surface in terms of light, the adhesive force and the characteristics such as wear-resisting scratch-resistant resistance of printing product surface are not only increased, while making to print
The increment of brush product, shows vast market prospect.
Ultraviolet cured gloss oil can the surface of printable fabric formed be similar to plastic foil film layer, this tunic be due to
The reticular structure that polymerization crosslinking generates, has many advantages, such as that toughness is strong, mechanical strength is big, makes the film layer to be formed resistant to chemical etching
Property, it is especially prominent in terms of the patience such as weatherability, rub resistance, significantly improve the durability of printing.But this excellent patience
Increase the difficulty of waste paper, waste ink recycling and reject product recovery processing.Other than carrying out deinking recycling to waste paper, there are also very
The printing packagings products such as more paper, film class, can not obtain it is effective recycle completely, but carry out garbage loading embeading or
It is exposed in natural environment, since this processing mode decompose the product will not within some time, environment can still be made
At huge pollution and harm.
United States Patent (USP) US 80489B2 report it is a kind of using natural reproducible resource-anacardol as main component synthesis
Light-cured polyurethane acrylic resin is obtained, the cross-linking double bond in the resin is between each other closer to therefore photocurable
Speed of performance faster, quality is higher.
The patent " a kind of ultraviolet cured gloss oil and preparation method thereof " of Publication No. CN101503580A, publication date is
On August 12nd, 009.The document reports a kind of ultraviolet cured gloss oil and preparation method thereof.The gloss oil mainly improves it
In the adhesive force of paper and surface of plastic products, make printable fabric surface from bottoming, does not refer to whether gloss oil can carry out biology
Degradation.
The patent " a kind of oil polish and its preparation method of waterborne wear-resisting ultraviolet-cured " of Publication No. N101967341A, it is public
Opening day is on March 9th, 2011.The document reports the oil polish and its preparation method of a kind of waterborne wear-resisting ultraviolet-cured.This is aqueous
Ultraviolet cured gloss oil emphasis improves wearability and water resistance, and water is used to have certain feature of environmental protection as retarder thinner,
But its dry speed is slow, and not can be carried out biodegrade.
The publication number solvent-free ultraviolet curing that has been respectively the patent report of 01748657A, ZL200410015113.5
The preparation method of oil polish, with reactive diluent monomer instead of organic solvent, however remaining reactive diluent still can be one
Certain pollution is brought to environment in fixed range, furthermore the gloss oil does not have biodegradation character, is stacked in environment still
Polluted problem.
Publication number be respectively ZL00117402.9, ZL200610035929.3 patent report in succession styrene-acrylic emulsion and
Water lustering oil containing the styrene-acrylic emulsion of cross-linked structure in N- hydroxyethyl acrylamide, but the oil polish is since paint film is using room
Temperature is dry, causes rate of drying slower, can not improve working efficiency.
The patent of Publication No. CN104387552A " use in paper by degradable UV-cured resin and preparation method thereof
Application in coating material ", data of publication of application is on March 4th, 2015.This patent reports a kind of degradable ultraviolet light solidifications
Resin and the preparation method and application thereof.There is good answer after the UV-cured resin coating material solidification of invention preparation
Power-strain property, higher stretch can slightly degrade with Young's modulus, the coating in alkaline phosphatase salt buffer solution.The hair
The bright resistance performance for improving coating material, but its degradation needs specific environment, does not have biodegradation character, Wu Faji
The waste of middle processing, which is stacked in natural environment, still has biggish pollution to environment.
