[disclosure of the Invention]
According to first feature of the present invention, provide and be suitable under water pressure the method for hydraulic transfer of the printed patterns of transfer printing transfer film on product surface, described transfer film forms by apply printed patterns on water-solubility membrane, this method is included in the step that applies the ultraviolet hardening resin composite on the printed patterns of transfer film, force goods to enter under water under the state that is recovered by the ultraviolet hardening resin composite with the adhesiveness of printed patterns therein with transfer film, the printed patterns that pressure comprises the ultraviolet hardening resin composite adhere on the product surface step and on goods the step of irradiation ultraviolet radiation, transfer printing has the printed patterns that comprises the ultraviolet hardening resin composite on these goods, and ultraviolet hardening resin composite thus hardens.
According to second feature of the present invention, provide and be suitable under water pressure the method for hydraulic transfer of the printed patterns of transfer printing transfer film on product surface, this transfer film forms by apply printed patterns on water-solubility membrane, this method comprises by apply the step that printed patterns prepares transfer film on the water-solubility membrane that contains the ultraviolet hardening resin composite that applies in advance thereon, keep therein under the adhering state of printed patterns, force goods with transfer film enter under water with the printed patterns of forcing to comprise the ultraviolet hardening resin composite adhere on the product surface step and on goods the step of irradiation ultraviolet radiation, transfer printing has the printed patterns that comprises the ultraviolet hardening resin composite on these goods, and ultraviolet hardening resin composite thus hardens.
In these features of the present invention, the water-solubility membrane that can be desirably in transfer film is in the step of carrying out irradiation ultraviolet radiation around goods in the state that wherein its is reeled, more be desirably in goods underwater the time or after goods come out from water, but before water-solubility membrane is removed by water washing.
According to first and second feature of the present invention; since on the printed patterns of transfer film or under the printed patterns that applies after the ultraviolet hardening resin composite transfer film be transferred on the product surface; so while hectographic printing pattern and ultraviolet hardening resin composite on product surface; it causes and is omitted in the operation that applies sealer on the decorative layer that is formed by printed patterns, and therefore hydraulic-transfer can have the last part technology of simplification.
Applying on the printed patterns of transfer film under the situation of ultraviolet hardening resin composite, because the ultraviolet hardening resin composite has the adhering mobilizing function of the printed patterns that recovers drying regime, so need not activate the independent operation of printed patterns by activator, therefore simplify the overall operation progress that comprises method of hydraulic transfer and last part technology.
Since therein ultraviolet hardening resin Composite Permeability printed patterns and with state that printed patterns mixes under by UV cured ultraviolet hardening resin composite; decorative layer self has the surface protection function that it is given, so printed patterns has machinery and the excellent surface property of chemistry.
Even since under water or goods from water, come out carrying out the step of irradiation ultraviolet radiation to the ultraviolet hardening resin composite before the water washing of removing water-solubility membrane, so dust never adheres on the printed patterns, therefore can obtain the good appearance of decorative layer.
According to the 3rd feature of the present invention; be provided at the method that forms UV cured type sealer on the goods; this method is included in and applies UV cured type protective agent on the water-solubility membrane to form the step of sealer transfer film; when the sealer transfer film floats on water surface and water-solubility membrane when becoming wet, on the goods on the step of the UV cured type sealer of transfer surface protective layer transfer film under the water pressure and UV cured type sealer in transfer printing on the goods irradiation ultraviolet radiation with the step of hardened surface protective layer.
In the 3rd feature of the present invention; thereby can form the sealer transfer film as printing or spraying by on water-solubility membrane, applying UV cured type protective agent by suitable measure; but water-solubility membrane should be coated in UV cured type protective agent on the water-solubility membrane by spraying under the situation of floating on the water surface that should be used for hydraulic-transfer therein.Under any circumstance, UV cured type protective agent is being coated on the water-solubility membrane with after forming sealer thereon, sealer has the adhering hydraulic-transfer that carries out simultaneously.
The UV cured type protective agent that is used for the method for the 3rd feature according to the present invention can be that UV cured type applies agent or UV cured type printing ink.In addition, the UV cured type sealer on the water-solubility membrane can have the decoration relief pattern that is formed therein by appropriate action.Goods have under the situation of the decoration that is applied by hydraulic-transfer therein, and it is transparent or semitransparent requiring sealer.
According to the 3rd feature of the present invention, can provide not only mechanical surface characteristic such as excellent in abrasion resistance by using the hydraulic-transfer technology, and the sealer of chemical surface properties such as resistance physical properties excellent.
Especially in the method, be plane form owing to apply the protectant water-solubility membrane of UV cured type thereon, so can UV cured type protective agent be coated on the upper surface of water-solubility membrane equably by intaglio printing, silk screen-masterplate etc.The sealer that is transferred to above the goods from the sealer transfer film of such formation can be applied on all surface of goods equably, therefore can be obtained the product of good product quality by sealer, and this product is the outward appearance of deterioration goods never.
Owing to can after the hydraulic-transfer of printed patterns, carry out the hydraulic-transfer of sealer, for example can not use conventional independent process for surface coating to form sealer cheaply by the technology that simplifies the operation.
In addition, because can be by the irradiation ultraviolet radiation UV cured type sealer that hardens thereon immediately hydraulic-transfer after, external material such as dirt or dust never adhere to sealer, so can obtain the product of good appearance.
According to the 4th feature of the present invention, the method of hydraulic transfer that is suitable for the printed patterns of transfer printing transfer film on product surface is provided, this transfer film forms by apply printed patterns on water-solubility membrane, this method is included in and applies no-solvent type ultraviolet hardening resin composite on the printed patterns of transfer film to be recovered the adhering step of printed patterns by the solvent-free activator of solvent-free uv-hardening resin composite, force goods with transfer film enter under water with the printed patterns of forcing to comprise the uv-hardening resin composite adhere on the product surface step and on goods the step of irradiation ultraviolet radiation, transfer printing has the printed patterns that comprises the uv-hardening resin composite on these goods, hardens the uv-hardening resin composite to form decorative layer under the state that uv-hardening resin and printed patterns are united fully therein thus.
According to the 5th feature of the present invention, a kind of method of hydraulic transfer that is suitable for the printed patterns of transfer decorative transfer film on product surface is provided, this decoration transfer printing film forms by apply this printed patterns on water-solubility membrane, this method is included on the printed patterns of decoration transfer printing film and applies no-solvent type ultraviolet hardening resin composite, to recover the adhering step of printed patterns by the solvent-free activating component of this solvent-free uv-hardening resin composite, force goods to enter under water with the printed patterns of forcing to comprise the uv-hardening resin composite and adhere to step on the product surface with the decoration transfer printing film, the step of irradiation ultraviolet radiation on goods, transfer printing has the printed patterns that comprises the uv-hardening resin composite on these goods, harden this uv-hardening resin composite with the formation decorative layer with on the goods that contain the decorative layer that forms thereon under the state that uv-hardening resin and printed patterns are united fully therein thus, transfer surface is covered with paint, lacquer, colour wash, etc. the step of the ultraviolet hardening resin composite layer of transfer film, form this top finishing transfer film by apply transparent, UV hardening resin composite on water-solubility membrane under single color state, the ultraviolet hardening resin composite from the top finishing transfer film forms face coat thus.
In the 4th and the 5th feature of the present invention, the solvent-free activating component that is used to recover the adhering ultraviolet hardening resin composite of printed patterns can comprise photo polymerization monomer.Carry out irradiation ultraviolet radiation when preferably the water-solubility membrane of decoration transfer printing film is wound on around the goods.In addition, ultraviolet ray and ultraviolet hardening resin composite can be replaced by electronics line and electronics line hardening resin composite.
According to the 4th and the 5th feature of the present invention, the adhesiveness of printed patterns can be recovered fully by the solvent-free activating component of ultraviolet hardening resin composite, described activating component can be typically and preferably photo polymerization monomer make adhesiveness have with just printed patterns is printed on the water-solubility membrane after the identical degree of adhesiveness.Owing to can not using any organic solvent to carry out adhering recovery, do not produce because the organic solvent generation air pollution of using or the problem of labourer's health damage.
Since the printing ink of the printed patterns of solvent-free activating component infiltration therein with the state that mixes with printing ink down and therefore solvent-free therein ultraviolet hardening resin composite fully with the state of printed patterns associating under the harden solvent-free activating component such as the photo polymerization monomer of ultraviolet hardening resin composite; decorative layer on the goods self has its machinery that applies and chemical surface defencive function such as wearability; solvent resistance, resistance rerum natura and weatherability etc.This is identical with the effect that first and second feature of the present invention have.
If giving the surface protection function of decorative layer is enough as solvent resistance for product (goods); decorative layer self can be provided as the superficial layer of goods; if but require higher surface protection, can by use the hydraulic-transfer technology by the method for describing in later the 5th feature at the face coat that forms the transparent, UV hardening resin composite that on water-solubility membrane, applies with single color state on the goods.Expect that this face coat is applied to increase the thickness of product surface outward appearance and further improves the protection of machinery and chemical surface.
