CN116948459B - High-performance low-temperature ink suitable for inorganic sheet and preparation and use methods thereof - Google Patents
High-performance low-temperature ink suitable for inorganic sheet and preparation and use methods thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 68
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 52
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 229920003180 amino resin Polymers 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 230000008033 biological extinction Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 8
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 8
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 3
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims 4
- 238000007639 printing Methods 0.000 abstract description 17
- 239000011521 glass Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 229910000831 Steel Inorganic materials 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 5
- 239000010959 steel Substances 0.000 abstract description 5
- 239000001038 titanium pigment Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000006872 improvement Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000005336 safety glass Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
Abstract
The invention discloses high-performance low-temperature ink suitable for inorganic sheets, which comprises the following components: the component A comprises 45-57% of acrylic epoxy resin, 36-52.5% of titanium pigment and 4.5-16.5% of dibasic ester by weight; the component B comprises, by weight, 18% -30% of matting powder, 36% -54% of amino resin, 27% -28.5% of dibasic ester, 0.3% -0.9% of defoaming agent and 3% -9% of silane coupling agent; the mass ratio of the component A to the component B is 1 (1.5-2.5). The invention also discloses a preparation method and an application method of the high-performance low-temperature ink. According to the high-performance low-temperature ink disclosed by the invention, after the component A and the component B are mixed, the unsaturated groups in the acrylic epoxy resin and other groups can be accelerated to be added and crosslinked, so that the curing of main resin and the curing of the ink can be accelerated, the curing temperature can be controlled below 200 ℃, the curing time is quick, and the printing effect can be rapidly realized. The printing ink is suitable for most inorganic sheets, the printing stock comprises glass, steel, ceramics and the like, and the printing ink has good performances and can be applied to industrial production on a large scale.
Description
Technical Field
The invention belongs to the technical field of low-temperature ink, and particularly relates to high-performance low-temperature ink suitable for inorganic sheets and a preparation method and a use method thereof.
Background
With the development of society personalization, more and more products with unique decorations are required, and printing patterns on the surface by using ink is a lower-cost scheme. However, the ink which can be used for printing on the surfaces of various materials such as glass, steel, ceramics and the like is very little, and common glass ink can be used on the surfaces of other inorganic sheets, but the curing time of the common glass ink is at least one day, so that the printing effect cannot be quickly realized.
CN105062203a discloses a water-resistant single-component glass ink and a preparation method thereof, the raw material formulation is as follows: the heat-resistant epoxy resin modified organic silicon polyester comprises organic silicon modified polyester, heat-resistant epoxy resin, methylated amino resin, titanium pigment, a leveling agent, fumed silica, a tackifier and a defoaming agent. Such environmentally friendly inks produce less contamination, but some of their properties, such as adhesion and hardness, are inferior to two-component inks.
CN108624126a discloses a two-component silk-screen glass ink and preparation and use methods thereof. The glass ink consists of A, B components, wherein the component A consists of hydroxy acrylic resin, organic silicon resin, titanium pigment, dibasic ester, talcum powder, flatting agent, colorant and fluorescent whitening agent; the component B consists of a curing agent, a silane coupling agent, sodium lignin sulfonate and an odor neutralizer. However, the ink is naturally dried, cured and formed, and the curing time of the ink is at least one day, which increases the production cost and the time period. And the unsaturation degree of the main resin is low, even if the main resin is cured by heating, the effect of heating on unsaturated bond addition crosslinking is limited, the curing capability of accelerating the main resin is limited, and the effect of reducing the curing time of the ink is not obvious.
Disclosure of Invention
Aiming at one or more of the defects or improvement demands in the prior art, the invention provides the high-performance low-temperature ink suitable for inorganic sheets and the preparation and use methods thereof, and after the two-component ink is mixed, the unsaturated groups in the acrylic epoxy resin and other groups can be accelerated to be added and crosslinked, so that the curing of main resin and the curing of the ink are accelerated, the curing temperature can be controlled below 200 ℃, the curing time is fast, and the printing effect can be rapidly realized.
According to one aspect of the present invention, there is provided a high performance low temperature ink suitable for use in inorganic sheets, comprising:
the component A comprises 45-57% of acrylic epoxy resin, 36-52.5% of titanium pigment and 4.5-16.5% of dibasic ester by weight;
the component B comprises, by weight, 18% -30% of matting powder, 36% -54% of amino resin, 27% -28.5% of dibasic ester, 0.3% -0.9% of defoaming agent and 3% -9% of silane coupling agent;
the mass ratio of the component A to the component B is 1 (1.5-2.5).