The problem to be solved in the present invention is exactly to increase ultraviolet under the premise of guaranteeing gloss oil printability and print quality
The natural degradation characteristic of photocuring oil polish reduces it and is stacked at the pollution in natural environment to environment.The present invention can biology
The material polyhydroxyalkanoate (PHA) of decomposition is applied to printing industry, makes ultraviolet cured gloss oil can be in the natural environment
It is decomposed into carbon dioxide and water, the zero-emission of discarded gloss oil is realized, has more environmental protection characteristic than common gloss oil.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides a kind of biodegradable ultraviolet cured gloss oil and its
Preparation method.Technical problem to be solved by the present invention lies in guaranteeing gloss oil printability and under the premise of print quality,
The natural degradation characteristic for increasing ultraviolet cured gloss oil, reduces it and is stacked at the pollution in natural environment to environment.
To reach above-mentioned technical purpose, the present invention is achieved through the following technical solutions:
A kind of biodegradable ultraviolet cured gloss oil, is composed of the following raw materials in parts by weight: biodegradable
Light-cured resin 20~70, reactive diluent 15~55, photoinitiator 1~8, polymerization inhibitor 0.1~5, surfactant 0.5~6,
Defoaming agent 1~8；
Preferably, it is composed of the following raw materials in parts by weight: biodegradable light-cured resin 35~50, reactive diluent
20~50, photoinitiator 2~6, polymerization inhibitor 0.1~2, surfactant 1~3, defoaming agent 1~3；
It is further preferred that being composed of the following raw materials in parts by weight: biodegradable light-cured resin 45, activity dilution
Agent 45.8, photoinitiator 6, polymerization inhibitor 0.2, surfactant 1.5, defoaming agent 1.5.
Preferably, the biodegradable light-cured resin is biology base modified epoxy acrylic ester resin, biology
One or both of base modified urethane acrylate resin.
Preferably, the reactive diluent is the acrylate of two optical active groups of band or is three photolytic activity bases of band
One or both of the acrylate of group；
Wherein the acrylate of preferably described two optical active groups of band is tri (propylene glycol) diacrylate, 1,6-
Hexanediyl ester, ethoxylation 1,6 hexanediol diacrylate, dipropylene glycol diacrylate, ethoxylation dipropyl
One of butanediol acrylate and 1,4 butanediol diacrylate are a variety of；
Wherein the acrylate of preferably described two optical active groups of band is tri (propylene glycol) diacrylate, 1,6-
One or both of hexanediyl ester；
The acrylate of three optical active groups of band is trimethylolpropane trimethacrylate, three hydroxyl of ethoxylation
Propane tri, propoxylation trimethylolpropane trimethacrylate, O-phthalic acid diethylene glycol diacrylate
One of ester is a variety of；
Wherein the acrylate of preferably described three optical active groups of band is trimethylolpropane trimethacrylate, ethoxy
Change one or both of trimethylolpropane trimethacrylate.
Preferably, the photoinitiator be 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone,
One of 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxycyclohexyl phenyl ketone, 2- isopropyl thioxanthone are a variety of.
Preferably, the polymerization inhibitor is hydroquinone, 2,6- toluene di-tert-butyl phenol, one in p-hydroxyanisole
Kind is a variety of.
Preferably, the defoaming agent is organic silicon defoaming agent, and the organic silicon defoaming agent is polyether-modified poly-
Dimethyl siloxane, polyether-modified trisiloxanes, the polyether siloxane copolymer containing fumed silica, dimethyl silicone polymer
Or one of fluorosilicone or a variety of；
Wherein preferably the organic silicon defoaming agent is dimethyl silicone polymer.
The mixture that the surfactant is isopropanol and ethyl alcohol molar ratio is 3:2.
Preferably, the biodegradable light-cured resin is composed of the following raw materials in parts by weight: poly- hydroxy aliphatic
Acid esters 30~180, photo-curable polymer 20~190, modifying agent 30~100, polymerization inhibitor 0.1~5, catalyst 0.5~10；
It is further preferred that the biodegradable light-cured resin is composed of the following raw materials in parts by weight: poly- hydroxyl
Base aliphatic ester 70~165, photo-curable polymer 50~160, modifying agent 45~90, polymerization inhibitor 0.2~2, catalyst 1~3；
Still more preferably, the biodegradable light-cured resin is composed of the following raw materials in parts by weight: poly-
Hydroxy fatty acid 125, photo-curable polymer 102, modifying agent 73, polymerization inhibitor 0.5, catalyst 2.
