CN107384011A - A kind of PVC floor film intaglio printing water-based ink and preparation method thereof - Google Patents
A kind of PVC floor film intaglio printing water-based ink and preparation method thereof Download PDFInfo
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- CN107384011A CN107384011A CN201710810654.4A CN201710810654A CN107384011A CN 107384011 A CN107384011 A CN 107384011A CN 201710810654 A CN201710810654 A CN 201710810654A CN 107384011 A CN107384011 A CN 107384011A
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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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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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
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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Abstract
A kind of PVC floor film intaglio printing water-based ink, is made up of the raw material of following weight proportion：4 18 parts of pigment, 18 parts of polyvinyl alcohol grind resin, 0.8 3.1 parts of dispersant, 0.1 0.5 parts of defoamer, 15 45 parts of film-forming resin, 0.5 1.5 parts of wetting agent, 10 20 parts of low mass molecule alcohol, 0.5 3 parts of cosolvent, 10 67.1 parts of pure water；The water-based ink of the present invention can reach more than the bond level of oiliness ink to the adhesion strength of PVC floor film and wear plate, thickener need not be added in formula, formulation cost is saved, the printing effect of ink is better than the effect of oiliness ink on the market, and levelling effect and glossiness are better than oleaginous system.
Description
(1) technical field
The present invention relates to water-based ink and preparation method thereof, and in particular to one kind can apply to PVC (polyvinyl chloride) floor
Water-based ink of film intaglio printing and preparation method thereof.
(2) background technology
To accelerate energy-conserving and emission-cutting technology exploitation, country《Packaging industry " 12 " development planning outline》、《Plastics package work
Planning is revitalized in industry adjustment in 3 years from now on》、《National Hi-tech Industry Development " 12 " planning》、《National Development and Reform Commission closes
In the notice (Fa Gai enterprises [2007] 3251) for carrying out medium-sized and small enterprises energy-saving and emission-reduction work》, State General Administration for Quality Supervision is from 2008 1
What the moon 1 was carried out《Food use is packed, the production of articles such as container, instrument license general rule》Research and development and industrialization to water-based ink
Plan proposes requirement.Plastic foil water-based printing technology (clean manufacturing) Industrialization Projects belong to country and industry emphasis support and
" zero-emission " technology used is encouraged, meets the industrial policy and technical policy of national correlation.
PVC plastic decorating film mainly includes PVC floor film and PVC furniture films.PVC floor film is main with PVC furniture films
Difference is as follows：One, PVC floor film is substantially free of plasticizer or containing minimal amount of plasticizer, belongs to hard PVC film, and PVC furniture
Film contains more plasticizer, therefore belongs to flexible PVC film；Two, when the PVC floor film printed will pass through length of a film wear-resisting with PVC
Between hot pressing attaching process (120-130 DEG C, 30-60min, there is certain pressure requirements), and PVC furniture films will be with after printing
PVC wearing layers carry out the high temperature attaching process (160-170 DEG C, 6-15s, no specified pressure requirement) of short time；Three, PVC floor
Film wear plate is thick matter wear plate, and the one side being bonded with print film carries the concave convex groove that can be vented, and PVC furniture film wear plates
It is relatively thin, and do not possess such a groove structure.
Still based on solvent-based ink, solvent-based ink (typically constitutes from ink composition containing a large amount of for PVC floor film printing at present
More than 60%) volatile organic solvent (VOC), such as toluene, dimethylbenzene, ethyl acetate, butanone.When ink prints and dried,
Substantial amounts of organic solvent is discharged, and greatly infringement and pollution are all caused to printer's human and environment.Moreover, print
Floor film and PVC floor carry out after fitting into house ornamentation market, still can slowly discharge VOC, this is undoubtedly to consumer's
Health causes long-term injury at home.And water-based ink is due to using water as main dispersing medium, after ink is transferred to stock, water
Divide and evaporate into environment or penetrate into stock, ink is dried with the volatilization of moisture, has nontoxic, Environmental Safety
The features such as.Therefore, water-based ink is increasingly by the attention of government and favoring for industry, and the Water-borne modification of PVC floor film ink is
As the trend of industry development instantly.
For the difference of PVC floor film and PVC furniture films, PVC floor film intaglio plate is exclusively used in the invention provides a
The water-based ink of printing.
