CN102673211B - Active energy ray-curable transfer sheet and manufacture method thereof - Google Patents
Active energy ray-curable transfer sheet and manufacture method thereof Download PDFInfo
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- CN102673211B CN102673211B CN201110058854.1A CN201110058854A CN102673211B CN 102673211 B CN102673211 B CN 102673211B CN 201110058854 A CN201110058854 A CN 201110058854A CN 102673211 B CN102673211 B CN 102673211B
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Abstract
The invention provides a kind of have excellent resistance to adhesive, adaptation and shaping time the in-molded transfer sheet of active energy ray-curable of heat resistance and manufacture method.The in-molded transfer sheet of a kind of active energy ray-curable, it is characterized in that, use priming paint agent composition to carry out semi-solid preparation, this priming paint agent composition contains the active energy ray-curable crylic acid acrylic ester resin and/or active energy ray-curable urethane acrylate resin and polyisocyanate compounds with hydroxyl and (methyl) acryloyl group; Or use active energy ray-curable crylic acid acrylic ester resin and/or active energy ray-curable urethane acrylate resin to make curability hard conating and/or curability prime coat carry out semi-solid preparation.
Description
Technical field
The present invention relates to have resistance to adhesive, adaptation and shaping time all excellent hard conating of heat resistance, mouldability and the in-molded transfer sheet of active energy ray-curable (hereinafter referred to as transfer sheet) of prime coat.
Background technology
At the substrate surface of paper, timber, plastics, metal, glass, inorganic material etc., be coated with to protect surface to give the multiple performances such as hardness, marresistance, rub resistance, chemical reagent resistance, organic solvent resistance.As coating agent, most material used based on Actinic-radiation curable composition.Because this is compared with using the situation of thermoplastic resin or thermosetting resin, marresistance, the rub resistance on surface are more excellent.
Using the surface protection of the plastic shaping thing for occasions such as household appliances, computer, mobile phones as object, the surperficial Coating agent of article shaped after shaping.In recent years, the method and adopting replacing coating make in advance sealer as transfer sheet, on diaphragm capsule, configure this transfer sheet, use molding resin by the method for molding procedure transfer surface protective layer in article shaped.
In patent document 1, disclose a kind of transfer materials formed by the heat cross-linking reaction product of actinic energy ray curable resion composition, described actinic energy ray curable resion composition contain as active ingredient, (methyl) acrylic equivalent is 100 ~ 300g/eq, hydroxyl value is 20 ~ 500, weight average molecular weight is 5000 ~ 50000 polymer and many functional group isocyanates.But, along with the propelling of cross-linking reaction, there is the problem of the adaptation hindering lower one deck priming paint.And many functional group isocyanates's composition makes adhesive have the tendency (with reference to patent document 1) of decline.
In patent document 2; disclose the transfer sheet that its ionizing radiation line style resin protective layer a kind of contains uncrosslinked thermoplastic's acrylic resin and prepolymer; the mean molecule quantity of described uncrosslinked thermoplastic's acrylic resin is 50000 ~ 600000, glass transition temperature is 50 ~ 130 DEG C, has acryloyl group or the methacryl of more than 2 in described prepolymer 1 molecule.But, because containing uncrosslinked thermoplastic's acrylic resin, be difficult to obtain sufficiently high case hardness (with reference to patent document 2).
In patent document 3, disclose one and be firmly coated with transfer foil, it is characterized in that, it is the surface of the one side in fissility substrate sheet, and the hard conating formed according to the ionizing radiation gel-type resin by hard and the sequential laminating of this record of hard conating formed by soft ionizing radiation gel-type resin form.But, because hard conating is formed by 2 layers, the problem (with reference to patent document 3) having cost to increase.In addition, in patent document 4, disclose the polymethyl methacrylate that a kind of mean molecule quantity as prime coat is 20,000 ~ 200,000.But, inadequate as the heat resistance of prime coat, be difficult to the heat resistance (with reference to patent document 4) when obtaining transfer printing.
In patent document 5, disclosing a kind of transfer sheet, it is characterized in that, between transfer sheet upper surface protective layer and decorative pattern printed layers, there is the prime coat of the cementability for improving sealer and decorative pattern printed layers.But, not as the heat resistance of prime coat, the heat resistance (with reference to patent document 5) during abundant transfer printing cannot be obtained.
