CN102408779B - Printing ink composition and preparation method thereof and stainless steel workpiece - Google Patents
Printing ink composition and preparation method thereof and stainless steel workpiece Download PDFInfo
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- CN102408779B CN102408779B CN 201010289425 CN201010289425A CN102408779B CN 102408779 B CN102408779 B CN 102408779B CN 201010289425 CN201010289425 CN 201010289425 CN 201010289425 A CN201010289425 A CN 201010289425A CN 102408779 B CN102408779 B CN 102408779B
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Abstract
The invention provides a printing ink composition, which comprises the following components in percentage by weight: 30 to 40 percent of epoxy vinyl ester resin, 20 to 30 percent of thermoset hydroxy acrylic resin, 10 to 15 percent of silane modified polyisobutene resin, 3 to 10 percent of polyamide adduct, 5 to 10 percent of liquid paraffin, 5 to 10 percent of glycerol and 10 to 20 percent of organic solvent. The printing ink composition still can be transferred to the surface of a die from a release film after being surface-dried at room temperature, the transfer patterns are high in accuracy and a transfer process is simplified.
Description
Technical field
The invention belongs to ink area, be specifically related to a kind of ink composite and preparation method thereof and a kind of stainless steel work-piece.
Background technology
The various decorative patterns on inner and outer decorative parts of automobile surface, defect that on the one hand can the concealed product surface, make product appearance attractive in appearance, caters to the demand of vision, makes on the other hand between product surface and mold cavity surface to hold a little air, unlikely formation vacuum suck, the easily demoulding.For example the automobile dermatoglyph mainly forms texture by chemical corrosion at die surface, and the injection moulding inside gadget forms after spraying paint.Before chemical corrosion need to die surface form can be anti-etching texture graphics, generally first by the anti-etching photosensitive-ink of mold integral surface spraying, the softer film of fitting, after exposure imaging can die surface form can be anti-etching figure.But, because mold shape differs, can be inhomogeneous and unintelligible because of intensity of illumination by the pattern line texture after film exposure imaging.
In order to make the pattern line clean mark, also can be by the anti-etching printing ink silk-screen on release film, various anti-etching printing ink of the prior art is not in the situation that need have complete surface drying to be fitted in die surface at ink layer in transfer process, thereby the ink logo on release film is transferred to die surface; Otherwise be difficult to come off from release film after the complete surface drying of ink layer, be difficult to realize transfer printing.And if ink layer does not have complete surface drying, be prone to deviation in the contraposition process, cause ink layer laminating positional fault, the pattern precision reduces.Now, the ink layer wiped clean need to be printed to then transfer printing of transfer film again, technique is very complicated.
Summary of the invention
The invention solves that the pattern precision that the anti-etching printing ink transfer printing that exists in prior art obtains is lower, the technical problem of complex process.
The invention provides a kind of ink composite, contain following component:
Epoxy vinyl ester resin 30-40wt%;
Thermoset Hydroxylated acrylic resin 20-30wt%;
Silane-modified polyisobutylene resin 10-15wt%
;
Polymeric amide affixture 3-10wt%;
Whiteruss 5-10wt%;
Glycerine 5-10wt%;
Organic solvent 10-20wt%
.
The present invention also provides the preparation method of described ink composite, comprise epoxy vinyl ester resin, thermoset Hydroxylated acrylic resin, silane-modified polyisobutylene resin, polymeric amide affixture, whiteruss, glycerine and organic solvent are mixed in proportion, can obtain described ink composite.
The present invention finally provides a kind of stainless steel work-piece, comprises stainless steel substrate and the ink design layer that is positioned at the stainless steel substrate surface; Described ink design layer, by ink composite provided by the invention is printed on release film, is transferred to stainless steel substrate surface curing obtaining after the room temperature surface drying.
Ink composite of the present invention still can be transferred to die surface from release film after the room temperature surface drying, therefore can realize the decorative pattern accurate contraposition of ink logo and die surface, thereby guarantees the precision of pattern transferring, and ink design layer has stronger etching resistence.In addition, because ink composite of the present invention can be realized transfer printing after the room temperature surface drying, therefore can realize accurate contraposition by primary transfer, without repeatedly contraposition, correction, work simplification.
Embodiment
The invention provides a kind of ink composite, contain following component:
Epoxy vinyl ester resin 30-40wt%;
Thermoset Hydroxylated acrylic resin 20-30wt%;
Silane-modified polyisobutylene resin 10-15wt%
;
Polymeric amide affixture 3-10wt%;
Whiteruss 5-10wt%;
Glycerine 5-10wt%;
Organic solvent 10-20wt%
.