(3) content of the invention
It is an object of the invention to provide a kind of water-based ink available for PVC floor film intaglio printing and its preparation side
Method.With reference to the PVC floor film printed will (120-130 DEG C, 30-60min, have by overlaying conjunction with PVC wear plate Long Time Thermals
Certain pressure requirements) process characteristic, and PVC floor film wear plate carry can be vented concave convex groove the characteristics of, the present invention
It is used as the optimum choice of specific components in film-forming resin, and ink formula by making the emulsion resin with special construction by oneself, both
The printing quality of ink is ensure that, also ensure that the peel strength of PVC floor print film and PVC wear plates.
Technical scheme is as follows：
A kind of PVC floor film intaglio printing water-based ink, is made up of the raw material of following weight proportion：
Pigment 4-18 parts, polyvinyl alcohol grind resin 1-8 parts, dispersant 0.8-3.1 parts, defoamer 0.1-0.5 parts, film forming
Resin 15-45 parts, wetting agent 0.5-1.5 parts, low mass molecule alcohol 10-20 parts, cosolvent 0.5-3 parts, pure water 10-67.1 parts.
Preferably, the PVC floor film intaglio printing water-based ink is made up of the raw material of following weight proportion：
Pigment 5-15 parts, polyvinyl alcohol grind resin 2-6 parts, dispersant 1-3 parts, defoamer 0.1-0.5 parts, film-forming resin
20-40 parts, wetting agent 0.5-1.5 parts, low mass molecule alcohol 10-20 parts, cosolvent 1-2 parts, pure water 13-59.4 parts.
The pigment is preferably in organic red, the benzimidazole ketone organic yellow of azo condensed type, the organic blue, carbon black of phthalocyanines
Any one；Particularly preferred paratonere 166 (P.R.166, Zhejiang Lily Group Co., Ltd.), pigment yellow P-HG
(P.Y.180, Zhejiang Lily Group Co., Ltd.), BF435 (P.B.15：3, the limited public affairs of Zhejiang lily group share
Department), any one in SPECIAL BLACK 4 (German goldschmidt chemical corporation).
The polyvinyl alcohol grind resin is self-control, using polyvinylalcohol solids resin as raw material, the polyvinylalcohol solids
Resin is, for example, UF 170M (Japanese You Niji can company).Specifically, the polyvinyl alcohol grind resin is prepared as follows
Obtain (in following preparation method, number refers both to parts by weight)：
At room temperature, toward the pure water of 70 parts of addition in reactor, stirring is opened with 150rpm speed, 40 parts of addition gathers
Vinyl alcohol hard resin, stirring start to warm up after being swelled 1h, and when system reaches 90 DEG C, mixing speed is adjusted to 300rpm, and
1h is kept, room temperature is finally down to, filtering and discharging, that is, obtains described polyvinyl alcohol grind resin.
The dispersant can be low molecule amount polycarboxylic acid polymers alkane hydroxylammonium salts solution (such as DISPERBYK,
BYK companies), polyacrylic acid derivative (such as Disponer W-511, De Qian company；Disponer W-519, De Qian companies), it is suitable
Butadiene anhydride multipolymer (such as diisobutylene-cis-butenedioic anhydride copolymer or styrene-maleic anhydride copolymer；Or such as SMA1000P, Sha Duo
Agate company) one or both of any of the above ratio mixture；The alkane of particularly preferred low molecule amount polycarboxylic acid polymers
Hydroxylammonium salts solution (DISPERBYK, BYK company).
The defoamer can be mineral oil defoaming agent (such as Drewplus T-4507, ASHLAND-AQUALON company；
ADVANTAGE AM-1512, ASHLAND-AQUALON companies), lower alcohols defoamer (such asDF 1492, the modest public affairs of moral
Department；DF 1760, De Qian company；DF 3163, De Qian company), organic silicon defoamer (such as Pulcra
1918, Kekai Fine Chemical (Shanghai) Co., Ltd.；Pulcra 1920, Kekai Fine Chemical (Shanghai) Co., Ltd.；
Drewplus T-4201, ASHLAND-AQUALON companies；Drewplus TS-4400, ASHLAND-AQUALON companies；
Drewplus TS-4481, ASHLAND-AQUALON companies) one or both of any of the above ratio mixture；It is preferred that
Lower alcohols defoamer, particularly preferablyDF 1760 (De Qian companies).
The film-forming resin is preferably homemade poly-vinegar acrylic emulsion ink resin (vinylacetate-co- methyl methacrylates
Ester-co- acrylic acid -4- hydroxybutyl-co- glycidyl acrylates), its composition of raw materials and preparation method can be found in invention specially
Sharp application documents：A kind of PVC floor film water inkwood fat and preparation method thereof, number of patent application：201710613042.6.