In recent years, in order to the high design that obtains and high physical property, carrying out overlapping Coating agent, laminated trial always.But, because Actinic-radiation curable composition is generally at room temperature in aqueous, residual tack.In order to be coated with other masking liquids in these Actinic-radiation curable composition, needing to irradiate active energy beam and first surface being become solid-state (without sticky state).That is, inviscid in order to obtain at present, before the overlapping coating of enforcement, active energy beam to be irradiated in advance.But carry out the occasion be coated with further on the surface having irradiated active energy beam in advance, adaptation declines, and mouldability declines.And implementing repeatedly laminated occasion, need multiple active energy beam irradiation unit, cost increases, the problem on initiation equipment.Therefore, need to seek to have resistance to adhesive etc., productivity ratio is good, the active energy ray-curable transfer sheet of adaptation and all excellent hard conating of mouldability and prime coat.Meanwhile, even if also seek to obtain inviscid and irradiate active energy beam in advance before the overlapping coating of enforcement, adaptation does not also decline and can maintain the active energy ray-curable transfer sheet of good mouldability.In the coating agent of delustring, carry out semi-solid preparation although known when hard conating is formed, and do not know the active energy ray-curable transfer sheet (with reference to patent document 6) of the surface layer with gloss.
[patent document 1] Unexamined Patent 10-58895 publication
[patent document 2] Unexamined Patent 7-314995 publication
[patent document 3] Unexamined Patent 3-130199 publication
[patent document 4] JP 2001-180190 publication
[patent document 5] Unexamined Patent 9-24699 publication
[patent document 6] JP 2006-198911 publication
Summary of the invention
The problem that invention will solve
Problem of the present invention be to provide have resistance to adhesive, adaptation and shaping time all excellent hard conating of heat resistance, mouldability and the in-molded transfer sheet of active energy ray-curable of prime coat and manufacture method thereof.
The solution of problem
Therefore, in order to solve above-mentioned problem, wholwe-hearted research contemplates the present invention finally, and it has the formation of crylic acid acrylic ester resin and urethane acrylate resin for hard conating, and the transfer sheet of the heat resistance time shaping structure relevant to the prime coat of cross-linking type.
In other words, the present invention provides respectively:
The in-molded transfer sheet of a kind of active energy ray-curable, it is for forming the solidification of the polyisocyanate compounds of active energy ray-curable sheet material, with regard to this active energy ray-curable sheet material, in the one side of basement membrane with release layer, as the transfer printing layer can peeled off from this basement membrane, have: curability hard conating, described hard conating is formed by hard coating material composition, described hard coating material composition comprises and has (methyl) acryloyl group and active energy ray-curable crylic acid acrylic ester resin and the active energy ray-curable urethane acrylate resin without carbamate bond structure, with the curability prime coat that this hard conating is contact condition, described prime coat is formed by priming paint agent composition, and described priming paint agent composition comprises the active energy ray-curable crylic acid acrylic ester resin and/or active energy ray-curable urethane acrylate resin and polyisocyanate compounds with hydroxyl and (methyl) acryloyl group, and, bond layer, (being called the 1st invention),
And, the in-molded transfer sheet of a kind of active energy ray-curable, it forms for the curability hard conating of active energy ray-curable sheet material and/or prime coat being solidified with retaining curability, with regard to this active energy ray-curable sheet material, in the one side of basement membrane with release layer, as the transfer printing layer can peeled off from this basement membrane, have: curability hard conating, described hard conating is formed by hard coating material composition, described hard coating material composition comprises and has (methyl) acryloyl group and active energy ray-curable crylic acid acrylic ester resin and the active energy ray-curable urethane acrylate resin without carbamate bond structure, with the curability prime coat that this hard conating is contact condition, described prime coat is formed by priming paint agent composition, and described priming paint agent composition comprises the active energy ray-curable crylic acid acrylic ester resin and/or active energy ray-curable urethane acrylate resin with (methyl) acryloyl group, and, bond layer.(being called the 2nd invention).
