CN101173033B - Method for producing expediting setting type aquosity ultraviolet light solidifying composition - Google Patents
Method for producing expediting setting type aquosity ultraviolet light solidifying composition Download PDFInfo
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Abstract
The invention relates to a preparation method for full gloss and high-speed curing type aqueous ultraviolet light curing combination used on a printing surface. The combination comprises: (1) making polyhydric alcohol or polyatomic acid with double keys in different proportion polymerized into unsaturated polyester of the hydroxyl on outlet end as the flexible section of the polyurethane, and using the aqueous monomer with double keys of the hydroxyl on self-control end to react with isophorone diisocyanate for preparing the aqueous light curing polyurethane prepolymer; (2) making epoxy resinand crylic acid reacted to enable an epoxy group to open loop, and then using acid anhydride to be reacted with the a hydroxy group in the epoxy prepolymer to prepare aqueous light curing epoxy resinprepolymer; (3) making two prepolymers combined in cold manner, and using weak base for neutralization, and then adding water for dispersing and eliminating solvent under the condition of high-speed mixing, thereby getting self emulsifying type aqueous light curing compound resin. The invention can adjust the different function of resin (paint) through adjusting the mole ratio of raw material in theresin, and the prepared dispersoid has small particle diameter (20nm to 120 nm) and good performance, and industrialization is easy to be realized.
Description
Technical field:
The present invention relates to aqueous epoxy resins light-cured resin synthetic of aqueous polyurethane light-cured resin, the self-emulsifying type of self-emulsifying type, particularly by introducing homemade unsaturated polyester and homemade photolytic activity aqueous monomers raw material as the aqueous polyurethane light-cured resin of self-emulsifying type, to increase the two key density in the resin, reach the purpose that improves solidification rate, increases the curing cross-linked degree.
Background technology:
At present, both at home and abroad the overlay film on the paper generally is use polyethylene film, its complex manufacturing, and also this film can't degrade at all, also brought certain pressure to environment.Overlay film with on the coating rete substitute paper can significantly reduce the pollution to environment.Along with the raising of environmental requirement, water-borne coatings then is the trend of coating development from now on.Yet the paper water-absorbent is strong, inflammable, has been brought very big difficulty in the paper coating film forming.And ultraviolet-curing paint makes water-borne coatings film forming on paper become possibility because the characteristic of himself meets solidifying requirements fully.As the United States Patent (USP) net respectively on October 29th, 2002 disclosed publication number be 6,472,028, on April 12nd, 2005, disclosed publication number was 6,878,413 patent of invention " is applied in the preparation method of the hard-gloss paint of print surface ", be on the paper of printed matter, to be coated with aqueous polyurethane coating, under the condition of photocuring, obtain waterproof coating with high glossiness.
The aqueous polyurethane macromolecular main chain is to be formed by rigid chain segment (hard section) block that subambient soft segment of second-order transition temperature (soft section) and second-order transition temperature are higher than room temperature, simultaneously hydrophilic radical is grafted on the molecular backbone, gives its water-dispersible.Give film forming matter flexibility and elasticity for soft section, hard section is given the mechanical strength of film forming matter.Reactive force is big between soft segment molecule, and cohesive strength is big, and physical strength is just high.Be made up of oligomer polyol (normally polyethers or polyester polyol) for soft section, hard section is made up of polyisocyanates or itself and small molecule chain extender.Because its special structure, its Main physical character is characteristics such as intensity height, wear-resisting, oil resistant.
The special molecular structure of aqueous epoxy resins, its different performance has been given in each molecular composition, make epoxypaint have excellent cohesive force, chemical-resistant resistance, protection against corrosion and water resistance, numerous advantages such as film adhesive is good, and thermostability and electrical insulating property are good.
With of the cold assembly blend of two kinds of resins by different ratios, make the performance of two kinds of resins obtain better complementation, make the coating film performance better, meet or exceed the performance of polyethylene overlay film.
Summary of the invention:
The objective of the invention is in order to obtain a kind of expediting setting type aquosity ultraviolet light solidifying composition that can replace polyethylene overlay film on the printed matter.
The realization of purpose of the present invention, to utilize the characteristics of molecular structure of aqueous polyurethane and aqueous epoxy resins,, make the performance of two kinds of resins obtain better complementation of the cold assembly blend of two kinds of resins by different ratios, make the coating film performance better, meet or exceed the performance of polyethylene overlay film.
