CN108603061A - The excellent color ink compositions for steel material of adhesiveness, the method using its manufacture printed steel plate and the printed steel plate manufactured according to this method - Google Patents
The excellent color ink compositions for steel material of adhesiveness, the method using its manufacture printed steel plate and the printed steel plate manufactured according to this method Download PDFInfo
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- CN108603061A CN108603061A CN201680076294.3A CN201680076294A CN108603061A CN 108603061 A CN108603061 A CN 108603061A CN 201680076294 A CN201680076294 A CN 201680076294A CN 108603061 A CN108603061 A CN 108603061A
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Abstract
The present invention relates to the excellent color ink compositions for printed steel plate such as adhesiveness, processability, solvent resistance to steel plate, the printed steel plates that manufacture the method for printed steel plate using it and manufactured according to this method.In particular to the method and printed steel plate of color ink compositions, manufacture printed steel plate for steel material, the color ink compositions for steel material include：The mixture of xenogenesis acrylate oligomer except the urethaneacrylates oligomer of 10 parts by weight to 30 parts by weight and the urethaneacrylates oligomer；The light-cured type monomer of 50 parts by weight to 80 parts by weight is the mixture of the light-cured type monomer of simple function group light-cured type monomer and difunctional or more；The photoinitiator of 5 parts by weight to 20 parts by weight；The pigment of 0.1 parts by weight to 10 parts by weight；And 3 parts by weight to 300 parts by weight dispersant, be every 100 parts by weight pigment in dispersant solid content；Wherein, the urethaneacrylates oligomer and xenogenesis acrylate oligomer are with 1:1 to 10:1 weight ratio mixing, and light-cured type monomer more than the simple function group light-cured type monomer and difunctional is with 5:1 to 100:1 weight ratio mixing；The method of the manufacture printed steel plate includes the following steps：To the color ink compositions for steel plate of the steel plate injection present invention；And it carries out being solidified to form printing layer；The printed steel plate includes：Steel plate；And printing layer, it is formed on the steel plate by the color ink compositions for steel plate of the present invention.
Description
Technical field
The method of printed steel plate and the print according to this method manufacture are manufactured the present invention relates to color ink compositions, using it
Brush steel plate.In further detail, the present invention relates to adhesiveness, processability, solvent resistance to steel plate etc. it is excellent for printing steel
The color ink compositions of plate, the printed steel plate for manufacturing the method for printed steel plate using it and being manufactured according to this method.
Background technology
Textured printed steel plate is made by way of silk-screen printing or roller printing in existing steel plate.But
When manufacturing printed steel plate by way of silk-screen printing, using intermittence batch-type (batch type) technique at piece (sheet)
On the technique printed manufacture, rather than manufactured using the technique printed on roll bending (coil).Pass through roll marks
When the mode of brush manufactures steel plate, by making ink or paint be stained on through on overetched roller after the etch printing texture on roller, and
Mode on the steel plate is coated to manufacture printed steel plate.
As described above, existing printed steel plate is made by way of silk-screen printing, roller printing or lamination, but it is this existing
Some mode of printings can not print high-resolution pattern.Moreover, also have and made caused by making silk screen or roller
The rising of cost, can not produce the shortcomings that product of multiple color at low actual recovery.To solve the above-mentioned problems, it is intended to spray
Ink print mode is used in the shortcomings that existing mode for making printed steel plate is made up in steel.
But when directly spraying color ink compositions on steel material, due to there is no absorbed layer, it is difficult to ensure ink
Adhesiveness between material, therefore product can not be utilized as.In addition, not only needing to meet adhesiveness, but also also need to meet
All processabilities, solvent resistance etc., therefore replace having limitation in terms of existing printed steel plate.
Invention content
Technical problems to be solved
The purpose of the present invention is to provide the color ink compositions that the adhesiveness to steel material is excellent.In addition, this hair
The coloured silk for steel material of the bright ejection being designed to provide in the showerhead, operability, processability, excellent solvent resistance
Color ink composition.
The purpose of the present invention is to provide color ink compositions are used on steel plate by way of ink-jet, to
Excellent ejection and operability manufacture the printing steel of the adhesiveness to the printing layer of steel plate, processability and excellent solvent resistance
The method of plate.
The purpose of the present invention is to provide the printed steel plates with printing layer, wherein the printing layer is by steel plate
The color ink compositions of adhesiveness, processability and excellent solvent resistance are formed.
Technical solution
The present invention is provided to the color ink compositions of steel material, it includes：
The urethaneacrylates oligomer of 10 parts by weight to 30 parts by weight and the urethanes propylene
The mixture of xenogenesis acrylate oligomer except acid esters oligomer；
The light-cured type monomer of 50 parts by weight to 80 parts by weight is simple function group light-cured type monomer and difunctional with
On light-cured type monomer mixture；
The photoinitiator of 5 parts by weight to 20 parts by weight；
The pigment of 0.1 parts by weight to 10 parts by weight；And
The dispersant of 3 parts by weight to 300 parts by weight, for the dispersant solid content in the pigment of every 100 parts by weight；
Wherein, the urethaneacrylates oligomer and xenogenesis acrylate oligomer are with 1:1 to 10:1
Weight ratio mixes, and light-cured type monomer more than the simple function group light-cured type monomer and difunctional is with 5:1 to
100:1 weight ratio mixing.
It is 500 to 12,000 amino first that the urethaneacrylates oligomer, which can use weight average molecular weight,
Acetoacetic ester acrylate oligomer.
The urethaneacrylates oligomer can use aliphatic urethane acrylate.
It is 3 urethanes below that the urethaneacrylates oligomer, which can use number of functional groups,
Ester acrylate oligomer.
The xenogenesis acrylate oligomer is preferably selected from polyester acrylate oligomers and epoxyacrylate oligomers
Object.
It is that 4 polyester acrylates below are oligomeric that the polyester acrylate oligomers, which can use number of functional groups,
Object.
The polyester acrylate that the polyester acrylate oligomers can use weight average molecular weight to be 500 to 3,000 is low
Polymers.
It is 2 epoxyacrylate oligomers below that the epoxy acrylate oligomer, which can use number of functional groups,
Object.
The epoxy acrylate that the epoxy acrylate oligomer can use weight average molecular weight to be 500 to 2,000 is low
Polymers.
It is preferable to use selected from Isooctyl acrylate monomer, cyclic trimethylolpropane contracting first for the simple function group light-cured type monomer
Aldehyde acrylate (cyclic trimethylolpropane formal acrylate), phenoxy benzyl acrylic ester, front three
Butylcyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, lauryl acrylate, isodecyl acrylate, phenoxy group second
Base acrylate, tetrahydrofurfuryl acrylate, ethoxyethoxyethyl acrylate, octadecyl acrylate, acrylic acid hydroxyl second
Ester, hydroxypropyl acrylate, acryloyl morpholine (acryl morpholine), vinyl ethers, vinyl esters, N- vinyl -2-
It is more than at least one of pyrrolidones and N- caprolactams.