Invention effect
In the 1st invention, polyisocyanate compounds is used as priming paint agent in the active energy ray-curable resin containing hydroxyl and (methyl) acryloyl group, and this polyisocyanate compounds is solidified; On the other hand, in the 2nd invention, the active energy ray-curable resin being included in hard paint or priming paint agent or both sides is solidified with retaining curability, thus, the in-molded transfer sheet of active energy ray-curable of Outstanding Quality can be obtained separately.
The in-molded transfer sheet of active energy ray-curable of the present invention have resistance to adhesive, adaptation, shaping time heat resistance and all excellent hard conating of mouldability, case hardness and prime coat.Hard conating has excellent resistance to adhesive, gets final product primer coating layer in the fabrication process without curing process, and, basement membrane is coated with the hard conating stage, can also temporarily reels.In addition, irradiate active energy beam by the arbitrary or both sides' moment before priming paint coating, after priming paint coating, can improve inviscid, resistance to adhesive can also be improved.And, the free degree of the exposure of active energy beam when manufacturing for the transfer sheet having influence on the applicable character such as the breaking of products formed, adaptation can be provided also to become large in-molded transfer sheet.
So-called in-molded, be meant to the shaping of molding resin in injection moulding and the transfer printing of transfer paper that is used for giving surface protection or design etc. to carry out integration, implementation method that shaping and transfer printing is carried out simultaneously.The method is: use transfer sheet, with regard to this transfer sheet, in the one side of basement membrane with release layer, as the transfer printing layer can peeled off from this basement membrane, there is hard conating, be prime coat and the bond layer of contact condition with this hard conating, be arranged on metal die diaphragm capsule according to the mode making described release layer be in metal die side, by shaping to bond layer surface injection, can products formed being obtained, after taking away mould, obtaining the method for the products formed of finished product by peeling off release layer.The present invention utilizes active energy beam when implementing this forming method.
With regard to the in-molded transfer sheet of active energy ray-curable of the present invention (hereinafter referred to as transfer sheet), as the 1st invention and the 2nd invention, there is feature as above.In the present invention, active energy beam refers to ultraviolet or electron ray.In order to make aftermentioned hard coating material composition or priming paint agent composition have ultra-violet solidified, preferably and with known conventional Photoepolymerizationinitiater initiater.Also printing ink layer or evaporation layer can be had between prime coat and bond layer.
The basement membrane with peel ply forming transfer printing layer of the present invention is made up of plastic foil/releasing agent layer.As base material film, the plastics that general use is commercially available.Concrete example as, PETG, PTT, polybutylene terephthalate (PBT) etc. can be used, preferred PETG.
Releasing agent layer is the layer of the closely sealed non-transferability well to basement membrane.Its occasion that temperature is high when transfer printing, or the occasion that the performance of peeling agent layer is insufficient, have and prevent transfer printing layer not to be transferred and remain in basement membrane side, easily from basement membrane stripping transfer printing layer, the effect improving operability.Known material can be used as the releasing agent forming releasing agent layer.Concrete example is as, the releasing agent such as Urea Series, melamine series, benzoguanamine system.
Form the curability hard conating of transfer sheet of the present invention; in the 1st invention and the 2nd invention all, by comprising, there is (methyl) acryloyl group and the hard coating material composition of the active energy ray-curable crylic acid acrylic ester resin and active energy ray-curable urethane acrylate resin without carbamate bond structure is formed.
The active energy ray-curable crylic acid acrylic ester resin that the preferred acrylic double bond equivalent of the active energy ray-curable crylic acid acrylic ester resin that hard coating material composition contains is 200 ~ 2500g/eq, weight average molecular weight is 50000 ~ 250000, glass transition temperature is 40 ~ 130 DEG C.
Not there is about having (methyl) acryloyl group the active energy ray-curable crylic acid acrylic ester resin of carbamate bond structure and the ratio of components both active energy ray-curable urethane acrylate resin, being preferably there is (methyl) acryloyl group and not there is the active energy ray-curable crylic acid acrylic ester resin of carbamate bond structure, the active energy ray-curable urethane acrylate resin of 1 ~ 50 quality % of 50 ~ 99 quality %.What be more preferably 60 ~ 90 quality % has (methyl) acryloyl group and does not have the active energy ray-curable crylic acid acrylic ester resin of carbamate bond structure, the active energy ray-curable urethane acrylate resin of 10 ~ 40 quality %.