Specifically, the film-forming resin is made up of the raw material of following weight proportion：
Polyvinyl alcohol type protecting colloid 5-9 parts, reactive emulsifier 0.3-1.1 parts, pH buffer 0.08-0.11 parts, draw
Hair agent 0.15-0.23 parts, Vinyl Acetate Monomer 17.94-26.52 parts, methyl methacrylate monomer 10.53-17.55 parts,
Acrylic acid -4- hydroxybutyl monomer 1.9-3.6 parts, glycidyl acrylate monomer 0.39-1.14 parts, TBHP
0.068-0.082 parts, rongalite 0.068-0.082 parts, deionized water 48.123-58.96 parts.
Specifically, the film-forming resin is prepared as follows obtaining (in following preparation method, number refers both to parts by weight)：
(1) at room temperature, by the Vinyl Acetate Monomer of 17.94-26.52 parts, the methyl methacrylate of 10.53-17.55 parts
Ester monomer, the acrylic acid -4- hydroxybutyls monomer of 1.9-3.6 parts, 0.39-1.14 parts glycidyl acrylate monomer,
The reactive emulsifier of 0.3-1.1 parts mixes and with 500-800rpm speed stirring and dissolving 30-60min, monomer dropping is made
Phase；
(2) at room temperature, the pH buffer of the initiator of 0.15-0.23 parts, 0.08-0.11 parts is dissolved in 7.5-10.1 parts
Deionized water in, be made initiator be added dropwise phase；
(3) at room temperature, toward the deionized water of addition 39.823-48.06 parts in reactor, opened with 100-150rpm speed
Stirring is opened, adds the polyvinyl alcohol type protecting colloid of 5-9 parts, and is started to warm up, when system reaches 90-93 DEG C, mixing speed
200-300rpm is adjusted to, and keeps 20-40min；Monomer dropping phase obtained by step (1) and step (2) institute is added dropwise simultaneously afterwards
Phase is added dropwise in initiator, monomer dropping phase time for adding be 4-4.5h, and initiator dropwise addition phase time for adding is 4.5-5h, initiator
Dropwise addition drips compared to monomer dropping phase retardation 0.5h；Then system temperature is risen to 95-98 DEG C, be cooled to after being incubated 1-2h
70-75 DEG C, add the TBHP aqueous solution, the TBHP aqueous solution by 0.068-0.082 parts uncle
Butylhydroperoxide is dissolved in 0.4 part of deionized water and obtained, insulated and stirred 10-20min, and it is water-soluble then to add rongalite
Liquid, the rongalite aqueous solution is dissolved in 0.4 part of deionized water by the rongalite of 0.068-0.082 parts to be obtained, and insulation is stirred
10-20min is mixed, room temperature is finally down to, filtering and discharging, produces described film-forming resin.
The wetting agent is polyacrylate levelling agent (such as M3077, Shanghai De Yu get trade Co., Ltds；
Resiflow W50, BYK companies), organic siliconresin class levelling agent (such as Silcn 353, Shanghai De Yu get trade Co., Ltds),
One or both of fluoroolefins levelling agent (such as 9100, Long Shida Chemical Industry Science Co., Ltd) any of the above ratio is mixed
Compound；It is preferred that polyacrylate levelling agent, particularly preferred Resiflow W50 (BYK companies).
The low mass molecule alcohol is methanol, ethanol, the mixture of one or two kinds of any of the above ratio in isopropanol.
The cosolvent is particularly preferably the methyl-1-butanol of 3- methoxyl groups -3 (Kuraray Co., Ltd.).
Present invention also offers the preparation method of the PVC floor film intaglio printing water-based ink, described preparation method
For：
(1) master grind
Stocked up according to formula, at room temperature, by the pure water of formula ratio 30%~62%, low point of formula ratio 33%~50%
Sub- alcohol, dispersant, polyvinyl alcohol grind resin, the defoamer of formula ratio 60%~80% are added sequentially in Scattered Kettle, with 50-
150rpm speed adds pigment after being uniformly mixed, and is transferred to after being uniformly mixed with 150-300rpm speed sleeping
Be ground 2-5 roads in formula sand mill (TBM-50, too also (Shanghai) Industrial Co., Ltd.), to mill base particle diameter reach 500nm with
Filtering and discharging after lower, obtains aqueous color paste；
(2) ink is prepared
At room temperature, successively by the pure water of remaining formula ratio, aqueous color paste obtained by step (1), film-forming resin, wetting agent,
Low mass molecule alcohol, cosolvent, the defoamer of remaining formula ratio of remaining formula ratio are added in dispersion cylinder, with 150-200rpm speed
Filtering and discharging after degree stirring 0.5-1h, obtains described PVC floor film intaglio printing water-based ink.