The present invention is characterized in that comprising the steps:
(1) the aqueous polyurethane performed polymer of synthetic self-emulsifying type:
Under protection of nitrogen gas, it with mass parts 20～40 parts terminal hydroxy group unsaturated polymer, 2～8 parts chainextender, 1～5 part acetone, 0.01～0.1 part catalyzer is in the four-hole reactor that has stirring, temperature in the reactor should be controlled between 55 ℃～90 ℃, the dropping mass ratio is 30～50 parts a polyisocyanates, and insulation reaction 0.5～1 hour is measured NCO content and reached theoretical value, according to experimental design, the hydroxyl reaction degree in the raw material is 1 o'clock a NCO content; The aqueous monomers that contains terminal hydroxy group that adds 5～10 parts, reaction is measured NCO content and is reached theoretical value, and according to experimental design, the hydroxyl reaction degree in the raw material is 1 o'clock a NCO content; Add a certain amount of end-capping reagent, measure NCO content≤0.12%; Add the encapsulant of metering, the sealing dosage of adding is measurement standard with complete closed NCO, in 0.5～1 hour reaction times, obtains the aqueous polyurethane performed polymer of self-emulsifying type;
Wherein: chainextender can choose 1, ammediol, 1, and 4-butyleneglycol, 1, one or more in the 6-hexylene glycol are used with; Polyisocyanates can be chosen two (4-isocyanate phenyl) methane, tolylene diisocyanate, isophorone diisocyanate, 1, and one or more of 6-hexamethylene diisocyanate, two (4-isocyanate group cyclohexyl) methane are used with; Catalyzer can be chosen dibutyl tin laurate; End-capping reagent can choose vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate one or more use with; Encapsulant can choose methyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, di-n-butyl amine, diethanolamine, methyl ethyl ketoxime one or more use with.
The above-mentioned unsaturated polyester molecular weight that contains terminal hydroxy group is a standard to measure the hydroxyl value calculated value.Above-mentioned polyisocyanates constant current drips in reaction flask.The end-blocking dosage of above-mentioned adding is measurement standard with complete closed NCO.
In the aqueous polyurethane performed polymer of synthetic self-emulsifying type; the described terminal hydroxy group that contains contains hydroxy-terminated polymer and can select the commercially available unsaturated polyester that contains terminal hydroxy group for use; or obtain: under protection of nitrogen gas by following method preparation; it with mass parts 20～75 parts polyvalent alcohol; 20～65 parts polyprotonic acid or acid anhydrides (wherein contain 10-30 part unsaturated monomer; as maleic anhydride); 0.01～0.3 part catalyzer C; 0.1～0.2 part stopper, 0.1～0.4 part oxidation inhibitor are put into the four-hole reactor that has stirring, mass polymerization; by packing tower micromolecular water is drawn; after acid number is reduced to 25～30mgKOH/g resin, packing tower is removed, change water trap into; and the xylene solvent that adds 3～8 parts refluxes; reach the 5mgKOH/g resin to acid number, under vacuum filtration, remove dimethylbenzene, obtain containing the unsaturated polyester of terminal hydroxy group.
Wherein: described polyvalent alcohol can be chosen neopentyl glycol, 2-butyl-2-ethyl-1, ammediol, 1, and one or more in 4-butyleneglycol, 1,3 butylene glycol, hexylene glycol, glycerol, synourin oil, TriMethylolPropane(TMP), the tetramethylolmethane are used with; Polyprotonic acid can choose hexanodioic acid, Tetra hydro Phthalic anhydride, isophthalic anhydride, MALEIC ANHYDRIDE one or more use with; Catalyzer C can choose organic tin salt; It is 246 or 1010 oxidation inhibitor that oxidation inhibitor can be chosen commercial disignation; Stopper can be chosen Resorcinol or to the methylol methyl-phenoxide.
In the technology of preparation terminal hydroxy group unsaturated polymer, be warming up to 150 ℃, stir, slowly be warming up to 190 ℃, the heating-up time is 2-3 hour, after 190 ℃ of insulation reaction 0.5-1 hours, after reaction is finished, carried out the vacuum decompression drying 0.5～2 hour, vacuum tightness is at least 0.050kPa, and temperature is 40 ℃～105 ℃.