As a further improvement of the invention, the raw materials of the acrylic epoxy resin comprise 20 to 30 percent of epoxy resin, 40 to 60 percent of solvent, 20 to 30 percent of hard monomer and 1 to 2 percent of initiator by weight;
preferably, the molar ratio of the hard monomer to the epoxy resin is 1 (1-1.05).
As a further improvement of the present invention, in the acrylic epoxy resin,
the epoxy resin is bisphenol A type epoxy resin; and/or the number of the groups of groups,
the solvent is one or two of n-butanol and ethylene glycol butyl ether; and/or the number of the groups of groups,
the hard monomer is one or two of methacrylic acid and acrylic acid; and/or the number of the groups of groups,
the initiator is dibenzoyl peroxide.
As a further improvement of the present invention, the preparation method of the acrylic epoxy resin comprises the steps of:
adding a set amount of epoxy resin and solvent into a reaction kettle, and uniformly stirring;
heating to 110 ℃, slowly adding a mixture of a set amount of hard monomer and an initiator, and continuously stirring for 2.5-3.5 hours until the reaction is completed after the mixture is completely added;
and finally adding alkali to neutralize the pH to 6-9, uniformly stirring, and cooling and discharging to obtain the acrylic epoxy resin.
As a further improvement of the invention, in the component A, the titanium dioxide is rutile titanium dioxide; preferably, the particle size of the titanium dioxide is 50-100 nm.
As a further improvement of the present invention, in the B component,
the extinction powder is oily extinction powder; and/or the number of the groups of groups,
the amino resin is a fully methylated melamine formaldehyde resin; and/or the number of the groups of groups,
the defoamer is a polysiloxane compound containing hydrophobic particles; and/or the number of the groups of groups,
the silane coupling agent is one or a mixture of a plurality of KH550, KH560, vinyl triethoxysilane, allyl trimethoxysilane and allyl triethoxysilane.
As a further improvement of the present invention,
in the component A, dibasic ester is a combination of three solvents of dimethyl succinate, dimethyl glutarate and dimethyl adipate; and/or the number of the groups of groups,
in the component B, dibasic acid ester is a combination of three solvents of dimethyl succinate, dimethyl glutarate and dimethyl adipate.
As a further improvement of the invention, the ratio of the dimethyl succinate, the dimethyl glutarate and the dimethyl adipate is 1 (0.9-1.1) to 0.9-1.1.
According to a second aspect of the present invention, there is provided a method for producing a high-performance low-temperature ink suitable for an inorganic sheet, for producing the high-performance low-temperature ink, comprising the steps of:
mixing and grinding 45-57% of acrylic epoxy resin, 36-52.5% of titanium dioxide and 4.5-16.5% of dibasic ester uniformly to obtain the component A;
mixing and grinding 18-30% of extinction powder, 36-54% of amino resin, 27-28.5% of dibasic ester, 0.3-0.9% of defoamer and 3-9% of silane coupling agent uniformly to obtain a component B;
mixing the component A and the component B according to the mass ratio of 1 (1.5-2.5) to prepare the high-performance low-temperature ink.
According to three aspects of the invention, a use method of high-performance low-temperature ink suitable for inorganic sheets is provided, when the high-performance low-temperature ink is used, the component A and the component B are uniformly mixed according to the mass ratio of 1 (1.5-2.5), ground to 3-10 mu m, screen printed by using 80-420 meshes and baked in an oven at 160-200 ℃ for 8-10 min for curing and molding.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
(1) The high-performance low-temperature ink suitable for inorganic sheets is a bi-component ink, wherein the component A is a main resin, wherein acrylic epoxy resin is prepared from epoxy resin, acrylic acid and/or methacrylic acid through ring opening esterification, and has a plurality of unsaturated groups; the main component of the component B is a curing agent, and unsaturated groups in the acrylic epoxy resin and other groups can be accelerated to be added and crosslinked after the main component B and the curing agent are mixed, so that the curing of the main resin and the curing of the ink are accelerated, the curing temperature can be controlled below 200 ℃, the curing time is quick, and the printing effect can be quickly realized only by 8-10 min.