Even since under water or goods from water, come out carrying out the step of irradiation ultraviolet radiation to the ultraviolet hardening resin composite before the water washing of removing water-solubility membrane, therefore substantially not have dust adhesion wherein to the chance of printed patterns improving excellent goods speed, so can obtain to have the goods of decorative layer good appearance.
According to the 6th feature of the present invention; a kind of printed patterns of transfer printing transfer film on product surface and method of hydraulic transfer of top finishing protective layer of being suitable for is provided; this transfer film forms by apply top finishing protective layer and printed patterns in order on water-solubility membrane; this method is included on the printed patterns of transfer film and applies no-solvent type ultraviolet hardening resin composite; to recover the adhering step of printed patterns by the solvent-free activating component of no-solvent type ultraviolet hardening resin composite; force goods to enter under water with the printed patterns of forcing to comprise the uv-hardening resin composite and adhere to step on the product surface with transfer film; the step of irradiation ultraviolet radiation on goods; transfer printing has the printed patterns that comprises the ultraviolet hardening resin composite and the top finishing protective layer on printed patterns on these goods, thus ultraviolet hardening resin composite and printed patterns and the state of uniting fully with at least a portion top finishing protective layer sclerosis uv-hardening resin composite down therein.
In the 6th feature of the present invention, the solvent-free activating component that is used to recover the adhering ultraviolet hardening resin composite of printed patterns can adopt with the 3rd of the present invention and the 4th mode that feature is identical and comprise photo polymerization monomer.Carry out irradiation ultraviolet radiation when preferably the water-solubility membrane of transfer film is wound on around the goods.In addition, ultraviolet ray and ultraviolet hardening resin composite can be replaced by electronics line and electronics line hardening resin composite.
In the 6th feature of the present invention, the top finishing protective layer can be transparent ink or ultraviolet hardening resin composite and preferred no-solvent type ultraviolet hardening resin composite.
Because the 6th of the present invention is characterised in that the adhesiveness of being recovered printed patterns by the solvent-free activating component of the UV-cured resin composite materials of no-solvent type, does not produce because the organic solvent generation air pollution of using or the problem of labourer's health damage.Equally; because sclerosis ultraviolet hardening resin composite and printed patterns when they are united each other fully; decorative layer on the goods self has its machinery that applies and chemical surface defencive function such as wearability, solvent resistance, resistance rerum natura and weatherability etc.
When face coat is during with transfer printings such as surface protection function of giving decorative layer such as solvent resistances; the surface of decorative layer can be by the face coat of transfer printing protection on decorative layer under water pressure; in addition owing to being used to recover also impermeable surface covering with paint protective layer of adhering a part of ultraviolet hardening resin composite, so can improve the adhesiveness performance of face coat and decorative layer.Especially; because face coat is the ultraviolet hardening resin composite; can strengthen machinery and chemical surface protection by combining of ultraviolet hardening resin composite of uniting fully with decorative layer and top finishing ultraviolet hardening resin composite, this applies for its adhering recovery with the composite that decorative layer is united fully.Face coat is given the degree of depth of product surface outward appearance to it.
Because, even can be under water or goods from water, come out before the water washing of removing water-solubility membrane for recovering irradiation ultraviolet radiation on adhering ultraviolet hardening resin composite and the top finishing ultraviolet hardening resin composite, so substantially not have dust adhesion wherein to the chance of printed patterns improving excellent goods speed, so can obtain to have the goods of decorative layer good appearance.
According to the 7th feature of the present invention; a kind of method of hydraulic transfer that is suitable for the sealer of transfer surface protective layer transfer film on product surface is provided; this sealer transfer film forms by applying on water-solubility membrane with the desiccated surface protective layer; this method is included in and applies the ultraviolet hardening resin composite on the sealer of sealer transfer film to recover the adhering step of sealer; force goods with transfer film enter under water with the sealer of forcing to comprise the uv-hardening resin composite adhere on the product surface step and on goods the step of irradiation ultraviolet radiation; transfer printing has the sealer that comprises the uv-hardening resin composite on these goods, thus sclerosis uv-hardening resin composite under the state that the uv-hardening resin material is complete and sealer is united therein.
In the 7th feature of the present invention, surface protectant can be a transparent ink or will be by the coating material of drying sclerosis.
According to the 8th feature of the present invention, provide by first hydraulic-transfer goods that obtain to any method of hydraulic transfer of the 7th feature according to the present invention.
By according to of the present invention first; the decorative layer of the hydraulic-transfer goods that second and the 4th obtain to the method for hydraulic transfer of the 6th feature and the sealer of hydraulic-transfer goods can preferably be suitable for never by solvent resistance test deterioration, will comprise the reciprocal wiping of gauze eight times of ten accumulations of dimethylbenzene when wherein rubbing on decorative layer.
[best mode of embodiment of the present invention]
Embodiment of the present invention are described with reference to the drawings, and Fig. 1 brief description is according to the method for hydraulic transfer of first kind of form of the present invention.This method of hydraulic transfer is a kind of like this method, the transfer film 16 that is floating and comprising water-solubility membrane 14 on the water 18 in the transfer printing that does not show is bathed wherein, water-solubility membrane 14 contains the printed patterns 12 and the printed patterns that apply thereon and is directed upwardly, the goods 10 of hectographic printing pattern are forced through transfer film 16 and enter under water thereon, therefore finish hydraulic-transfer.
Water-solubility membrane 14 forms by containing the water-soluble material as main component of polyvinyl alcohol for example, and it becomes wet and by absorbing water softening.This water-solubility membrane 14 is when it reels around the softening and goods 10 that will decorate when water during transfer printing is bathed contact, so can finish hydraulic-transfer.Under the situation of common hydraulic-transfer, printed patterns 12 can be applied on the water-solubility membrane 14 by intaglio printing etc.The meaning that it should be noted that " printed patterns " 12 expression is removed and is comprised the printed patterns (printed patterns that does not contain pattern) that also comprises the plane the initial printed patterns that just has a pattern.
The method of first kind of form will apply or apply the ultraviolet hardening resin composite to the printed patterns 12 of transfer film 16 according to the present invention, to permeate printed patterns 12 before hectographic printing pattern on the goods under water pressure.Although in the embodiment of the following stated, UV cured type coating material can be used as the ultraviolet hardening resin composite, can use UV cured type printing ink.The example of the concrete steps of method of hydraulic transfer of the present invention illustrates in Fig. 2.In the form of Fig. 2, operation is in the state (referring to Fig. 2 A) of drying condition from wherein being printed on printed patterns 12 on the water-solubility membrane 14.Although do not show, in fact, the form of transfer film 16 is the volume by before printing printed patterns 12 and dry printed patterns 12 obtain on the water-solubility membrane 14 of elongation.Transfer film 16 can used from the continuous feed of film roller or by cutting it thereafter.
In the form of Fig. 2, UV cured type coating material 20 is applied on the dry printed patterns 12 of transfer film 16 of Fig. 2 A (referring to Fig. 2 B), therefore printed patterns 12 is recovered under the adhering state of printed patterns 12 by UV cured type coating material 20 activation therein, float on the water 18 of transfer film 16 in transfer printing is bathed (referring to Fig. 2 C), goods 10 with transfer film 16 forced enter under water thereafter, face toward the surperficial 10S (referring to Fig. 2 D) of goods and irradiation ultraviolet radiation 22 on goods 10 with the printed patterns of forcing to comprise UV cured type coating material 20 12, transfer printing has the printed patterns 12 that comprises UV cured type coating material 20 on goods 10, and UV cured type coating material 20 (referring to Fig. 2 E) therefore hardens.Although show in the accompanying drawings, can when supporting by anti-triangular shape conveyer conveying or by the robots arm, goods 10 force goods 10 to enter under water.In some cases, on printed patterns 12, apply the step (referring to Fig. 2 B) of UV cured type coating material 20 and the step (referring to Fig. 2 C) of the transfer film 16 that floats on the water can be carried out on the contrary, therefore can UV cured type coating material 20 be applied on the printed patterns that swims in transfer film waterborne 16 by spraying, to recover the adhesiveness of printed patterns 12.
UV cured type coating material 20 is that the ultraviolet hardening resin composite and this material that are used for activating suitably the dry printed patterns 12 of transfer film 16 can comprise the composition with following composition.
(1) oligomer 30-50wt%
(2) polyfunctional acrylic ester 10-30wt%
(3) monofunctional acrylate 10-40wt%
(4) non-reacted additive 1-20wt%
(5) Photoepolymerizationinitiater initiater 0.5-5wt%
(6) solvent surplus
Oligomer is to influence the composition of the adhesiveness of coating material and physical property and can use a kind of use of acrylic compounds oligomer, polyester oligomer, epoxy acrylate oligomer and urethane acrylate oligomer separately or they can at random be used in combination according to required characteristic.