In the present invention, described room temperature is 20~30 DEG C.
Compared with prior art, the beneficial effects of the present invention are：
1st, water-based ink of the invention can reach more than the viscous of oiliness ink to the adhesion strength of PVC floor film and wear plate
Bear water flat.
2nd, thickener need not be added in inventive formulation, has saved formulation cost.
3rd, the printing effect of ink of the present invention is better than the effect of the ink of oiliness on the market (levelling effect and glossiness is intended to excellent
In oleaginous system).
(4) illustrate
Fig. 1 refers to the spot color ink that the ink of the present invention and the on the market ink of commercialization are made into identical colour saturation
Afterwards, in the comparison diagram for printing to obtain with 60m/min print speed printing speed in intaglio press same roller.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Particle diameter and the particle diameter distribution test of mill base are carried out on Malvern ZETASIZER 3000HAS particle size analyzers, are tested
Temperature is 25 DEG C.
The bin stability of ink refers to that emulsion stands 9 days under the conditions of 60 DEG C, not precipitate, it is not stratified represent ink storage
Deposit stability>6 months.
The peel strength test of ink is as follows：Water-based monochromatic ink is (red, yellow, blue, black) to use KPP gravure proof press, with 40m/
Min print speed printing speed, ink of the present invention is respectively printed on PVC floor film, it is wear-resisting with PVC floor film after 60 DEG C of drying
Piece is cooled to room temperature and carries out test peel strength test by GB/T2790 in 130 DEG C of hot pressing 30min on hot press after taking-up；Water
Property spot color ink with oiliness spot color ink peel strength be more then by ink and ink are made into identical colour saturation spot color ink
Afterwards, in after being printed in intaglio press same roller with identical print speed printing speed on PVC floor film through 60 DEG C drying after, with
PVC floor film wear plate is cooled to room temperature and carries out test stripping by GB/T2790 in 130 DEG C of hot pressing 30min on hot press after taking-up
From strength test.
The printing effect evaluation of ink is as follows：After ink and ink are made into the spot color ink of identical colour saturation, in intaglio process
Printed in brush machine same roller with identical print speed printing speed, the levelling effect of the bigger color lump of naked eyes, and with the gloss of WGG 60
Degree measures layer of ink glossiness with (Shanghai Modern Environmental Engineering Technology Co., Ltd.).
Used film-forming resin is prepared as follows obtaining (in following preparation method, number refers both to parts by weight)：
1) at room temperature, by 21.84 parts of Vinyl Acetate Monomer (Guangzhou Na Xin Chemical Co., Ltd.s), 14.43 parts
Methyl methacrylate monomer (Guangzhou Zhong Ye Chemical Co., Ltd.s), 2.73 parts of acrylic acid -4- hydroxybutyl monomers (Mitsubishi
The Chinese commerce and trade Co., Ltd of chemistry), 0.39 part of glycidyl acrylate monomer (Shanghai and create chemical Science and Technology Ltd.)
And 1 part of reactive emulsifier Emulsogen APS100 (Clariant companies) are with 600rpm speed stirring and dissolving
Monomer dropping phase is made in 40min；
2) at room temperature, 0.17 part of initiator ammonium persulfate (Wujiang Wei Tong Chemical Co., Ltd.s), 0.1 part of pH are delayed
Electuary ammonium hydrogen carbonate (Wujiang Hong Xiang Chemical Co., Ltd.s), which is dissolved in 10.1 parts of deionized water, is made initiator dropwise addition phase；
3) stirring is opened with 130rpm speed, adds 5 toward the deionized water of 45.876 parts of addition in reactor at room temperature
Part polyvinyl alcohol type protecting colloid UF 170M (Japanese You Niji can company), and start to warm up, when system reaches 93 DEG C,
Adjustment of rotational speed is 250rpm, and keeps 20min；Then start that monomer dropping phase and initiator dropwise addition phase, monomer drop are added dropwise simultaneously
It is 4h to add phase time for adding, and it is 4.5h that phase time for adding, which is added dropwise, in initiator；Then system temperature is risen to 95 DEG C, dropped after being incubated 2h
Temperature adds the TBHP aqueous solution, the TBHP aqueous solution is by 0.082 part of tert-butyl group mistake to 70 DEG C
Hydrogen oxide (Chemical Co., Ltd. of Shanghai 101), which is dissolved in 0.4 part of deionized water, to be obtained, insulated and stirred 10min, adds carving
The white powder aqueous solution, the rongalite aqueous solution are dissolved in 0.4 part by 0.082 part of rongalite (the auspicious Chemical Co., Ltd.s of Shanghai Feng)
Deionized water in obtain, insulated and stirred 10min is finally down to room temperature, filtering and discharging, produces described film-forming resin.