It is preferable to use selected from ethylene glycol diacrylate, hexylene glycol dipropyl for light-cured type the monomer more than difunctional
Olefin(e) acid ester, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, tetraethylene glycol diacrylate
Ester, neopentylglycol diacrylate, Tricyclodecane Dimethanol diacrylate, polyethylene glycol 400 diacrylate, trihydroxy methyl
Propane triacrylate, three propylene of ethoxylated trimethylolpropane triacrylate, glycerol tri-acrylate and pentaerythrite
It is more than at least one of acid esters.
The viscosity of the color ink compositions for steel material at normal temperatures is preferably 40cps or less.
The surface tension of the color ink compositions for steel material can be 20~50 dynes/cm (dyne/
cm)。
The method that the present invention provides manufacture printed steel plate comprising following steps：It is used for steel to the steel plate injection present invention
The color ink compositions of plate；And the color ink compositions of injection are cured, to form printing layer.
The present invention provides printed steel plate comprising：Steel plate；And printing layer, by the colour for steel plate of the present invention
Printing ink composition is formed on the steel plate.
The printed steel plate can include selected from color coating layer, layers of chrome and without layers of chrome between the steel plate and printing layer
At least one of pretreatment layer.
Invention effect
For the color ink compositions for steel material of the present invention, had to steel by the printing layer that it is formed
Excellent adhesiveness.Moreover, the printing layer has excellent processability, solvent resistance, intensity and color sense, therefore shape
The printed steel plate for high-quality is used at the printed steel plate for having the printing layer.In addition, the coloured silk for steel material of the present invention
The viscosity of color ink composition at normal temperatures is sufficiently low, therefore can be used in steel material by ink-jet.
Description of the drawings
Fig. 1 shows the side cross-sectional view with the printed steel plate of the printing layer of steel plate and formation on the steel plate.
Fig. 2 shows the side cross-sectional views of the printed steel plate with printing layer, wherein the printing layer, which is formed in, to be had at chromium
On the steel plate of the pretreatment layer of reason or chromium-free treatment.
Fig. 3 shows the side cross-sectional view of the printed steel plate with printing layer, wherein the printing layer, which is formed in, has pre- place
On the steel plate for managing layer, color coating layer.
Specific implementation mode
In the following, being illustrated to the preferred embodiment of the present invention with reference to attached drawing.But embodiments of the present invention can be with
Various other modes are modified to, the scope of the present invention is not limited to embodiments described below.
According to embodiment of the present invention, provide for steel material color ink compositions (hereinafter also referred to as
" color ink compositions of an embodiment "), it includes：
The urethaneacrylates oligomer of 10 parts by weight to 30 parts by weight and the urethanes propylene
The mixture of xenogenesis acrylate oligomer except acid esters oligomer；
The light-cured type monomer of 50 parts by weight to 80 parts by weight is simple function group light-cured type monomer and difunctional with
On light-cured type monomer mixture；
The photoinitiator of 5 parts by weight to 20 parts by weight；
The pigment of 0.1 parts by weight to 10 parts by weight；And
The dispersant of 3 parts by weight to 300 parts by weight, be every 100 parts by weight pigment in dispersant solid content,
Wherein, the urethaneacrylates oligomer and xenogenesis acrylate oligomer are with 1:1 to 10:1
Weight ratio mixes, and light-cured type monomer more than the simple function group light-cured type monomer and difunctional is with 5:1 to
100:1 weight ratio mixing.Hereinafter, being illustrated to the composition of the color ink compositions for steel material of the present invention.
The color ink compositions for steel material of the present invention are made comprising urethaneacrylates oligomer
For main material.Usually using polyester acrylate oligomers, epoxy acrylic in ultraviolet light (UV) curable resin composition
Ester oligomer, urethaneacrylates oligomer.But the solvent resistance of polyester acrylate oligomers and scratch-resistant
Property is good, but poor in processability.The hardness and excellent solvent resistance of epoxy acrylate oligomer, but exist and generate asking for xanthochromia
Topic.Urethaneacrylates oligomer meets the printing of the printed steel plates such as processability, solvent resistance, hardness, adhesiveness
The required most of physical property of layer, especially has the effect of brilliance in terms of processability.Therefore, using urethanes
Acrylate oligomer is as main material.
In adhesiveness, curability, hardness etc., the urethaneacrylates oligomer does not include preferably
The aliphatic urethane acrylate oligomer of phenyl ring.
It is 3 urethanes below that the urethaneacrylates oligomer, which can use number of functional groups,
Ester acrylate oligomer, it is 1~3 urethaneacrylates oligomer that can preferably use number of functional groups.
When the number of functional groups of urethaneacrylates oligomer is more than 3, the flexibility of film is insufficient, to lead to add
Work reduces.At least there are one can form film by curing reaction when functional group for tool.
It is preferable to use the ammonia that weight average molecular weight (Mw) is 500 to 12,000 for the urethaneacrylates oligomer
Base urethane acrylates oligomer.If the weight average molecular weight of urethaneacrylates oligomer is less than 500,
Crosslink density can be got higher, to processability be caused to reduce, if the Weight-average molecular of urethaneacrylates oligomer
Amount would generally then be such that the viscosity of substance increases more than 12,000, in the viscosity spray for realizing printing ink composition
Aspect is restricted, and the crosslink density of film can reduce, and solvent resistance is caused to die down.
The non-limitative example of the urethane oligomer can enumerate Miwon companies Miramer PU210,
Miramer PU2034C、Miramer PU2100、Miramer PU2200、Miramer PU330、Miramer PU340、
Miramer PU3200, Miramer PU2560, the EBECRYL 244 of Qing Te companies (Cytec), EBECRYL 245,
EBECRYL 254、EBECRYL 264、EBECRYL 265、EBECRYL 270、EBECRYL 280、EBECRYL 284、
EBECRYL 285、EBECRYL 294、EBECRYL 1259、EBECRYL 1290、EBECRYL 4830、EBECRYL 4835、
EBECRYL 4883、EBECRYL 8296、EBECRYL 8402、EBECRYL 8465、EBECRYL 8800、EBECRYL
8803、EBECRYL 8804、EBECRYL 8805、EBECRYL 8806、EBECRYL 9215、EBECRYL 9216、EBECRYL
9259, EBECRYL 9260, EBECRYL 9270, EBECRYL 9370, UA 7933, UP 112, UP 136, UP 137 etc..Root
According to needs, one or more of these urethaneacrylates oligomer can be selected to be used.These amino first
Acetoacetic ester acrylate oligomer can be used alone, or be used together as needed two or more.
Except the urethaneacrylates oligomer and the urethaneacrylates oligomer
Xenogenesis acrylate oligomer is used together.That is, in terms of the required physical property of control, by the urethanes third
Olefin(e) acid ester oligomer and xenogenesis acrylate oligomer are used cooperatively, so as to suitably control adhesiveness, hardness, solvent resistant
The physical properties such as property, processability, viscosity.
In the composition of the present invention, on the basis of the weight of color ink compositions, relative to an embodiment
Color ink compositions other compositions content, the urethaneacrylates oligomer and xenogenesis acrylate
The content of the mixture of oligomer can be 10~30 parts by weight.If the urethaneacrylates oligomer and different
The content of the mixture of kind acrylate oligomer is less than 10 parts by weight, then adhesiveness, processability, solvent resistance etc. can die down.