For hard coating material composition, further as required, also can containing being selected from active energy ray-curable monomer, not there is active energy ray-curable and there is the resin combination of carbamate bond structure and not there is active energy ray-curable and there is more than a kind in the resin combination of ester bond structure.
Form and there is (methyl) acryloyl group and the monomer component without the active energy ray-curable crylic acid acrylic ester resin of carbamate bond structure can be illustrated as ethyl (methyl) acrylate, ethylhexyl (methyl) acrylate, styrene, methyl styrene, the Monofunctional monomers such as NVP and polyfunctional monomer, such as, trimethylolpropane (methyl) acrylate, hexylene glycol (methyl) acrylate, tripropylene glycol two (methyl) acrylate, diethylene glycol (DEG) (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol (methyl) acrylate etc.
Form the composition of active energy ray-curable urethane acrylate resin, can illustrate as compound, the polyisocyanate compounds in multi-group alcohol's composition, molecule with more than one alcoholic extract hydroxyl group and more than one (methyl) acrylate or (methyl) acrylamide.
Form multi-group alcohol's composition of active energy ray-curable urethane acrylate resin, can be used alone and be selected from more than one compounds in following illustrative compound or as required can arbitrary proportion used in combination two or more.
Ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, 1,2-PD, two (1,2-PDs), three (1,2-PDs), 1,3-PD, 1,2-butanediol, 1,3-BDO, 2,3-butanediol, BDO, 2-methyl isophthalic acid, ammediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-PD, 1,5-PD, 1,2-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2,2,4-trimethyl-1,6-hexylene glycol, 1,6-hexylene glycol, 1,2-hexylene glycol, 1,8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, two (methylol) cyclohexane of 1,2-, two (methylol) cyclohexane of 1,3-, Isosorbide-5-Nitrae-bis-(methylol) cyclohexane, two (methylol) tristane, two (methylol) adamantane of 1,3-, two (methylol) norbornane of 2,3-, two (methylol) norbornane of 2,5-, two (methylol) norbornane of 2,6-, hydrogenated bisphenol A, hydrogenated bisphenol A epoxy ethane additive product, bisphenol A epoxy ethane additive product,
Neopentyl glycol single 3-hydroxypivalic acid ester, the spiroglycol (3, 9-two (1, 1-dimethyl-2-hydroxyethyl)-2, 4, 8, 10-tetra-oxa-volution [5.5] hendecane), trimethylolethane, trimethylolpropane, ethylene-oxide-modified trimethylolpropane, three (hydroxyethyl) isocyanuric acid, glycerine, ethylene-oxide-modified glycerine, epoxy pronane modification glycerine, pentaerythrite, ethylene-oxide-modified pentaerythrite, epoxy pronane modification pentaerythrite, two trimethylolpropanes, ethylene-oxide-modified two trimethylolpropanes, epoxy pronane modification two trimethylolpropane, dipentaerythritol, ethylene-oxide-modified dipentaerythritol, epoxy pronane modification dipentaerythritol, refined caster oil etc.
In the constituent of active energy ray-curable urethane acrylate resin, be exemplified below in the molecule enumerated the compound with more than one alcoholic extract hydroxyl group and more than one (methyl) acrylate or (methyl) acrylamide for the compound giving end free base polymerism unsaturated bond.
Having (methyl) esters of acrylic acid of an alcoholic extract hydroxyl group or (methyl) acrylic amide in molecule can illustrate as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, 6-hydroxyl hexyl (methyl) acrylate, 4-Hydroxymethyl-cyclo-hexyl methyl (methyl) acrylate, Alpha-hydroxy methyl methacrylate, Alpha-hydroxy EMA, 6-caprolactone modification 2-hydroxyethyl (methyl) acrylate, gamma-butyrolacton modification 2-hydroxyethyl (methyl) acrylate,
PEG list (methyl) acrylate, poly-(propane diols) single (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, two trimethylolpropane tris (methyl) acrylate, dipentaerythritol five (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, glycerine (methyl) acrylate stearate, glycerine (methyl) acrylate oleate, glycerine two (methyl) acrylate, glyceryl acrylate methacrylate, two [(methyl) acrylyl oxy-ethyl] isocyanuric acid, N-(2-hydroxyethyl) (methyl) acrylamide etc.
