CN106833111A - A kind of glass ink - Google Patents
A kind of glass ink Download PDFInfo
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- CN106833111A CN106833111A CN201510880846.3A CN201510880846A CN106833111A CN 106833111 A CN106833111 A CN 106833111A CN 201510880846 A CN201510880846 A CN 201510880846A CN 106833111 A CN106833111 A CN 106833111A
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a kind of glass ink, including resin Composition and curing component, it is characterised in that the resin Composition contains acrylic acid modified bisphenol A type epoxy resin, the curing component contains isocyanate resin., in hot setting, paint film is without Yellowing for the glass ink that the present invention is provided.
Description
Technical field
The invention belongs to glass ink field, more particularly to the white glass ink that a kind of high temperature resistant turns yellow.
Background technology
At present, the film forming matter of mobile phone glass frame ink widely uses epoxy resin, because its is cheap and has on glass excellent adhesive force, thus is the first-selected resin of glass ink, and its functional group is mainly epoxide group.This glass ink includes resin Composition and curing component, and resin Composition is mainly by epoxy resin, pigment, filler, various auxiliary agents（Such as coupling agent, levelling agent, defoamer）Constituted with solvent.It is ground to below 15 microns of fineness by three-roll grinder in production and is obtained.Curing component is polyamine curing agent, needs to mix the two when using, and under high-temperature baking, epoxy resin and amine quickly crosslink curing reaction and forms the paint film for meeting performance requirement.
, it is known that prior art uses epoxy resin and amine double-component system, in high temperature, 140 DEG C -160 DEG C are toasted 30-60 minutes, and paint film can occur the problem of xanthochromia.The reason for producing xanthochromia, it is considered that：（1）Amine curing agent aoxidizes xanthochromia at high temperature；（2）The unhindered amina of amine curing agent directly and epoxy-based polymerization, discharges heat, causes local temperature too high in hot environment, accelerates xanthochromia.
The content of the invention
The invention aims to solve in the prior art, in hot setting, xanthochromia problem in paint film to glass ink there is, there is provided it is a kind of under the high temperature conditions, glass ink of the paint film without Yellowing.
For the problem that prior art is present, the invention provides a kind of glass ink, including resin Composition and curing component, the resin Composition contains acrylic acid modified bisphenol A type epoxy resin, and the curing component contains isocyanate resin.
In the glass ink that the present invention is provided, using acrylic acid modified bisphenol A type epoxy resin, acrylic modified epoxy resin refer to acrylic acid in the presence of ionized catalyst, make epoxy ring-opening, introduce hydroxyl（-OH）Functional group modification, the double grading for making it have epoxy resin and Hydroxylated acrylic resin concurrently, the present invention specific excellent adhesive force on glass from unique acrylic acid modified bisphenol A type epoxy resin, but it is poor as branched linear polymeric chemical resistance, present inventors have unexpectedly found that from PIC as curing agent, the synergy of the unique acrylic acid modified bisphenol A type epoxy resin selected with the present invention, the shortcoming of epoxy resin can preferably be overcome, the properties of paint film can be effectively improved.The hydroxyl of the acrylic acid modified bisphenol A type epoxy resin of specific material of the invention（-OH）With-NCO the functional group reactionses on polyisocyanate molecules chain, adhesive force of the obtained paint film on glass is strong, without Yellowing.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that specific embodiment described herein is merely to illustrate and explain the present invention, it is not intended to limit the invention.
Specifically, the invention provides a kind of glass ink, including resin Composition and curing component, the resin Composition contains acrylic acid modified bisphenol A type epoxy resin；The curing component contains isocyanate resin.
