CN108641475A - A kind of one-component acrylated polyester two-piece can ink and preparation method thereof - Google Patents
A kind of one-component acrylated polyester two-piece can ink and preparation method thereof Download PDFInfo
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- CN108641475A CN108641475A CN201810474939.XA CN201810474939A CN108641475A CN 108641475 A CN108641475 A CN 108641475A CN 201810474939 A CN201810474939 A CN 201810474939A CN 108641475 A CN108641475 A CN 108641475A
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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
- C09D11/104—Polyesters
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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
- C09D11/102—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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Abstract
To fly ink when overcoming the problems, such as that existing two-piece can ink deposits coating discoloration at high temperature, mechanical-physical declines and printing, the present invention provides a kind of one-component acrylated polyester two-piece can ink, including following components by weight percent：30~50 parts of acrylic acid modified polyester resin, 10~15 parts of amino resins, 3~15 parts of organic solvent, 0.5~1.5 part of catalyst, 20~45 parts of pigment, 0.5~2 part of modified urea；The molecular weight of the acrylic acid modified polyester resin is 2000~5000, and hydroxyl value is 20~100mg KOH/g.Meanwhile the invention also discloses the preparation methods of above-mentioned one-component acrylated polyester two-piece can ink.One-component acrylated polyester two-piece can ink provided by the invention has higher boiling resistance, gloss oil compatibility, solid content and anti-winged performance of ink.
Description
Technical field
The invention belongs to high speed machine printing ink technical fields, and in particular to a kind of one-component acrylated polyester two-piece can
Ink and preparation method thereof.
Background technology
Traditional food mental package incrustation is first to carry out lithographic printing in metal surface, after baking is dry, then into
Row food packaging jar is manufactured, and the ink being printed on outside packing jar is generally 4-6 microns, the process cycle of production compared with
It is long, it in process of production, is easy to generate abrasion to the pattern of ink outside tank, to influence to pack the fresh degree of reflecting and pattern of color
Perfection.In addition for traditional packing tin for foodstuff ink during printing use, energy consumption is relatively high, and batch production efficiency is low,
VOC discharge capacities are largely only limitted to the molding tinplate lithographic printing of three-piece can and use also greater than national regulatory range, for
Stretching aluminium and other mental section high-speed integrated chemical conversion types printing can manufacturing technology can not apply.
With advances in technology and the raising of living standards of the people, for canned food and drink demand increasingly
Greatly, it is desirable that it is also higher and higher, nutrition and the safety of food are not only required, it is also more and more exquisite simultaneously for packing instructions.Thus
It is a kind of domestic from foreign countries' introduction as the high speed two-piece can tank production line of proximate matter to stretch aluminium, different from manufacturing for former three-piece can
Technique is first printed, reshaping tank, but first passes through uncoiling, cross cutting, and first punching is stretched, and is stretched again, the cleaning of base tank, dry, print
Brush applies outside, internal spray, and disposable manufacture such as dry prints molding.This production efficiency is high, and energy consumption is relatively low, production loss
Small, VOC discharge capacities are also well below the standard limited value of country.Printed patterns are clearly exquisite, safe and practical, are suitable for all kinds of beverages
Production packaging, storage transport, consumption use and final recycling.
Dedicated two-piece can ink is needed in the production of the two-piece can tank production line, at present this field product of the country
For blank, some existing external (such as Ban Tian companies of Japan) ink, there is the mechanical performance for being suitable for two-piece can production, however should
Class ink can not be suitable for the packing tin for foodstuff of high temperature sterilization, and after 121 DEG C/30 minutes high temperature sterilizations, there are white spotted finiss, machines
The problem of tool physical decline.External ink flies black more in high speed printing simultaneously, influences press quality.
Invention content
Fly asking for ink when depositing coating discoloration at high temperature, mechanical-physical decline and printing for existing two-piece can ink
Topic, the present invention provides a kind of one-component acrylated polyester two-piece can ink and preparation method thereof.
Technical solution is as follows used by the present invention solves above-mentioned technical problem：
On the one hand, an embodiment of the present invention provides a kind of one-component acrylated polyester two-piece can ink, including it is following
Components by weight percent：30~50 parts of acrylic acid modified polyester resin, 10~15 parts of amino resins, 3~15 parts of organic solvent, catalyst
0.5~1.5 part, 20~45 parts of pigment, 0.5~2 part of modified urea；
The molecular weight of the acrylic acid modified polyester resin is 2000~5000, and hydroxyl value is 20~100mg KOH/g.