If the content of the mixture of the urethaneacrylates oligomer and xenogenesis acrylate oligomer is more than 30 weights
Part is measured, then viscosity is excessively got higher, and to be difficult to be sprayed, therefore can not be used in ink-jet system.
The xenogenesis acrylate oligomer can use low selected from polyester acrylate oligomers and epoxy acrylate
Acrylate oligomer in polymers.These acrylate oligomers can be used alone or be used together two or more.
It is that 4 polyester acrylates below are oligomeric that the polyester acrylate oligomers, which can use number of functional groups,
Object, it is 1 or more and 4 polyester acrylate oligomers below that can preferably use number of functional groups.If polyester
The number of functional groups of acid esters oligomer is more than 4, then crosslink density is got higher, to processability be caused to reduce.At least have one
Printing layer can be formed when a functional group by polymerisation.
The weight average molecular weight of the polyester acrylate oligomers is preferably 500 to 3,000.If weight average molecular weight is less than
500 or more than 3,000, then it is difficult to efficiently control physical property.
The non-limitative example of the polyester acrylate oligomers can enumerate the Miramer of Miwon companies
PS4040, Miramer PS420, the EBECRYL 80 of Qing Te companies (Cytec), EBECRYL 81, EBECRYL 84,
EBECRYL 452、EBECRYL 657、EBECRYL 800、EBECRYL 810、EBECRYL 851、EBECRYL 852、
EBECRYL 884, EBECRYL 1657, EBECRYL 1810, UP 039 etc..As needed, these polyester acrylates are oligomeric
Object can be used alone or be used together two or more.
It is 2 epoxyacrylate oligomers below that the epoxy acrylate oligomer, which can use number of functional groups,
Object, it is 1 or more and 2 epoxy acrylate oligomers below that can preferably use number of functional groups.If propylene oxide
The number of functional groups of acid esters oligomer is more than 2, then processability can reduce.At least there are one can be by poly- when functional group for tool
It closes reaction and forms printing layer.
The weight average molecular weight of the epoxy acrylate oligomer is preferably 500 to 2,000.If weight average molecular weight is less than
500 or more than 2,000, then it is difficult to meet required physical property.
The epoxy acrylate oligomer is not limited to the types such as bisphenol A-type, bisphenol-f type, phenol aldehyde type, unrestricted
Property example can enumerate Miramer EA2235, Miramer EA2255, Miramer EA2259, the Miramer of Miwon companies
The EBECRYL 600 of EA2280, Qing Te company (Cytec), EBECRYL 604, EBECRYL 605, EBECRYL 606,
EBECRYL 608、EBECRYL 629、EBECRYL 645、EBECRYL 648、EBECRYL 1608、EBECRYL 1940、
EBECRYL 2959、EBECRYL 3105、EBECRYL 3200、EBECRYL 3201、EBECRYL 3500、EBECRYL
3502、EBECRYL 3600、EBECRYL 3605、EBECRYL 3700、EBECRYL 3701、EBECRYL 3702、EBECRYL
3703、EBECRYL 3708、EBECRYL 3720、EBECRYL 6040、EBECRYL 9686、EBECRYL 9706、EBECRYL
9704 etc..As needed, these epoxy acrylate oligomers can be used alone or be used together and is two or more.
Preferably, the urethaneacrylates oligomer and xenogenesis acrylate oligomer are with 1:1 to 10:1
Weight ratio, preferably with 1.2:1 to 7:1 weight ratio, further preferably with 1.2:1 to 5:1 weight ratio is mixed and is made
With.In terms of realizing balanced physical property, preferably by the urethaneacrylates oligomer and xenogenesis propylene
Acid esters oligomer is mixed and is used with above-mentioned mixing ratio range.
The color ink compositions of the present invention include that light-cured type monomer is low as the urethaneacrylates
The diluent of the mixture of polymers and xenogenesis acrylate oligomer.It is used together simple function group as the light-cured type monomer
Light-cured type monomer more than light-cured type monomer and difunctional.By being used together simple function group light-cured type monomer and double
Light-cured type monomer more than functional group, so as to which when forming printing layer, adhesiveness, processability, solvent resistance, surface are hard
Degree is improved.
In the printing ink composition of the present invention, on the basis of the weight of color ink compositions, relative to an embodiment
Color ink compositions other compositions content, the content of the light-cured type monomer can be 50 parts by weight to 80 weight
Part.If the content of the light-cured type monomer is less than 50 parts by weight, viscosity can be got higher, thus can not be by printing ink composition profit
In steel material for using ink-jet system.On the other hand, right if the content of light-cured type monomer is more than 80 parts by weight
The physical property of whole film causes deleterious effect.
Simple function group light-cured type monomer makes the color ink compositions of the present invention have low viscosity, and improves by the present invention
Color ink compositions formed printing layer adhesiveness and processability.The non-limiting example of simple function group light-cured type monomer
Son can enumerate Isooctyl acrylate monomer, cyclic trimethylolpropane formal acrylate, phenoxy benzyl acrylic ester, front three
Butylcyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, lauryl acrylate, isodecyl acrylate, phenoxy group second
Base acrylate, tetrahydrofurfuryl acrylate, ethoxyethoxyethyl acrylate, octadecyl acrylate, acrylic acid hydroxyl second
Ester, hydroxypropyl acrylate, acryloyl morpholine, vinyl ethers, vinyl esters, n-vinyl-2-pyrrolidone and N- vinyl
Caprolactam etc..As needed, one or more of these simple function group light-cured type monomers can be selected to be used.According to
It needs, these simple function group light-cured type monomers can be used alone or be used together two or more.
Light-cured type monomer more than difunctional improves the printing layer formed by the color ink compositions of the present invention
Solvent resistance and surface strength.The non-limitative example of light-cured type monomer more than difunctional can enumerate diacrylate second
Diol ester, hexanediyl ester, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate
Ester, tetraethylene glycol diacrylate, neopentylglycol diacrylate, Tricyclodecane Dimethanol diacrylate, polyethylene glycol 400 two
Acrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, three acrylic acid of glycerine
Ester, pentaerythritol triacrylate etc..As needed, one or more of these difunctional light-cured type monomers can be selected
It is used.As needed, light-cured type monomers more than these difunctionals can be used alone or be used together two kinds with
On.The functional group in light-cured type monomer more than difunctional at most can be six functional groups.This is because the photocuring
The number of functional groups that type monomer can have is up to 6.
Light-cured type monomer more than the simple function group light-cured type monomer and difunctional is with 5:1 to 100:1 weight
Amount compares, preferably with 5:1 to 90:1 weight ratio, further preferably with 6:1 to 90:1 weight ratio is mixed and is used.It is adjusting
It saves the aspect of viscosity and efficiently controls the aspect of the physical property of whole film, preferably by the simple function group light-cured type list
Light-cured type monomer more than body and difunctional is mixed with above-mentioned ratio.
The color ink compositions of the present invention include photoinitiator, to utilize urethanes third described in ultraviolet induction
The polymerisation of the mixture and light-cured type monomer of olefin(e) acid ester oligomer and xenogenesis acrylate oligomer.Photoinitiator can
To use the photoinitiator of the photopolymerization reaction of any color ink compositions that can induce the present invention.