Preferably, the polyhydroxyalkanoate is poly 3-hydroxy butyrate, poly- 3-hydroxybutyrate -3- hydroxypentanoic acid
One of ester, poly- 3-hydroxybutyrate -3- hydroxycaproic ester, poly- 3-hydroxybutyrate -4 hydroxybutyric acid ester are a variety of；
The photo-curable polymer is one of epoxy resin, polyacrylate, polyurethane, polyester or a variety of；
The polymerization inhibitor is hydroquinone, 2,5 di tert butyl hydroquinone, methyl hydroquinone, one in 1,4-benzoquinone
Kind is a variety of；
The catalyst is one of Tetrabutylammonium bromide, triethylamine, diethylamine or a variety of；
The modifying agent is maleic anhydride or diisocyanate；
Preferably, the diisocyanate is aliphatic diisocyanate or alicyclic diisocyanate；
It is further preferred that the diisocyanate is isoflurane chalcone diisocyanate, cyclopenta isocyanates, 4,4- bis-
Diphenylmethane diisocyanate, Methylcyclohexyl diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, hexa-methylene two
One of isocyanates is a variety of；
Still more preferably, the diisocyanate is isoflurane chalcone diisocyanate, 4,4- dicyclohexyl methyl hydride two
One of isocyanates is a variety of.
A method of preparing foregoing biodegradable ultraviolet cured gloss oil, which is characterized in that including
Following steps:
(1) preparation of biodegradable light-cured resin
Photo-curable polymer is added in the round-bottomed flask equipped with reflux condensate device, dropping funel and agitating device,
The polyhydroxyalkanoate of polymerization inhibitor, mass percent 35% is added under constant temperature stirring condition, is warming up to 85 ± 10 DEG C, stirs,
Mixture is made in dissolution, keeps the temperature 2~3 hours, the polyhydroxyalkanoate of modifying agent, mass percent 35% is added dropwise, 2~3 is small
When drip off, keep the temperature 2.5~3.5 hours, continue that remaining polyhydroxyalkanoate, catalyst is added dropwise, be warming up to 110 ± 5 DEG C, instead
10mgKOH/g should be less than to acid value, last rewinding is up to biodegradable light-cured resin；
(2) it stirs pre-dispersed
Reactive diluent is weighed up by both certainty ratios, is added into reaction vessel, blender is started and is maintained at 500 revs/min
Clock, is slowly added to photoinitiator, and carry out uniform stirring by 30~45 DEG C of heating water bath, adds after being completely dissolved to photoinitiator
Enter light-cured resin and defoaming agent biodegradable made from step (1), revolving speed is adjusted to 1200 revs/min, stirs evenly, control
For heating temperature processed at 30~50 DEG C, mixing time is 60 minutes；
(3) evenly dispersed
Polymerization inhibitor is diluted in surfactant, is then added to the mixture in the solution of step (2), continues to stir
It mixes 30~60 minutes, water-bath keeps the temperature 30~50 DEG C, and last rewinding is up to biodegradable ultraviolet cured gloss oil.
Compared with the existing technology, the beneficial technical effect of the present invention lies in:
The present invention, which devises one kind, can carry out biodegradable ultraviolet cured gloss oil, which can be in a natural environment
It is degraded to carbon dioxide (CO2) and water (H2O), the zero-emission for realizing waste has more the feature of environmental protection than common oil polish, can be effective
Solve ultraviolet-curing paint scrap concrete difficulty, the increasingly strict environmental protection policy faced and the petroleum base prices of raw materials not
Disconnected the problems such as going up, the sustainable development of photocureable coating is promoted, positive impetus is played to environmental protection.
Specific embodiment
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art answer
It should be appreciated that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form repair
Change or replace, but these modifications and replacement are fallen within the protection scope of the present invention.