Technique and final performance requirement, the present invention is used to provide according to one-component acrylated polyester two-piece can ink
A kind of acrylic acid modified polyester resin containing terminal hydroxy group group, preferably low molecular weight and the acrylic acid limited within the scope of hydroxyl value change
Property polyester resin, can be reacted with amino resins in printing process, form fine and close ink coating, the ink coating is follow-up
It can provide gloss oil good adhesive force with gloss oil co-curing during wet on wet.Wherein acrylic acid modified polyester resin and amino
Resin reaction provides the good adhesion of ink layer and can body, and the flexility needed for necking down processing is provided simultaneously for coating,
With preferable processability.After acrylic acid modified polyester resin is reacted with amino resins, it can provide ink coating sorrow different resistance to
Thermophilic digestion performance and thermophilic digestion sterilize the mechanical performances such as ink layer hardness and abrasion resistance properties.It introduces and is modified in formula
Urea, the modified urea are poly- urine class formation auxiliary agent, realize the microcoacervation of resin each component in formula.It is generated between molecular resin certain
Hydrogen bond and intermolecular force between each roller when ink layer separation, can be detached uniformly rapidly and can be in high speed printing
Quickly spring back on former roller, to reduce ink in high speed printing due to the effect of centrifugal force and generate ink splatter.
Optionally, the acrylic acid modified polyester resin is solid containing being more than 90%, and glass transition temperature is -35 DEG C~0
Between DEG C.
Optionally, the acrylic acid modified polyester resin is esterified by acrylic polymer and polyester prepolyer and is made, described
The weight ratio of polyester prepolyer and the acrylic polymer is 1.6~1.8：0.9~1.1；
The solid of the polyester prepolyer contains more than 90%, and molecular weight is 1000~3000, and acid value is less than or equal to 17mg
KOH/g, viscosity are 1200~2000mpa.s；
Molecular weight is 1000~4000 containing being greater than or equal to 85% for the acrylic polymer solid, acid value is 90~
95mg KOH/g, viscosity are 1000~2000mPa.s.
Optionally, the raw material composition of the polyester prepolyer includes components by weight percent：20~30 parts of neopentyl glycol, MPD 2~
10 parts, 10~20 parts of 1,6-HD, 5~10 parts of phthalic anhydride, 30~50 parts of adipic acid, Mono-n-butyltin 0~0.1
Part, 5~10 parts of ethylene glycol ether acetate；
The raw material composition of the acrylic polymer includes components by weight percent：10~20 parts of acrylic acid, butyl acrylate 30~
50 parts, 10~20 parts of styrene, 15~30 parts of butyl methacrylate, 1~3 part of neopentyl peroxide, ethylene glycol ethyl ether vinegar
5~15 parts of acid esters.
Optionally, the organic solvent includes one or more in ethylene glycol monobutyl ether, ethylene glycol ether acetate, institute
It includes closed p-methyl benzenesulfonic acid to state catalyst.
Optionally, the pigment includes one or more in inorganic pigment and organic pigment；
The inorganic pigment includes one or more in titanium dioxide and carbon black；
The organic pigment includes PY 83, PY 180, PY 151, PR 254, PR 170, PR 176, PB15:3 and PG 7
In it is one or more.
Optionally, the modified urea includes the one or more of BYK 410 and BYK 430.
Optionally, the one-component acrylated polyester two-piece can ink further includes following components by weight percent：
1~3 part of 3~5 parts of auxiliary agent, 1~3 part of nano fumed silica and adhesion promoter；
The auxiliary agent includes one or more in wetting agent, antifoaming agent and levelling agent；
The nano fumed silica includes N20, one or more in N40 and H15.
On the other hand, an embodiment of the present invention provides one-component acrylated polyester two-piece can ink as described above
Preparation method includes the following steps：
Obtain acrylic acid modified polyester resin；
30~50 parts of acrylic acid modified polyester resins and 3~15 parts of organic solvent mixing, add 20~45 parts of face while stirring
Material is stirring evenly and then adding into 10~15 parts of amino resins, 0.5~1.5 part of catalyst and 0.5~2 part of modified urea, crosses three-roller and grinds
Mill, obtains one-component acrylated polyester two-piece can ink.
Optionally, described " obtaining acrylic acid modified polyester resin " includes：
In parts by weight, it weighs 20~30 parts of neopentyl glycol, 2~10 parts of MPD, 10~20 parts of 1,6- hexylene glycols, adjacent benzene
5~10 parts of 5~10 parts of dicarboxylic acid anhydride, 30~50 parts of adipic acid, 0~0.1 part of Mono-n-butyltin and ethylene glycol ether acetate；
All materials are thrown in reaction kettle, stirring is warming up to 160 DEG C, keeps the temperature 3h, and logical nitrogen is simultaneously gradually dehydrated to 235 DEG C, is esterified
To acid value≤17mgKOH/g, viscosity is that 1500mpa.s is terminal, obtains polyester prepolyer；
In parts by weight, 10~20 parts of acrylic acid, 30~50 parts of butyl acrylate, 10~20 parts of styrene, methyl are weighed
15~30 parts of butyl acrylate, 1~3 part of neopentyl peroxide, 5~15 parts of ethylene glycol ether acetate；By acrylic acid, propylene
Acid butyl ester, styrene and butyl methacrylate and 70% neopentyl peroxide be uniformly mixed, obtain mix monomer,
Ethylene glycol ether acetate and 30% mix monomer are put into a kettle, stirring is warming up to reflux temperature, keeps the temperature 30min,
The mix monomer of residue 70% is added dropwise in reaction kettle, 1h is kept the temperature after being added dropwise to complete, the neopentyl peroxide of residue 30% is added
Compound continues reflux heat preservation 1.5h, obtains acrylic polymer；
By polyester prepolyer and acrylic polymer according to 1.6~1.8：In 0.9~1.1 weight ratio input reaction kettle,
200 DEG C are warming up to, sloughs ethylene glycol ether acetate, esterification to acid value≤15mgKOH/g, cool down filtering and discharging, obtains propylene
Sour modified polyester resin.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
One embodiment of the invention discloses a kind of one-component acrylated polyester two-piece can ink, including following weight group
Point：30~50 parts of acrylic acid modified polyester resin, 10~15 parts of amino resins, 3~15 parts of organic solvent, catalyst 0.5~1.5
Part, 20~45 parts of pigment, 0.5~2 part of modified urea；
The molecular weight of the acrylic acid modified polyester resin is 2000~5000, and hydroxyl value is 20~100mg KOH/g.