The particular instantiation of photoinitiator includes following compounds or combination thereof, and but not limited to this.Photoinitiator
Example can enumerate benzophenone and substituted benzophenone, 1- hydroxycyclohexyl phenyl ketones, such as isopropyl thiophene
Thioxanthones, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, the 2- benzyl -2- dimethylaminos-(4- morpholinyl phenyls) fourth of ton ketone
Alkane -1- ketone, benzyl dimethyl ketal, bis- (2,6)-dimethylbenzoyls) -2,4,4- trimethylpentylphosphine oxides, 2,4,6-
Trimethyl benzoyl diphenyl base phosphine oxide, 2,4,6- trimethylbenzoyl phenyls phosphinic acid ethyl ester, 2- methyl-1s-[4 (first sulphur
Base) phenyl] -2- morpholinopropane -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, bis- iodo- 3- fourths oxygen of 5,7-
Base -6- fluorones, diphenyl iodine fluoride and triphenylsulfonium hexafluorophosphoric acid ester etc..As needed, these photoinitiators can be with
It is used alone or is used together and is two or more.
In addition, the non-limitative example of the photoinitiator in the color ink compositions of the present invention that can be used can enumerate184、500、369、379、907、819、1173, MBF, TPO, BP, ITX etc..As needed, may be used
To select one or more of these photoinitiators and use.As needed, these photoinitiators can be used alone or together
Using two or more.
In the color ink compositions of the present invention, on the basis of the weight of color ink compositions, implement relative to one
The content of the content of the other compositions of the color ink compositions of mode, the photoinitiator can be 5 parts by weight to 20 weight
Part.If the content of the photoinitiator is less than 5 parts by weight, printing layer cannot fully cure, to realize well
The performance of printing layer.On the other hand, if the content of the photoinitiator is more than 20 parts by weight, printing layer will produce xanthochromia or
The storage stability of composition can reduce.
The color ink compositions of the present invention include the pigment for assigning color to steel material.It is combined with colored ink
On the basis of the weight of object, the content of the other compositions of the color ink compositions relative to an embodiment, the pigment
Content can be 0.1 parts by weight to 10 parts by weight.If the content of pigment is less than 0.1 parts by weight, tinting strength, tinting power can reduce, if
The content of pigment is more than 10 parts by weight, then dispersibility can reduce, and is reduced so as to cause the stability of ink.
The pigment can use organic pigment, inorganic pigment etc..
The non-limitative example of the inorganic pigment can enumerate carbon black, titanium oxide, zinc oxide, zinc yellow, iron oxide red (red
Oxide), cadmium red, ultramarine, dark purple etc..The non-limitative example of the organic pigment can enumerate insoluble azo colour, solvable
Property azo pigments, quinacridine ketone organic pigment, is organic pigment, the organic face of isoindoline ketone at phthalocyanines organic pigment
Material, pyranthrone organic pigment, thioindigo class organic pigment, polymerization azo organic pigment, benzimidazole ketone organic pigment, quinoline
Phthalein ketone organic pigment, isoindoline class organic pigment, nickel azophosphine, dioxazine violet etc..As needed, the pigment can be single
It solely uses or is used together and is two or more.
The pigment can be cyan, magenta, yellow, black, white, red, green, blue, orange, purple, palm fibre
Color, their mixture etc..
By organic pigment with color index (Color Index, C.I.) number illustrate when, can enumerate C.I. pigment yellows 1,
2、3、12、13、14、16、17、20、24、73、74、75、83、93、95、97、98、109、110、114、117、120、125、128、
129、130、137、138、139、147、148、150、151、153、154、155、166、168、180、185、213、214；C.I.
Paratonere 5,7,9,12,48,49,52,53,57,97,112,122,123,149,168,177,180,184,192,202,206,
209、215、216、217、220、223、224、226、227、228、238、240、254；C.I. pigment Green 7,36,58；C.I. face
Material basket 15,15:1、15:3、15:4、15:6、16、22、60、64；C.I. pigment orange 16,36,43,51,55,59,61；C.I. face
Material purple 19,23,29,30,37,40,50；C.I. pigment brown 23,25,26 etc..
The color ink compositions of the present invention include dispersant, for disperseing pigment.The dispersant can use height
Dispersal agent molecule is not particularly limited its type.The non-limitative example of workable macromolecule dispersing agent can enumerate road
The SOLSPERSE dispersants of Bo Run companies (Lubrizol), the DISPERBYK dispersants of Bi Ke companies (BYK), BASF AG
(BASF) EFKA dispersants etc..As needed, these dispersants can be used alone or be used together and is two or more.
The content of dispersant in the color ink compositions generally according to pigment type and concentration and difference.With regard to institute
For stating dispersant, the dispersant solid content in the pigment of every 100 parts by weight is 3~300 parts by weight, preferably 5~200 weights
It is preferred in terms of dispersibility and dispersion stabilization when measuring part.
The average particle size of pigment in the color ink compositions of the present invention is important feature for ejection
One of.Pigment particles needs are sufficiently small, can be sprayed by inkjet head, and will not cause spray nozzle clogging.In addition,
Although different according to the type of pigment, in order to which the dispersibility and dispersion stabilization that make pigment are good and show adequately
The average particle size of color, pigment is preferably 10~500nm, more preferably 50~300nm.The average particle size of pigment is small
When 10nm, light fastness can reduce, and when the average particle size of pigment is more than 500nm, big particle can block ink-jet system
The nozzle of the nozzle of system reduces so as to cause jetting stability.Use the Nanotrac 250 of Mai Qike companies (Microtrac)
Particle Size Analyzer (Particle Size Analyzer) measures the average particle size of the pigment.
The particle size of pigment in the color ink compositions of the present invention is very small, and therefore, it is difficult to be evenly dispersed in group
It closes in object.Therefore, pigment is individually scattered in the dispersant first and is prepared into dispersible pigment dispersion, then with colored ink group
The other compositions for closing object are coordinated, to prepare color ink compositions.
On the other hand, the average particle size of desired pigment can be by the way that pigment and dispersant to be added to point together
It moistened, crushed in dispersion media, being disperseed to obtain.The preparation method of the dispersible pigment dispersion is simultaneously not particularly limited, example
Such as the particle size of pigment can be adjusted to desired ruler by bead mill method, ball-milling method, three roller polishing breaking methods
It is very little and prepare.
It as needed, can be the model of required physical property will not be reduced in the color ink compositions of the present invention
Content in enclosing includes levelling agent, antifoaming agent, antioxidant, light stabilizer, ultra-violet absorber, adhesion enhancer etc..
In order to form printing layer, color ink compositions of the invention and existing silk-screen printing or roller by ink-jet system
The composition of mode of printing, which is compared, has low viscosity.Specifically, the present invention color ink compositions in room temperature (for example, 15
~25 DEG C) under have 40cps viscosity below, preferably have 30cps viscosity below, further preferably have 20cps extremely
The viscosity of 30cps.The color ink compositions of the range of viscosities are suitable for forming film on steel material by ink-jet system.