In the aqueous polyurethane performed polymer of synthetic self-emulsifying type; the described aqueous monomers that contains terminal hydroxy group can be selected commercially available dimethylol propionic acid or dimethylolpropionic acid for use; or obtain: under protection of nitrogen gas by following method preparation; it with mass parts 130～150 parts TriMethylolPropane(TMP); 90～100 parts MALEIC ANHYDRIDE; 0.01-0.3 the catalyzer D of part; 0.1～0.2 part stopper adds and has in the four-hole reactor of agitator; oil bath react to acid number be the 240-245mgKOH/g resin; vacuum extracts moisture again, obtains containing the aqueous monomers of terminal hydroxy group.
Wherein: catalyzer D is an anhydrous sodium acetate; Stopper is a Resorcinol or to the methylol methyl-phenoxide.
Contain in the technology of aqueous monomers of terminal hydroxy group in preparation, temperature of reaction is preferably 80～90 ℃ between 60 ℃～110 ℃, reaction times 0.5-1 hour, necessary vacuum decompression was dry 0.5-2 hour after reaction was finished, and vacuum tightness is at least 0.050kPa, and temperature is at 40 ℃～105 ℃.
(2) the aqueous epoxy resins performed polymer of synthetic self-emulsifying type:
Under protection of nitrogen gas; with mass parts 300～1000 parts Resins, epoxy; 0.01～0.3 part catalyst A; 0.1 putting into to have ,～0.2 part stopper stirs the four-hole reactor; be heated to 90 ℃; begin to drip 144～180 parts acid; temperature in the reactor should be controlled at 90 ℃～120 ℃; react to acid number be below the 5mgKOH/g resin; the MALEIC ANHYDRIDE that adds 98 parts again; 0.01～0.3 part catalyst B, react to acid number be the 80mgKOH/g resin, obtain the aqueous epoxy resins performed polymer of self-emulsifying type.
Wherein: it is the Resins, epoxy of E-51, E-44 or E-20 that Resins, epoxy can be selected commercial disignation for use; Acid can be selected acrylic or methacrylic acid for use, drips in reaction flask with current constant mode; Catalyst A can be selected tetrabutylammonium iodide or hexadecyl amine bromide for use; Stopper can be selected Resorcinol for use or to the methylol methyl-phenoxide; Catalyst B can be selected anhydrous sodium acetate for use.
(3) preparation of aqueous photo-curing composite composition:
With mass parts is the aqueous polyurethane performed polymer of 10～95 parts self-emulsifying type, the aqueous epoxy resins performed polymer of 5～90 parts self-emulsifying type mixed 0.5～1 hour under stirring fast, add the weak base neutralization again, degree of neutralization is controlled at 75～95%, the temperature of reaction is controlled at 50 ℃～60 ℃, constant current dropping appropriate amount of deionized water is made into 30% water dispersion under stirring fast, in vacuum tightness is to remove solvent under the 0.050-0.070MPa, reduce to room temperature, add 0.1～1.0 part of light trigger, 400 order nylon net filters obtain expediting setting type aquosity ultraviolet light solidifying composition.
Wherein: described weak base can select for use ammoniacal liquor, triethylamine, tripropyl amine, 2-dimethylaminoethanol, 2-amino-2-methyl-1-propanol-kind or multiple using with; It is 1173 or 2959 light trigger that light trigger can be selected commercial disignation for use.
By the expediting setting type aquosity ultraviolet light solidifying composition that the inventive method makes, can be the emulsion of band blue light, the translucent body or the hyalosome of band blue light.
The expediting setting type aquosity ultraviolet light solidifying composition that makes by the inventive method, add various auxiliary agent such as proper quantity of defoaming agent, wetting agent, thickening material institute coatings formulated, can be used for coating to paper printing matter, coating has excellent properties to the paper Lacquer finish, can meet or exceed the performance of polyethylene overlay film.Because aqueous coating can be degraded, and can significantly reduce the pollution to environment.