In order to realize the high-speed production and the printing that stretch aluminium two-piece can, the present invention provides one kind with polyester acrylate resin
Based on suitable high speed letterpress two-piece can ink, preferably low molecular weight and limit hydroxyl value within the scope of it is acrylic acid modified
Polyester resin can react in printing process with amino resins, form fine and close ink coating, the ink coating is follow-up wet
Touch it is wet during can provide gloss oil good adhesive force with gloss oil co-curing.Wherein acrylic acid modified polyester resin and amino tree
Fat reaction provides the good adhesion of ink layer and can body, and the flexility needed for necking down processing, tool are provided simultaneously for coating
There is preferable processability.After acrylic acid modified polyester resin is reacted with amino resins, it can provide ink coating sorrow different resistance to height
Warm cooking characteristic and thermophilic digestion sterilize the mechanical performances such as ink layer hardness and abrasion resistance properties.Modified urea is introduced in formula,
The modified urea is poly- urine class formation auxiliary agent, realizes the microcoacervation of resin each component in formula.Certain hydrogen is generated between molecular resin
Key and intermolecular force between each roller when ink layer separation, can be detached uniformly rapidly and can be fast in high speed printing
Speed is sprung back on former roller, to reduce ink in high speed printing due to the effect of centrifugal force and generate ink splatter.
One-component acrylated polyester two-piece can ink provided by the invention has high speed printing performance good, anti-skinning
Good, anti-winged Mo Xinghao, the advantage that water-resistance is good, wet chromatography is good and anti-ization ink is good.It is formed using the two-piece can ink
Coating layer thickness need to only be controlled at 1-2 microns, so that it may realize that site is clear, the bright-coloured purpose of pattern.Match with existing outer glazing oil
Set property is good, after co-curing, is suitble to long-term storage, and unchanged during storage, long-distance transport is suitble to all kinds of drink without abrasion
The high-speed packaging of product.
In some embodiments, the acrylic acid modified polyester resin is solid containing being more than 90%, glass transition temperature-
Between 35 DEG C~0 DEG C.
It should be noted that the acrylic acid modified polyester resin can be obtained by commercially available or self-control.
In a preferred embodiment, it is the property of the raising one-component acrylated polyester two-piece can ink, wherein
Acrylic acid modified polyester resin is obtained by making by oneself.
The acrylic acid modified polyester resin is esterified by acrylic polymer and polyester prepolyer and is made, the polyester pre-polymerization
The weight ratio of object and the acrylic polymer is 1.6~1.8：0.9~1.1；
The solid of the polyester prepolyer contains more than 90%, and molecular weight is 1000~3000, and acid value is less than or equal to 17mg
KOH/g, viscosity are 1200~2000mpa.s；
Molecular weight is 1000~4000 containing being greater than or equal to 85% for the acrylic polymer solid, acid value is 90~
95mg KOH/g, viscosity are 1000~2000mPa.s.
By the raw material composition and ratio, the polyester prepolyer and the propylene that limit the acrylic acid modified polyester resin
The characteristics such as acid value, the viscosity of sour prepolymer are used using the good flexibility of polyester prepolyer in prepolymer containing hydroxyl telechelic polyester
Acrylic polymer with acidic group is esterified, and assigns resin good boiling resistance.In order to ensure can be with during wet on wet
Gloss oil co-curing contains a certain amount of hydroxyl value in acrylic acid modified polyester resin.The resin properties of high solid ensure that propylene
Sour modified polyester resin has the characteristics that good transferability and environmentally friendly.
Specifically, the raw material composition of the polyester prepolyer includes components by weight percent：20~30 parts of neopentyl glycol, MPD (methyl
Propylene glycol) 2~10 parts, 10~20 parts of 1,6-HD, 5~10 parts of phthalic anhydride, 30~50 parts of adipic acid, monobutyl oxygen
Change 0~0.1 part of tin, 5~10 parts of ethylene glycol ether acetate；
The raw material composition of the acrylic polymer includes components by weight percent：10~20 parts of acrylic acid, butyl acrylate 30~
50 parts, 10~20 parts of styrene, 15~30 parts of butyl methacrylate, 1~3 part of neopentyl peroxide, ethylene glycol ethyl ether vinegar
5~15 parts of acid esters.