The resin that the present invention is used is acrylic acid modified bisphenol A type epoxy resin, acrylic modified epoxy resin refer to acrylic acid in the presence of ionized catalyst, make epoxy ring-opening, introduce hydroxyl（-OH）Functional group modification, the double grading for making it have epoxy resin and Hydroxylated acrylic resin concurrently, the present invention specific excellent adhesive force on glass from unique acrylic acid modified bisphenol A type epoxy resin, but it is poor as branched linear polymeric chemical resistance, present inventors have unexpectedly found that from PIC as curing agent, the synergy of the unique acrylic acid modified bisphenol A type epoxy resin selected with the present invention, the shortcoming of epoxy resin can preferably be overcome, the properties of paint film can be effectively improved.The hydroxyl of the acrylic acid modified bisphenol A type epoxy resin of specific material of the invention（-OH）With-NCO the functional group reactionses on polyisocyanate molecules chain, adhesive force of the obtained paint film on glass is strong, without Yellowing.
In the present invention, acrylic acid modified bisphenol A type epoxy resin, hydroxyl value is 140-220mgKOH/g, and preferred hydroxyl value makes the crosslink density of paint film suitable, and paint film ethanol-tolerant is wiped, at the same paint film will not embrittlement, do not interfere with adhesive force, it is preferable that 150-210mgKOH/g.
Acrylic acid modified bisphenol A type epoxy resin of the present invention, can specifically select the A102 modified epoxies of Taiwan LAOLAI companies, hydroxyl value 160mgKOH/g, Hexion（HEXION）The modified epoxy trees of Epikote 1009 of chemical industry, the mgKOH/g of hydroxyl value 210.
The isocyanate resin that the present invention is provided is preferably selected from one or more in toluene di-isocyanate(TDI), IPDI, hexamethylene-diisocyanate and dicyclohexyl methyl hydride diisocyanate, 4,4 '-MDI, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, dicyclohexyl methyl hydride diisocyanate tripolymer, hexahydrotoluene diisocyanate trimer.Under preferable case, including hexamethylene diisocyanate trimer（HDI）, you being hexamethylene diisocyanate trimer（HDI）Or hexamethylene diisocyanate trimer（HDI）With the mixture of other isocyanate resins.Further optimize the weatherability and gloss retention of ink, non yellowing.Specifically, TPA 90SB, the Desmodur-HDI base N3390BA of Bayer AG of Asahi Kasei Corporation can be selected, admittedly containing 90%, NCO bases content 19.6%.The present invention is by the NCO of isocyanate resin（-NCO）With the hydroxyl of acrylic acid modified bisphenol A type epoxy resin（-OH）Reaction generates carbamate and makes film curing.
In the ink formulations that the present invention is provided, it is preferable that the hydroxyl mol ratio in the NCO of the isocyanate resin and acrylic acid modified bisphenol A type epoxy resin is 1.0-1.2：1, i.e.-NCO are 1.0-1.2 with the mol ratio of-OH：1, it is preferable that 1.0-1.1：1.
It is preferred that, pigment is also contained in resin Composition, pigment of the present invention can be selected from one or more in rutile type titanium white, anatase thpe white powder, zinc oxide, lithopone, it is preferable that rutile type titanium white.CR90, CR93 of Ishihara Sangyo Kaisha, Ltd., the CR828 in CR826, CR828 of TRONOX companies can specifically be selected.
It is preferred that, glass ink of the present invention also contains anti-yellowing agent, the anti-yellowing agent is selected from one or more in Hinered phenols anti-yellowing agent, hindered amines anti-yellowing agent, phosphorous acid esters anti-yellowing agent, sulphur class anti-yellowing agent, it is preferred that, Hinered phenols anti-yellowing agent and phosphorous acid esters anti-yellowing agent.Anti-yellowing dose of Hinered phenols can catch peroxylradicals, and anti-yellowing dose of energy hydroperoxide decomposition of phosphorous acid esters, the two collaboration, effect is more preferable.
Resin Composition of the present invention also contains one or more in coupling agent, levelling agent, auxiliary rheological agents, defoamer, dispersant and solvent.