As described above, the color ink compositions of the present invention by ink-jet system spray and have can be used in the viscous of subject material
Degree, therefore can be used in steel material by ink-jet system.As described above, the color ink compositions of the present invention have such as
Lower advantage, that is, can also ensure that the horizontal viscosity that can be used in ink-jet system in the case where not using organic solvent.
The color ink compositions of the present invention are not wrap solvent-laden solvent-free system, but have before curing sufficiently low
Viscosity, ink-jet system can be used to form printing layer on material, and the printing formed on steel material after curing
Layer has satisfactory horizontal adhesiveness, processability, solvent resistance, hardness to steel material.
In addition, being used in steel material to be sprayed in ink-jet system, color ink compositions preferably have
Surface tension appropriate.The color ink compositions of the present invention have 20~50 dynes/cm under room temperature (for example, 15~25 DEG C)
Surface tension, preferably with 22~40 dynes/cm surface tension.If surface tension is less than 20 dynes/cm, ink meeting
It condenses in the nozzle position of the nozzle of ink-jet system and plug nozzle, to there is a phenomenon where hindering to spray, or nozzle occurs
The phenomenon that falling off, and ink leak phenomenon occurs in nozzle segment.If surface tension is more than 50 dynes/cm, printed to ink-jet
The supply of the ink of brush head has some setbacks, when to be difficult to continuously be sprayed, or spray steel material, in material table
The levelability (leveling) in face can reduce, and to be difficult to realize preferred film, and be difficult to meet required physical property.
The steel material is not particularly limited, for example, steel plate can be enumerated.The steel plate can not be had using surface
It separately carries out the steel plate of pretreatment application and surface separately carries out pretreated coated steel plate, surface treated steel plate etc. and owns
Steel plate.It is not limited particularly using the type of the steel plate of the color ink compositions of the present invention, but its non-limitative example
Can enumerate cold-rolled steel sheet, hot rolled steel plate, galvanized steel plain sheet, aludip, stainless-steel sheet, magnesium steel plate, aluminium steel plate, zinc steel plate,
Titanium steel plate, colored coated steel plate, anti-finger print steel plate etc..The printing ink composition of the present invention is used in the surface of steel plate, therefore utilizes
The thickness of the steel plate of printing ink composition is not particularly limited.Can usually it use 0.1mm to the steel plate of 10mm thickness.
According to another implementation of the invention, the method that manufacture printed steel plate is provided comprising following steps：Xiang Gang
The color ink compositions for steel plate of the plate injection present invention；And the color ink compositions of injection are cured, from
And form printing layer.Content described in the color ink compositions is equally applicable in the manufacturing method of steel plate.
There is excellent adhesiveness to steel material by the printing layer that the color ink compositions of the present invention are formed, and such as
The upper viscosity at normal temperatures is low, therefore can be sprayed steel plate by ink-jet system to use.
The color ink compositions of the present invention are used to the steel material by ink-jet systems eject, it is specific and
Speech, injection are used to steel plate.It is widely used as substantially being divided into thermojet for the print head of ink-jet printing system
(Thermal jet) mode and piezoelectric type (Piezoelectric) nozzle, wherein the thermojet mode is to pass through print head
Moment of interior heating plate generates heat and forms bubble to spray ink, and the piezoelectric type nozzle is made in print head by applying voltage
Piezoelectric ceramic energy converter converted and fill ink and sprayed, may include additionally such as continous way, electrostatic
The multiple types such as formula.Used in the present invention piezoelectric type (Piezoelectric) nozzle as ink-jet printing system nozzle,
But it is not defined in this particularly, above-mentioned a plurality of types of nozzles can be used.
Due to the potential volatility of the ingredient of one or more of color ink compositions and the durability of reactivity, nozzle
Deng, ink jet printing head usually with 65 DEG C or less, preferably with 50 DEG C or less, further preferably with 50 DEG C with down toward room temperature (for example, 15
~25 DEG C) temperature sprayed.The drop (drop) sprayed have 4m/s to 15m/s movement speed, steel material with
The distance of nozzle be 1mm to 10mm, be preferably formed as 1mm to 7mm apart from when, be advantageously implemented accurate image.
It can be according to the resolution ratio or printing layer of the image to be realized by the thickness of the film for the droplet formation sprayed
Quantity and it is different, but 5 μm to 50 μm of thickness is formed, when being preferably formed as 5 μm to 30 μm of thickness, it is advantageously ensured that film
Physical property.
Later, cured to the color ink compositions of injection irradiation ultraviolet light, to form film.With regard to cured side
For formula, can with the print head assembled arrangement of ink-jet printer, and while being moved together with print head irradiate ultraviolet light, Huo Zhetong
Static fixation curing mode is crossed to irradiate ultraviolet light.These curing modes can use one such or be used together two kinds
More than.
The ultraviolet light irradiated by the curing mode can usually be classified as 400nm to the regions 320nm according to wavelength
Ultraviolet light-A (UV-A), 320nm are to the ultraviolet-B (UV-B) in the regions 290nm, the Ultraviolet-C of 290nm to the regions 100nm
(UV-C).In the case of mercury lamp or metal halide lamp, gallium lamp, it can be carried out with composite wavelength in ultraviolet light whole region
Ultraviolet light irradiates, can be according to the ultraviolet light of the composition irradiation particular range of wavelengths of LED module in the case of LED light.
Ultraviolet hardening lamp can be divided into mercury lamp, metal halide lamp, gallium lamp etc. according to the type of luminescent substance in lamp,
And H- light bulbs (H-Bulb), D- light bulbs, A- light bulbs etc. can be divided into according to the wavelength of irradiation.
The printing ink composition of the present invention uses H- light bulbs (H-Bulb) ultraviolet radiator of Integration companies as solidification
Mode, but it is not defined in this particularly, the lamp of any kind can be used.
The printing ink composition of the present invention can pass through ultraviolet curing mode after ink jet printing head is ejected into steel material
Cured, to form film.The amount of solidification energy is according to the amount and type of correlated response object, energy source and energy source
Depending on the several factors such as distance and the thickness of wanting cured film, usual ultraviolet irradiation amount is about 0.1J/cm2To 10J/
cm2, and the time being exposed in ultraviolet light can be approximately less than 1 second to 10 minutes or less.In addition, ultraviolet irradiation can be with
It carries out in air or in the inert environments such as nitrogen.By being cured with above-mentioned ultraviolet irradiation amount and exposure time, to
The film with desired physical property can be formed.
In addition, for the steel plate using the color ink compositions of the present invention, color ink compositions are being utilized
Before, color coating layer, layers of chrome can be formed or without layers of chrome.By utilizing the present invention on the steel plate for being formed with color coating layer
Color ink compositions, so as to realize desired colored print by color contrast with strikingly color and/or texture
Brush layer.In addition, by forming layers of chrome or without layers of chrome, so as to improve the adhesiveness of color coating layer or printing layer.In turn, root
According to needs, clear top coat layer, ultraviolet can be further formed in the printing layer that the color ink compositions by the present invention are formed
Line cured coating film layer etc..The color coating layer, layers of chrome belong to this without layers of chrome, clear top coat layer, ultraviolet curing film layer etc.
The steel plate of technical field routine is handled, therefore does not thus limit the present invention, and those skilled in the art can be according to need
It to be suitably combined to use.