In application scheme, compared to commercially available acrylic acid modified polyester resin, it is made of and is prepared above-mentioned raw materials
Acrylic acid modified polyester resin be applied to two-piece can ink in, have better boiling resistance, gloss oil compatibility, solid content
And processing performance.
In some embodiments, the organic solvent includes one kind in ethylene glycol monobutyl ether, ethylene glycol ether acetate
Or it is a variety of.
The organic solvent is used for the dissolving point of other components in the one-component acrylated polyester two-piece can ink
It dissipates.
The catalyst is used to promote the reaction between the acrylic acid modified polyester resin and the amino resins, specifically
, the catalyst is acid catalyst, it is preferred that the catalyst includes closed p-methyl benzenesulfonic acid.
In some embodiments, the pigment includes one or more in inorganic pigment and organic pigment.
The inorganic pigment includes one or more in titanium dioxide and carbon black；It is former that the titanium dioxide can be selected from Japanese stone
CR-60-2, the carbon black can be selected from Degussa P35 carbon blacks.
The organic pigment includes PY 83, PY 180, PY 151, PR 254, PR 170, PR 176, PB15:3 and PG 7
In it is one or more.
More colors can be obtained by one or more combinations of above-mentioned inorganic pigment and organic pigment.
Above-mentioned preferred inorganic pigment and organic pigment are high-temperature resisting pigment, thermophilic digestion can be avoided in pigment itself
Colour fading.
In some embodiments, the modified urea includes the one or more of BYK 410 and BYK 430.
In some embodiments, the one-component acrylated polyester two-piece can ink further includes following components by weight percent：
1~3 part of 3~5 parts of auxiliary agent, 1~3 part of nano fumed silica and adhesion promoter；
The auxiliary agent includes one or more in wetting agent, antifoaming agent and levelling agent.
The wetting agent can be selected from the one or more of German BYK110 and BYK170, and the antifoaming agent can be selected from Germany
BYK051, the levelling agent can be selected from German BYK392.
The nano fumed silica includes one or more in N20, N40 and the H15 of Germany watt gram.
Two silicon of nano-gas-phase can reduce the mobility of ink, to realize ink after printing, ensure that pattern printing is clear
Clear degree and fresh degree of reflecting.
Another embodiment of the present invention discloses the system of one-component acrylated polyester two-piece can ink as described above
Preparation Method includes the following steps：
Obtain acrylic acid modified polyester resin；
30~50 parts of acrylic acid modified polyester resins and 3~15 parts of organic solvent mixing, add 20~45 parts of face while stirring
Material, is stirring evenly and then adding into 10~15 parts of amino resins, 0.5~1.5 part of catalyst and 0.5~2 part of modified urea, after mixing
Three-roller grinding is crossed, one-component acrylated polyester two-piece can ink is obtained.
In some embodiments, the one-component acrylated polyester two-piece can ink further includes following components by weight percent：
1~3 part of 3~5 parts of auxiliary agent, 1~3 part of nano fumed silica and adhesion promoter.
The auxiliary agent includes one or more in wetting agent, antifoaming agent and levelling agent.
In some embodiments, the acrylic acid modified polyester resin is that self-control obtains, specifically, described " obtain propylene
Sour modified polyester resin " includes：
In parts by weight, it weighs 20~30 parts of neopentyl glycol, 2~10 parts of MPD, 10~20 parts of 1,6- hexylene glycols, adjacent benzene
5~10 parts of 5~10 parts of dicarboxylic acid anhydride, 30~50 parts of adipic acid, 0~0.1 part of Mono-n-butyltin and ethylene glycol ether acetate；
All materials are thrown in reaction kettle, stirring is warming up to 160 DEG C, keeps the temperature 3h, and logical nitrogen is simultaneously gradually dehydrated to 235 DEG C, is esterified
To acid value≤17mgKOH/g, viscosity is that 1500mpa.s is terminal, obtains polyester prepolyer；
In parts by weight, 10~20 parts of acrylic acid, 30~50 parts of butyl acrylate, 10~20 parts of styrene, methyl are weighed
15~30 parts of butyl acrylate, 1~3 part of neopentyl peroxide, 5~15 parts of ethylene glycol ether acetate；By acrylic acid, propylene
Acid butyl ester, styrene and butyl methacrylate and 70% neopentyl peroxide be uniformly mixed, obtain mix monomer,
Ethylene glycol ether acetate and 30% mix monomer are put into a kettle, stirring is warming up to reflux temperature, keeps the temperature 30min,
The mix monomer of residue 70% is added dropwise in reaction kettle, 1h is kept the temperature after being added dropwise to complete, the neopentyl peroxide of residue 30% is added
Compound continues reflux heat preservation 1.5h, obtains acrylic polymer；
By polyester prepolyer and acrylic polymer according to 1.6~1.8：In 0.9~1.1 weight ratio input reaction kettle,
200 DEG C are warming up to, sloughs ethylene glycol ether acetate, esterification to acid value≤15mgKOH/g, cool down filtering and discharging, obtains propylene
Sour modified polyester resin.