Monofunctional acrylate monomer is that the function of reactant diluent and this material is that the dry printed patterns 12 of activation is to recover its adhesiveness.It is to adopt the mode identical with monofunctional acrylate monomer to activate the printed patterns 12 of drying to recover its adhesiveness with the other function that provides weatherability and intensity to printed patterns 12 and have that the polyfunctional acrylic ester monomer is into bridge composition and the characteristic of giving chemistry and mechanics excellence to coating material after it UV cured.
Use polyacrylate such as PMA etc. to alleviate contraction by the coating that becomes the bridge composition to cause.If the convergent force of coating uprises, the adhesiveness of coating descends, and then polyacrylate can usefully be prevented situation here.
Conventional acetophenone, benzophenone etc. can be used as solvent as Photoepolymerizationinitiater initiater and ethyl acetate, butyl acetate, acetate propylene glycol monomethyl alcohol ester, cyclohexanone (cyclohexanone), toluene, dimethylbenzene etc.
Although applying the step of UV cured type coating material 20 can apply and any of spraying carries out by photogravure roller, coiling rod, because spraying applies a large amount of coating materials of processes expend, therefore preferably the photogravure roller applies technology or the rod that winds the line applies technology and is used to apply coating material.
When being applied to UV cured type coating material 20 on the printed patterns 12, dry printed patterns 12 by the monofunctional acrylate monomer in the UV cured type coating material 20 or the activation of polyfunctional acrylic ester monomer and in addition under possible situation by activation such as solvents, therefore recover the adhesiveness of printing ink.Therefore, UV cured type coating material 20 can have with the activator identical functions that applies usually on dry printing ink so omit applying of activator.
When being applied to UV cured type coating material 20 on the printed patterns 12, the coating material composition infiltrates through printed patterns 12 and therefore ink composition and coating material composition are mixed with each other with The combined.Therefore, when irradiation ultraviolet radiation 22 is with the cured coating material composition when be transferred to goods 10 at the printed patterns 12 that the coating material composition is mixed with it after, will give printed patterns 12 mechanical strength and chemical characteristic such as hear resistance and weatherability.Although Fig. 2 B and 2C do not illustrate the wherein ink composition of printed patterns 12 and the state that UV cured type coating material is united fully, if these figure attempt showing such state, then can not to be distinguished from each other both, but to be to be understood that in order conveniently being that state with layer shows them.
Ultraviolet ray 22 is shone contain the goods of the printed patterns 20 of its transfer printing on after, water spray 24 is ejected on the water-solubility membrane 14 of transfer film 16 with therefore washings soluble film 14, shown in Fig. 2 F, therefore water-solubility membrane 14 is removed from the surface of goods 10., as Fig. 2 G shown in, hot blast 26 be radiated at the surface of goods 10 on, on goods 10, be stained with the printed patterns 12 that comprises UV cured type coating material 20,, therefore finish 10 ' (with reference to the figure 3) that contains decorative layer 30 with the surface of dried product 10 thereafter.
Preferably at the water-solubility membrane 14 of transfer film 16 irradiation ultraviolet radiation 22 when reeling around the goods 10, transfer printing comprises the printed patterns 12 of UV cured type coating material 20 on goods 10, although therefore preferably goods 10 still under water after or it from water, come out to shine in water washing with before removing water-solubility membrane 14.Ultraviolet ray 22 is by conventional ultraviolet curing equipment irradiation, and this equipment comprises illuminator such as high-pressure sodium lamp or metal halide lamp and irradiating machine (lamp house).Because ultraviolet ray can penetrate under water, so can when goods 10 are underwater, ultraviolet ray 22 be shone on the goods 10.
Adopt this mode, irradiation ultraviolet radiation 22 when water-solubility membrane 14 is wound on around the goods, thereby any dirt etc. can not adhere on the goods before printed patterns 12 bone dries, can reduce the possibility that dirt adheres to, this is owing to printed patterns 12 when removing water-solubility membrane 14 has hardened, and therefore can easily obtain to have the decorative layer 30 of good appearance.In environment that does not contain dust or dirt such as tunnel-like clean room, carry out therein under the situation of ultraviolet ray 22 irradiation, can be in the irradiation of water-solubility membrane 14 being carried out ultraviolet 22 from goods 10 water washings are fallen after.
(embodiment 1)
In the specific embodiments of first kind of form according to the present invention, formation is available from FUJIKURA KASEI CO., LTD., the material of Ri Ben FUJIHARD HH9986 U-N7 main component carries out technology as UV cured type coating material 20 and employing Fig. 2 A to the order of step shown in the 2G.Just transfer film 16 is introduced before the transfer printing bath shortly, applies technology by photogravure UV cured type coating material 20 is applied or is coated on the printed patterns 12 of transfer film 16.Adopt this mode, float on the water surface of bathing as Fig. 2 transfer printing that D the is shown in transfer film 16 that applies coating material thereon and after activating printed patterns 12 with UV cured type coating material 20 and recovering enough adhesiveness pushes goods 10 under water by transfer film 16.After after transfer printing, goods 10 being taken out from water, irradiation ultraviolet radiation on goods, thereafter with goods water cleaning and dry with obtain hydraulic-transfer goods 10 shown in Figure 3 '.
When the decorative layer of the hydraulic-transfer goods (A) that obtain like this by cross cutting belt adhesiveness method of testing (1mm otch measure 100 times) test, confirm that goods (A) have with the hydraulic-transfer goods (B) that do not contain face coat and contain the identical adhesiveness of hydraulic-transfer goods (C) of the conventional acrylic resin face coat that applies on decorative layer.On the goods under predetermined load by carrying out the test of solvent resistance 30 times with the reciprocal wiping of rag that comprises isopropyl alcohol, confirm that the solvent resistance of hydraulic-transfer goods (A) significantly is better than the conventional hydraulic-transfer goods (C) that contain face coat.Certainly, the hydraulic-transfer goods (B) that do not contain face coat do not have solvent resistance.Therefore, notice that the hydraulic-transfer goods of first kind of form have weatherability and have high mechanical strength according to embodiments of the present invention, these performances are realized by the UV cured type coating material that infiltrates through decorative layer.
In first kind of form of embodiment shown in Figure 2, the transfer film 16 that use contains dry printed patterns 12 carries out transfer operation, but in second kind of form of embodiment shown in Figure 4, transfer operation can be undertaken by following mode: apply or apply UV cured type coating material 20 to water-solubility membrane 14, printing printed patterns 12 by off-contact printing mode such as ink-jet system on the coating material 20 and before printed patterns 12 dryings transfer film 16 is being introduced transfer printings and bathe thereafter.
In the case, because the ink composition of printed patterns 12 has kept adhesiveness, do not have the function of activation printing ink so require UV cured type coating material 20, but by printing printed patterns 12 on coating material 20, coating material 20 infiltrates through ink composition, therefore UV cured type coating material 20 and ink composition adopt with the identic mode of Fig. 2 embodiment and unite fully, so the decorative layer of hydraulic-transfer goods has the identic characteristic with Fig. 3.
First kind and second kind of form according to embodiments of the present invention; since therein on the printed patterns 12 of transfer film 16 or under apply the hydraulic-transfer that carries out goods 10 surfaces under the state of UV cured type coating material 20; so on product surface transfer printing simultaneously printed patterns 12 and ultraviolet hardening resin composite; can notice not require the operation that applies sealer at the decorative layer that forms by printed patterns 12, so the later stage technology of hydraulic-transfer obtains simplifying.
Because UV cured type coating material 20 has mobilizing function to recover the adhesiveness of dry printed patterns 12, do not require independent operation adopting activator activation printed patterns 12, so the overall craft of hydraulic-transfer and possible later stage technology become simpler.
Since therein UV cured type coating material 20 infiltrate through printed patterns 12 inner and with state that printed patterns 12 mixes under; by UV cured type coating material 20, thus to the decorative layer self of goods given the surface protection effect and therefore printed patterns 12 have machinery and the excellent surface property of chemistry.
Even since under water or goods from water, come out in water washing and carry out the step of irradiation ultraviolet radiation before removing water-solubility membrane, dust, dirt etc. adhere to less than on the printed patterns 12, so can obtain the decorative layer of good appearance.
Even UV cured type coating material 20 can be replaced also can reaching identical effect by the UV cured type printing ink of having described.
In Fig. 5, show the method for hydraulic transfer of the third form (forming the method for sealer) according to embodiments of the present invention.Although the method typically is applied in by this hydraulic-transfer of Fig. 2 and decorates on the product surface afterwards, with the surface of protection decorated articles 10, certain the method for the present invention also can similarly be used on the product surface of being decorated by other appropriate action.
In the method for the present invention; as shown in Figure 5; the initial sealer transfer film 216 that contains UV cured type sealer 240 that forms forms UV cured type sealer 240 (referring to Fig. 5 A) by apply UV cured type protective agent (ultraviolet hardening resin composite) on water-solubility membrane 214.As the water-solubility membrane 14 of the transfer film 16 that is used for first kind of form of embodiment, water-solubility membrane 214 can comprise water-soluble material, and this water-soluble material contains for example main component of polyvinyl alcohol, and it becomes wet and softening by absorbing water.