(2) The high-performance low-temperature ink suitable for inorganic sheets is suitable for most inorganic sheets, and the printing stock not only comprises glass, but also comprises steel, ceramics and the like, and still has higher performance. And the ink has better performances and can be applied to large-scale industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The high-performance low-temperature ink provided by the embodiment of the invention comprises the following components:
the component A comprises 45-57% of acrylic epoxy resin, 36-52.5% of titanium pigment and 4.5-16.5% of dibasic ester by weight;
the component B comprises, by weight, 18% -30% of matting powder, 36% -54% of amino resin, 27% -28.5% of dibasic ester, 0.3% -0.9% of defoaming agent and 3% -9% of silane coupling agent;
the mass ratio of the component A to the component B is 1 (1.5-2.5).
Further, in the component A, the raw materials of the acrylic epoxy resin comprise 20-30% of epoxy resin, 40-60% of solvent, 20-30% of hard monomer and 1-2% of initiator by weight. Preferably, the molar ratio of the hard monomer to the epoxy resin is 1 (1-1.05).
In a preferred embodiment, the epoxy resin is bisphenol A type epoxy resin, and more preferably one or more of type A epoxy resins E-12, E-20, E-44, E-51 are blended.
In a preferred embodiment, the solvent is one or a mixture of n-butanol and ethylene glycol butyl ether.
In a preferred embodiment, the hard monomer is one or a mixture of methacrylic acid and acrylic acid.
In a preferred embodiment, the initiator is dibenzoyl peroxide.
In the acrylic epoxy resin of the embodiment of the invention, the feeding mole ratio of the hard monomer (methacrylic acid and/or acrylic acid) to the epoxy resin is 1: (1-1.05), the epoxy resin is slightly excessive, and the residual methacrylic acid and/or acrylic acid can be prevented from adversely affecting the substrate.
Specifically, the preparation method of the acrylic epoxy resin comprises the following steps:
adding 20% -30% of epoxy resin and 40% -60% of solvent into a reaction kettle provided with a stirring device, and uniformly stirring; the stirring speed is preferably 400-700 r/min;
heating to 110 ℃, slowly adding a mixture of 20% -30% of hard monomer and 1% -2% of initiator, and continuously stirring for 2.5-3.5 hours until the reaction is completed after the mixture is completely added;
and finally adding alkali (preferably sodium hydroxide) to neutralize the pH to 6-9, uniformly stirring, and cooling and discharging to obtain the acrylic epoxy resin.
The acrylic acid epoxy resin is prepared from epoxy resin, acrylic acid and/or methacrylic acid through ring opening esterification. Taking acrylic acid as an example, the epoxy resin and the acrylic acid are subjected to ring opening esterification under the action of an initiator, and the protonated acrylic acid opens epoxy bonds of the epoxy resin and is added with the epoxy bonds under the action of the initiator. The energy is reduced after the cyclic C-O bond of the epoxy resin is converted into a linear C-O bond, the energy is released, and the reaction releases heat. The exothermic reaction is a forward reaction, and the reaction proceeds more easily. After ring opening esterification is completed, a plurality of unsaturated acrylic groups are added on two sides of the epoxy resin, and the unsaturated acrylic groups are easier to be added and crosslinked with other groups after being heated, so that quick curing is completed.
In addition, since the ring opening of acrylic acid and epoxy groups is an exothermic reaction, the reaction is controlled in temperature at the initial stage, so that the hard monomer is slowly charged, and the addition is not performed too fast to prevent rapid temperature change. Because the solvent in the reaction is n-butyl alcohol and/or ethylene glycol butyl ether, the rapid change of the temperature has the risk of causing the reaction bumping; and a rapid increase in temperature inhibits the progress of the exothermic reaction.
Further, in the component A, the titanium dioxide is preferably rutile titanium dioxide; the particle size of the titanium dioxide is preferably 50-100 nm. The rutile type titanium dioxide has higher stability and excellent performances such as crystal shape, refractive index, tinting strength, fluorescence index and the like.
Further, in the component B, the matting powder is preferably oily matting powder, so that the surface glossiness of the dried ink layer can be improved, and the wear resistance and scratch resistance are enhanced.
Furthermore, in the component B, the amino resin is preferably fully methylated melamine formaldehyde resin, which is used as a curing agent and is a key for controlling the main curing of the acrylic epoxy resin after A, B two components are mixed, and the reaction activity is high and the curing speed is high.