Coupling agent of the present invention is selected from one or more in silanes, titanate ester, organochromium complexes, aluminic acid compound, preferably silane coupler.Glass is silicate material, silane coupler one end is hydrolyzable group, and the other end is the organic group of non-hydrolytic, and chemical bond can be formed with glass surface group after hydrolyzable groups hydrolysis, resin chemical in non-hydrolytic group and ink is combined, and is formed " molecular bridge ".
Levelling agent of the present invention is selected from one or more in Siloxane-Oxyalkylene Copolymers, alkyl-modified polysiloxanes, polyacrylate, polyester-modified polysiloxanes and its solution, it is preferable that polyacrylate solution.Polyacrylate levelling agent can not only improve the levelability of ink, prevent shrinkage cavity, and not influence recoatability or the ply adhesion of ink.
Auxiliary rheological agents of the present invention are selected from one or more in organobentonite, aerosil, castor oil derivative, polyamide wax, Tissuemat E, modified urea solution, it is preferable that modified urea solution.Main is liquid because of it, it is easy to added, and addition is few, rheology efficiency high.After such auxiliary rheological agents add coating system, three-dimensional net structure can be set up, the pseudoplastic behavior and thixotropy of formation can anti-pigment sedimentations.
Defoamer of the present invention is selected from one or more in organosiloxane, polyethers, polyethylene glycol, ethylene-acrylic acid copolymer or polyglyceryl fatty acid ester, it is preferred that, organosiloxane, organosiloxane defoamer defoaming effectiveness is high, can obtain optimal froth breaking with minimum Incompatible Substance.
Dispersant of the present invention is selected from one or more in modified polyurethane high polymer, modified polyacrylate polymer, polyester modification polyphosphate compound, polyvalent carboxylic acid's class.It is preferred that, the wetting dispersing agent of polyvalent carboxylic acid's class, specifically, from the BYK-110 of BYK companies, it is particularly well-suited to inorganic pigment, especially titanium dioxide, not only consumption is few, wetting and dispersing efficiency high, and can substantially reduce mill base viscosity.
Solvent of the present invention is selected from one or more in propylene glycol methyl ether acetate, nylon acid dimethyl ester, cyclohexanone, it is preferable that nylon acid dimethyl ester.Nylon acid dimethyl ester has the advantages that low toxicity, solvability are strong, rate of volatilization is low, smell is small.
The present invention is on the basis of resin components gross weight, the resin Composition contains acrylic acid modified bisphenol A type epoxy resin 22%-31%, pigment 33%-40%, dispersant 1%-3%, coupling agent 0.5%-1%, levelling agent 0.05%-1%, defoamer 0.1%-0.7%, auxiliary rheological agents 0.1-0.4%, solvent 27%-38%, anti-yellowing agent 0.3%-1%.
The specific manufacture craft of resin Composition of the present invention is：（1）First acrylic acid modified bisphenol A type epoxy resin is dissolved in the solvent of metal bucket splendid attire；（2）Again by solvent acrylic acid modified bisphenol A type epoxy resin solution and dispersant, sequentially add pigment, auxiliary rheological agents and disperse at a high speed, stir；（3）The scattered material of high speed is ground to below 15 microns of fineness on three-roll grinder, stops grinding；（4）Ground material is weighed, levelling agent, coupling agent, defoamer is proportionally added into, high-speed stirred is uniform, anti-yellowing agent filtering, packaging.
In the present invention, curing component is directly from commercially available isocyanate resin.
Resin Composition and curing component in the present invention mixed by a certain percentage, according to live viscosity requirement, can add solvent nylon acid dimethyl ester open it is dilute adjust viscosity, after mixing up ink, upper screen printer print.Advantage by above-mentioned formula and the glass ink of technique productions is：When the good glass ink of silk-screen is toasted 30-60 minutes under 140 DEG C of -160 DEG C of high temperature, the hydroxyl (- OH) of the modified epoxy containing hydroxyl and NCO (- NCO) radical reaction of isocyanate resin, generate the macromolecular of polyurethane chain segment structure, high temperature Yellowing is not produced, hence it is evident that better than prior art.