The present invention relates to hard-gloss paint that the preparation of chemistry, physical bond method is applied in printed matter surface with light curable water-borne resin.Preparation method of the present invention is that polyvalent alcohol is polycondensation together with MALEIC ANHYDRIDE and other polyprotonic acids, has reached the purpose of introducing two keys in the backbone molecule of polyester.Utilize the reaction of MALEIC ANHYDRIDE and TriMethylolPropane(TMP), make to have two keys in the aqueous monomers side chain.With unsaturated polyester and homemade aqueous monomers and polyisocyanates reaction, the aqueous polyurethane of preparation self-emulsifying type has increased the double bond content in the aqueous polyurethane greatly.Utilize double bond containing terminal hydroxy group monomer to seal remaining NCO group then, make the two key density maximizations in the aqueous polyurethane.The preparation of self-emulsifying water borne epoxy resin is with acid and epoxy ring-opening, utilizes the hydroxyl in the Resins, epoxy that the acid anhydrides open loop of MALEIC ANHYDRIDE is obtained the water-based group then, increases the two key density in the aqueous epoxy resins.Utilize the quick stirring of machinery, aqueous epoxy resins and aqueous polyurethane are mixed, after the neutralization, under stirring condition, drip deionized water, resin phase and water can be changed fully, obtain stable water dispersion.Coating through cryogenic baking, is removed moisture after coating on the printed matter, under the irradiation of UV-light, urethane and Resins, epoxy rete have formed inierpeneirating network structure, the excellent properties of maximum two kinds of resins of performance.
Specific implementation method:
Embodiment 1:
(1) under protection of nitrogen gas; with 19.784gMA (maleic anhydride); (44.204gAD hexanodioic acid); (33.372gNPG neopentyl glycol); 26.810gBEPD (2-butyl-2-ethyl-1; ammediol), 17.560gTMPME (TriMethylolPropane(TMP) mono allyl ether), the catalyzer of 0.200g (organic tin salt); 0.100g the stopper (to the methylol methyl-phenoxide) of part; 0.200g oxidation inhibitor put into and have stirring, thermometer, nitrogen airway; in the four-hole reaction flask of packing tower; be warming up to 150 ℃, stir, slowly be warming up to 190 ℃ (heating-up time is 3 hours).After 0.5 hour, begin to measure acid number, 190 ℃ of insulations after acid number is reduced to 25～30mgKOH/g resin, packing tower is removed, change water trap into, and add the xylene solvent backflow of 5g, to acid number≤5mgKOH/g resin, under vacuum filtration, remove dimethylbenzene, after reaction is finished, vacuum decompression drying 0.5～2 hour, vacuum tightness is at least 0.050kPa, temperature is 60 ℃～80 ℃, obtains containing the unsaturated polyester (number-average molecular weight: 800) of terminal hydroxy group.
(2) under protection of nitrogen gas, with the above-mentioned unsaturated polyester of 37.028g, 4.394g butyleneglycol, 4.0ml acetone, 0.200g the catalyzer (dibutyl tin laurate) of part adds and has in the four-hole boiling flask of agitator, thermometer, nitrogen airway, prolong, stirs, and is warming up to 80 ℃, dripping mass ratio is the isophorone diisocyanate (IPDI) of 28.210g, and the dropping time is 1 hour; React after 2 hours, begin to measure NCO content, when NCO content reaches theoretical value (according to experimental design, hydroxyl reaction degree in the raw material is 1 o'clock a NCO content), the dimethylolpropionic acid (DMPA) that adds 4.800g, continue reaction down at 60 ℃, measure NCO content and reach theoretical value (according to experimental design, the hydroxyl reaction degree in the raw material is 1 o'clock a NCO content).Add 4.100gHEA, 9.400gSR444 end-capping reagent down at 50 ℃, reacted 3 hours, measure NCO content,, add the 0.510g diethanolamine, reacted 0.5 hour, obtain the ultraviolet light solidfication water polyurethane performed polymer of self-emulsifying type when NCO content≤0.12%.
(3) under protection of nitrogen gas; 45.00g Resins, epoxy (E-51) with the component design ratio; cetyl trimethylammonium bromide (1%); Resorcinol (1%) adds and has thermometer; prolong, the nitrogen airway has and stirs in the four-hole boiling flask; temperature to 90 ℃ in the question response bottle begins to drip 14.40g vinylformic acid.React after 2 hours, be warming up to 100 ℃, react after 3 hours, begin to measure acid number, to system acid number≤5mgKOH/g resin; Be cooled to 60 ℃, 1% anhydrous sodium acetate and the 9.800g MALEIC ANHYDRIDE that add design flow, after MALEIC ANHYDRIDE in the system is dissolved fully, be warming up to 90 ℃, react and measure acid number after 1 hour, acid number reaches theoretical value (according to design, calculating with carboxyl amount remaining after the MA open loop that adds) and gets final product, and obtains the aqueous epoxy resins performed polymer of self-emulsifying type.