The present invention is further detailed by the following examples.
Embodiment 1
The preparation of acrylic acid modified polyester resin
1) polyester prepolyer (mass parts)
27 parts of neopentyl glycol, 5.6 parts of MPD, 12.5 parts of 1,6-HD, 8.9 parts of phthalic anhydride, 38 parts of adipic acid,
0.02 part of Mono-n-butyltin, 7.98 parts of ethylene glycol ether acetate；
Synthesis technology：All materials and reflux solvent are launched in reaction kettle, stirring is warming up to 160 DEG C, keeps the temperature 3H, leads to nitrogen
Gas is simultaneously gradually dehydrated to 235 DEG C, is esterified to and is contained ＞ 90% admittedly, and molecular weight is 1000~3000, acid value≤17mgKOH/g, viscosity
It is terminal for 1500mpa.s.
2) acrylic polymer (mass parts)
12.4 parts of acrylic acid, 44 parts of butyl acrylate, 12 parts of styrene, 20 parts of butyl methacrylate, neopentyl peroxide
1.6 parts of compound L531；
10 parts of ethylene glycol ether acetate.
Synthesis technology：By in whole monomers, chain-transferring agent and formula 70% neopentyl peroxide L531 in head tank
In be uniformly mixed, obtain mix monomer.In reaction kettle, solvent ethylene glycol ethyl ether acetate ester and 30% mix monomer are put into,
Stirring is warming up to reflux temperature (about 120 DEG C), keeps the temperature 30min, and the mix monomer of residue 70% is added dropwise, is dripped off in 3h or so, and
1h is kept the temperature, remaining neopentyl peroxide L531 is added, continues reflux heat preservation 1.5h, the technical indicator for measuring resin is qualified
Afterwards, cooling discharge is spare.
The technical indicator of acrylic polymer：
Color (Fe-Co) number≤2, acid value：90~95, Gu containing (120 DEG C of tests) >=85%, viscosity/mPa.s 1000-
2000, molecular weight is 1000~4000.
After technical indicator qualification, cooling discharge is spare.
3) preparation of acrylic acid modified polyester resin
By polyester prepolyer and acrylic polymer according to 1.6:In 1 weight ratio input reaction kettle, heat up (desolventizing)
To 200 DEG C, esterification to acid value≤15mgKOH/g, viscosity, cool down filtering and discharging.
The quality index of resin is：
Admittedly containing：＞ 90%；TG:- 35~0 DEG C；Molecular weight Mn：2000~5000；Hydroxyl value：20~100.
Embodiment 2
Two-piece can ink white ink is prepared, each component weight percent content is as follows：
Preparation method is as follows：By acrylic acid modified polyester resin, ethylene glycol monobutyl ether, BYK110, BYK051, BYK392 is mixed
It closes, with high speed dispersor high-speed stirred, CR-60-2 is then added while stirring, CR-60-2 stirrings 5~after ten minutes, side is added
It stirs side and N20 is added, after stirring 5 minutes or so, amino resins is added and closed p-methyl benzenesulfonic acid, BYK410 and attachment are made every effort to promote
Into agent, 600-800 turns high-speed stirred half an hour, crosses three-roller grinding.When ink fineness be less than 10 μm, test viscosity, fluidity,
Fly ink, is packed after qualified.Any of the above raw material passes through SGS and detects certification, meets ink and meet REACH regulation management and control
Height concern substance (SVHC), RoHS2.0, the no benzene/Halogen/high-environmental quality requirement without bisphenol-A.
Embodiment 3
Two-piece can ink black ink is prepared, each component weight percent content is as follows：
Preparation method is as follows：By acrylic acid modified polyester resin, ethylene glycol monobutyl ether, BYK170, BYK051, BYK392 is mixed
It closes, with high speed dispersor high-speed stirred, Degussa P35 carbon blacks is then added while stirring, P35 carbon blacks are added and stir 5-10 minutes
Afterwards, it is added N20 while stirring, after stirring 5 minutes or so, is added amino resins and closed p-methyl benzenesulfonic acid, BYK410 and attached
Adhesion promoter, 600-800 turn high-speed stirred half an hour, cross three-roller grinding.When ink fineness be less than 10 μm, test viscosity,
Fluidity flies ink, is packed after qualified.Any of the above raw material passes through SGS and detects certification, meets the height of REACH regulation management and control
Pay close attention to substance (SVHC), RoHS2.0, the no benzene/Halogen/high-environmental quality requirement without bisphenol-A.