Embodiment 1
The present embodiment is used to illustrate coating disclosed by the invention and preparation method thereof.
The composition and percentage by weight of the present embodiment white glass ink resin component are as follows：Contain acrylic acid modified bisphenol A type epoxy resin（Resin A 102, the mgKOH/g of hydroxyl value 160）29%th, dispersant（The BYK-110 of BYK companies）3%th, titanium dioxide (CR828 of TRONOX companies) 37.8%, levelling agent (BYK-358N of BYK companies) 0.2%, defoamer (TEGO 900 of Di Gao companies) 0.3%, auxiliary rheological agents (BYK-410 of BYK companies) 0.2%, coupling agent (Z-6040 of Dow Corning Corporation) 0.5%, anti-yellowing agent（The V-76P of the Chemical Co., Ltd. of Guangzhou will one）0.3%th, nylon acid dimethyl ester 28.7%.Modified epoxy in resin Composition and solvent nylon acid dimethyl ester is first solvent, then ground by three-roll grinder with dispersant, titanium dioxide, auxiliary rheological agents, ground rear addition levelling agent, coupling agent, defoamer are uniformly dispersed at a high speed.
The composition and percentage by weight of curing component are as follows：Isocyanate resin（The N3390 BA/SN of Beyer Co., Ltd, admittedly containing 90%, NCO bases content 19.6%）100%.On the basis of glass ink gross weight, isocyanate resin is 19.7%, and the hydroxyl mol ratio in NCO and acrylic acid modified bisphenol A type epoxy resin is 1：1, specifically it is shown in Table 1.
The resin Composition and curing component of ink are pressed 100:19.7 part by weight mixing, according to viscosity needs, solvent nylon acid dimethyl ester is added to open dilute regulation viscosity, 380 mesh silk screen silk-screens are on glass, toasted 30 minutes, 60 minutes and 120 minutes respectively at 150 DEG C, respectively obtain coating S11, S12, S13 of film thickness 6um.
Embodiment 2
The present embodiment is used to illustrate coating disclosed by the invention and preparation method thereof.
The composition and percentage by weight of the present embodiment white glass ink resin component are as follows：Contain acrylic acid modified bisphenol A type epoxy resin（Resin Epikote 1009, hydroxyl value 210
mgKOH/g）24.3%th, dispersant（The BYK-110 of BYK companies）3%th, titanium dioxide (CR828 of TRONOX companies) 35%, levelling agent (BYK-358N of BYK companies) 0.2%, defoamer (TEGO 900 of Di Gao companies) 0.3%, auxiliary rheological agents (BYK-410 of BYK companies) 0.2%, coupling agent (Z-6040 of Dow Corning Corporation) 0.5%, anti-yellowing agent（The V-76P of the Chemical Co., Ltd. of Guangzhou will one）0.3%th, solvent nylon acid dimethyl ester 36.2%.Modified epoxy in resin Composition and solvent nylon acid dimethyl ester is first solvent, then ground by three-roll grinder with dispersant, titanium dioxide, auxiliary rheological agents, ground rear addition levelling agent, coupling agent, defoamer are uniformly dispersed at a high speed.
The composition and percentage by weight of curing component are as follows：Isocyanate resin（The N3390 BA/SN of Beyer Co., Ltd, admittedly containing 90%, NCO bases content 19.6%）100%.On the basis of glass ink gross weight, isocyanate resin is 23.8%, and the hydroxyl mol ratio in NCO and acrylic acid modified bisphenol A type epoxy resin is 1.1：1, specifically it is shown in Table 1.