The embodiment 1 of table 1., comparative example 1-1, comparative example 1-2 water-based ink composition of raw materials
Embodiment 1
(1) master grind
According to the formula ratio of embodiment 1 in table 1, at room temperature by pure water, alcohol, DISPERBYK dispersants, polyvinyl alcohol
Grind resin andDF defoamers are added sequentially in Scattered Kettle, are added after being uniformly mixed with 50rpm speed
Paratonere 166, horizontal sand mill (TBM-50, too also (Shanghai) industry are transferred to after being uniformly mixed with 300rpm speed
Co., Ltd) in grinding 3 after filtering and discharging, obtain water-based red slurry.
(2) ink is prepared
According to the formula ratio of embodiment 1 in table 1, at room temperature, successively by pure water, above-mentioned aqueous color paste, acrylate and vinyl acetate emulsion into
Film resin, Resiflow W50 wetting agents, alcohol, the methylene diacetate butyl ester cosolvent of 3- methoxyl groups -3 andDF defoamers
It is added in dispersion cylinder, with filtering and discharging after 150rpm speed stirring 1h, it is water-based obtains described PVC floor film intaglio printing
Red ink.
Comparative example 1-1
According to the formula ratio of comparative example 1-1 in table 1, homemade acrylate and vinyl acetate emulsion film-forming resin in embodiment 1 is replaced
Into 6120 film-forming resins, other components dosage keeps constant, and PVC floor film intaglio printing is made into by the operating procedure of embodiment 1
Water-based red ink.
Comparative example 1-2
According to the formula ratio of comparative example 1-2 in table 1, homemade polyvinyl alcohol grind resin in embodiment 1 is replaced
Into 678 resin liquid grind resins, other components dosage keeps constant, in addition to the step for making grind resin by oneself is omitted, by implementation
The operating procedure of example 1 is made into the water-based red ink of PVC floor film intaglio printing.
The embodiment 1 of table 2., comparative example 1-1, comparative example 1-2 properties of product tables
From the embodiment 1 of table 2 and comparative example 1-1 data, the stripping of the ink system of self-control film-forming resin is used
Apparently higher than the peel strength using commercial film-forming resin system, (6120 resins are the special use that Wan Hua chemical companies develop to intensity
In the resin of attachment PVC base)；From embodiment 1 and comparative example 1-2 data, homemade polyvinyl alcohol is ground and set
Fat replaces with 678 commercial resin liquids, and (678 resin liquids are conventional grind resin the most classical in industry, belong to styrene-the third
Olefin(e) acid ester copolymer type, it is clear that do not have the good of polyvinyl alcohol with the compatibility of homemade film-forming resin in the present invention) after, mill base
The grain diameter influence of middle pigment is little, but the peel strength of ink has declined；Integrated embodiment 1, comparative example 1-1 simultaneously
And from the point of view of comparative example 1-2 data, the peel strength of ink depends primarily on film-forming resin, and grind resin and film forming tree
The excellent compatibility of fat can further enhance the cohesive force of ink.As can be seen here, from the homemade PVC with special construction
Plate film is poly- (vinylacetate-co- methyl methacrylate-co- acrylic acid -4- hydroxybutyl-co- glycidyl acrylates)
Acrylate and vinyl acetate emulsion is the film-forming resin of ink, with reference to homemade polyvinyl alcohol master grind, can significantly improve ink to PVC
The peel strength of plate film and wear plate.Water-based yellow ink, Lan Mo, the experimental result of tusche and red ink are basically identical below, therefore no longer
Repeat.
The embodiment 2 of table 3., comparative example 2-1, comparative example 2-2 water-based ink composition of raw materials
Embodiment 2
(1) master grind
According to the formula ratio of embodiment 2 in table 3, at room temperature by pure water, isopropanol, DISPERBYK dispersants, polyethylene
Alcohol grind resin andDF defoamers are added sequentially in Scattered Kettle, after being uniformly mixed with 100rpm speed again
Add pigment yellow P-HG, be transferred to after being uniformly mixed with 150rpm speed horizontal sand mill (TBM-50, too also (Shanghai)
Industrial Co., Ltd.) in filtering and discharging after grinding 2, obtain water-based yellow slurry.