Embodiment 4
Two-piece can ink red ink is prepared, each component weight percent content is as follows：
Preparation method is as follows：By acrylic acid modified polyester resin, ethylene glycol monobutyl ether, BYK170, BYK051, BYK392 is mixed
It closes, with high speed dispersor high-speed stirred, C.I.PR 254, C.I.PR170, C.I.PR 176 is then added while stirring and stirs 5-
After ten minutes, N20 is sequentially added while stirring, and after stirring 5 minutes or so, amino resins and closed p-methyl benzenesulfonic acid is added,
BYK410 and adhesion promoter, 600-800 turn high-speed stirred half an hour, cross three-roller grinding.When ink fineness be less than 10 μm,
It tests viscosity, fluidity, fly ink, packed after qualified.Any of the above raw material passes through SGS and detects certification, meets REACH methods
Regulate the high concern substance (SVHC) of control, RoHS2.0, the no benzene/Halogen/high-environmental quality requirement without bisphenol-A.
Embodiment 5
Two-piece can ink Yellow ink is prepared, each component weight percent content is as follows：
Preparation method is as follows：By acrylic acid modified polyester resin, ethylene glycol monobutyl ether, BYK110, BYK051, BYK392 is mixed
It closes, with high speed dispersor high-speed stirred, is then added while stirring after C.I.PY 83, C.I.PY 151 after stirring 5-10 minutes,
N20 is added while stirring, after stirring 5 minutes or so, amino resins and closed p-methyl benzenesulfonic acid, BYK410 and adhesive force is added
Accelerating agent, 600-800 turn high-speed stirred half an hour, cross three-roller grinding.When ink fineness is less than 10 μm, test viscosity flows
Degree flies ink, is packed after qualified.Any of the above raw material passes through SGS and detects certification, meets the high concern of REACH regulation management and control
Substance (SVHC), RoHS2.0, the no benzene/Halogen/high-environmental quality requirement without bisphenol-A.
Embodiment 6
Two-piece can ink blue ink is prepared, each component weight percent content is as follows：
Preparation method is as follows：By acrylic acid modified polyester resin, BYK170, BYK051, high speed dispersion is used in BYK392 mixing
Then C.I.PB 15 is added in machine high-speed stirred while stirring:After 3 stirrings 5-10 minutes, N20 is added while stirring, stirs 5 points
After clock or so, amino resins is added and closed p-methyl benzenesulfonic acid, BYK410 and adhesion promoter, 600-800 turn high-speed stirring
It mixes half an hour, crosses three-roller grinding.When ink fineness is less than 10 μm, test viscosity, flies ink at fluidity, is packed after qualified.With
Upper various raw materials pass through SGS and detect certification, meet the high concern substance (SVHC) of REACH regulation management and control, RoHS2.0, nothing
Benzene/Halogen/high-environmental the quality requirement without bisphenol-A.
Performance test
Model prepares 1
The two-piece can ink and existing commercially available ink being prepared using above-described embodiment 2~6 carry out ink base
Plinth performance test, test result are shown in Table one.It is 0.5-2g/m to take appropriate ink multistage color spreading instrument color development, ink dry film weight2, apply
Cloth is directly coated with gloss oil on the good Bai Keding aluminiums of Passivation Treatment, with bar spreader, and (gloss oil dry film weight is 3-4g/m2),
2min is toasted in 205 DEG C of baking ovens, solidification temperature is 193-199 DEG C.The physical and chemical performance for testing film is steamed using 85 DEG C of * 30min
After boiling, the boiling resistance of coating is tested, test the results are shown in Table two.
Model prepares 2
The two-piece can ink and existing commercially available ink that above-described embodiment 2~6 is prepared equally are taken, with multistage exhibition
Color instrument color development, ink dry film weight are 0.5-2g/m2, are coated on the good aluminium pot of Passivation Treatment, are directly coated with bar spreader
Gloss oil (gloss oil dry film weight is 3-4g/m2), toasts 2min in 205 DEG C of baking ovens, and solidification temperature is 193-199 DEG C.Test film
Physical and chemical performance test the thermophilic digestion resistance of coating after 121 DEG C of * 30min boilings, test the results are shown in Table three.
Table one：The performance parameter table of ink
Table two：Physical and chemical performance list of the ink on Bai Keding aluminiums
Table three：Physical and chemical performance list of the ink on aluminium pot
In table one to table three：
(1) viscosity is detected using sticky instrument, and in 32 DEG C of operating temperature, rotating speed is 400 turns of readings after lower 1 minute.
(2) fluidity is at a temperature of 25 DEG C, and 0.1g ink is by the ink film deployment diameter after 100g pressure 10min.
(3) fly performance of ink to test using sticky instrument, in 32 DEG C of operating temperature, rotating speed is knot of 1200 rotating speeds after lower 1 minute
Fruit.O grades represent winged ink less, and 4 grades of representatives fly black more.
(4) fineness is the result with the direct test reading of SHEEN fineness gauges.
(5) transferability is detected using multistage color spreading instrument, and transferring effect of the ink from squeegee to steel rider, OK represents good
It is good.
(6) solvent resistance is stained on four layers of gauze with butanone, wipes specified coating area back and forth with the power of 1KG, is come
It is back-calculated primary.