The resin Composition and curing component of ink are pressed 100:23.8 part by weight mixing, according to viscosity needs, solvent nylon acid dimethyl ester is added to open dilute regulation viscosity, 380 mesh silk screen silk-screens are on glass, toasted 30 minutes, 60 minutes and 120 minutes respectively at 150 DEG C, respectively obtain coating S21, S22, S23 of film thickness 6um.
Embodiment 3
The present embodiment is used to illustrate coating disclosed by the invention and preparation method thereof.
The composition and percentage by weight of the present embodiment white glass ink resin component are as follows：Modified epoxy containing hydroxyl（Resin A 102, the mgKOH/g of hydroxyl value 160）29%th, dispersant（The BYK-110 of BYK companies）3%th, titanium dioxide (CR828 of TRONOX companies) 37.8%, levelling agent (BYK-358N of BYK companies) 0.2%, defoamer (TEGO 900 of Di Gao companies) 0.3%, auxiliary rheological agents (BYK-410 of BYK companies) 0.2%, coupling agent (Z-6040 of Dow Corning Corporation) 0.5%, anti-yellowing agent（The V-76P of the Chemical Co., Ltd. of Guangzhou will one）0.3%th, nylon acid dimethyl ester 28.7%.Modified epoxy in resin Composition and solvent nylon acid dimethyl ester is first solvent, then ground by three-roll grinder with dispersant, titanium dioxide, auxiliary rheological agents, ground rear addition levelling agent, coupling agent, defoamer are uniformly dispersed at a high speed.
The composition and percentage by weight of curing component are as follows：Isocyanate resin（The N3390 BA/SN of Beyer Co., Ltd, admittedly containing 90%, NCO bases content 19.6%）100%.On the basis of glass ink gross weight, isocyanate resin is 23.6%, and the hydroxyl mol ratio in NCO and acrylic acid modified bisphenol A type epoxy resin is 1.2：1, specifically it is shown in Table 1.
The resin Composition and curing component of ink are pressed 100:23.6 part by weight mixing, according to viscosity needs, solvent nylon acid dimethyl ester is added to open dilute regulation viscosity, 380 mesh silk screen silk-screens are on glass, toasted 30 minutes, 60 minutes and 120 minutes respectively at 150 DEG C, respectively obtain coating S31, S32, S33 of film thickness 6um.
Embodiment 4
This comparative example is used for comparative illustration coating disclosed by the invention and preparation method thereof.
The composition and percentage by weight of this comparative example white glass ink resin component are as follows：Modified epoxy containing hydroxyl（Resin A 102, the mgKOH/g of hydroxyl value 160）29%th, dispersant（The BYK-110 of BYK companies）3%th, titanium dioxide (CR828 of TRONOX companies) 37.8%, levelling agent (BYK-358N of BYK companies) 0.2%, defoamer (TEGO 900 of Di Gao companies) 0.3%, auxiliary rheological agents (BYK-410 of BYK companies) 0.2%, coupling agent (Z-6040 of Dow Corning Corporation) 0.5%, anti-yellowing agent（The V-76P of the Chemical Co., Ltd. of Guangzhou will one）0.3%th, nylon acid dimethyl ester 28.7%.Modified epoxy in resin Composition and solvent nylon acid dimethyl ester is first solvent, then ground by three-roll grinder with dispersant, titanium dioxide, auxiliary rheological agents, ground rear addition levelling agent, coupling agent, defoamer are uniformly dispersed at a high speed.
The composition and percentage by weight of curing component are as follows：Isocyanate resin（The N3390 BA/SN of Beyer Co., Ltd, admittedly containing 90%, NCO bases content 19.6%）100%.On the basis of glass ink gross weight, isocyanate resin is 29.5%, and the hydroxyl mol ratio in NCO and acrylic acid modified bisphenol A type epoxy resin is 1.5：1, specifically it is shown in Table 1.
The resin Composition and curing component of ink are pressed 100:29.5 part by weight mixing, according to viscosity needs, solvent nylon acid dimethyl ester is added to open dilute regulation viscosity, 380 mesh silk screen silk-screens are on glass, toasted 30 minutes, 60 minutes and 120 minutes respectively at 150 DEG C, respectively obtain coating S41, S42, S43 of film thickness 6um.