(2) ink is prepared
According to the formula ratio of embodiment 2 in table 3, at room temperature, successively by pure water, above-mentioned aqueous color paste, acrylate and vinyl acetate emulsion into
Film resin, Resiflow W50 wetting agents, isopropanol, the methylene diacetate butyl ester cosolvent of 3- methoxyl groups -3 andDF is defoamed
Agent is added in dispersion cylinder, with filtering and discharging after 200rpm speed stirring 0.5h, obtains described PVC floor film intaglio printing
Water-based yellow ink.
Comparative example 2-1
According to the formula ratio of comparative example 2-1 in table 3, homemade acrylate and vinyl acetate emulsion film-forming resin in embodiment 2 is replaced
Into 6120 film-forming resins, other components dosage keeps constant, and PVC floor film intaglio printing is made into by the operating procedure of embodiment 2
Water-based yellow ink.
Comparative example 1-2
According to the formula ratio of comparative example 2-2 in table 3, homemade polyvinyl alcohol grind resin in embodiment 2 is replaced
Into 678 resin liquid grind resins, other components dosage keeps constant, in addition to the step for making grind resin by oneself is omitted, by implementation
The operating procedure of example 2 is made into the water-based yellow ink of PVC floor film intaglio printing.
The embodiment 2 of table 4., comparative example 2-1, comparative example 2-2 properties of product tables
The embodiment 3 of table 5., comparative example 3-1, comparative example 3-2 water-based ink composition of raw materials
Embodiment 3
(1) master grind
According to the formula ratio of embodiment 3 in table 5, at room temperature by pure water, alcohol, DISPERBYK dispersants, polyvinyl alcohol
Grind resin andDF defoamers are added sequentially in Scattered Kettle, are added after being uniformly mixed with 50rpm speed
Alizarol saphirol BF435, horizontal sand mill is transferred to after being uniformly mixed with 300rpm speed, and (TBM-50, too also (Shanghai) is real
Industry Co., Ltd) in grinding 5 after filtering and discharging, obtain aqueous blue slurry.
(2) ink is prepared
According to the formula ratio of embodiment 3 in table 5, at room temperature, successively by pure water, above-mentioned aqueous color paste, acrylate and vinyl acetate emulsion into
Film resin, Resiflow W50 wetting agents, alcohol, the methylene diacetate butyl ester cosolvent of 3- methoxyl groups -3 andDF defoamers
It is added in dispersion cylinder, with filtering and discharging after 200rpm speed stirring 0.5h, obtains described PVC floor film intaglio process swabbing
Property blue ink.
Comparative example 3-1
According to the formula ratio of comparative example 3-1 in table 5, homemade acrylate and vinyl acetate emulsion film-forming resin in embodiment 3 is replaced
Into 6120 film-forming resins, other components dosage keeps constant, and PVC floor film intaglio printing is made into by the operating procedure of embodiment 3
Aqueous blue ink.
Comparative example 3-2
According to the formula ratio of comparative example 3-2 in table 5, homemade polyvinyl alcohol grind resin in embodiment 3 is replaced
Into 678 resin liquid grind resins, other components dosage keeps constant, in addition to the step for making grind resin by oneself is omitted, by implementation
The operating procedure of example 3 is made into PVC floor film intaglio printing aqueous blue ink.
The embodiment 3 of table 6., comparative example 3-1, comparative example 3-2 properties of product tables
The embodiment 4 of table 7., comparative example 4-1, comparative example 4-2 water-based ink composition of raw materials
Embodiment 4
(1) master grind
According to the formula ratio of embodiment 4 in table 7, at room temperature by pure water, isopropanol, DISPERBYK dispersants, polyethylene
Alcohol grind resin andDF defoamers are added sequentially in Scattered Kettle, after being uniformly mixed with 150rpm speed again
Pigment black SPECIAL BLACK 4 are added, horizontal sand mill (TBM- is transferred to after being uniformly mixed with 150rpm speed
50, too also (Shanghai) Industrial Co., Ltd.) in filtering and discharging after grinding 4, obtain water-based black wash.