(7) flexibility is by substrate punching into a diameter of 45mm, is highly the cup-shaped of 10mm, observes appearance of coat.OK generations
Table flexibility is good.
(8) boiling resistance is to observe appearance of coat and adhesive force by finished product after constant temperature boils 30min in 85 DEG C of water-baths.O grades
Represent that adhesive force is good, coating is without whitening, the phenomenon that no colour fading.
(9) thermophilic digestion resistance is to observe appearance of coat and attached by finished product in 121 DEG C of water-baths after constant temperature boiling 30min
Put forth effort.O grades represent that adhesive force is good, and coating is without whitening, the phenomenon that no colour fading.
(10) the case where heat resistance is that finished product is placed on 10min in 220 DEG C of baking oven, and observation coating color changes.O grades
Represent the phenomenon that coating is without fading.
(11) light-protection rate is indicated with % numbers with the finished product gloss ratio after boiling before boiling.Light-protection rate is higher, and performance is more excellent
It is different.
(12) adhesive force (mark the shape of cross grid on finished product coating with blade of carving knife, each standardized knife of transverse and longitudinal, type at
100 tiny grids, grid are 1mm × 1mm.The notch for drawing lattice device should be to paint filler.It is attached on notch and is drawn with adhesive tape
It opens, the adhesion strength of adhesive tape is 350-400g/ square meters.The case where finally using amplification sem observation grid area is by ink 1mm ten
The adhesion property of word interior extrapolation method or tape method verification product surface coating or ink)：0 grade represents ink film and does not fall off, 4 grades of generations
Table adhesive force falls off 60%.
It was found from from table one to the test result of table three：The optimization of present component, the anti-winged Mo Xinghao of obtained ink product,
Flexibility is good, and good in 121 DEG C of cooking characteristics, adhesive force is excellent after boiling.Both domestic blank had been compensated for, ink is both realized
Production domesticization, also solves that resistance to 121 DEG C of boilings existing for external ink are bad, flies the problem more than ink.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of one-component acrylated polyester two-piece can ink, which is characterized in that including following components by weight percent：Acrylic acid changes
30~50 parts of polyester resin of property, 10~15 parts of amino resins, 3~15 parts of organic solvent, 0.5~1.5 part of catalyst, pigment 20~
45 parts, 0.5~2 part of modified urea；
The molecular weight of the acrylic acid modified polyester resin is 2000~5000, and hydroxyl value is 20~100mg KOH/g.
2. one-component acrylated polyester two-piece can ink according to claim 1, which is characterized in that the acrylic acid
The solid of modified polyester resin contains more than 90%, and glass transition temperature is between -35 DEG C~0 DEG C.
3. one-component acrylated polyester two-piece can ink according to claim 1, which is characterized in that the acrylic acid
Modified polyester resin is esterified by acrylic polymer and polyester prepolyer and is made, the polyester prepolyer and the acrylic acid pre-polymerization
The weight ratio of object is 1.6~1.8：0.9~1.1；
The solid of the polyester prepolyer contains more than 90%, and molecular weight is 1000~3000, and acid value is less than or equal to 17mg KOH/g,
Viscosity is 1200~2000mpa.s；
The solid of the acrylic polymer contains more than or equal to 85%, and molecular weight is 1000~4000, and acid value is 90~95mg
KOH/g, viscosity are 1000~2000mPa.s.
4. one-component acrylated polyester two-piece can ink according to claim 3, which is characterized in that
The raw material composition of the polyester prepolyer includes components by weight percent：20~30 parts of neopentyl glycol, 2~10 parts of MPD, 1,6- oneself
10~20 parts of glycol, 5~10 parts of phthalic anhydride, 30~50 parts of adipic acid, 0~0.1 part of Mono-n-butyltin, ethylene glycol ethyl ethers
5~10 parts of ether acetate；
The raw material composition of the acrylic polymer includes components by weight percent：10~20 parts of acrylic acid, 30~50 parts of butyl acrylate,
10~20 parts of styrene, 15~30 parts of butyl methacrylate, 1~3 part of neopentyl peroxide, ethylene glycol ether acetate 5
~15 parts.
5. one-component acrylated polyester two-piece can ink according to claim 1, which is characterized in that described organic molten
Agent includes one or more in ethylene glycol monobutyl ether, ethylene glycol ether acetate, and the catalyst includes closed to toluene
Sulfonic acid.
6. one-component acrylated polyester two-piece can ink according to claim 1, which is characterized in that the pigment packet
It includes one or more in inorganic pigment and organic pigment；
The inorganic pigment includes one or more in titanium dioxide and carbon black；
The organic pigment includes PY 83, PY 180, PY 151, PR 254, PR 170, PR 176, PB15:In 3 and PG 7
It is one or more.
7. one-component acrylated polyester two-piece can ink according to claim 1, which is characterized in that the modified urea
Including the one or more of BYK 410 and BYK 430.