Further, in the component B, the antifoaming agent is preferably a polysiloxane compound containing hydrophobic particles, which can reduce foaming of the ink.
Further, in the component B, the silane coupling agent is preferably one or a mixture of more of KH550, KH560, vinyl triethoxysilane, allyl trimethoxysilane, allyl triethoxysilane and the like, so that the adhesive force between the ink and the substrate can be enhanced.
Further, in the component A and the component B, the dibasic ester is preferably a combination of three solvents of dimethyl succinate, dimethyl glutarate and dimethyl adipate, and the mass ratio of dimethyl glutarate to dimethyl adipate is preferably 1 (0.9-1.1): 0.9-1.1. The dibasic ester of the invention is a biodegradable high boiling point solvent, which can increase the smoothness of the ink.
The invention provides a preparation method of the high-performance low-temperature ink, which comprises the following steps:
mixing 45-57% of acrylic epoxy resin, 36-52.5% of titanium dioxide and 4.5-16.5% of dibasic ester, and grinding uniformly, wherein a three-roll mill is preferably adopted to grind the mixture until the particle size is smaller than 10 microns, so that a component A is prepared;
mixing 18-30% of extinction powder, 36-54% of amino resin, 27-28.5% of dibasic ester, 0.3-0.9% of defoamer and 3-9% of silane coupling agent, and grinding uniformly to prepare a component B;
the mass ratio of the component A to the component B is 1: (1.5-2.5) and preparing the high-performance low-temperature ink.
The invention also provides a use method of the high-performance low-temperature ink, which comprises the following steps: when in use, the mass ratio of the component A to the component B is 1: (1.5-2.5), grinding (preferably using a three-roller machine) to 3-10 mu m, printing with 80-420 meshes of silk screen, and baking in an oven at 160-200 ℃ for 8-10 min for curing and molding.
The high-performance low-temperature ink is a bi-component ink, wherein the component A is main resin, the main component B is curing agent, and the component B is used for accelerating the curing of acrylic epoxy resin in the component A, and the two components are mixed when in use. After the component A and the component B are mixed, the unsaturated groups in the acrylic epoxy resin and other groups can be accelerated to be added and crosslinked, so that the main resin is accelerated to be cured, and the ink is accelerated to be cured; and the addition crosslinking of unsaturated groups can be promoted by combining the heating temperature below 200 ℃ so that the unsaturated groups are cured faster. In the curing process, one end of the silane coupling agent in the component B can be combined with partial unsaturated bonds on the acrylic epoxy resin, and the-SiOR group at the other end of the silane coupling agent can be well combined with inorganic materials such as glass, steel, ceramic and the like.
For the curing of acrylic epoxy resin, the high temperature of 200 ℃ can promote the addition crosslinking of unsaturated groups and other groups, the structures of other groups are stable, and the main resin is not denatured. Therefore, the acrylic epoxy resin prepared by the method has good heat resistance, and can ensure that the main body of the ink is not denatured when the glass ink is cured at 200 ℃.
The high-performance low-temperature ink is suitable for most inorganic sheets, and the printing stock not only comprises glass, but also comprises steel, ceramics and the like, and still has higher performance. The curing temperature can be controlled below 200 ℃, the curing time is quick, and the printing effect can be quickly realized only by 8-10 min. The low-temperature ink has better performances, and can be applied to large-scale industrial production.
For a better understanding of the present invention, the present invention will be described in detail with reference to examples.
Example 1:
preparation of component A: sequentially adding 45% of acrylic epoxy resin, 45% of titanium dioxide and 10% of dibasic ester into a reaction container, and grinding the mixture uniformly by a three-roller machine until the particle size is smaller than 10 microns;
the preparation method of the acrylic epoxy resin comprises the following steps: adding 20% of epoxy resin and 59% of solvent into a reaction kettle provided with a stirring device, controlling the stirring speed to be 400r/min, heating to 110 ℃, slowly adding a mixture of 20% of hard monomer and 1% of initiator, and continuously stirring for 2.5h until the reaction is completed after the addition is completed. And finally adding sodium hydroxide to neutralize the pH to 6.5, uniformly stirring, cooling, discharging, filtering and drying to obtain the acrylic epoxy resin.