Under the situation of goods 10 by decorations such as hydraulic-transfers; UV cured type protective agent is that UV cured type clear dope material and this coating material can comprise the composition with following composition; with because this is identical composition with the UV cured type coating material that is used for first kind and second kind form of embodiment, so omission detailed description.
(1) oligomer 30-50wt%
(2) polyfunctional acrylic ester 10-30wt%
(3) monofunctional acrylate 10-40wt%
(4) non-reacted additive 1-20wt%
(5) Photoepolymerizationinitiater initiater 0.5-5wt%
(6) solvent surplus
Adopt this mode, after forming sealer transfer film 216, float on the surface of the water 218 of this transfer film 216 in transfer printing is bathed and sealer 240 directions towards (referring to Fig. 5 B).When the water-solubility membrane 214 of transfer film 216 was become wet fully by water 218, the goods 10 that will contain the surface that will protect forced to enter the hydraulic-transfer (referring to Fig. 5 C and 5D) to carry out UV cured type sealer 240 on goods 10 in the water 218 by sealer transfer film 216.
Thereafter, on the UV cured type sealer 240 that is transferred on the goods 10 irradiation ultraviolet radiation 222 with hardened surface protective layer 240 (referring to Fig. 5 E).Remove water-solubility membrane 214 (referring to Fig. 5 F) to the surface of goods 10 by spray washing water 224.At last, hot blast 226 is blown on the surface of goods 10 with dry it (referring to Fig. 5 G), therefore finish product 210 ' (referring to Fig. 6) by sealer 240 ' protection.In Fig. 5 D and 5E,, do not indicate the water-solubility membrane 214 and the sealer 240 of transfer film 216 although they are distinguished each other.
As the hydraulic-transfer that Fig. 2 is used to decorate, wish to be wound on goods 10 carry out ultraviolet ray 220 on every side irradiation at the water-solubility membrane 214 of transfer film 216.This can harden UV cured type coating material and do not adhere to dust, dirt wait until the sealer 240 of UV cured type coating material and therefore can form the sealer with good appearance 240 that do not contain the dust that adheres on it, dirt etc. '.
(embodiment 2)
In the specific embodiments of the third form according to the present invention, formation is available from FUJIKURA KASEI CO., LTD., the material of Ri Ben FUJIHARD HH9986 U-N7 main component carries out this technology as UV cured type clear dope material and employing Fig. 5 A to the sequence of steps shown in the 5F.Before being about to be introduced into the transfer printing bath, transfer film on water-solubility membrane 16, applies UV cured type clear dope material by photogravure technology.Adopt this mode, contain and swim on the water surface that transfer printing bathes and sealer is directed upwardly and thereafter goods is pushed under water by transfer film by the transfer film that applies the sealer that coating material forms.Behind the transfer surface protective layer goods are being taken out from water on the product surface; irradiation ultraviolet radiation on sealer; at last goods are washed with water and dry with the product 210 that obtains to contain the UV cured sealer 214 ' that forms thereon ', as shown in Figure 6.
When by cross cutting belt adhesiveness method of testing (1mm otch measure 100 times) test during, confirm that goods (D) have with the hydraulic-transfer goods (B) that do not contain face coat and contain the identical adhesiveness of hydraulic-transfer goods (C) of the conventional acrylic resin that applies on decorative layer by the adhesiveness of hydraulic-transfer goods (product) sealer (D) of the transparent surface protective layer protection of such acquisition.On the goods under predetermined load by carrying out the test of solvent resistance 30 times with the reciprocal wiping of rag that comprises isopropyl alcohol, confirm that the solvent resistance of hydraulic-transfer goods (D) significantly is better than the conventional hydraulic-transfer goods (C) that contain the face coat that forms thereon.Certainly, the hydraulic-transfer goods (B) that do not contain face coat do not have solvent resistance.Therefore, notice that the hydraulic-transfer goods according to specific embodiments of the present invention have good weatherability and have high mechanical strength, these performances are realized by UV cured type coating material.
In the above-mentioned form of embodiment; although the clear dope material is used as UV cured type protective agent, can use translucent coating material and the goods can be by decorating by the sealer self that uses UV cured type printing ink rather than coating material to form.Adopt this mode, if use UV cured type printing ink, then sealer causes having decoration and two kinds of functions of surface protection.
As shown in Figure 7; on water-solubility membrane 214, apply UV cured type protective agent with after the formation sealer 240, can in sealer 240, be processed to form suitable relief pattern 240a such as particle pattern and other pattern by relief pattern processing or explosion.
In Fig. 8, show the method for hydraulic transfer of the 4th kind of form according to embodiments of the present invention.The method is with identical according to the method for first kind of form of embodiment, except will not being UV cured type coating material 20 at the material that applies or apply on the printed patterns 12 of transfer film 16 but can adopting the mode identical with first kind of mode of embodiment to carry out (referring to Fig. 8 A to 8G) with this no-solvent type ultraviolet hardening resin composite 20A.
The resin that " ultraviolet hardening resin " expression is hardened by the relative shorter time of ultraviolet chemical action effect and take forms such as UV cured type coating material, UV cured type printing ink, UV cured type adhesive according to its purposes.These reagent comprise (1) photopolymerization prepolymer as indispensable composition, (2) photo polymerization monomer and (3) light (optics) initator.Contain solvent such as the alcohol that joins wherein although on market, contain solvent usually as diluent and some the UV cured printing ink that join wherein as the material that is used for the UV cured type coating material of first kind of form of embodiment of the present invention, common UV cured type printing ink do not contain the solvent that joins wherein and with the photo polymerization monomer blend with as diluent." ultraviolet hardening resin composite ", it is the purpose of the 4th kind of form of embodiment of the present invention, substantially with photopolymerization prepolymer, photo polymerization monomer and Photoepolymerizationinitiater initiater blend no matter the type of service of ultraviolet hardening resin and do not add any solvent and before by ultraviolet ray irradiation sclerosis, also have liquid form.
Material by " ultraviolet hardening resin composite " expression that will be used for the 4th kind of form of embodiment of the present invention is got rid of the solvent-free ultraviolet hardening resin composite that wherein comprises the ultraviolet hardening resin composite of solvent and be limited to the solvent that does not contain adding.This is that it is photo polymerization monomer typically because to recover the printed patterns of transfer film adhering be solvent-free activating component in the no-solvent type ultraviolet hardening resin composite.The ultraviolet hardening resin composite that is applicable to the 4th kind of form of embodiment of the present invention comprises the composition with following composition;
(1) oligomer (photopolymerization prepolymer) 30-50wt%
(2) polyfunctional acrylic ester
(photo polymerization monomer) 10-30wt%
(3) monofunctional acrylate
(photo polymerization monomer) 10-40wt%
(4) Photoepolymerizationinitiater initiater 0.5-5wt%
(5) non-reacted additive 1-20wt%
The photopolymerization prepolymer be can be further by the polymer of photochemical effect sclerosis and be called as " photopolymerization unsaturated polymer ", " base resin " or " photopolymerization oligomer.As this prepolymer of coat film after the sclerosis is that basic ingredient and acrylic compounds oligomer, polyester oligomer, epoxy acrylate oligomer and the urethane acrylate oligomer that influences many important physical properties can independently or arbitrarily be used in combination.Although the degree of polymerization of photopolymerization prepolymer is not as final polymerization object height, it is not monomer and has been aggregated to certain degree therefore it has suitable viscosity and therefore considers the operating effect when it uses and require to use diluent.
Photo polymerization monomer keeps the actual effect of resin composite materials operation simultaneously and self participates in polymerization as the diluent of photopolymerization prepolymer.There are monofunctional monomer that contains single functional group and the polyfunctional monomer that contains two or more functional groups.Monofunctional monomer is used to improve gives flexibility with the coat film after sclerosis and polyfunctional monomer is used as bridge joint prepolymer molecule becomes the bridge agent to the adhesiveness of goods.For example, polyacrylate such as PMA are used to alleviate the contraction by the coat film that becomes bridge to cause.If the convergent force of coat film uprises, the adhesiveness of coat film will be reduced, but polyacrylate can usefully be prevented situation here.These photo polymerization monomers are as the diluent of regulating ultraviolet hardening resin composite viscosity and also as the adhering functional component (activating component) of recovering dry printed patterns.
Photoepolymerizationinitiater initiater is used for absorbing ultraviolet ray with initiated polymerization be also referred to as " Photoepolymerizationinitiater initiater ".Acetophenone, benzophenone etc. can be used when UV cured reaction is radical reaction, and when UV cured reaction is ionic reaction, diazonium compound etc. can be used.
The ultraviolet hardening resin composite can contain the sensitizer of oriented its adding, filler, nonactive organic polymer, levelling agent, thixotropy imparting agent, thermal polymerization inhibitor etc.