Under preferable case, in described ink composite, the content of each component is:
Epoxy vinyl ester resin 30-35wt%;
Thermoset Hydroxylated acrylic resin 25-30wt%;
Silane-modified polyisobutylene resin 10-12wt%
;
Polymeric amide affixture 3-6wt%;
Whiteruss 5-8wt%;
Glycerine 5-8wt%;
Organic solvent 10-15wt%
.
Existing transfer printing ink composite, if resin volatilization is too fast, ink viscosity increases, and ink logo is difficult to come off from release film, and ink transfer on mould the time, can destroy pattern form, reduces transfer printing precision.The present inventor passes through great many of experiments, each component in ink composite is selected, and by the allotment of content, still there is good transfer printing ability after making ink composite room temperature surface drying of the present invention, easily from the release film surface, remove, then release film and mould accurate contraposition, make the pattern on release film be transferred to die surface fully, therefore can guarantee the precision of pattern transfer.In addition, after ink composite of the present invention solidifies, the patterned layer of formation and the sticking power of mould are very high.
In ink composite in the present invention, matrix resin is epoxy vinyl ester resin and thermoset Hydroxylated acrylic resin, and cross-linked resin is the polymeric amide affixture.Wherein, epoxy vinyl ester resin is by epoxy resin and methacrylic acid-respons and make, and it combines, and the height of epoxy resin is hot, fast setting and the performance easy to operate of mechanical property and chemical resistant properties and unsaturated polyester resin.Therefore, epoxy vinyl ester resin has extremely strong acid-resistant corrosion, and has splendid self-vulcanizing performance.Described polymeric amide affixture, as the amine accelerator, can promote the self-vulcanizing of ink composite.
In the present invention, the contents of ethylene of described epoxy vinyl ester resin is 30-45wt%.More preferably, in situation, described epoxy vinyl ester resin adopts elastomer-modified epoxy vinyl ester resin.In the present invention, described epoxy vinyl ester resin can directly adopt and be purchased product, for example can adopt 8084 of 411-400 epoxy vinyl ester resin or DERAKANE company.
The hydroxyl value of described thermoset Hydroxylated acrylic resin is 80-120mgKOH/g.In the present invention, the various resins that described thermoset Hydroxylated acrylic resin can adopt those skilled in the art to commonly use, for example can adopt the SC341 of long day space chemical company or Shanghai Ai Lijin coating company limited A900, A909, NUPLEX company 1762,1757.
Described silane-modified polyisobutylene resin is for guaranteeing weather resistance and the snappiness of printing ink, thus the anti-etching ability of assurance ink design layer.In described silane-modified polyisobutylene resin, siloxanes, as end group, can be hydrolyzed into the hydroxyl reaction of steel surface the silicon hydroxyl, thereby printing ink and steel surface are produced, stablizes excellent cementability; The iso-butylene group, for stablizing the viscosity of printing ink under all temps, guarantees weather resistance, the snappiness of printing ink.Under preferable case, in described silane-modified polyisobutylene resin, silicone content is 5-20wt%.Described silane-modified polyisobutylene resin also can adopt and be purchased product, for example the EPION of Japanese clock deep pool chemical company
tMthe silane-modified polyisobutylene resin.
The amine value 180-320mgKOH/g of described polymeric amide affixture.Described polymeric amide affixture also can directly adopt and be purchased product, for example the kingcure450 of Fuqing trump chemical industry company limited.
In the present invention, described glycerine and the whiteruss second-order transition temperature for regulating printing ink, thus regulate the snappiness that ink composite solidifies the rear ink layer formed, guarantee the anti-etching ability of ink layer.
As those skilled in the art's common practise, in described ink composite, contain organic solvent.Described organic solvent can directly adopt all kinds of SOLVENTS of the prior art.Under preferable case, the organic solvent that the present invention adopts comprises the first solvent and the second solvent; Wherein, the first solvent is high boiling solvent, is selected from least one in mixed dibasic acid ester (DBE), 2-Butoxyethyl acetate (DBGA), your ketone of different fluorine; The second solvent is low boiling point solvent, is selected from least one in cyclohexanone, toluene, ethyl acetate, isopropylcarbinol.More preferably in situation, organic solvent of the present invention adopt the first solvent with the second solvent volume than being the mixed solvent of 1:0.3-0.5, for example can adopt the mixture that mixture that your ketone of different fluorine and cyclohexanone volume ratio are 2:1 or different fluorine that ketone, cyclohexanone and isopropylcarbinol volume ratio are 1:0.2:0.2.