According to another implementation of the invention, printed steel plate is provided, with steel plate；And the colour by the present invention
The printing layer that printing ink composition is formed.The color ink compositions and the content manufactured described in the method for printed steel plate are same
It is suitable for the invention in printed steel plate.The printed steel plate for having the printing layer of steel plate and formation on the steel plate is shown in Fig. 1
Side cross-sectional view.The side cross-sectional view for having the printed steel plate of printing layer is shown, wherein the printing layer, which is formed in, to be had in Fig. 2
It is handled by chromium or Chrome-free pre-processes on the steel plate for the pretreatment layer to be formed.In addition, showing the printing steel with printing layer in Fig. 3
The side cross-sectional view of plate, wherein the printing layer is formed on the steel plate for having the pretreatment layer, color coating layer.
The printing layer formed as described above by the color ink compositions of the present invention not only glues steel plate with excellent
Attached property, and printing layer also has excellent solvent resistance, hardness, color sense etc..Therefore, include the present invention of the printing layer
Printed steel plate be also high-quality steel plate, meet the physical property needed for printed steel plate.
In the following, carrying out more specific description to the present invention by specific embodiment.Following embodiments merely help to manage
The illustration of the present invention is solved, it's not limited to that for the scope of the present invention.
1. the preparation of color ink compositions
(embodiment 1)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 5 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the acrylic acid four of the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, 20 parts by weight
The hexanediyl ester of tetrahydrofurfuryl ester (THFA), the isobornyl acrylate (IBOA) of 20 parts by weight, 5 parts by weight
(HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(embodiment 2)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the epoxy acrylate oligomers of 5 parts by weight (EBECRYL 3200, Qing Te company (Cytec), difunctionality
Group, weight average molecular weight (Mw) are 500), the propylene of the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, 20 parts by weight
Sour tetrahydro furfuryl ester (THFA), the isobornyl acrylate (IBOA) of 20 parts by weight, 5 parts by weight hexanediyl ester
(HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(embodiment 3)
Mix the blue pigment (PB15 of 3 parts by weight:3, Clariant Corporation (Clariant)), the carbamic acids of 10 parts by weight
Urethane acrylate oligomer (Miramer PU2560, Miwon companies, difunctional, weight average molecular weight (Mw) are 10,400),
(Miramer PS420, Miwon companies, four-functional group, weight average molecular weight (Mw) are the polyester acrylate oligomers of 5 parts by weight
1,800), the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, the tetrahydrofurfuryl acrylate of 20 parts by weight
(THFA), the isobornyl acrylate (IBOA), the hexanediyl ester (HDDA) of 5 parts by weight of 20 parts by weight, 2 parts by weight
Photoinitiator Irgacure 184 (BASF AG (BASF)), 3 parts by weight 369 (BASF of photoinitiator Irgacure
Company (BASF)), the levelling agent of the photoinitiator Darocur TPO (BASF AG (BASF)) of 5 parts by weight, 0.5 parts by weight
Dispersant (Solsperse35000, Lubrizol Corp. of (BYK-UV3510, Bi Ke company (BYK)), 2 parts by weight
(Lubrizol)), to prepare printing ink composition.The composition of used ingredient is shown in following table 1.
(embodiment 4)
Mix the violet pigment (PV19, Clariant Corporation (Clariant)) of 3 parts by weight, the urethane of 10 parts by weight
Ester acrylate oligomer (Miramer PU2560, Miwon companies, difunctional, weight average molecular weight (Mw) are 10,400), 5
(Miramer PS420, Miwon companies, four-functional group, weight average molecular weight (Mw) are the polyester acrylate oligomers of parts by weight
1,800), the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, the tetrahydrofurfuryl acrylate of 20 parts by weight
(THFA), the isobornyl acrylate (IBOA), the hexanediyl ester (HDDA) of 5 parts by weight of 20 parts by weight, 2 parts by weight
Photoinitiator Irgacure 184 (BASF AG (BASF)), 3 parts by weight 369 (BASF of photoinitiator Irgacure
Company (BASF)), the levelling agent of the photoinitiator Darocur TPO (BASF AG (BASF)) of 5 parts by weight, 0.5 parts by weight
Dispersant (Solsperse35000, Lubrizol Corp. of (BYK-UV3510, Bi Ke company (BYK)), 2 parts by weight
(Lubrizol)), to prepare printing ink composition.The composition of used ingredient is shown in following table 1.
(embodiment 5)
Mix the yellow uitramarine (PY155, Clariant Corporation (Clariant)) of 3 parts by weight, the carbamic acid of 10 parts by weight
Urethane acrylate oligomer (Miramer PU2560, Miwon companies, difunctional, weight average molecular weight (Mw) are 10,400),
(Miramer PS420, Miwon companies, four-functional group, weight average molecular weight (Mw) are the polyester acrylate oligomers of 5 parts by weight
1,800), the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, the tetrahydrofurfuryl acrylate of 20 parts by weight
(THFA), the isobornyl acrylate (IBOA), the hexanediyl ester (HDDA) of 5 parts by weight of 20 parts by weight, 2 parts by weight
Photoinitiator Irgacure 184 (BASF AG (BASF)), 3 parts by weight 369 (BASF of photoinitiator Irgacure
Company (BASF)), the levelling agent of the photoinitiator Darocur TPO (BASF AG (BASF)) of 5 parts by weight, 0.5 parts by weight
Dispersant (Solsperse35000, Lubrizol Corp. of (BYK-UV3510, Bi Ke company (BYK)), 2 parts by weight
(Lubrizol)), to prepare printing ink composition.The composition of used ingredient is shown in following table 1.
(embodiment 6)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 5 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the isobomyl acrylate of the tetrahydrofurfuryl acrylate (THFA) of 20 parts by weight, 20 parts by weight
Hexanediyl ester (HDDA), 2 weights of ester (IBOA), the hydroxypropyl acrylate (2-HPA) of 24.5 parts by weight, 5 parts by weight
Measure the photoinitiator Irgacure 184 (BASF AG (BASF)) of part, 3 parts by weight photoinitiator Irgacure 369 (bar
Si Fu companies (BASF)), the stream of the photoinitiator Darocur TPO (BASF AG (BASF)) of 5 parts by weight, 0.5 parts by weight
Flat agent (BYK-UV3510, Bi Ke company (BYK)), 2 parts by weight dispersant (Solsperse35000, Lubrizol Corp.
(Lubrizol)), to prepare printing ink composition.The composition of used ingredient is shown in following table 1.