When being applied to no-solvent type ultraviolet hardening resin composite 20A on the printed patterns 12, photo polymerization monomer among the no-solvent type ultraviolet hardening resin composite 20A infiltrates through the dry printing ink of printed patterns 12 with dissolving printing ink, therefore can recover the adhesiveness of printing ink, this printing ink has and just prints printed patterns identical wet condition afterwards.Therefore, no-solvent type ultraviolet hardening resin composite 20A can have the function that is equal to normally used activator, with therefore omit activator, diluent etc. apply and since the volatility that comprises every kind of composition in the ultraviolet hardening resin composite of photo polymerization monomer usually far below solvent etc., the degree of adhesion of recovering after adhesiveness is recovered neither changes also and does not descend, this can realize activating stable expectation, can not realize in solvent-borne type and activation is stable.
When with printed patterns 12 transfer printings on goods 10 and thereon during irradiation ultraviolet radiation 22, the every kind of composition of ultraviolet hardening resin composite 20A such as photo polymerization monomer infiltrate through under the state of printing ink of printed patterns 12 therein, sclerosis ultraviolet hardening resin composite, so ultraviolet hardening resin composite and printing ink are united fully.This gives mechanical surface defencive function such as wearability etc. and chemical surface defencive function such as solvent resistance to decorative layer self, resistance rerum natura etc.This form of implementation also has those function identical functions with first kind of form of embodiment.Because photo polymerization monomer self participates in polymerization after the ultraviolet ray irradiation, this monomer never separates therefore not have a negative impact after it.
As mentioned above; the ultraviolet hardening resin composite that contains the oriented solvent that wherein adds all self is given the surface protection function to printed patterns 12 usually as commercially available general ultraviolet line constrictive type coating material that is used for first kind of form of embodiment and the no-solvent type ultraviolet hardening resin composite that is used for the 4th kind of form of embodiment; because these composites and printed patterns are united fully, but owing to following reason no-solvent type ultraviolet hardening resin composite more is better than containing the oriented wherein ultraviolet hardening resin composite of the solvent of adding.
Because ultraviolet hardening resin is hardened by ultraviolet short irradiation, if the solvent that adds is to have high-volatile low boiling point solvent, then solvent is waved evaporation fully therefore to provide poor transfer printing owing to lacking adhesiveness before goods are forced to enter under water, if and the solvent that adds is the high boiling solvent that is difficult to volatilize, can avoid adhering shortage when goods are forced under water, but after volatilizing fully, solvent just can carry out the ultraviolet ray irradiation, if and under the state of the insufficient volatilization of solvent, shine sclerosis uv-hardening resin composition by ultraviolet ray, described resinous principle is in the state that wherein relates to solvent, can produce the defective as surface roughness later on.Therefore, if use the ultraviolet hardening resin composite contain the oriented solvent that wherein adds, this solvent is a low boiling or high boiling, exists because the health damage that air pollution or absorption of human body cause and technology or quality are produced the possibility of variety of issue.
On the other hand, as part explanation, if use no-solvent type ultraviolet hardening resin composite, because photo polymerization monomer also can be regulated the diluent of purpose as the viscosity degree, so compare the solvent-free ultraviolet hardening resin composite that can prepare greater number with the type that comprises solvent.This only makes it possible to realize abundant and stable adhering recovery by the effect of solvent-free activating component in the no-solvent type ultraviolet hardening resin composite that this composition is photo polymerization monomer typically.In addition, because ultraviolet hardening resin composite 20A and printed patterns 12 is united each other fully and sclerosis and functional equivalent participate in polymerization in the photo polymerization monomer self of normally used solvent is so this photo polymerization monomer never separates therefore not have a negative impact after it.
In the 5th kind of form of embodiment of the present invention, on decorative layer, form UV-cured resin surface coating by the method for using Figure 10, obtain these decorative layers so that apply this decorative layer again by the printed patterns 12 that ultraviolet hardening resin composite 20A activates by transfer printing under water pressure by the hydraulic-transfer of independent operation.The transfer film 116 that contains transparent, UV hardening resin composite 120A by use hydraulic-transfer thus carries out the operation that face coat applies, on the whole surface at plane water-solubility membrane 114 under the single color state (non-pattern state), apply composite 120A and form transfer film 116, as shown in figure 10.This transfer film 116 and becoming suitably when water-solubility membrane 114 when wetting floating on the water surface immediately after the applying of ultraviolet hardening resin composite 120A, and pressure contains goods 10 to its decorative layer that applies ' enter in the water 118.Thereafter, carry out the ultraviolet ray irradiation as the step of Fig. 8 E and figure subsequently, water washing and drying, they are undertaken by the window dressing operation of hydraulic-transfer, therefore obtain to contain the hydraulic-transfer product 110 of face coat ', by forming this face coat (referring to Figure 11) by ultraviolet hardening resin face coat 130 outer coatings.
Can be used for the operation that the face coat of hydraulic-transfer applies by the transfer film that use contains the ultraviolet hardening resin composite, form this transfer film by sclerosis in advance, thereby after on plane water-solubility membrane 14, applying the ultraviolet hardening resin composite, do not cause adhesion rather than promptly will before this transfer film that floats on the water surface, apply the ultraviolet hardening resin composite with single color state with single color state (non-pattern state).In the case, before swimming in transfer film on the water surface, no-solvent type ultraviolet hardening resin composite or photo polymerization monomer composition can be applied to monochrome on the ultraviolet hardening resin composite that hardens in advance of transfer film, therefore to recover the adhesiveness of ultraviolet hardening resin and can press the operation of transfer printing to carry out the step of Fig. 8 C and figure subsequently as decorative water then.
Adopt this mode on decorative layer 30, to apply face coat 130, given the degree of depth and in addition, further improve the machinery and the chemical surface protection of decorative layer 30 to the outward appearance of decorative layer 30.
By using no-solvent type ultraviolet hardening resin composite, the 4th kind of embodiment of the present invention and the 5th kind of form can obtain various advantages.Do not mean that by the term " no-solvent type " in the no-solvent type ultraviolet hardening resin composite of the present invention's use " solvent composition " definitely is zero, but never get rid of the solvent composition contain adding to avoid the present invention or to contain the type of the solvent composition that is useful on manufacture order body or prepolymer, but condition is can be by the solvent-free activating component in the ultraviolet hardening resin composite, this solvent-free activating component is photo polymerization monomer typically, the adhesion function again that obtains printed patterns to must and degree completely.Similarly, term " no-solvent type " does not mean that photo polymerization monomer " volatility " definitely is zero, but mean volatility be not so good as solvent high and therefore the volatility degree that has of photo polymerization monomer in fact can not consider.In addition, although be to be understood that operation claimed apparatus and the equipment investment or the security control of hydraulic-transfer, the notion of ultraviolet hardening resin composite can comprise electron ray hardening resin composite, this is because of comprising photopolymerization prepolymer and the photo polymerization monomer electron ray hardening resin composite as neccessary composition, it can omit Photoepolymerizationinitiater initiater by more high-octane electron ray of irradiation and sclerosis on resin composite materials, the function and the photo polymerization monomer self that have by the photo polymerization monomer activation participate in polymerization, work as the initial ultraviolet hardening resin composite that comprises Photoepolymerizationinitiater initiater.
(embodiment 3)
In the specific embodiment of the 4th kind of form (embodiment 3) according to embodiments of the present invention, use no-solvent type ultraviolet hardening resin composite, it is the UV cured type printing ink of buying with " UV MAT-000MREDIUM ", from TEIKOKU INK MANUFACTURECO., LTD., Japan, commodity UV type silk-screen ink by name and employing Fig. 8 A carry out technology to the order of step shown in the 8G.Should before transfer film being introduced the transfer printing bath, on the printed patterns of transfer film, apply or apply the ultraviolet hardening resin composite of this no-solvent type by the excellent painting method of coiling.Floating the transfer film that contains the no-solvent type ultraviolet hardening resin composite that applies like this and adopt after the ultraviolet hardening resin composite recovers its adhesiveness on the water surface that transfer printing is bathed at printed patterns, force goods to enter under water, shown in Fig. 8 D by transfer film.After transfer printing, take out goods from water, then ultraviolet ray shine on goods and carry out water washing and dry with so obtain hydraulic-transfer goods (product) 10 shown in Figure 9 '.
(embodiment 4)
In embodiment 4, process using and embodiment 3 identical modes are carried out, difference is to use with title " UV PAL-000 MEDIUM " commercial UV cured type printing ink, from TEIKOKU INK MANUFACTURE CO., LTD., Japan, commodity are called UV type silk-screen ink, as no-solvent type ultraviolet hardening resin composite.
Be described in the situation of transfer printing in each embodiment, adopt the mode identical to finish hydraulic-transfer with conventional method, difference is because the resin composite materials on the market is not added the use of change, has certain degree of difficulty because the high viscosity of resin composite materials applies the operation of resin composite materials on transfer film.