In ink composite of the present invention, the pigment that also can contain respective color according to the needs of printed patterns.Under preferable case, the quality of ink composite of take is benchmark, and the content of pigment is 6-15wt%.Described pigment can be the pigment of various routines, for example can be selected from one or more in the blue or green pigment of carbon black, iron oxide red, titanium dioxide, pearlescence, pearl powder, aluminium paste, silver-colored slurry, azo pigment and phthalein, according to the difference of printed patterns, is selected.Described pigment can directly adopt and be purchased product, for example can adopt Clariant company to produce 1533,1541,7005s and 1441.
As the preferred embodiment of the present invention, for improving the various performances of ink composite, in described ink composite, also can contain as required various auxiliary agents.Under preferable case, also contain the auxiliary agent of 0.5-8wt% in described ink composite; Auxiliary agent is selected from least one in defoamer, flow agent, wetting dispersing agent.
The kind of the defoamer described in ink composite of the present invention and consumption are conventionally known to one of skill in the art, for example, described defoamer can be selected from EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354, in BYK357, BYK054 one or more.The quality of ink composite of take is benchmark, and the content of described defoamer is the 0-2 % by weight, is preferably the 0-1.5 % by weight.
Described flow agent is mainly in order to guarantee the surface effect of ink composite excellence, the kind of flow agent and consumption are conventionally known to one of skill in the art, for example described flow agent can be selected from EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, in BYK307, DEGO410 one or more.Wherein EFKA series is Dutch Ai Fuka company product, and BYK series is BYK company product, and DEGO series is German Di Gao company product, and above its trade mark is conventionally known to one of skill in the art.The quality of ink composite of take is benchmark, and the content of described flow agent is the 0-2 % by weight, is preferably the 0-1.5 % by weight.
Described wetting dispersing agent refers to any material that can improve described matrix resin dispersion state in solvent, as Kerper-602, and Kerper-605, Kerper630, CFC-500HP, CFC-510, CFC-637, one or more in CFC-604S, BYK163.Wherein Kerper series is U.S. Kerper company product, and CFC series is French CFC company product.The quality of ink composite of take is benchmark, and the content of described wetting dispersing agent is that the 0-5 % by weight, be preferably the 0-3 % by weight.
The invention provides the preparation method of described ink composite, comprise epoxy vinyl ester resin, thermoset Hydroxylated acrylic resin, silane-modified polyisobutylene resin, polymeric amide affixture, whiteruss, glycerine and organic solvent are mixed in proportion, can obtain described ink composite.
In the present invention, for the order of addition of each component in ink composite, be not particularly limited, can add in batches, also can add together, finally mix and get final product.Under preferable case, for each component in ink composite is evenly mixed, can first each component except organic solvent be mixed, adopt three-roll grinder to grind until fineness is below 10 microns, and add organic solvent in process of lapping, mix and can obtain ink composite of the present invention.
The present invention also provides a kind of stainless steel work-piece, comprises stainless steel substrate and the ink design layer that is positioned at the stainless steel substrate surface; Described ink design layer, by ink composite provided by the invention is printed on release film, is transferred to stainless steel substrate surface curing obtaining after the room temperature surface drying.
In the present invention, the various release films commonly used for those skilled in the art of the release film that adopts, for example can adopt the PET release film.It is also conventionally known to one of skill in the art that ink composite is printed in to the mode of printing adopted on release film, for example can be by the mode of silk screen printing.
After the ink composite room temperature surface drying on release film, release film and stainless steel substrate are carried out to accurate contraposition, then the ink composite after surface drying is transferred to the stainless steel substrate surface, wherein transfer printing can be by the not one side of printing ink composition of release film that rubs under certain pressure, treat that it is peelable release film that ink layer is transferred to the stainless steel substrate surface fully, finally ink layer is solidified, can form ink design layer on the stainless steel substrate surface.Described curing condition comprises that solidification value is 40-90 ℃, and be 20-30 minute set time.
In the present invention, the thickness of the ink design layer on stainless steel substrate surface is not particularly limited, and according to the requirement of printed pattern, determines.
Below in conjunction with embodiment, the present invention will be further described.In embodiment and Comparative Examples, the raw material that adopts all is commercially available.