8. one-component acrylated polyester two-piece can ink according to claim 1, which is characterized in that the one-component
Acrylated polyester two-piece can ink further includes following components by weight percent：
1~3 part of 3~5 parts of auxiliary agent, 1~3 part of nano fumed silica and adhesion promoter；
The auxiliary agent includes one or more in wetting agent, antifoaming agent and levelling agent；
The nano fumed silica includes N20, one or more in N40 and H15.
9. the preparation method of the one-component acrylated polyester two-piece can ink as described in any one of claim 1~8,
It is characterized by comprising the following steps：
Obtain acrylic acid modified polyester resin；
30~50 parts of acrylic acid modified polyester resins and 3~15 parts of organic solvent mixing, add 20~45 parts of pigment, stir while stirring
10~15 parts of amino resins, 0.5~1.5 part of catalyst and 0.5~2 part of modified urea is added after mixing uniformly, crosses three-roller grinding, obtains
To one-component acrylated polyester two-piece can ink.
10. the preparation method of one-component acrylated polyester two-piece can ink according to claim 9, feature exist
In " the obtaining acrylic acid modified polyester resin " includes：
In parts by weight, it weighs 20~30 parts of neopentyl glycol, 2~10 parts of MPD, 10~20 parts of 1,6- hexylene glycols, O-phthalic
5~10 parts of 5~10 parts of acid anhydrides, 30~50 parts of adipic acid, 0~0.1 part of Mono-n-butyltin and ethylene glycol ether acetate；By institute
There is material to be thrown in reaction kettle, stirring is warming up to 160 DEG C, keeps the temperature 3h, and logical nitrogen is simultaneously gradually dehydrated to 235 DEG C, is esterified to acid
Value≤17mgKOH/g, viscosity are that 1500mpa.s is terminal, obtain polyester prepolyer；
In parts by weight, 10~20 parts of acrylic acid, 30~50 parts of butyl acrylate, 10~20 parts of styrene, metering system are weighed
15~30 parts of acid butyl ester, 1~3 part of neopentyl peroxide, 5~15 parts of ethylene glycol ether acetate；By acrylic acid, acrylic acid fourth
Ester, styrene and butyl methacrylate and 70% neopentyl peroxide be uniformly mixed, mix monomer is obtained, anti-
It answers and puts into ethylene glycol ether acetate and 30% mix monomer in kettle, stirring is warming up to reflux temperature, keeps the temperature 30min, will remain
70% mix monomer of remaininging is added dropwise in reaction kettle, and 1h is kept the temperature after being added dropwise to complete, and the neopentyl peroxide of residue 30% is added,
Continue reflux heat preservation 1.5h, obtains acrylic polymer；
By polyester prepolyer and acrylic polymer according to 1.6~1.8：In 0.9~1.1 weight ratio input reaction kettle, heating
To 200 DEG C, ethylene glycol ether acetate is sloughed, esterification to acid value≤15mgKOH/g, cool down filtering and discharging, obtains acrylic acid and changes
Property polyester resin.
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| CN111205443A (en) * | 2020-03-02 | 2020-05-29 | 上海超彩油墨有限公司 | Polyester resin for two-piece can printing ink, two-piece can printing ink and preparation method of two-piece can printing ink |
| CN111440481A (en) * | 2020-05-21 | 2020-07-24 | 佛山市儒林化工有限公司 | Aluminum tank bottomless high-temperature water-boiling printing ink and preparation method thereof |
| CN111690292A (en) * | 2020-07-09 | 2020-09-22 | 江苏扬瑞新型材料股份有限公司 | Touch ink for two-piece can and preparation method thereof |
| CN112480737A (en) * | 2020-12-29 | 2021-03-12 | 厦门德瑞雅喷码科技有限公司 | Water-based ink composition resistant to boiling |
| CN115197605A (en) * | 2022-06-17 | 2022-10-18 | 佛山市儒林化工有限公司 | Printing ink with wrinkle texture effect and preparation method thereof |
| EP4083709A4 (en) * | 2019-12-27 | 2024-01-10 | Kao Corporation | Binder resin for toners |
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|---|---|---|---|---|
| EP4083709A4 (en) * | 2019-12-27 | 2024-01-10 | Kao Corporation | Binder resin for toners |
| CN111205443A (en) * | 2020-03-02 | 2020-05-29 | 上海超彩油墨有限公司 | Polyester resin for two-piece can printing ink, two-piece can printing ink and preparation method of two-piece can printing ink |
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| CN111690292A (en) * | 2020-07-09 | 2020-09-22 | 江苏扬瑞新型材料股份有限公司 | Touch ink for two-piece can and preparation method thereof |
| CN112480737A (en) * | 2020-12-29 | 2021-03-12 | 厦门德瑞雅喷码科技有限公司 | Water-based ink composition resistant to boiling |
| CN112480737B (en) * | 2020-12-29 | 2022-06-28 | 厦门德瑞雅喷码科技有限公司 | Water-based ink composition resistant to boiling |
| CN115197605A (en) * | 2022-06-17 | 2022-10-18 | 佛山市儒林化工有限公司 | Printing ink with wrinkle texture effect and preparation method thereof |
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