The preparation of the biodegradable ultraviolet cured gloss oil of embodiment 1
(1) preparation of biodegradable light-cured resin
Following components is weighed by weight: polyhydroxyalkanoate 40g, photo-curable polymer 45.6g, modifying agent 30g, polymerization inhibitor
Agent 2.25g, catalyst 0.5g；
Wherein, polyhydroxyalkanoate is poly- 3-hydroxybutyrate -4 hydroxybutyric acid ester (4HB molar content is 85%), light
Curable polymer is epoxy resin, and modifying agent is maleic anhydride, and polymerization inhibitor is the dioxane solution (hydroquinone of hydroquinone
Mass percent 2%), catalyst is triethylamine；
Photo-curable polymer is added in the round-bottomed flask equipped with reflux condensate device, dropping funel and agitating device,
The polyhydroxyalkanoate of polymerization inhibitor, mass percent 35% is added under constant temperature stirring condition, is warming up to 85 ± 10 DEG C, stirs,
Mixture is made in dissolution, keeps the temperature 2~3 hours, the polyhydroxyalkanoate of modifying agent and mass percent 35% is added dropwise, 2~3 is small
When drip off, keep the temperature 2.5~3.5 hours, continue that remaining polyhydroxyalkanoate, catalyst is added dropwise, be warming up to 110 ± 5 DEG C, instead
10mgKOH/g should be less than to acid value, last rewinding is up to biology base modified epoxy acrylate resin；
(2) it stirs pre-dispersed
Weigh following components by weight: degradable light-cured resin 25g, reactive diluent 25g, photoinitiator 4.98g disappear
Infusion 1g；
Wherein, biodegradable light-cured resin is the biodegradable photocuring tree being prepared in embodiment 1
Rouge, reactive diluent are tri (propylene glycol) diacrylate (TPGDA) and 1,6- hexanediyl ester (HDDA) quality
Than the mixture for 1:4, photoinitiator is 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone (IHT-
PI 907), defoaming agent is dimethyl silicone polymer；
The reactive diluent weighed up is placed in beaker, is slowly stirred, 500 revs/min, 30~45 DEG C of heating water bath,
It is slowly added to photoinitiator, and carries out uniform stirring, is completely dissolved to photoinitiator, biodegradable light is then slowly added into
Solidified resin and defoaming agent, revolving speed are adjusted to 1200 revs/min, stir evenly, and wherein heating and temperature control is at 30~50 DEG C, stirring
Time is 60 minutes；
(3) evenly dispersed
Following components is weighed by weight: polymerization inhibitor 0.3g, surfactant 0.8g；
Wherein polymerization inhibitor is hydroquinone, the mixture (city that surfactant is isopropanol and ethyl alcohol molar ratio is 3:2
It sells)；
Polymerization inhibitor is diluted in surfactant, is then added to the mixture in the solution of step (2), continues to stir
It mixes 60 minutes, water-bath keeps the temperature 30~50 DEG C, and last rewinding is up to biodegradable ultraviolet cured gloss oil.