When by cross cutting belt adhesiveness method of testing (1mm otch measure 100 times) test during by the adhesiveness of the decorative layer of embodiment 3 and 4 each the hydraulic-transfer goods (E) that obtains, each goods (E) of confirming embodiment have and the printed patterns that contains by conventional activator transfer printing, but do not contain the hydraulic-transfer goods (B) and the identical adhesiveness of hydraulic-transfer goods (C) that contains the conventional acrylic resin that is applied on the decorative layer of face coat.
The reciprocal wiping of gauze eight times that the time will comprise ten accumulations of dimethylbenzene when friction on product surface is tested as solvent resistance, the product of confirming any embodiment is not all substantially to the infringement of decorative layer, and it is not as containing good the same with conventional hydraulic-transfer product (C) the good solvent resistance with demonstration of hydraulic-transfer goods (C) of conventional face coat.Positive according to expectation, obtain to have the solvent resistance of non-constant by conventional activator activation with the conventional hydraulic-transfer goods (B) that do not contain the face coat that applies thereon.
Adopt the no-solvent type ultraviolet hardening resin composite that uses from these results verifications; be used for the initial accurately suitable composition of transfer printing although require to regulate it to have; can be typically by the printed patterns of photo polymerization monomer activation transfer film to making transfer printing become possible state and in associating fully, ultraviolet irradiation after, harden ultraviolet hardening resin composite and printed patterns, therefore can give mechanical and chemical surface defencive function such as wearability and solvent resistance to the decorative layer of acquisition.
In Figure 12, show the method for hydraulic transfer of the 6th kind of form according to an embodiment of the present invention.This method of hydraulic transfer is a kind of like this method; wherein provide and contain face coat and float with the transfer film 16 of printed patterns 12 with on, make that printed patterns 12 is directed upwardly and forces to be used for to enter water 18 therefore to carry out hydraulic-transfer by transfer film 16 at the goods 10 of hectographic printing pattern 12 under the water pressure the water 18 of this transfer film in unshowned transfer printing is bathed with protective layer 40 with at the decoration that applies on the water-solubility membrane 14.Water-solubility membrane 12 can be used for first kind of embodiment, second kind, the 4th kind with the 5th kind of form in identical.
Can be composite such as suitable dry hardening coat material and other composite although be used for the protective layer 40 of face coat with wearability and chemical-resistant; it can be preferably transparent ink or ultraviolet hardening resin composite and more preferably solvent-free ultraviolet hardening resin composite; this solvent-free ultraviolet hardening resin composite is identical with the adhering material that recovers printed patterns 16, as described later.Can on the whole surface of water-solubility membrane 14, apply this protective layer 40 by the suitable measure that applies.In general hydraulic-transfer, can on the protective layer on the water-solubility membrane 14 40, apply printed patterns 12 by photogravure and other suitable measure.This printed patterns 12 also comprises plane (non-pattern) printed layers the pattern in stricti jurise.Under the situation that the protective layer 40 that is used for face coat is formed by the ultraviolet hardening resin composite, under the state of dry resin composite in advance, apply printed patterns 12 thereon, therefore can be requiredly by ink-jet system printing printed patterns 12.
Same in the 6th kind of form of embodiment, can apply the adhesiveness that no-solvent type ultraviolet hardening resin composite is used to recover the printed patterns 12 of transfer film 16.In Figure 13, show according to the specific embodiment of the method for hydraulic transfer of the 6th kind of form of embodiment and be in wherein at the protective layer 40 that applies on the water-solubility membrane 14 and printed patterns 12 that they are (referring to Figure 13 A) under the dry status.
When carrying out hydraulic-transfer, on the dry printed patterns 12 of transfer film 16, apply no-solvent type ultraviolet hardening resin composite 20A (referring to Figure 13 B).Recover under the adhering state of printed patterns 12 by no-solvent type ultraviolet hardening resin composite 20A therein, float on the water 18 of transfer film 16 in transfer printing is bathed (referring to Figure 13 C).Thereafter; goods 10 are forced under water with transfer film 16; the surperficial 10S that makes the printed patterns 12 that comprises ultraviolet hardening resin composite 20A face toward goods 10 engages (referring to Figure 13 D); comprise ultraviolet hardening resin composite 20 and face coat with the printed patterns 12 of protective layer 40 and irradiation ultraviolet radiation 22 on goods 10 then with therefore transfer printing, therefore be hardened in the printed patterns 12 (referring to Figure 13 E) that comprises ultraviolet hardening resin composite 20A and face coat usefulness protective layer 40 on the resin composite materials.Under the situation that protective layer 40 is formed by the ultraviolet hardening resin composite, harden fully with being used to recover adhering ultraviolet hardening resin composite 20A with the ultraviolet hardening resin composite of this ultraviolet ray irradiation with protective layer 40.Protective layer 40 is hardened with being used to recover adhering ultraviolet hardening resin composite by the step of irradiation ultraviolet radiation for explaining, will the protective layer 40 that be formed by the ultraviolet hardening resin composite be described.
Although show, in fact goods carry by anti-triangular shape conveyer or situation about supporting by the robots arm under goods be forced under water.In some cases, in the step that applies no-solvent type ultraviolet hardening resin composite 20A on the printed patterns 12 (referring to Figure 13 B) and the step (referring to Figure 13 C) of the transfer film that floats on the water order can thus no-solvent type ultraviolet hardening resin composite 20A can be applied to by spraying on the contrary on the printed patterns 12 of unsteady on the water transfer film 16, to recover the adhesiveness of printed patterns thus.
" ultraviolet hardening resin composite " got rid of and to be contained solvent-borne type ultraviolet hardening resin composite, as be used for the 4th kind and the 5th kind form of embodiment those and therefore be limited to and do not contain the oriented wherein no-solvent type ultraviolet hardening resin composite of the solvent of adding.To be printed patterns and face coat be based on solvent-free activating component in the no-solvent type ultraviolet hardening resin composite with the adhering recovery of protective layer to reason, and it is photo polymerization monomer typically.Be applicable to that ultraviolet hardening resin composite of the present invention comprises the composition with following composition.Since this composition be used for the identical of the 4th kind and the 5th kind form of embodiment, so omit detailed explanation.
(1) oligomer (photopolymerization prepolymer) 30-50wt%
(2) polyfunctional acrylic ester
(photo polymerization monomer) 10-30wt%
(3) monofunctional acrylate
(photo polymerization monomer) 10-40wt%
(4) Photoepolymerizationinitiater initiater 0.5-5wt%
(5) non-reacted additive 1-20wt%
When being applied to no-solvent type ultraviolet hardening resin composite 20A on the printed patterns 12; as the photo polymerization monomer of solvent-free activating component among the no-solvent type ultraviolet hardening resin composite 20A infiltrate through the dry printing ink of printed patterns 12 and also infiltrate through face coat with at least a portion of protective layer 40 to dissolve them; therefore can recover adhesiveness, this adhesiveness is in and the printed patterns 12 after just printing printed patterns 12 and applying protective layer 40 and the identical wet condition of wet condition of protective layer 40.Therefore, as described in the 4th kind of embodiment and the 5th kind of form, can realize and conventional activator identical functions.Can omit activator, the applying of diluent etc.Because every kind of composition in the ultraviolet hardening resin composite such as photo polymerization monomer have the volatility far below solvent etc. usually, the degree of adhesion of recovery neither changes and does not also reduce, and therefore can wish to make the activation of printed patterns stable.
When after the hectographic printing pattern thereon 12 on goods during irradiation ultraviolet radiation 24; the every kind of composition of ultraviolet hardening resin composite 20A such as photo polymerization monomer infiltrate through the ink composition of printed patterns 12 and face coat with protective layer 40, therefore the following therein state that both unite the fully ink composition of sclerosis ultraviolet hardening resin composite 20A and printed patterns 12 and the also following therein state that both unite fully sclerosis ultraviolet hardening resin composite 20A and at least a portion face coat protective layer 40 down down.Therefore, with mechanical surface defencive function such as wearability etc. and chemical surface defencive function such as solvent resistance, resistance rerum natura etc. is given decorative layer self and also can be improved face coat is used printed patterns 12 with 40 pairs of decorative layers of protective layer adhesiveness.Simultaneously when ultraviolet hardening resin composite 20A when UV cured, the ultraviolet hardening resin composite of the protective layer 40 that also hardens.In Figure 13 B and 13C; although not do not show the ink composition of printed patterns 12 with their states of uniting fully therein; the face coat composition and the ultraviolet hardening resin composite 20A of protective layer 40; but it should be noted that owing in these figure, show and to distinguish them institute thinks and convenient they is presented under the layer state with united state.In addition as previously mentioned, because photo polymerization monomer self participates in polymerization, it never separates, and has prevented thereafter because the adverse effect of separating.
Then shown in Figure 13 F, injection water spray 24 with by the water washing goods therefore to remove the water-solubility membrane 14 of the transfer film 16 of convering.Subsequently; shown in Figure 13 G; hot blast 26 is blowed to goods 10; transfer printing has printed patterns 12 and the face coat protective layer 40 that comprises ultraviolet hardening resin composite 20A on the goods 10; with the therefore surface of dried product 10, therefore finish product 10 ' (referring to the Figure 14) that contains decorative layer 30 and face coat 32.