(4) with the aqueous polyurethane performed polymer of 40.00g self-emulsifying type, the aqueous epoxy resins performed polymer of 10g self-emulsifying type mixed 0.5 hour under stirring fast, added the triethylamine neutralization, stirred fast to drip appropriate amount of deionized water down and be made into 30% water dispersion.50 ℃ is to remove solvent under the 0.050MPa in vacuum tightness, reduces to room temperature, adds 0.500 part of light trigger 1173,400 order nylon net filter, obtains aquosity ultraviolet light solidifying composition (resin).
This water-base resin adds various auxiliary agent such as proper quantity of defoaming agent (BYK-028,0.1%), wetting agent (BYK-346,0.5%), thickening material (RM-2020,1%) institute coatings formulated the paper Lacquer finish is had excellent properties.
Embodiment 2:
(1) under protection of nitrogen gas; with mass parts is the TriMethylolPropane(TMP) of 134.00g; 98.00g the MALEIC ANHYDRIDE of part; 0.300g catalyzer (anhydrous sodium acetate), the stopper of 0.100g (Resorcinol) is put into to have and is stirred the four-hole reaction flask, temperature is controlled at 90 ℃; react after 1 hour; begin to measure acid number, when acid number is the 240-250mgKOH/g resin, be cooled to 60 ℃.After reaction is finished, vacuum decompression drying 0.5～2 hour, vacuum tightness is at least 0.050kPa, and temperature is 60 ℃～80 ℃, obtains the photoactive aqueous functional monomer of terminal hydroxy group.
(2) under protection of nitrogen gas; with 18.116gMA (maleic anhydride); (26.984gAD hexanodioic acid), 37.523gNPG (neopentyl glycol), 8.118gBDO (butyleneglycol)); 0.100g catalyzer (organic tin salt); 0.100g the stopper (Resorcinol) of part, the oxidation inhibitor 246 of 0.150g is put into the four-hole reaction flask that has stirring, thermometer, nitrogen airway, packing tower, is warming up to 150 ℃; stir, slowly be warming up to 190 ℃ (heating-up time is 3 hours).190 ℃ the insulation 0.5 hour after, begin to measure acid number, after acid number is reduced to 25～30mgKOH/g resin, packing tower is removed, change water trap into, and the xylene solvent backflow of adding 5g, to acid number≤5mgKOH/g resin, under vacuum filtration, remove dimethylbenzene, reaction was finished the final vacuum drying under reduced pressure 0.5～2 hour, vacuum tightness is at least 0.050kPa, and temperature is 60 ℃～80 ℃, obtains containing the unsaturated polyester (number-average molecular weight: 1000) of terminal hydroxy group.
(3) under protection of nitrogen gas; the unsaturated polyester that contains terminal hydroxy group (molecular weight the is 1000) 26.134g that above-mentioned (2) are obtained; BDO4.662g; 4.0ml acetone; 0.0500g adding, catalyzer (dibutyl tin laurate) has agitator; thermometer; the nitrogen airway; in the four-hole boiling flask of prolong, stir, be warming up to 65 ℃; drip the IPDI of 42.406g; the dropping time is 1 hour, and insulation reaction began to measure NCO content after 2 hours; when NCO content reaches theoretical value (according to experimental design; hydroxyl reaction degree in the raw material is 1 o'clock a NCO content), the aqueous monomers that contains terminal hydroxy group that above-mentioned (1) of adding 7.504g obtains is cooled to 60 ℃ and continues reaction 3h down; measure NCO content and reach theoretical value (according to experimental design, the hydroxyl reaction degree in the raw material is 1 o'clock a NCO content).Add 7.150gHEA (Hydroxyethyl acrylate), 18.125gSR444 (pentaerythritol triacrylate) end-blocking, reacted 3 hours, measure NCO content, when NCO content≤0.12%, add the 1.100g diethanolamine, reacted 0.5 hour, obtain the aqueous polyurethane performed polymer of self-emulsifying type.