Embodiment 1
(1) each component except organic solvent is mixed, just grind until fineness is below 10 microns with three-roll grinder, add organic solvent in process of lapping, mix, each component concentration ratio is as follows; Obtain the ink composite of the present embodiment, be designated as S1;
Epoxy vinyl ester resin: 8084, contents of ethylene 42wt% 30%
Thermoset Hydroxylated acrylic resin: SC341, hydroxyl value 86 mgKOH/g 25%
Silane-modified polyisobutylene resin: EPION
tM, silicone content 10wt% 10%
Polymeric amide affixture: kingcure 450, amine value 300mgKOH/g 3%
Whiteruss 5%
Glycerine 6%
Auxiliary agent: defoamer: EFKA2022 0.5%
Flow agent: EFKA3883 0.5%
Wetting dispersing agent: Kerper-602 0.8%
Pigment: carbon black 6%
Organic solvent: different fluorine that ketone, cyclohexanone volume ratio 2:1 13.2%
(2) by ink composite S1, the mode by silk screen printing is printed in PET release film surface, after the room temperature surface drying, release film is fitted in to the die steel surface, and the one side that wherein on the PET release film, is printed with printing ink contacts with die steel; Repeatedly the rub another side of PET release film, treat that ink layer is transferred to the die steel surface fully, peels off the PET release film, and 50 ℃ of dry 30min in left and right then obtain the stainless steel substrate of the present embodiment, are designated as S11.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare ink composite S2, and be transferred to the stainless steel substrate surface, solidify and to prepare stainless steel work-piece S22, difference is, in ink composite S2, each component and weight percentage are as follows:
Epoxy vinyl ester resin: 411-400, contents of ethylene 33wt% 35%
Thermoset Hydroxylated acrylic resin: A909, hydroxyl value 70mgKOH/g 22%
Silane-modified polyisobutylene resin: EPION
tM, silicone content 15wt% 12%
Polymeric amide affixture: kingcure46, amine value 190mgKOH/g 7%
Whiteruss 5%
Glycerine 5%
Auxiliary agent: defoamer: BYK352 0.5%
Wetting dispersing agent: CFC-500HP 0.5%
Pigment: iron oxide red 3%
Organic solvent: different fluorine that ketone, cyclohexanone, isopropylcarbinol volume ratio 1:0.2:0.2 10%.
Embodiment 3-4
Adopt the step identical with embodiment 1 to prepare ink composite S3-S5 and stainless steel substrate S33-S55, difference, be that the weight percentage of each component in step (1) is as shown in table 1 respectively.
Comparative Examples 1-3
Adopt the step identical with embodiment 1 to prepare ink composite DS1-DS3 and stainless steel substrate DS11-DS33, difference, be that the weight percentage of each component in step (1) is as shown in table 1 respectively.
Table 1
| Component | S33 | S44 | S55 | DS11 | DS22 | DS33 |
| Epoxy vinyl ester resin | 31 | 33 | 30 | - | 40 | - |
| The thermoset Hydroxylated acrylic resin | 25 | 25 | 24 | 35 | - | - |
| The silane-modified polyisobutylene resin | 10 | 10 | 14 | 21 | 20 | 45 |
| The polymeric amide affixture | 3 | 5 | 5 | 12 | 5 | 23 |
| Whiteruss | 5 | 5 | 5 | 5 | 5 | 5 |
| Glycerine | 6 | 5 | 5 | 6 | 6 | 6 |
| Auxiliary agent | - | 1.8 | - | 1.8 | 1.8 | 1.8 |
| Pigment | 6 | - | - | 6 | 6 | 6 |
| Organic solvent | 14 | 15.2 | 17 | 13.2 | 16.2 | 13.2 |
Performance test:
1, pattern accuracy test:
Check after transfer printing whether residual ink is arranged above release film paper, noresidue is Y, otherwise is N; Compare with the former film, check that whether die steel surface ink layer line bar has the disappearance distortion, is deformed into Y without lacking, otherwise is N.
2, sticking power test:
Draw the square lattice of 100 1mm * 1mm at sprayed surface with drawing the lattice device, smooth being bonded on grid of scotch tape that the model of producing with Minnesota Mining and Manufacturing Company is 600, do not stay a space, then with utmost dispatch, vertically uncovers, and observes cut edge and have or not depainting.As the depainting amount, between 0-5%, be 5B, be 4B between 5-10%, between 10-20%, is 3B, between 20-30%, is 2B, between 30-50%, is B, more than 50%, is being 0B.