Therefore, when decorative layer 30 and face coat 32 were provided, face coat 32 can be given the degree of depth to the outward appearance of decorative layer 30, and can further strengthen machinery and chemical surface protection to decorative layer 30.
(embodiment 5)
In the specific embodiment of the 6th kind of form (embodiment 5) according to an embodiment of the present invention; containing on the plane water-solubility membrane of polyvinyl alcohol main component in uniform mode on whole surface; coiling rod and the #8 number excellent applicator of coiling wiry of having diameter 12mm by use apply or apply commodity " KLCF IMPROVEMNET 3 MEDIUM " commercially available material and THE INTECK CO. by name; LTD.; Japan. ethyl acetate 1: 1 mixture in proportion; as face coat with protective layer and under normal temperature atmosphere air dry it after 10 minutes; employing contains the CO. by THE INTECH; LTD.; it is that " pattern is write at the brush tip of the brown printing ink of KLCF IMPROVEMENT 3 BROWN arbitrarily, so obtains to contain face coat protective layer and the decoration transfer film of ink logo (it is corresponding to printed patterns) of lamination that Japanese printing ink alkyd resins of making and nitrocotton are connected thereto trade name.Adopt Figure 13 A to use transfer film to carry out hydraulic-transfer and apply with ink logo to recover the adhesiveness in the printing ink for decoration to transfer film to the sequence of steps shown in the 13G, use no-solvent type ultraviolet hardening resin composite, it is with trade name " UV PAL-000 MEDIUM " commercially available UV cured type printing ink, from TEIKOKU INK MANUFACTURE CO., the UV type silk-screen ink of LTD.Just before transfer film will being introduced the transfer printing bath, this no-solvent type ultraviolet hardening resin composite is applied on the ink logo (printed patterns) of transfer film by the excellent painting method of coiling.The transfer film that contains the no-solvent type ultraviolet hardening resin composite that applies like this floats on the water surface that transfer printing is bathed.After the ultraviolet hardening resin composite recovers thus, shown in Figure 13 D, force goods to enter under water in the adhesiveness of ink logo by transfer film.Adopt this mode transfer ink pattern and face coat with protective layer after, goods are taken out from water, irradiation ultraviolet radiation and goods are washed with water and dry on goods, therefore obtain hydraulic-transfer goods (product) 10 shown in Figure 14 '.
(embodiment 6)
Adopt the mode identical to carry out hydraulic-transfer with embodiment 5; difference is to use the face coat protective layer that passes through at 1: 1 in proportion to mix as transfer film; by THE MUSASHITORYO CO.; LTD., the Japanese manufacturer name of an article is called the acrylic compounds varnish of " PLA-ACE " and the material that ethyl acetate obtains.
(embodiment 7)
Adopt the mode identical to carry out hydraulic-transfer with embodiment 5 and 6; difference is applying the CO. by THE TEIKOKU INK MANUFACTURE; LTD.; the UV cured type printing ink of Japan's produce and market commodity " UV PAL-000 MEDIUM " by name as the face coat of transfer film with after the protective layer; this printing ink is identical with the sort of printing ink that is used for hydraulic-transfer film adhesiveness recovery (activation) purpose that is applied; carry out by this composite initially harden requirement irradiation 1% or more smallest number very faint ultraviolet ray irradiation sclerosis and stop before the touch drying referring to sooning; the suitable pattern of printing on protective layer; by using by THE SEIKO EPSONCO.; LTD.; the MC-10000 of the large scale ink-jet printer MAXART series that Japan makes and the pigments system oil-based ink of six kinds of colors prepare this pattern by paint systems software and then with pattern under normal temperature atmosphere dry 30 minutes, so obtain containing the transfer film of face coat and ink logo (corresponding to printed patterns).
In embodiment 5 to 7 in any; because dissolving ink logo and face coat these two layers of protective layer; although the situation of the transfer film of the ink logo that provides thereon only is provided with transfer printing to be compared; require more more time to recover the adhesiveness of ink logo; but the hydraulic-transfer according to any embodiment all is to carry out in good mode, except particularly having the disappearance of pattern fold is delayed around the dark colour part.In addition, the hydraulic-transfer goods (G) of Huo Deing contain face coat and the affirmation that applies simultaneously in transfer printing and compare with 7 hydraulic-transfer goods according to embodiment 6 on whole decorative layer in these embodiments, hydraulic-transfer goods according to embodiment 5 have low slightly glossiness, but have the gloss sensation of the hydraulic-transfer goods (E) (referring to embodiment 4) that do not contain face coat that the printed patterns that significantly is better than to be gone into by no-solvent type ultraviolet hardening resin Composite Permeability by the adhesiveness of being recovered printed patterns by resin composite materials by transfer printing obtains and also have the outward appearance degree of depth to its decorative layer of giving.
When the adhesiveness of the decorative layer of the hydraulic-transfer goods that obtain by each embodiment by cross cutting belt adhesiveness method of testing (1mm otch measure 100 times) test and face coat, affirmation has and does not have any face coat but have conventional hydraulic-transfer goods (B) by the printed patterns of transfer printing by conventional activator activation printed patterns according to the goods of any embodiment, contains the conventional hydraulic-transfer goods (C) and the adhesiveness identical according to the hydraulic-transfer goods of embodiment 4 or 5 of the conventional acrylic resin that applies on decorative layer.
The reciprocal wiping of gauze eight times that the time will comprise ten accumulations of dimethylbenzene when friction on product surface is as the solvent resistance test, and the product of confirming any embodiment shows the good solvent resistance of the conventional hydraulic-transfer goods (F) that are equal to the face coat that contains UV cured type coating material.
In embodiment 5 to 7; the face coat that use contains lamination is with protective layer and decorate with the transfer film of ink logo (printed patterns) and carrying out hydraulic-transfer by applying the ultraviolet hardening resin composite after activating ink logo; but because; in any embodiment; purpose is to confirm the adhering recovery of protective layer of ink logo (printed patterns) and face coat; pattern-transfer article (goods) on every side ink logo and face coat under the water pressure with the coiling characteristic of protective layer and they each other fully in the associating by the ultraviolet hardening resin composite on ultraviolet ray irradiation sclerosis pattern-transfer article; the ability of ink logo and face coat; so improve the space of lustrous surface degree and surface smoothness in addition; therefore being to be understood that can be by considering coating material; printing ink and as the ultraviolet hardening resin composite of face coat; the constituent of these kinds and they and give more excellent lustrous surface; mechanical strength, solvent resistance etc.
In Figure 15, show the method for hydraulic transfer of the 7th kind of form according to an embodiment of the present invention.This method of hydraulic transfer is a kind of like this method; wherein provide to contain and float on the sealer transfer film 316 of sealer 340 and the water 318 in unshowned transfer printing is bathed, make sealer 340 be directed upwardly and forcing to be pressed in the water 318 therefore to carry out hydraulic-transfer by transfer film 316 at the goods 10 of transfer surface protective layer 340 under the water pressure in the protection of the product surface that applies on the water-solubility membrane 314.Water-solubility membrane 312 can be used for first kind of embodiment identical to the 5th kind of form.
The transparent ink that sealer 340 can be suitable composite such as dry hardening coat material, have wearability and resistance rerum natura.Can sealer 340 be applied on the whole surface of water-solubility membrane 314 by suitable measure such as photogravure measure.Sealer 340 can be formed by the ultraviolet hardening resin composite.
In the method for hydraulic transfer according to the 7th kind of form of embodiment, the sealer 340 that applies on water-solubility membrane 314 is in drying regime (referring to Figure 15 A), and it is different from the sealer 240 according to the not drying regime of the third form of embodiment.
When carrying out hydraulic-transfer, ultraviolet hardening resin composite 320A is applied on the desiccated surface protective layer 340 of transfer film 316 (referring to Figure 15 B).Recover under the adhering state of sealer 340 by ultraviolet hardening resin composite 320A therein, unsteady (referring to Figure 15 C) and sealer 340 on the water 18 of transfer film 316 in transfer printing is bathed are directed upwardly.Thereafter; the goods (unadorned goods) 10 of forcing not contain the decoration that applies enter under water with transfer film 316; make the sealer 340 comprise ultraviolet hardening resin composite 320A engage (referring to Figure 15 D) and comprise the sealer 340 of ultraviolet hardening resin composite 320A and irradiation ultraviolet radiation 322 on the goods 10 that contain transfer printing sealer thereon then with therefore transfer printing facing to the surperficial 10S of goods 10; this sealer comprises the ultraviolet hardening resin composite, and ultraviolet hardening resin composite 320A and sealer 340 (referring to Figure 15 E) therefore harden.