(4) with the aqueous polyurethane performed polymer of the self-emulsifying type of 45.00g, 5.00g self-emulsifying type aqueous epoxy resins performed polymer (sample that embodiment 1 they (3) obtains) 50 ℃, mixed 0.5～1 hour under stirring fast, the neutralization of adding triethylamine, the dropping appropriate amount of deionized water is made into 30% water dispersion under stirring fast.In vacuum tightness is to remove solvent under the 0.050MPa, reduces to room temperature, adds 0.500 part of light trigger 2959,400 order nylon net filter, obtains aquosity ultraviolet light solidifying composition (resin).
This composite waterborne resin adds various auxiliary agent such as proper quantity of defoaming agent (BYK-028,0.1%), wetting agent (BYK-346,0.5%), thickening material (RM-2020,1%) institute coatings formulated the paper Lacquer finish is had excellent properties.
Claims (6)
1. the preparation method of expediting setting type aquosity ultraviolet light solidifying composition is characterized in that comprising the steps:
(1) the aqueous polyurethane performed polymer of synthetic self-emulsifying type:
Under protection of nitrogen gas, it with mass parts 20～40 parts the unsaturated polyester that contains terminal hydroxy group, 2～8 parts chainextender, 1～5 part acetone, 0.01～0.1 part dibutyl tin laurate is in the four-hole reactor that has stirring, temperature in the reactor should be controlled between 55 ℃～90 ℃, the dropping mass ratio is 30～50 parts a polyisocyanates, and insulation reaction 0.5～1 hour is measured NCO content and reached theoretical value, according to experimental design, the hydroxyl reaction degree in the raw material is 1 o'clock a NCO content; The aqueous monomers that contains terminal hydroxy group that adds 5～10 parts, reaction is measured NCO content and is reached theoretical value, and according to experimental design, the hydroxyl reaction degree in the raw material is 1 o'clock a NCO content; Add a certain amount of end-capping reagent, measure NCO content≤0.12%; Add the encapsulant of metering, the sealing dosage of adding is measurement standard with complete closed NCO, in 0.5～1 hour reaction times, obtains the aqueous polyurethane performed polymer of self-emulsifying type;
Wherein, the aqueous monomers that contains terminal hydroxy group is dimethylol propionic acid or dimethylolpropionic acid, or obtain: under protection of nitrogen gas by following method preparation, with mass parts is 130～150 parts TriMethylolPropane(TMP), 90～100 parts MALEIC ANHYDRIDE, 0.01～0.3 part anhydrous sodium acetate, 0.1～0.2 part stopper adds and has in the four-hole reactor of agitator, oil bath react to acid number be the 240-245mgKOH/g resin, vacuum extracts moisture again, obtains containing the aqueous monomers of terminal hydroxy group;
(2) the aqueous epoxy resins performed polymer of synthetic self-emulsifying type:
Under protection of nitrogen gas, with mass parts 300～1000 parts Resins, epoxy, 0.01～0.3 part tetrabutylammonium iodide or cetyl trimethylammonium bromide, 0.1 putting into to have ,～0.2 part stopper stirs the four-hole reactor, be heated to 90 ℃, begin to drip 144～180 parts acrylic or methacrylic acid, temperature in the reactor should be controlled at 90 ℃～120 ℃, react to acid number be below the 5mgKOH/g resin, the MALEIC ANHYDRIDE that adds 98 parts again, 0.01～0.3 part anhydrous sodium acetate, react to acid number be the 80mgKOH/g resin, obtain the aqueous epoxy resins performed polymer of self-emulsifying type; Wherein, described Resins, epoxy is that commercial disignation is the Resins, epoxy of E-51, E-44 or E-20;
(3) preparation of aqueous photo-curing composite composition:
With mass parts is the aqueous polyurethane performed polymer of 10～95 parts self-emulsifying type, the aqueous epoxy resins performed polymer of 5～90 parts self-emulsifying type mixed 0.5～1 hour under stirring fast, add the weak base neutralization again, temperature of reaction is controlled between 50 ℃～60 ℃, the dropping appropriate amount of deionized water is made into 30% water dispersion under stirring fast, in vacuum tightness is to remove solvent under the 0.050-0.070MPa, reduce to room temperature, add 0.1～1.0 part of light trigger, 400 order nylon net filters obtain expediting setting type aquosity ultraviolet light solidifying composition.