Embodiment 5
The present embodiment is used to illustrate coating disclosed by the invention and preparation method thereof.
The composition and percentage by weight of the present embodiment white glass ink resin component are as follows：Contain acrylic acid modified bisphenol A type epoxy resin（Resin A 102, the mgKOH/g of hydroxyl value 160）29%th, dispersant（The BYK-110 of BYK companies）3%th, levelling agent (BYK-358N of BYK companies) 0.2%, defoamer (TEGO 900 of Di Gao companies) 0.3%, auxiliary rheological agents (BYK-410 of BYK companies) 0.2%, coupling agent (Z-6040 of Dow Corning Corporation) 0.5%, nylon acid dimethyl ester 66.8%.Modified epoxy in resin Composition and solvent nylon acid dimethyl ester is first solvent, then pass through with dispersant, auxiliary rheological agents, levelling agent, coupling agent, defoamer, high-speed stirred is uniformly dispersed.
The composition and percentage by weight of curing component are as follows：Isocyanate resin（The N3390 BA/SN of Beyer Co., Ltd, admittedly containing 90%, NCO bases content 19.6%）100%.On the basis of glass ink gross weight, isocyanate resin is 19.7%, and the hydroxyl mol ratio in NCO and acrylic acid modified bisphenol A type epoxy resin is 1：1, specifically it is shown in Table 1.
The resin Composition and curing component of ink are pressed 100:19.7 part by weight mixing, is coated on glass, is toasted 30 minutes, 60 minutes and 120 minutes respectively at 150 DEG C, respectively obtains coating S51, S52, S53 of film thickness 6um.
Comparative example 1
This comparative example is used for comparative illustration coating disclosed by the invention and preparation method thereof.
The composition and percentage by weight of this comparative example white glass ink resin component are as follows：Modified epoxy containing hydroxyl（Resin A 102, the mgKOH/g of hydroxyl value 160）29%th, dispersant（The BYK-110 of BYK companies）3%th, titanium dioxide (CR828 of TRONOX companies) 37.8%, levelling agent (BYK-358N of BYK companies) 0.2%, defoamer (TEGO 900 of Di Gao companies) 0.3%, auxiliary rheological agents (BYK-410 of BYK companies) 0.2%, coupling agent (Z-6040 of Dow Corning Corporation) 0.5%, anti-yellowing agent（The V-76P of the Chemical Co., Ltd. of Guangzhou will one）0.3%th, nylon acid dimethyl ester 28.7%.Modified epoxy in resin Composition and nylon acid dimethyl ester is first solvent, then ground by three-roll grinder with dispersant, titanium dioxide, auxiliary rheological agents, ground rear addition levelling agent, coupling agent, defoamer, anti-yellowing agent are uniformly dispersed at a high speed.
The composition and percentage by weight of curing component are as follows：Blocked isocyanate resin（The N3175 SN of Beyer Co., Ltd, admittedly containing 75%, NCO bases content 11.1%）100%.So-called blocked isocyanate, refers to by reactive isocyanate groups（NCO）With the reaction of some compounds, the compound of ambient-temp-stable is generated, NCO group temporary protection is got up, but at high temperature, the compound can be decomposed again（Deblocking reaction）It is isocyanates.On the basis of glass ink gross weight, blocked isocyanate resin is 41.7%.Hydroxyl mol ratio in NCO and acrylic acid modified bisphenol A type epoxy resin is 1：1, specifically it is shown in Table 1.
The resin Composition and curing component of ink are pressed 100:41.7 part by weight mixing, according to viscosity needs, solvent nylon acid dimethyl ester is added to open dilute regulation viscosity, 380 mesh silk screen silk-screens are on glass, toasted 30 minutes, 60 minutes and 120 minutes respectively at 150 DEG C, respectively obtain coating D11, D12, D13 of film thickness 6um.