(embodiment 7)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 5 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, the acrylic acid of 20 parts by weight it is different
Two propylene of hexylene glycol of norbornene ester (IBOA), the ethoxyethoxyethyl acrylate (EOEOEA) of 20 parts by weight, 5 parts by weight
The photoinitiator of acid esters (HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(embodiment 8)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 5 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the acrylic acid four of the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, 20 parts by weight
The dipropylene glycol diacrylate of tetrahydrofurfuryl ester (THFA), the isobornyl acrylate (IBOA) of 20 parts by weight, 5 parts by weight
(DPGDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(comparative example 1)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 5 parts by weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, Miwon companies, difunctional, weight average molecular weight (Mw)
Be 10,400), (Miramer PS420, Miwon companies, four-functional group, weight are equal for the polyester acrylate oligomers of 10 parts by weight
Molecular weight (Mw) is 1,800), the acrylic acid tetrahydrochysene of the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, 20 parts by weight
Furfuryl group ester (THFA), the isobornyl acrylate (IBOA) of 20 parts by weight, the hexanediyl ester (HDDA) of 5 parts by weight, 2
The photoinitiator Irgacure 184 (BASF AG (BASF)) of parts by weight, the photoinitiator Irgacure 369 of 3 parts by weight
The photoinitiator Darocur TPO (BASF AG (BASF)) of (BASF AG (BASF)), 5 parts by weight, 0.5 parts by weight
Dispersant (Solsperse35000, Lubrizol Corp. of levelling agent (BYK-UV3510, Bi Ke company (BYK)), 2 parts by weight
(Lubrizol)), to prepare printing ink composition.The composition of used ingredient is shown in following table 1.
(comparative example 2)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 14 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 1 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the acrylic acid four of the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, 20 parts by weight
The hexanediyl ester of tetrahydrofurfuryl ester (THFA), the isobornyl acrylate (IBOA) of 20 parts by weight, 5 parts by weight
(HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(comparative example 3)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 5 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the acrylic acid four of the phenoxyethyl acrylate (2-PEA) of 24.5 parts by weight, 15 parts by weight
The hexanediyl ester of tetrahydrofurfuryl ester (THFA), the isobornyl acrylate (IBOA) of 15 parts by weight, 15 parts by weight
(HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(comparative example 4)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 10 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 5 parts by weight (Miramer PS420, Miwon companies, four-functional group, weight
Average molecular weight (Mw) is 1,800), the acrylic acid tetrahydrochysene of the phenoxyethyl acrylate (2-PEA) of 29 parts by weight, 20 parts by weight
The hexanediyl ester of furfuryl group ester (THFA), the isobornyl acrylate (IBOA) of 20 parts by weight, 0.5 parts by weight
(HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
(comparative example 5)
Mix black pigment (carbon black (Carbon Black), Degussa Corporation (Degussa)), 25 weight of 3 parts by weight
Urethaneacrylates oligomer (Miramer PU2560, the Miwon companies, difunctional, weight average molecular weight of part
(Mw) be 10,400), the polyester acrylate oligomers of 10 parts by weight (Miramer PS420, Miwon companies, four-functional group,
Weight average molecular weight (Mw) is 1,800), the acrylic acid of the phenoxyethyl acrylate (2-PEA) of 14.5 parts by weight, 15 parts by weight
The hexanediyl ester of tetrahydro furfuryl ester (THFA), the isobornyl acrylate (IBOA) of 15 parts by weight, 5 parts by weight
(HDDA), the photoinitiator Irgacure 184 (BASF AG (BASF)) of 2 parts by weight, 3 parts by weight photoinitiator
The photoinitiator Darocur TPO (BASF AG of Irgacure 369 (BASF AG (BASF)), 5 parts by weight
(BASF)), the levelling agent (BYK-UV3510, Bi Ke company (BYK)) of 0.5 parts by weight, 2 parts by weight dispersant
(Solsperse35000, Lubrizol Corp. (Lubrizol)), to prepare printing ink composition.The composition of used ingredient shows
In following table 1.
[table 1]
(composition unit：Parts by weight)
(surface tension of the color ink compositions of * Examples 1 to 8 and the Comparative Examples 1 to 5 is 25~30 dynes/cm, first
First pass through bead mill method adjust pigment granularity while coordinated with dispersant, to be prepared into dispersible pigment dispersion, then with
Other compositions are coordinated.)
2. the manufacture of test piece
On with the white coated steel plate of 10~15 μm of progress applications, ultraviolet light (UV) printing machine of InkTec companies is utilized
JETRIX KX6SD spray the color ink compositions of the Examples 1 to 8 and the Comparative Examples 1 to 5, and carry out ultraviolet curing and
The printing layer for forming 5~10 μ m thicks, to manufacture test piece.Specific printing condition is as follows.
The equipment used：The JETRIX KX6SD of InkTec companies
The nozzle used：The KM1024SHB of Konica Minolta company (Konica Minolta)
Nozzle temperature：45℃
Image resolution ratio：1440×720dpi
Output mode：Fine pattern (Fine art) (12 times (pass))
Ultraviolet light source：The Subzero lamp 170mm H- light bulbs of Integration companies
Solidification pattern：It is normally fully cured (Normal Full Cure)
Ultraviolet light irradiate light quantity：It is measured with the ultraviolet energy meter (UV Power Puck II) of EIT companies, accumulated light
About 2J/cm2
Ultraviolet irradiation time：3 seconds
Coating thickness：7μm
The distance between material and print head：2mm
The movement speed of drop：4m/ seconds to 15m/ seconds
3. evaluation method
Viscosity to the test piece and color ink compositions that make as described above, adhesiveness (attachment by the following method
Property), processability, solvent resistance, pencil hardness evaluated, and the results are shown in table 2.
(1) viscosity
Using the DV II+ viscosimeter CPE-40 rotors of Bo Lefei companies (BrookField), measures, evaluates at 25 DEG C
The viscosity of printing ink composition.
(2) average particle size
Average particle size is the average particle size of pigment, uses the Nanotrac 250 of Mai Qike companies (Microtrac)
Particle Size Analyzer (Particle Size Analyzer) measures.
(3) adhesiveness (adhesion)
For adhesiveness, 100 are made with vertical and horizontal each stroke of 10 lines in the interval of 1mm with cutter (cutter) in test piece
It is a, and taken off after pasting cellophane tape in the above, to evaluate the adhesiveness of printing layer.
(◎：(not falling off) without exception, zero：It falls off within 10, △：It falls off within 50, X：It completely falls off)
(4) processability
For processability, after carrying out 3T (thickness of 3 materials) 180 ° of bending machinings to test piece, it is thus identified that whether generate
Crackle (crack).
(◎：(not cracking) without exception, X：It cracks)
(5) solvent resistance
For solvent resistance, it is stained with MEK (methyl ethyl ketone) on gauze, applies certain power and wipes back and forth, so
The good state of printing layer is observed afterwards.By distinguish film because solvent is peeling-off or damage when number evaluated.
(◎：50 times or more, zero：Less than 20 times, △：Less than 10 times, X：Less than 5 times)
(6) pencil hardness
Pencil hardness is measured according to JIS K5600-5-4KS.Wherein, the pencil hardness is measured to 9H, more from 9B successively
Close to 9B, then hardness is weaker, and closer to 9H, then hardness is stronger.
[table 2] evaluation of physical properties
As shown in Table 2 above, meet the implementation of the color ink compositions of the composition of the color ink compositions of the present invention
Example 1~8 ensures the viscosity and average particle size that injection will not be caused difficult.In addition, the printing layer being consequently formed show it is excellent
Different adhesiveness, processability, solvent resistance and pencil hardness.