The preparation of the biodegradable ultraviolet cured gloss oil of embodiment 2
(1) preparation of biodegradable light-cured resin
Following components is weighed by weight: polyhydroxyalkanoate 170g, photo-curable polymer 180g, modifying agent 90g, polymerization inhibitor
Agent 4.8g, catalyst 7.6g；
Wherein, polyhydroxyalkanoate is poly- 3-hydroxybutyrate -4 hydroxybutyric acid ester (4HB molar content is 85%), light
Curable polymer is polyurethane, and modifying agent is diisocyanate, and polymerization inhibitor is the dioxane solution (hydroquinone of hydroquinone
Mass percent 2%), catalyst is triethylamine；
Photo-curable polymer is added in the round-bottomed flask equipped with reflux condensate device, dropping funel and agitating device,
The polyhydroxyalkanoate of polymerization inhibitor, mass percent 35% is added under constant temperature stirring condition, is warming up to 85 ± 10 DEG C, stirs,
Mixture is made in dissolution, keeps the temperature 2~3 hours, the polyhydroxyalkanoate of modifying agent, mass percent 35% is added dropwise, 2~3 is small
When drip off, keep the temperature 2.5~3.5 hours, continue that remaining polyhydroxyalkanoate, catalyst is added dropwise, be warming up to 110 ± 5 DEG C, instead
10mgKOH/g should be less than to acid value, last rewinding is up to biology base modified epoxy acrylate resin；
(2) it stirs pre-dispersed
Weigh following components by weight: degradable light-cured resin 35g, reactive diluent 50g, photoinitiator 5.2g disappear
Infusion 5.8g；
Wherein, biodegradable light-cured resin is the biodegradable photocuring tree being prepared in step (1)
Rouge, reactive diluent are tri (propylene glycol) diacrylate (TPGDA) and 1,6- hexanediyl ester (HDDA) quality
Than the mixture for 1:4, photoinitiator is 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone (IHT-
PI 907), defoaming agent is the polyether siloxane copolymer containing fumed silica；
The reactive diluent weighed up is placed in beaker, is slowly stirred, 500 revs/min, 30~45 DEG C of heating water bath,
It is slowly added to photoinitiator, and carries out uniform stirring, is completely dissolved to photoinitiator, biodegradable light is then slowly added into
Solidified resin and defoaming agent, revolving speed are adjusted to 1200 revs/min, stir evenly, and wherein heating and temperature control is at 30~50 DEG C, stirring
Time is 60 minutes；
(3) evenly dispersed
Following components is weighed by weight: polymerization inhibitor 4.2g, surfactant 3.7g；
Wherein polymerization inhibitor is 2,6- toluene di-tert-butyl phenol, and surfactant is isopropanol and ethyl alcohol molar ratio is 3:2
Mixture (commercially available)；
Polymerization inhibitor is diluted in surfactant, is then added to the mixture in the solution of step (2), continues to stir
It mixes 60 minutes, water-bath keeps the temperature 30~50 DEG C, and last rewinding is up to biodegradable ultraviolet cured gloss oil.
The preparation of the biodegradable ultraviolet cured gloss oil of embodiment 3
(1) preparation of biodegradable light-cured resin
Following components is weighed by weight: polyhydroxyalkanoate 125g, photo-curable polymer 102g, modifying agent 73g, polymerization inhibitor
Agent 0.5g, catalyst 2g；
Wherein, polyhydroxyalkanoate is 3-hydroxybutyrate ester, and photo-curable polymer is polyacrylate, and modifying agent is different
Fluorine that ketone diisocyanate, polymerization inhibitor is 1,4-benzoquinone, and catalyst is tetrabutylammonium；
Photo-curable polymer is added in the round-bottomed flask equipped with reflux condensate device, dropping funel and agitating device,
The polyhydroxyalkanoate of polymerization inhibitor, mass percent 35% is added under constant temperature stirring condition, is warming up to 85 ± 10 DEG C, stirs,
Mixture is made in dissolution, keeps the temperature 2~3 hours, the polyhydroxyalkanoate of modifying agent, mass percent 35% is added dropwise, 2~3 is small
When drip off, keep the temperature 2.5~3.5 hours, continue that remaining polyhydroxyalkanoate, catalyst is added dropwise, be warming up to 110 ± 5 DEG C, instead
10mgKOH/g should be less than to acid value, last rewinding is up to biology base modified epoxy acrylate resin；
(2) it stirs pre-dispersed