(2) ink is prepared
According to the formula ratio of embodiment 4 in table 7, at room temperature, successively by pure water, above-mentioned aqueous color paste, acrylate and vinyl acetate emulsion into
Film resin, Resiflow W50 wetting agents, isopropanol, the methylene diacetate butyl ester cosolvent of 3- methoxyl groups -3 andDF is defoamed
Agent is added in dispersion cylinder, with filtering and discharging after 150rpm speed stirring 1h, obtains described PVC floor film intaglio process swabbing
Property tusche.
Comparative example 4-1
According to the formula ratio of comparative example 4-1 in table 7, homemade acrylate and vinyl acetate emulsion film-forming resin in embodiment 3 is replaced
Into 6120 film-forming resins, other components dosage keeps constant, and PVC floor film intaglio printing is made into by the operating procedure of embodiment 4
Water-based tusche.
Comparative example 4-2
According to the formula ratio of comparative example 4-2 in table 7, homemade polyvinyl alcohol grind resin in embodiment 4 is replaced
Into 678 resin liquid grind resins, other components dosage keeps constant, in addition to the step for making grind resin by oneself is omitted, by implementation
The operating procedure of example 4 is made into the water-based tusche of PVC floor film intaglio printing.
The embodiment 4 of table 8., comparative example 4-1, comparative example 4-2 properties of product tables
The water-based spot color ink of table 9.PVC floor films and oiliness spot color ink print performance comparison
As shown in Figure 1, the water-based ink prepared using the present invention prints sample surface without obvious printing defects (such as " ripples
Line ", " pinprick " etc. print Levelling defects), and the printing defects of " water ripples " then be present in oiliness sample；In addition, as shown in Table 9,
The glossiness of ink printing layer of the present invention will be apparently higher than oiliness ink, it is seen that the printing effect of water-based ink of the present invention is obvious excellent
In the oil-based ink of commercialization；From the peel strength data of table 9, water-based ink of the invention is to PVC floor film and wear plate
Adhesion strength can reach the bond level of oiliness ink.As can be seen here, PVC floor film intaglio printing water-based ink of the invention has
Hope substitution current market commercialized oil-based ink product.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, to any modifications and changes of the invention made, protection scope of the present invention is both fallen within.
Claims (10)
1. a kind of PVC floor film intaglio printing water-based ink, is made up of the raw material of following weight proportion：
Pigment 4-18 parts, polyvinyl alcohol grind resin 1-8 parts, dispersant 0.8-3.1 parts, defoamer 0.1-0.5 parts, film-forming resin
15-45 parts, wetting agent 0.5-1.5 parts, low mass molecule alcohol 10-20 parts, cosolvent 0.5-3 parts, pure water 10-67.1 parts.
2. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the pigment contracts for azo
Any one in the organic blue, carbon black of organic red, the benzimidazole ketone organic yellow of mould assembly, phthalocyanines.
3. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the polyvinyl alcohol grinding
Resin is prepared as follows obtaining：
At room temperature, toward the pure water of 70 parts of addition in reactor, stirring is opened with 150rpm speed, adds 40 parts of polyethylene
Alcohol hard resin, stirring start to warm up after being swelled 1h, and when system reaches 90 DEG C, mixing speed is adjusted to 300rpm, and keeps
1h, room temperature is finally down to, filtering and discharging, that is, obtains described polyvinyl alcohol grind resin.
4. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the dispersant is low point
Son measures one in the alkane hydroxylammonium salts solution, polyacrylic acid derivative, suitable butadiene anhydride multipolymer of polycarboxylic acid polymers
The mixture of kind or two or more arbitrary proportions.
5. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the defoamer is mineral
The mixture of one or both of oils defoamer, lower alcohols defoamer, organic silicon defoamer any of the above ratio.
6. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the film-forming resin is poly-
Acrylate and vinyl acetate emulsion ink resin, is prepared as follows obtaining：
(1) at room temperature, by the Vinyl Acetate Monomer of 17.94-26.52 parts, the methyl methacrylate list of 10.53-17.55 parts
Body, acrylic acid -4- hydroxybutyls monomer, the glycidyl acrylate monomer, 0.3-1.1 of 0.39-1.14 parts of 1.9-3.6 parts
The reactive emulsifier of part mixes and with 500-800rpm speed stirring and dissolving 30-60min, monomer dropping phase is made；
(2) at room temperature, the pH buffer of the initiator of 0.15-0.23 parts, 0.08-0.11 parts is dissolved in going for 7.5-10.1 parts
In ionized water, initiator is made phase is added dropwise；
(3) at room temperature, toward the deionized water of addition 39.823-48.06 parts in reactor, opened and stirred with 100-150rpm speed
Mix, add the polyvinyl alcohol type protecting colloid of 5-9 parts, and start to warm up, when system reaches 90-93 DEG C, mixing speed adjustment
For 200-300rpm, and keep 20-40min；It is added dropwise obtained by monomer dropping phase and step (2) obtained by step (1) and draws simultaneously afterwards
Send out agent and phase is added dropwise, monomer dropping phase time for adding is 4-4.5h, and it is 4.5-5h that phase time for adding, which is added dropwise, in initiator, and initiator is added dropwise
Dripped compared to monomer dropping phase retardation 0.5h；Then system temperature is risen to 95-98 DEG C, 70-75 is cooled to after being incubated 1-2h
DEG C, add the TBHP aqueous solution, the TBHP aqueous solution by 0.068-0.082 parts tert-butyl group mistake
Hydrogen oxide is dissolved in 0.4 part of deionized water and obtained, insulated and stirred 10-20min, then adds the rongalite aqueous solution, described
The rongalite aqueous solution is dissolved in 0.4 part of deionized water by the rongalite of 0.068-0.082 parts and obtained, insulated and stirred 10-
20min, room temperature is finally down to, filtering and discharging, produces described film-forming resin.
7. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the wetting agent is poly- third
One or both of olefin(e) acid esters levelling agent, organic siliconresin class levelling agent, fluoroolefins levelling agent any of the above ratio
Mixture.
8. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the low mass molecule alcohol is first
The mixture of one or two kinds of any of the above ratio in alcohol, ethanol, isopropanol.
9. PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that the cosolvent is 3- first
The methyl-1-butanol of epoxide -3.
10. the preparation method of PVC floor film intaglio printing water-based ink as claimed in claim 1, it is characterised in that described
Preparation method is：
(1) master grind
Stocked up according to formula, at room temperature, by the pure water of formula ratio 30%~62%, the low molecule of formula ratio 33%~50%
Alcohol, dispersant, polyvinyl alcohol grind resin, the defoamer of formula ratio 60%~80% are added sequentially in Scattered Kettle, with 50-
150rpm speed adds pigment after being uniformly mixed, and is transferred to after being uniformly mixed with 150-300rpm speed sleeping
2-5 roads are ground in formula sand mill, filtering and discharging after reaching below 500nm to mill base particle diameter, obtain aqueous color paste；
(2) ink is prepared
At room temperature, successively by aqueous color paste, film-forming resin, wetting agent, residue obtained by the pure water of remaining formula ratio, step (1)
Low mass molecule alcohol, cosolvent, the defoamer of remaining formula ratio of formula ratio are added in dispersion cylinder, are stirred with 150-200rpm speed
Filtering and discharging after 0.5-1h is mixed, obtains described PVC floor film intaglio printing water-based ink.
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| CN108997838A (en) * | 2018-08-20 | 2018-12-14 | 江苏尚珩达科技有限公司 | Water-based ink PVC floor |
| CN109401433A (en) * | 2018-11-08 | 2019-03-01 | 杭州海维特化工科技有限公司 | A kind of PVC furniture film hooks print water-based ink and preparation method thereof |
| CN109439064A (en) * | 2018-11-08 | 2019-03-08 | 杭州海维特化工科技有限公司 | A kind of PVC edge band intaglio printing water-based ink and preparation method thereof |
| CN111876015A (en) * | 2020-08-20 | 2020-11-03 | 珠海格力绿色再生资源有限公司 | Gravure printing water-based ink for PVC plastic film and preparation method thereof |
| CN112592623A (en) * | 2020-12-17 | 2021-04-02 | 河南千卡绘纸制品有限公司 | Water-based quick-drying binder and preparation method thereof |
| EP3967735A1 (en) * | 2020-09-14 | 2022-03-16 | Tai Chang Colorful Press Industrial Co., Ltd. | Water-based ink and printing film comprising the same |
| CN114644854A (en) * | 2022-04-26 | 2022-06-21 | 镇江富又康新型装饰材料有限公司 | Water-based ink for PVC decorative film and preparation method thereof |
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| CN116640477A (en) * | 2023-05-17 | 2023-08-25 | 杭州海维特化工科技有限公司 | Quick-drying ink preparation method and application thereof in automotive interior PVC decorative film |
| CN116640477B (en) * | 2023-05-17 | 2024-05-28 | 杭州海维特化工科技有限公司 | Quick-drying ink preparation method and application thereof in automotive interior PVC decorative film |
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