2. the preparation method of expediting setting type aquosity ultraviolet light solidifying composition as claimed in claim 1; it is characterized in that: the described unsaturated polyester that contains terminal hydroxy group is obtained by following method preparation: under protection of nitrogen gas; it with mass parts 20～75 parts polyvalent alcohol; 20～65 parts polyprotonic acid or acid anhydrides; 0.01～0.3 part organic tin salt; 0.1～0.2 part Resorcinol or to the methylol methyl-phenoxide; 0.1～0.4 part oxidation inhibitor is put into the four-hole reactor that has stirring; mass polymerization; by packing tower micromolecular water is drawn, after acid number is reduced to 25～30mgKOH/g resin, packing tower is removed; change water trap into; and the xylene solvent that adds 3～8 parts refluxes, and reaches the 5mgKOH/g resin to acid number, removes dimethylbenzene under vacuum filtration; obtain containing the unsaturated polyester of terminal hydroxy group
Wherein, described polyvalent alcohol is the TriMethylolPropane(TMP) mono allyl ether, perhaps being the TriMethylolPropane(TMP) mono allyl ether mixes use with following alcohol, described alcohol is neopentyl glycol, 2-butyl-2-ethyl-1, ammediol, 1, one or more of 4-butyleneglycol, 1,3 butylene glycol, hexylene glycol, glycerol, TriMethylolPropane(TMP) and tetramethylolmethane; Polyprotonic acid or acid anhydrides are MALEIC ANHYDRIDE, and perhaps being MALEIC ANHYDRIDE mixes use with following acid or acid anhydrides, and described acid or acid anhydrides are one or more of hexanodioic acid, Tetra hydro Phthalic anhydride and isophthalic anhydride; Oxidation inhibitor is that commercial disignation is 246 or 1010 oxidation inhibitor.
3. the preparation method of expediting setting type aquosity ultraviolet light solidifying composition as claimed in claim 2, it is characterized in that: contain in the technology of unsaturated polyester of terminal hydroxy group in preparation, be warming up to 150 ℃, stir, slowly be warming up to 190 ℃, heating-up time is 2～3 hours, 190 ℃ of insulation reaction 0.5～1 hour, after reaction is finished, vacuum decompression drying 0.5～2 hour, vacuum tightness is at least 0.050kPa, and temperature is 40 ℃～105 ℃.
4. the preparation method of expediting setting type aquosity ultraviolet light solidifying composition as claimed in claim 1, it is characterized in that: when preparation contains the terminal hydroxy group aqueous monomers, temperature of reaction is between 60 ℃～110 ℃, be preferably 80～90 ℃, reaction times 0.5-1 hour, after reaction is finished, vacuum decompression drying 0.5～2 hour, vacuum tightness is at least 0.050kPa, and temperature is at 40 ℃～105 ℃.
5. the preparation method of expediting setting type aquosity ultraviolet light solidifying composition as claimed in claim 1, it is characterized in that: described chainextender is 1, ammediol, 1,4-butyleneglycol, 1, one or more of 6-hexylene glycol are used with; Polyisocyanates is two (4-isocyanate phenyl) methane, tolylene diisocyanate, isophorone diisocyanate, 1, and one or more of 6-hexamethylene diisocyanate, two (4-isocyanate group cyclohexyl) methane are used with; End-capping reagent is that one or more of vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate are used with; Encapsulant is that one or more of methyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, di-n-butyl amine, diethanolamine, methyl ethyl ketoxime are used with.
6. the preparation method of expediting setting type aquosity ultraviolet light solidifying composition as claimed in claim 1 is characterized in that: described weak base is that one or more of ammoniacal liquor, triethylamine, tripropyl amine, 2-dimethylaminoethanol, 2-amino-2-methyl-1-propanol are used with; Light trigger is that commercial disignation is 1173 or 2959 light trigger.
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| CN101343341B (en) * | 2008-08-12 | 2010-06-23 | 无锡市虎皇漆业有限公司 | Preparation method for acrylic acid modified polyurethane water dispersion |
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