3, anti-etching test
Etching solution adopts the mixing acid (HCl:H of pH=1
2sO
4: the HNO3 volume ratio is 1:1:3); Stainless steel work-piece S11-S55 and DS11-DS33 are placed in to etching solution, soak 20 minutes, see whether ink design layer comes off; Be designated as Y without coming off, otherwise be designated as N.
Test result is as shown in table 2.
Table 2
| Test | S11 | S22 | S33 | S44 | S55 | DS11 | DS22 | DS33 |
| The pattern precision | Y | Y | Y | Y | Y | N | N | N |
| Sticking power | 5B | 5B | 5B | 5B | 5B | 3B | 2B | 2B |
| Etching resistence | Y | Y | Y | Y | Y | N | N | N |
From the test result of table 2, can find out, still transferability is to stainless steel surface after the room temperature surface drying for the ink composite of embodiments of the invention, and the precision of ink design layer obviously is better than Comparative Examples; In addition, the sticking power of ink layer of the present invention and base material is higher, and the etch resistant ability is also better.
Claims (11)
1. an ink composite, is characterized in that, contains following component:
Epoxy vinyl ester resin 30-40wt%;
Thermoset Hydroxylated acrylic resin 20-30wt%;
Silane-modified polyisobutylene resin 10-15wt%
;
Polymeric amide affixture 3-10wt%;
Whiteruss 5-10wt%;
Glycerine 5-10wt%;
Organic solvent 10-20wt%
.
2. ink composite according to claim 1, is characterized in that, the content of each component is:
Epoxy vinyl ester resin 30-35wt%;
Thermoset Hydroxylated acrylic resin 25-30wt%;
Silane-modified polyisobutylene resin 10-12wt%
;
Polymeric amide affixture 3-6wt%;
Whiteruss 5-8wt%;
Glycerine 5-8wt%;
Organic solvent 10-15wt%
.
3. ink composite according to claim 1 and 2, is characterized in that, the contents of ethylene of described epoxy vinyl ester resin is 30-45wt%; The hydroxyl value of thermoset Hydroxylated acrylic resin is 80-120mgKOH/g.
4. ink composite according to claim 1 and 2, is characterized in that, the silicone content of described silane-modified polyisobutylene resin is 5-20wt%.
5. ink composite according to claim 1 and 2, is characterized in that, the amine value of described polymeric amide affixture is 180-320mgKOH/g.
6. ink composite according to claim 1 and 2, is characterized in that, described organic solvent comprises the first solvent and the second solvent; The first solvent is selected from least one in diester, 2-Butoxyethyl acetate, your ketone of different fluorine, and the second solvent is selected from least one in cyclohexanone, toluene, ethyl acetate, isopropylcarbinol.
7. ink composite according to claim 1 and 2, is characterized in that, also contains the pigment of 6-15wt% in described ink composite; Pigment is selected from one or more in the blue or green pigment of carbon black, iron oxide red, titanium dioxide, pearlescence, pearl powder, aluminium paste, silver-colored slurry, azo pigment and phthalein.
8. ink composite according to claim 1 and 2, is characterized in that, also contains the auxiliary agent of 0.5-8wt% in described ink composite; Auxiliary agent is selected from least one in defoamer, flow agent, wetting dispersing agent.
9. the preparation method of ink composite claimed in claim 1, comprise epoxy vinyl ester resin, thermoset Hydroxylated acrylic resin, silane-modified polyisobutylene resin, polymeric amide affixture, whiteruss, glycerine and organic solvent are mixed in proportion, can obtain described ink composite.
10. a stainless steel work-piece, comprise stainless steel substrate and the ink design layer that is positioned at the stainless steel substrate surface; Described ink design layer, by the described ink composite of any one in claim 1-8 is printed on release film, is transferred to stainless steel substrate surface curing obtaining after the room temperature surface drying.
11. stainless steel work-piece according to claim 10, is characterized in that, described curing condition comprises that solidification value is 40-90 ℃, and be 20-30 minute set time.
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| CN1746236A (en) * | 2005-08-25 | 2006-03-15 | 复旦大学 | High-performance organic-inorganic resin coating material with hybrid acrylic ester and production thereof |
| TWI441875B (en) * | 2005-09-16 | 2014-06-21 | Mitsubishi Materials Corp | Printing ink and process for producing painted film using the same |
| US7399350B2 (en) * | 2006-10-17 | 2008-07-15 | Momentive Performance Materials Inc. | Fluorine-free disiloxane surfactant compositions for use in coatings and printing ink compositions |
| CN101457051B (en) * | 2007-12-14 | 2011-03-02 | 比亚迪股份有限公司 | Printing ink and preparation method thereof |
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