Preparation of component B: sequentially adding 28% of extinction powder, 36% of amino resin, 28% of dibasic ester, 0.5% of defoamer and 7.5% of silane coupling agent into a container, mixing, and uniformly grinding the mixture by a three-roller machine to obtain a component B.
The mass ratio of the component A to the component B is 1:1.5, grinding to 3-10 mu m by a three-roller machine, printing by using 80-mesh screen, and baking in an oven at 160 ℃ for 10min for curing and molding.
Example 2:
preparation of component A: 50% acrylic epoxy resin; 43% of titanium dioxide; sequentially adding 7% dibasic ester into a reaction vessel, and grinding the mixture to a particle size of less than 10 microns by a three-roll mill;
the preparation method of the acrylic epoxy resin comprises the following steps: adding 25% of epoxy resin and 48.5% of solvent into a reaction kettle provided with a stirring device, controlling the stirring speed to be 600r/min, heating to 110 ℃, slowly adding a mixture of 25% of hard monomer and 1.5% of initiator, and continuing stirring for 3 hours until the reaction is completed after the addition is completed. And finally adding sodium hydroxide to neutralize the pH to 7, uniformly stirring, cooling, discharging, filtering and drying to obtain the acrylic epoxy resin.
Preparation of component B: sequentially adding 25% of extinction powder, 42.6% of amino resin, 28.5% of dibasic ester, 0.9% of defoamer and 3% of silane coupling agent into a container, mixing, and uniformly grinding the mixture by a three-roller machine to obtain a component B.
The mass ratio of the component A to the component B is 1:2, uniformly mixing, grinding to 3-10 mu m by a three-roller machine, printing by using a 420-mesh screen, and baking for 9min at 180 ℃ in an oven for curing and molding.
Example 3
Preparation of component A: 57% acrylic epoxy resin; 36% of titanium dioxide; sequentially adding 7% dibasic ester into a reaction vessel, and grinding the mixture to a particle size of less than 10 microns by a three-roll mill;
the preparation method of the acrylic epoxy resin comprises the following steps: adding 28% of epoxy resin and 42% of solvent into a reaction kettle provided with a stirring device, controlling the stirring speed to be 700r/min, heating to 110 ℃, slowly adding a mixture of 28% of hard monomer and 2% of initiator, and continuously stirring for 3.5h until the reaction is completed after the addition is completed. And finally adding sodium hydroxide to neutralize the pH to 8.5, uniformly stirring, cooling, discharging, filtering and drying to obtain the acrylic epoxy resin.
Preparation of component B: sequentially adding 18% of extinction powder, 50% of amino resin, 27% of dibasic ester, 0.5% of defoamer and 4.5% of silane coupling agent into a container, mixing, and uniformly grinding the mixture by a three-roll machine to obtain a component B.
The mass ratio of the component A to the component B is 1:2.5, grinding to 3-10 mu m by a three-roller machine, printing by using a 200-mesh screen, and baking in an oven at 200 ℃ for 8min for curing and molding.
The ink coating formed by printing the ink in the embodiment is tested by boiling water resistance, cold and hot circulation resistance, wiping resistance, hardness, ultraviolet resistance, acid and alkali resistance, heat resistance, cold resistance, moisture resistance, stain resistance and organic solvent resistance according to the methods of measuring paint film hardness according to the GB/T6739 color paint and varnish pencil method, visual colorimetry of GB/T9761 color paint and varnish color paint, GB11614 flat glass, GB15763.2-2005 safety glass part 2 toughened glass for construction, GB15763.4-2005 safety glass part 4 average toughened glass for construction and GB/T29757-2013 color decorative glass, and the test results are as follows:
| test item | Example 1 | Example 2 | Example 3 |
| Boiling water resistance | Qualified product | Qualified product | Qualified product |
| Resistant to cold and hot cycles | Qualified product | Qualified product | Qualified product |
| Scratch resistance | Qualified product | Qualified product | Qualified product |
| Hardness of coating | 3H | 3H | 3H |
| Ultraviolet resistant | Qualified product | Qualified product | Qualified product |
| Acid and alkali resistance | Qualified product | Qualified product | Qualified product |
| Heat resistant | Qualified product | Qualified product | Qualified product |
| Cold-resistant | Qualified product | Qualified product | Qualified product |
| Moisture resistance | Qualified product | Qualified product | Qualified product |