Weigh following components by weight: degradable light-cured resin 45g, reactive diluent 45.8g, photoinitiator 6g disappear
Infusion 1.5g；
Wherein, biodegradable light-cured resin is the biodegradable photocuring tree being prepared in step (1)
Rouge, reactive diluent are that trimethylolpropane trimethacrylate is with ethoxylated trimethylolpropane triacrylate molar ratio
The mixture of 1:3, photoinitiator are 2- isopropyl thioxanthone, and defoaming agent is polyether-modified dimethyl silicone polymer；
The reactive diluent weighed up is placed in beaker, is slowly stirred, 500 revs/min, 30~45 DEG C of heating water bath,
It is slowly added to photoinitiator, and carries out uniform stirring, is completely dissolved to photoinitiator, biodegradable light is then slowly added into
Solidified resin and defoaming agent, revolving speed are adjusted to 1200 revs/min, stir evenly, and wherein heating and temperature control is at 30~50 DEG C, stirring
Time is 60 minutes；
(3) evenly dispersed
Following components is weighed by weight: polymerization inhibitor 0.2g, surfactant 1.5g；
Wherein polymerization inhibitor is p-hydroxyanisole, the mixture that surfactant is isopropanol and ethyl alcohol molar ratio is 3:2
(commercially available)；
Polymerization inhibitor is diluted in surfactant, is then added to the mixture in the solution of step (2), continues to stir
It mixes 60 minutes, water-bath keeps the temperature 30~50 DEG C, and last rewinding is up to biodegradable ultraviolet cured gloss oil.
The preparation of the biodegradable ultraviolet cured gloss oil of embodiment 4
(1) preparation of biodegradable light-cured resin
Following components is weighed by weight: polyhydroxyalkanoate 145g, photo-curable polymer 92g, modifying agent 73g, polymerization inhibitor
Agent 0.5g, catalyst 2g；
Wherein, polyhydroxyalkanoate is 3-hydroxybutyrate ester, and photo-curable polymer is polyacrylate, and modifying agent is different
Fluorine that ketone diisocyanate, polymerization inhibitor is 1,4-benzoquinone, and catalyst is tetrabutylammonium；
Photo-curable polymer is added in the round-bottomed flask equipped with reflux condensate device, dropping funel and agitating device,
The polyhydroxyalkanoate of polymerization inhibitor, mass percent 35% is added under constant temperature stirring condition, is warming up to 85 ± 10 DEG C, stirs,
Mixture is made in dissolution, keeps the temperature 2~3 hours, the polyhydroxyalkanoate of modifying agent, mass percent 35% is added dropwise, 2~3 is small
When drip off, keep the temperature 2.5~3.5 hours, continue that remaining polyhydroxyalkanoate, catalyst is added dropwise, be warming up to 110 ± 5 DEG C, instead
10mgKOH/g should be less than to acid value, last rewinding is up to biology base modified epoxy acrylate resin；
(2) it stirs pre-dispersed
Weigh following components by weight: degradable light-cured resin 40g, reactive diluent 30g, photoinitiator 5.2g disappear
Infusion 2g；
Wherein, biodegradable light-cured resin is the biodegradable photocuring tree being prepared in step (1)
Rouge, reactive diluent are that trimethylolpropane trimethacrylate is with ethoxylated trimethylolpropane triacrylate molar ratio
The mixture of 1:3, photoinitiator are 2- isopropyl thioxanthone, and defoaming agent is polyether-modified dimethyl silicone polymer；
The reactive diluent weighed up is placed in beaker, is slowly stirred, 500 revs/min, 30~45 DEG C of heating water bath,
It is slowly added to photoinitiator, and carries out uniform stirring, is completely dissolved to photoinitiator, biodegradable light is then slowly added into
Solidified resin and defoaming agent, revolving speed are adjusted to 1200 revs/min, stir evenly, and wherein heating and temperature control is at 30~50 DEG C, stirring
Time is 60 minutes；
(3) evenly dispersed
Following components is weighed by weight: polymerization inhibitor 3.2g, surfactant 4.5g；
Wherein polymerization inhibitor is p-hydroxyanisole, the mixture that surfactant is isopropanol and ethyl alcohol molar ratio is 3:2
(commercially available)；
Polymerization inhibitor is diluted in surfactant, is then added to the mixture in the solution of step (2), continues to stir
It mixes 60 minutes, water-bath keeps the temperature 30~50 DEG C, and last rewinding is up to biodegradable ultraviolet cured gloss oil.