Table 1
Performance test.
Adhesive force is tested
The measure of adhesive force is carried out as follows：100 1 millimeter × 1 millimeter of square lattice are drawn in sprayed surface with stroke lattice device, the adhesive tape of the model 600 produced with Minnesota Mining and Manufacturing Company is smooth to be bonded on grid, a space not being stayed, then vertically being uncovered with prestissimo, depainting is whether there is at observation scratching edge.As being 5B without coming off, depainting amount is 4B in 0-5%, is 3B between 5-15%, is 2B between 15-35%, is B between 35-65%, is 0B more than 65%.
Discoloration ranking
According to the visual colorimetric determination standard of GB/T9761, judge the intensity of variation of coating color and graded.Rating scale such as table 2 below：
Table 2
The result such as table 3 below for obtaining is tested above.
Table 3
Be can be seen that from the test result of table 3：Embodiment 1, embodiment 2, embodiment 3 show, ink disclosed by the invention selects acrylic acid modified epoxy resin, hydroxy functional group and the isocyanate resin reaction contained using it, coating has excellent resisting high-temperature yellowing performance in high-temperature baking environment after reaction solidification, and coating has excellent adhesive force to glass surface.Embodiment 1 relatively shows that isocyanate resin consumption excess will not produce high temperature xanthochromia with implementation 4, and because crosslinking is excessive, paint film becomes fragile, and adhesive force is had a certain impact.Embodiment 5 shows that the transparent paint film of free white powder also has preferable yellowing resistance in hot environment, due to not having during anti-yellowing agent, prolonged high-temperature baking, paint film still has very slight discoloration, illustrate under long-time hot environment, anti-yellowing agent can play a part of yellowing-resistant.Embodiment 1 and comparative example 1 compare and show, case type isocyanate resin and modified epoxy react, it is easier to produce xanthochromia.
In sum, the white glass ink that the present invention is provided, from acrylic acid modified bisphenol A type epoxy resin as resin Composition matrix resin, from isocyanate resin as curing component, reacted using the hydroxyl of acrylic acid modified bisphenol A type epoxy resin and the NCO group of isocyanate resin, the cured coating film obtained under hot conditions, not only has excellent adhesive force, and will not produce high temperature xanthochromia on glass.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. should be included within the scope of the present invention.
Claims (13)
1. a kind of glass ink, including resin Composition and curing component, it is characterised in that the resin Composition contains acrylic acid modified bisphenol A type epoxy resin, the curing component contains isocyanate resin.
2. glass ink according to claim 1, it is characterised in that the acrylic acid modified bisphenol A type epoxy resin hydroxyl value is 140-220mgKOH/g.
3. glass ink according to claim 2, it is characterised in that the acrylic acid modified bisphenol A type epoxy resin hydroxyl value is 150-210mgKOH/g.
4. glass ink according to claim 1, it is characterized in that, the isocyanate resin is selected from toluene di-isocyanate(TDI), IPDI, hexamethylene-diisocyanate, dicyclohexyl methyl hydride diisocyanate, 4, one or more in 4 '-MDI, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, dicyclohexyl methyl hydride diisocyanate tripolymer, hexahydrotoluene diisocyanate trimer.
5. glass ink according to claim 4, it is characterised in that the isocyanate resin includes hexamethylene diisocyanate trimer.
6. glass ink according to claim 1, it is characterised in that the hydroxyl mol ratio in the NCO of the isocyanate resin and acrylic acid modified bisphenol A type epoxy resin is 1.0-1.2：1.
7. glass ink according to claim 6, it is characterised in that the hydroxyl mol ratio in the NCO of the isocyanate resin and acrylic acid modified bisphenol A type epoxy resin is 1.0-1.1：1.