It is detached from the present invention's by the mixing ratio of urethaneacrylates oligomer and xenogenesis acrylate oligomer
The printing layer that the comparative example 1 and 2 of range is formed fails to meet balanced physical property.It has been confirmed that Monofunctional monomers and double
Comparative example 3 and 4 that the mixing ratio of monomer more than functional group departs from the scope of the present invention can lead to the evil of opposite physical property
Change.It has been confirmed that urethaneacrylates oligomer and the total content of xenogenesis acrylate oligomer are more than 30 weight
The viscosity that part and light-cured type monomer are less than the comparative example 5 of 50 parts by weight is high, and therefore, it is difficult to be sprayed by ink-jet system.
Claims (16)
1. for the color ink compositions of steel material, it includes：
The urethaneacrylates oligomer and the urethaneacrylates of 10 parts by weight to 30 parts by weight
The mixture of xenogenesis acrylate oligomer except oligomer；
The light-cured type monomer of 50 parts by weight to 80 parts by weight is simple function group light-cured type monomer and difunctional or more
The mixture of light-cured type monomer；
The photoinitiator of 5 parts by weight to 20 parts by weight；
The pigment of 0.1 parts by weight to 10 parts by weight；And
The dispersant of 3 parts by weight to 300 parts by weight, for the dispersant solid content in the pigment of every 100 parts by weight；
Wherein, the urethaneacrylates oligomer and xenogenesis acrylate oligomer are with 1:1 to 10:1 weight
Than mixing, and light-cured type monomer more than the simple function group light-cured type monomer and difunctional is with 5:1 to 100:1
Weight ratio mixes.
2. the color ink compositions according to claim 1 for steel material, wherein the urethanes third
The weight average molecular weight of olefin(e) acid ester oligomer is 500 to 12,000.
3. the color ink compositions according to claim 1 for steel material, wherein the urethanes third
Olefin(e) acid ester oligomer is aliphatic urethane acrylate.
4. the color ink compositions according to claim 1 for steel material, wherein the urethanes third
The number of functional groups of olefin(e) acid ester oligomer is 3 or less.
5. the color ink compositions according to claim 1 for steel material, wherein the xenogenesis acrylate is low
Polymers is selected from polyester acrylate oligomers and epoxy acrylate oligomer.
6. the color ink compositions according to claim 5 for steel material, wherein the polyester acrylate is low
The number of functional groups of polymers is 4 or less.
7. the color ink compositions according to claim 5 for steel material, wherein the polyester acrylate is low
The weight average molecular weight of polymers is 500 to 3,000.
8. the color ink compositions according to claim 5 for steel material, wherein the epoxy acrylate is low
The number of functional groups of polymers is 2 or less.
9. the color ink compositions according to claim 5 for steel material, wherein the epoxy acrylate is low
The weight average molecular weight of polymers is 500 to 2,000.
10. the color ink compositions according to claim 1 for steel material, wherein the simple function group light is solid
Change type monomer is selected from Isooctyl acrylate monomer, cyclic trimethylolpropane formal acrylate, phenoxy benzyl acrylic ester, three
Methylcyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, lauryl acrylate, isodecyl acrylate, phenoxy group
Ethyl propylene acid esters, tetrahydrofurfuryl acrylate, ethoxyethoxyethyl acrylate, octadecyl acrylate, acrylic acid hydroxyl
Ethyl ester, hydroxypropyl acrylate, acryloyl morpholine, vinyl ethers, vinyl esters, n-vinyl-2-pyrrolidone and N- ethylene
Base caprolactam.
11. the color ink compositions according to claim 1 for steel material, wherein more than the difunctional
Light-cured type monomer be selected from ethylene glycol diacrylate, hexanediyl ester, triethylene glycol diacrylate, tripropylene glycol
Diacrylate, dipropylene glycol diacrylate, tetraethylene glycol diacrylate, neopentylglycol diacrylate, tristane two
Methanol diacrylate, polyethylene glycol 400 diacrylate, trimethylolpropane trimethacrylate, ethoxylation trihydroxy methyl
Propane triacrylate, glycerol tri-acrylate and pentaerythritol triacrylate.
12. the color ink compositions according to claim 1 for steel material, wherein described to be used for steel material
Color ink compositions viscosity at normal temperatures be 40cps or less.
13. the color ink compositions according to claim 1 for steel material, wherein described to be used for steel material
Color ink compositions surface tension be 20~50 dynes/cm.
14. the method for manufacturing printed steel plate comprising following steps：
To the color ink compositions for steel material described in any one of steel plate injection claim 1-13；And
The color ink compositions of injection are cured, to form printing layer.
15. printed steel plate comprising：
Steel plate；And
Printing layer is formed in steel by the color ink compositions for steel material described in any one of claim 1-13
On plate.
16. printed steel plate according to claim 15, wherein the printed steel plate wraps between the steel plate and printing layer
It includes selected from color coating layer, layers of chrome and without at least one of layers of chrome pretreatment layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150185492A KR101858796B1 (en) | 2015-12-23 | 2015-12-23 | Color ink composition for print steel plate having superior adhesion, method for producing print steel plate using the same, and print steel plate prepared thereby |
| KR10-2015-0185492 | 2015-12-23 | ||
| PCT/KR2016/015039 WO2017111472A1 (en) | 2015-12-23 | 2016-12-21 | Color ink composition having excellent adhesiveness for steel material, method for manufacturing printed steel plate using same, and printed steel plate manufactured according to same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108603061A true CN108603061A (en) | 2018-09-28 |
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ID=59090705
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680076294.3A Pending CN108603061A (en) | 2015-12-23 | 2016-12-21 | The excellent color ink compositions for steel material of adhesiveness, the method using its manufacture printed steel plate and the printed steel plate manufactured according to this method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6684912B2 (en) |
| KR (1) | KR101858796B1 (en) |
| CN (1) | CN108603061A (en) |
| WO (1) | WO2017111472A1 (en) |
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| CN111454612A (en) * | 2019-01-22 | 2020-07-28 | 株式会社理光 | Curable transparent ink composition, ink set, container, and printing method |
| TWI700341B (en) * | 2019-07-11 | 2020-08-01 | 臺灣永光化學工業股份有限公司 | Photosensitive ink composition |
| CN113348073A (en) * | 2018-12-19 | 2021-09-03 | Posco公司 | Thin glass laminated printed steel sheet having excellent surface quality and method for producing same |
| CN113490599A (en) * | 2019-02-27 | 2021-10-08 | 株式会社则武 | Ink jet ink |
| CN114829134A (en) * | 2019-12-10 | 2022-07-29 | Posco公司 | Thin plate glass laminated printed steel plate with excellent flame retardancy and method for producing same |
| CN115055354A (en) * | 2022-08-15 | 2022-09-16 | 小仙炖霸州食品有限公司 | Manufacturing process of stainless iron bottle cap with printed pattern |
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| KR102075267B1 (en) * | 2018-09-28 | 2020-02-07 | 주식회사 포스코 | Heating steel plate and method for preparing the same |
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Also Published As
| Publication number | Publication date |
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| JP2019507203A (en) | 2019-03-14 |
| JP6684912B2 (en) | 2020-04-22 |
| WO2017111472A1 (en) | 2017-06-29 |
| KR20170075932A (en) | 2017-07-04 |
| KR101858796B1 (en) | 2018-05-18 |
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