As described in other form of reference implementation scheme, can force goods 10 to enter under water by anti-triangular shape conveyer conveying or under at goods by the situation of robots arm's support.Similarly, the step that applies ultraviolet hardening resin composite 320A on the sealer 340 (referring to Figure 15 B) and the order of the step (referring to Figure 15 C) of the transfer film that floats on the water 318 can be on the contrary and can by spraying with ultraviolet hardening resin composite 320A be applied on the sealer 340 with so recover the adhesiveness of sealer 340.
For recover the desiccated surface protective layer 340 that ultraviolet hardening resin composite 320A that its adhesiveness applies is used for activating suitably transfer film 316 on the sealer 340 of transfer film 316; with the adhesiveness of the sealer 340 that recovers transfer film 316 and can be for containing solvent-borne type ultraviolet hardening resin composite; with be used for the identical of first kind and second kind form of the present invention and maybe can be no-solvent type ultraviolet hardening resin composite, and be used for the 4th kind of identical to the 6th kind of form of the present invention.Below list an example containing solvent-borne type ultraviolet hardening resin composite and an example of no-solvent type ultraviolet hardening resin composite.
(containing solvent-borne type ultraviolet hardening resin composite)
(1) oligomer 30-50wt%
(2) polyfunctional acrylic ester 10-30wt%
(3) monofunctional acrylate 10-40wt%
(4) non-reacted additive 1-20wt%
(5) Photoepolymerizationinitiater initiater 0.5-5wt%
(6) solvent surplus
(no-solvent type ultraviolet hardening resin composite)
(1) oligomer (photopolymerization prepolymer) 30-50wt%
(2) polyfunctional acrylic ester
(photo polymerization monomer) 10-30wt%
(3) monofunctional acrylate
(photo polymerization monomer) 10-40wt%
(4) Photoepolymerizationinitiater initiater 0.5-5wt%
(5) non-reacted additive 1-20wt%
Since the adhering mechanism that the activating component of these ultraviolet hardening resin composites 320A is recovered sealer 340 with first kind in the third form and to be used to recover adhering ultraviolet hardening resin composite in the 4th kind to the 6th kind form identical, omission is to the detailed description of each composite function.Adopt this mode; ultraviolet hardening resin composite 320A is immersed sealer 340; therefore resin composite materials 320A and sealer 340 associating fully each other; if but Figure 15 attempts showing such state; then both can not be distinguished from each other, so be to be understood that in order conveniently to indicate them with the state of layer.
Then shown in Figure 15 F, spray shower water 324 with by water washing goods 310 therefore to remove the water-solubility membrane 314 of the transfer film 316 of convering 310.Subsequently; shown in Figure 15 G; hot blast 326 is blowed to goods with dry its surface, and transfer printing has the sealer 340 that comprises ultraviolet hardening resin composite 320A on goods, therefore obtains containing the product 310 (referring to Figure 16) of the sealer 340 of transfer printing.
Therefore, when applying sealer 340 ', can strengthen the machinery and the chemoproection of goods 310.Especially; immerse sealer 340 owing to be used to recover adhering ultraviolet hardening resin composite; therefore sealer 340 and ultraviolet hardening resin composite associating fully each other is so can adopt adhesiveness and the solvent resistance of improving sealer with the 5th kind of identic mode of embodiment.Owing to by hydraulic-transfer sealer 340 ' is applied to goods, sealer 340 ' contains the surface of never upset and its high glaze of giving is felt.
Although in the method for the 7th kind of form according to embodiments of the present invention; goods 10 do not contain the decoration that it is applied, but can sealer 340 be applied to the goods 10 ' that contain decorative layer 10 ' (as the goods according to Fig. 9 of embodiment 3) by hydraulic-transfer or other suitable measure.Figure 17 shows the decorated articles 310 on such protection surface.
As described in reference to the 4th kind to the 6th kind form; consider lower undesirable volatility of activating component and the promotion that its adhesiveness is recovered; be used to recover sealer 340 adhering ultraviolet hardening resin composite 320A and can be more preferably no-solvent type ultraviolet hardening resin composite rather than solvent-borne type ultraviolet hardening resin composite, therefore prevent the deterioration of atmosphere of operation.
(embodiment 8)
In the specific embodiment of the 7th kind of form (embodiment 8) according to an embodiment of the present invention; containing on the plane water-solubility membrane of polyvinyl alcohol main component in uniform mode on whole surface; use print drum to apply or apply commodity " KLCF IMPROVEMNET 3 MEDIUM " by name by the intaglio printing applying method available from THEINTECK CO. with 60 microns #10 silk screens; LTD.; the material of Japan and ethyl acetate in proportion 1: 1 mixture as the sealer of goods with by blowing after several seconds normal temperature atmosphere air-dry dry, therefore to obtain the sealer transfer film.The sequence of steps that adopts Figure 15 A to show in the 15G uses transfer film to carry out hydraulic-transfer to apply sealer on unadorned goods.Comprise with available from FUJIKURA KASEI CO. by on sealer, applying; LTD., the main component of the UV cured coating material of Japanese goods name FUJIHARD HH9 as the material of ultraviolet hardening resin composite to be used to recover the adhesiveness of transfer film sealer.Just before in transfer printing is bathed, introducing transfer film, this UV cured coating material is applied to the sealer resin of transfer film by the method identical with the coiling rod painting method that is used for embodiment 5.On the water surface that transfer printing is bathed, float and contain the transfer film of the UV cured coating material that applies like this.After the UV cured coating material recovers thus, force goods to enter under water in the adhesiveness of sealer with transfer film.Adopting this mode after the transfer surface protective layer, goods to be taken out from water on product surface, therefore irradiation ultraviolet radiation and by water washing and drying on goods obtains the hydraulic-transfer goods (product) 310 that contain sealer 340 ' shown in Figure 16.
(embodiment 9)
In another specific embodiment of the 7th kind of form (embodiment 9) according to an embodiment of the present invention; contain on the plane water-solubility membrane of polyvinyl alcohol main component adopt the mode identical with embodiment 8 apply or apply by in 1: 1 ratio mixing by THE MUSASHITORYO CO.; LTD., the Japanese manufacturer name of an article is called the acrylic paint of " PLA-ACE " and material that ethyl acetate the obtains sealer as transfer film.Decorating by hydraulic-transfer, but do not containing on the goods of the face coat that applies, adopting and use transfer film to carry out hydraulic-transfer to mode identical shown in the 15G, therefore to obtain the goods 310 of hydraulic-transfer shown in Figure 17 with Figure 15 A.This embodiment is equal to embodiment 8; difference is that by applying trade name be that " UV PAL-000 MEDIUM " is by THE TEIKOKU INK MANUFACTURE CO.; LTD., the no-solvent type ultraviolet hardening resin composite of the UV cured type silk-screen ink of Japanese produce and market is to recover the adhesiveness of sealer.
In embodiment 8 and 9 in any, can under water pressure, adopt the sealer 340 of good mode transfer surface protective layer 340 and transfer printing like this to have to contain less surface unordered (the uniform films thickness of inhomogeneities) and good gloss is felt.Affirmation has the degree of depth that it is given by the goods (H) of the hydraulic-transfer that embodiment 9 obtains; to have the unordered uniform films thickness in less surface high-grade sensation be provided by providing; therefore giving good gloss sensation than the goods (G) of hydraulic-transfer, the goods of described hydraulic-transfer (G) contain face coat with sealer and under water pressure in embodiment 5 to 7 the decorating printing pattern of transfer printing.This has with the gloss that is applied on decorative layer by conventional spraying method and the goods (C) of the hydraulic-transfer of the top finishing that dry acrylic resin forms are equal feels.
When by cross cutting belt adhesiveness method of testing (1mm otch measure 100 times) test during, confirm that the adhesiveness to the product surface (the not decorative layer of the surface of decorated articles or decorated articles) according to any embodiment is equal to the hydraulic-transfer goods according to embodiment 3 and 4 by the adhesiveness of the hydraulic-transfer product surface protective layer that each obtained of embodiment 8 and 9.
The reciprocal wiping of gauze eight times that the time will comprise ten accumulations of dimethylbenzene when friction on product (hydraulic-transfer goods) surface is as the solvent resistance test, confirms that embodiment 8 and 9 any products all show the good solvent resistance that is equal to according to the product of other embodiment.
In embodiment 8; as need be after suitable surface treatment on goods (moulding article) surface that forms by injection moulding etc., applying sealer and confirm that it has the top finishing (covering with paint of uniform films thickness and the sensation of the gloss through arranging) that is equal to the goods that contain surface protection; wherein by the coating robot that contains spray gun mounted thereto form above-mentioned surface protection with compare the more uniform sealers that can obtain to have more gloss sensations through arranging by the goods that contain the sealer that forms by the operator, wherein operator's operation is not as applying fashion at the truss rifle.
Embodiment 9 can be called the embodiment that similar step repeats, wherein transfer printing is wherein obtained the decorative layer 30 of goods 10 ' by apply the planographic layer that transparent ink or clear dope material obtain on the decorative layer 30 of goods 10 ' by the hydraulic-transfer of embodiment 4 under water pressure.