8. glass ink according to claim 1, it is characterised in that the resin Composition also contains pigment, pigment is selected from one or more in rutile type titanium white, anatase thpe white powder, zinc oxide, lithopone.
9. glass ink according to claim 8, it is characterised in that the glass ink also contains anti-yellowing agent.
10. glass ink according to claim 9, it is characterised in that the anti-yellowing agent is selected from one or more in Hinered phenols anti-yellowing agent, hindered amines anti-yellowing agent, phosphorous acid esters anti-yellowing agent, sulphur class anti-yellowing agent.
11. glass inks according to claim 10, it is characterised in that the anti-yellowing agent is one or two the mixture in Hinered phenols anti-yellowing agent, phosphorous acid esters anti-yellowing agent.
12. glass inks according to claim 10, it is characterised in that the resin Composition also contains one or more in coupling agent, levelling agent, auxiliary rheological agents, defoamer, dispersant and solvent.
13. glass inks according to claim 12, it is characterised in that the coupling agent is selected from one or more in silanes, titanate ester, organochromium complexes, aluminic acid compound；The levelling agent is selected from one or more in Siloxane-Oxyalkylene Copolymers, alkyl-modified polysiloxanes, polyacrylate, polyester-modified polysiloxanes and its solution；The auxiliary rheological agents are selected from one or more in organobentonite, aerosil, castor oil derivative, polyamide wax, Tissuemat E, modified urea solution；The defoamer is selected from one or more in organosiloxane, polyethers, polyethylene glycol, ethylene-acrylic acid copolymer or polyglyceryl fatty acid ester；The dispersant is selected from one or more in modified polyurethane high polymer, modified polyacrylate polymer, polyester modification polyphosphate compound, polyvalent carboxylic acid's class；The solvent is selected from one or more in propylene glycol methyl ether acetate, nylon acid dimethyl ester, cyclohexanone；On the basis of resin components gross weight, the acrylic acid modified bisphenol A type epoxy resin 22%-31%, pigment 33%-40%, dispersant 1%-3%, coupling agent 0.5%-1%, levelling agent 0.05%-1%, defoamer 0.1%-0.7%, auxiliary rheological agents 0.1-0.4%, solvent 27%-38%, anti-yellowing agent 0.3%-1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510880846.3A CN106833111A (en) | 2015-12-04 | 2015-12-04 | A kind of glass ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510880846.3A CN106833111A (en) | 2015-12-04 | 2015-12-04 | A kind of glass ink |
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| Publication Number | Publication Date |
|---|---|
| CN106833111A true CN106833111A (en) | 2017-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510880846.3A Pending CN106833111A (en) | 2015-12-04 | 2015-12-04 | A kind of glass ink |
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| CN (1) | CN106833111A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108841241A (en) * | 2018-07-09 | 2018-11-20 | 广东太古电器科技有限公司 | A kind of translucent printing ink and the preparation method and application thereof |
| CN110204203A (en) * | 2019-07-01 | 2019-09-06 | 于洪伟 | Marble glass manufacturing process |
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| EP0530812A1 (en) * | 1991-09-05 | 1993-03-10 | Nippon Paint Co., Ltd. | Thermosetting resinous composition containing polyfunctional oxazolidinone component and polyamine component |
| CN104263069A (en) * | 2014-08-29 | 2015-01-07 | 湖南新力华纳米科技有限公司 | Water-based thermosetting glass printing ink and preparation method thereof |
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| EP0530812A1 (en) * | 1991-09-05 | 1993-03-10 | Nippon Paint Co., Ltd. | Thermosetting resinous composition containing polyfunctional oxazolidinone component and polyamine component |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841241A (en) * | 2018-07-09 | 2018-11-20 | 广东太古电器科技有限公司 | A kind of translucent printing ink and the preparation method and application thereof |
| CN110204203A (en) * | 2019-07-01 | 2019-09-06 | 于洪伟 | Marble glass manufacturing process |
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Application publication date: 20170613 |