The performance test of the biodegradable ultraviolet cured gloss oil of the invention of embodiment 5
(1) the biodegradable ultraviolet cured gloss oil viscosity of Examples 1 to 3 preparation is 600~900mPas (25
DEG C), it is suitble to offline or online glazing to print, especially there is excellent adhesive force on a plastic film.
(2) the biodegradable ultraviolet cured gloss oil of preparation is drawn a design using IGT F1 flexographic printing adaptive instrument, so
Curing and drying is carried out in ultraviolet light curing apparatus afterwards (solidification power is 160W/cm, curing rate 25m/s)；After solidifying
Ink specimen page be cut into 1 × 1cm2, weight is that specimen page is embedded in wet by the specification of 20~30mg at room temperature using soil buries method
Soil in, sampled at interval of 10d primary, take three samples every time, weigh its average weight-loss ratio.And be washed with distilled water three times,
Film degradation situation is observed in vacuum drying.
It as shown in table 1, is film layer made of the gloss oil made from embodiment 1-3 in the flat of 10d, 30d, 60d, 90d, 360d
Equal weight-loss ratio, wherein test temperature is 25 DEG C.
Gloss oil film layer is decomposed more obvious in the soil it can be seen from test data in table 1, after 60 days it can be seen that
Lesser cavity, after 90 days it can be seen that more apparent cavity, after 360 days, gloss oil film layer has become tiny substantially
Fragment, and most of disappear；The gloss oil film layer decomposition rate wherein prepared in embodiment 3 is significantly greater than other embodiments preparation
Gloss oil film layer.
Organic solvent is absolutely not used in biodegradable ultraviolet cured gloss oil ingredient prepared by the present invention, so
There is no the discharge of VOC, no pollution to the environment.
Table 1
(3) in biodegradable ultraviolet cured gloss oil each component with compare gloss oil multinomial performance influence
Each ingredient and its ratio have extremely important influence to the performance of gloss oil in gloss oil.By change formula in difference at
The ratio divided, has investigated influence of the gloss oil each component ratio to gloss oil basic performance, as shown in table 2, wherein test temperature 25
DEG C, solidification power be 160W/cm, soil bury the time be 60 days.
Table 2
From Table 2, it can be seen that reactive diluent content subtracts with the increase of light-cured resin dosage in basic recipe
Few, the viscosity of gloss oil gradually increases, and curing degree is then first to rise to decline afterwards, and decomposition rate adds with the increase of resin content
Fastly, when the content of resin reaches 45%, and the content of reactive diluent is 45.8%, viscosity, curing degree and the adhesive force of gloss oil
Reach the more satisfactory range used.And the content of resin excessively then will affect the viscosity and solidification effect of gloss oil.The present invention is logical
The test design method for crossing a large number of experiments and science, finds the rational proportion between each ingredient of gloss oil, both ensure that gloss oil used
Every Essential Performance Requirements, while gloss oil being made to be provided with certain biodegradability again.
The basic proportion of each ingredient of gloss oil in the present invention, except guaranteeing gloss oil with certain biodegradation character, also
The properties of gloss oil are made to have reached the basic demand of offline or online glazing；More it is difficult to back ultraviolet cured gloss oil simultaneously
The problems such as receipts handle, are stacked at pollution environment in natural environment, petroleum resources are non-renewable is efficiently solved, and is more promoted
The sustainable development of ultraviolet-curing paint.