| Stain resistant | Qualified product | Qualified product | Qualified product |
| Organic solvent resistance | Qualified product | Qualified product | Qualified product |
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A high performance low temperature ink suitable for use in inorganic sheets comprising:
the component A comprises, by weight, 45% -57% of acrylic epoxy resin, 36% -52.5% of titanium dioxide, and 4.5% -16.5% of dibasic ester;
the component B comprises, by weight, 18% -30% of matting powder, 36% -54% of amino resin, 27% -28.5% of dibasic ester, 0.3% -0.9% of defoaming agent and 3% -9% of silane coupling agent;
the mass ratio of the component A to the component B is 1 (1.5-2.5);
the silane coupling agent is one or a mixture of several of vinyl triethoxysilane, allyl trimethoxysilane and allyl triethoxysilane;
the raw materials of the acrylic epoxy resin comprise, by weight, 20% -30% of epoxy resin, 40% -60% of solvent, 20% -30% of hard monomer and 1% -2% of initiator;
the molar ratio of the hard monomer to the epoxy resin is 1 (1-1.05);
the preparation method of the acrylic epoxy resin comprises the following steps:
adding a set amount of epoxy resin and solvent into a reaction kettle, and uniformly stirring;
heating to 110 ℃, slowly adding a mixture of a set amount of hard monomer and an initiator, and continuously stirring for 2.5-3.5 hours until the reaction is completed after the mixture is completely added;
and finally adding alkali to neutralize the pH to 6-9, uniformly stirring, and cooling and discharging to obtain the acrylic epoxy resin.
2. The high-performance low-temperature ink for inorganic sheets according to claim 1, wherein, in the acrylic epoxy resin,
the epoxy resin is bisphenol A type epoxy resin; and/or the number of the groups of groups,
the solvent is one or two of n-butanol and ethylene glycol butyl ether; and/or the number of the groups of groups,
the hard monomer is one or two of methacrylic acid and acrylic acid; and/or the number of the groups of groups,
the initiator is dibenzoyl peroxide.
3. The high performance low temperature ink for inorganic sheet according to claim 1 or 2, wherein in the a component, the titanium white powder is rutile titanium dioxide.
4. The high-performance low-temperature ink suitable for inorganic sheets according to claim 3, wherein the particle size of the titanium dioxide is 50-100 nm.
5. The high-performance low-temperature ink suitable for inorganic sheets according to claim 1 or 2, wherein, in the B component,
the extinction powder is oily extinction powder; and/or the number of the groups of groups,
the amino resin is a fully methylated melamine formaldehyde resin; and/or the number of the groups of groups,
the defoamer is a polysiloxane compound containing hydrophobic particles.
6. The high-performance low-temperature ink suitable for inorganic sheets according to any one of claim 1, 2, and 4,
in the component A, dibasic ester is a combination of three solvents of dimethyl succinate, dimethyl glutarate and dimethyl adipate; and/or the number of the groups of groups,
in the component B, dibasic acid ester is a combination of three solvents of dimethyl succinate, dimethyl glutarate and dimethyl adipate.
7. The high-performance low-temperature ink suitable for inorganic sheets according to claim 6, wherein the ratio of dimethyl succinate, dimethyl glutarate and dimethyl adipate is 1 (0.9-1.1): 0.9-1.1.
8. A method for preparing the high-performance low-temperature ink suitable for inorganic sheets, which is used for preparing the high-performance low-temperature ink according to any one of claims 1 to 7, characterized by comprising the steps of:
mixing 45% -57% of acrylic epoxy resin, 36% -52.5% of titanium dioxide and 4.5% -16.5% of dibasic ester, and uniformly grinding to obtain a component A;
mixing and grinding 18% -30% of extinction powder, 36% -54% of amino resin, 27% -28.5% of dibasic ester, 0.3% -0.9% of defoamer and 3% -9% of silane coupling agent uniformly to obtain a component B;
and mixing the component A and the component B according to the mass ratio of 1 (1.5-2.5) to prepare the high-performance low-temperature ink.
9. The application method of the high-performance low-temperature ink suitable for the inorganic sheet is characterized in that when the high-performance low-temperature ink is used, the component A and the component B are uniformly mixed according to the mass ratio of 1 (1.5-2.5), ground to 3-10 mu m, screen printed by using 80-420 meshes and baked in an oven at 160-200 ℃ for 8-10 min for curing and forming.
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