Claims (2)
1. a kind of biodegradable ultraviolet cured gloss oil, which is characterized in that be composed of the following raw materials in parts by weight: can give birth to
The light-cured resin 45 of object degradation, reactive diluent 45.8, photoinitiator 6, polymerization inhibitor 0.2, surfactant 1.5, defoaming agent
1.5；
Wherein, light-cured resin biodegradable described in every 1 part is composed of the following raw materials in parts by weight: poly-hydroxy fatty acid
Ester 125, photo-curable polymer 102, modifying agent 73, polymerization inhibitor 0.5, catalyst 2；The polyhydroxyalkanoate is 3- hydroxyl fourth
Acid esters, the photo-curable polymer are polyacrylate, and the modifying agent is isoflurane chalcone diisocyanate, and the polymerization inhibitor is
1,4-benzoquinone, the catalyst are tetrabutylammoniums；
The reactive diluent is that trimethylolpropane trimethacrylate rubs with ethoxylated trimethylolpropane triacrylate
You are than the mixture for 1:3；
The photoinitiator is 2- isopropyl thioxanthone；
The polymerization inhibitor is p-hydroxyanisole；
The mixture that the surfactant is isopropanol and ethyl alcohol molar ratio is 3:2；
The defoaming agent is polyether-modified dimethyl silicone polymer.
2. a kind of preparation method for preparing biodegradable ultraviolet cured gloss oil as described in claim 1, feature
It is, includes the following steps:
(1) preparation of biodegradable light-cured resin
Photo-curable polymer is added in the round-bottomed flask equipped with reflux condensate device, dropping funel and agitating device, in constant temperature
The polyhydroxyalkanoate of polymerization inhibitor, mass percent 35% is added under stirring condition, is warming up to 85 ± 10 DEG C, stirs, dissolution
Mixture is made, keeps the temperature 2~3 hours, the polyhydroxyalkanoate of modifying agent, mass percent 35% is added dropwise, drips within 2~3 hours
It is complete, 2.5~3.5 hours are kept the temperature, continues that remaining polyhydroxyalkanoate, catalyst is added dropwise, is warming up to 110 ± 5 DEG C, reaction is extremely
Acid value is less than 10mgKOH/g, and last rewinding is up to biodegradable light-cured resin；
(2) it stirs pre-dispersed
Reactive diluent is weighed up by both certainty ratios, is added into reaction vessel, blender is started and is maintained at 500 revs/min, water
30~45 DEG C of bath heating, is slowly added to photoinitiator, and carry out uniform stirring, and step is added after being completely dissolved to photoinitiator
(1) biodegradable light-cured resin and defoaming agent, revolving speed made from are adjusted to 1200 revs/min, stir evenly, control heating
For temperature at 30~50 DEG C, mixing time is 60 minutes；
(3) evenly dispersed
Polymerization inhibitor is diluted in surfactant, is then added to the mixture in the solution of step (2), stirring 30 is continued
~60 minutes, water-bath kept the temperature 30~50 DEG C, and last rewinding is up to biodegradable ultraviolet cured gloss oil.
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| CN111269638B (en) * | 2020-03-20 | 2021-12-31 | 广州市帝天印刷材料有限公司 | UV (ultraviolet) sun-proof coating varnish and preparation method thereof |
| CN112442318A (en) * | 2020-11-24 | 2021-03-05 | 中国林业科学研究院林产化学工业研究所 | Bio-based self-repairing photocureable coating and preparation method and application thereof |
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| CN104387552A (en) * | 2014-11-24 | 2015-03-04 | 鹤山雅图仕印刷有限公司 | Biodegradable UV (ultraviolet)-curable resin as well as preparation method and application thereof in coating material for paper |
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| JP2004034393A (en) * | 2002-07-01 | 2004-02-05 | Dainippon Ink & Chem Inc | Film for hydraulic transfer and manufacturing method for hydraulic transfer body using the same |
| CN102558580A (en) * | 2012-01-13 | 2012-07-11 | 中国印刷科学技术研究所 | Dissoluble light-cured resin and dissoluble ultraviolet (UV) printing ink and preparing method thereof |
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