In addition, (methyl) esters of acrylic acid with two or more alcoholic extract hydroxyl group, except glycerine (methyl) acrylate, can be illustrated as trimethylolpropane (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite two (methyl) acrylate, two trimethylolpropane two (methyl) acrylate, dipentaerythritol four (methyl) acrylate, two (hydroxyethyl) isocyanuric acids of (methyl) acrylyl oxy-ethyl etc.
In addition, can use by ethylene glycol diglycidylether, propylene glycol diglycidylether, 1, compound group that the aliphatic diglycidylethers such as 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, PEG diglycidyl ether, poly-(propane diols) diglycidyl ether and (methyl) acrylic acid are obtained by reacting, that be commonly referred to as epoxy acrylate.Also more than one compounds selected thus can be utilized the compound making to have at 2 ends 2-hydroxyl (methyl) acrylate structural import free-radical polymerised unsaturated bond in carbamate resins skeleton.
Polymerization initiator, wax, silica, plasticizer, levelling agent, surfactant, dispersant, defoamer etc. can be contained as other any compositions.
Solvent can be illustrated as the fragrant family hydrocarbon such as toluene, dimethylbenzene; The aliphatic such as n-hexane, cyclohexane or ester ring type hydrocarbon; The ester such as ethyl acetate, propyl acetate class; The alcohols such as methyl alcohol, ethanol, isopropyl alcohol; The ketone such as acetone, MEK; The alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether.
The coating of hard coating material composition, the object lesson of mode of printing can be illustrated as roller coat, heliogravure coating, dropping curtain coating, application mode such as spraying coating, extrusion coated etc., or the mode of printing such as photogravure, flexographic printing and serigraphy.About drying, it is the evaporation drying of carrying out about 5 ~ 30s with the hot blast of 60 ~ 180 DEG C.Coating thickness under preferred drying regime is about 3 ~ 7 μm.
The curability prime coat of transfer sheet of the present invention is formed by priming paint agent composition, and this priming paint agent composition contains the active energy ray-curable crylic acid acrylic ester resin with hydroxyl and (methyl) acryloyl group as neccessary composition and/or active energy ray-curable urethane acrylate resin.
In the 1st invention; as for curability prime coat; can by having the active energy ray-curable crylic acid acrylic ester resin of hydroxyl and (methyl) acryloyl group and/or active energy ray-curable urethane acrylate resin, with polyisocyanate compounds and with after, this polyisocyanate compounds is solidified.In the 2nd invention; as for curability prime coat; only can use the active energy ray-curable crylic acid acrylic ester resin and/or active energy ray-curable urethane acrylate resin with (methyl) acryloyl group, retain the solidification of curability ground in the following manner.
Therefore; in the 1st invention; as be comprised in for the formation of in the priming paint agent composition of curability prime coat, the active energy ray-curable crylic acid acrylic ester resin with (methyl) acryloyl group and/or active energy ray-curable urethane acrylate resin; by utilizing the material further containing hydroxyl; cause the reaction with the NCO of polyisocyanate compounds, can solidify thus.
From this viewpoint; as the active energy ray-curable resin that priming paint agent composition contains, that preferred hydroxyl value is 5 ~ 300 (mgKOH/g), that there is (methyl) acryloyl group active energy ray-curable crylic acid acrylic ester resin and/or active energy ray-curable urethane acrylate resin.
The monomer component forming crylic acid acrylic ester resin can use the monomer identical with the monomer component of the crylic acid acrylic ester resin utilized when being formed in and forming hard conating.
The monomer component forming urethane acrylate resin can use the monomer identical with the monomer component of the urethane acrylate resin utilized when being formed in and forming hard conating.
Such as, as polyisocyanate compounds, as fatty family, there are hexamethylene diisocyanate, IPDI, XDI, double-hexyl methane vulcabond, hydrogenated xylylene vulcabond; 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI)s, methyl diphenylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenylene PIC, dimethyl diphenyl vulcabond etc. are then had as fragrant family.
There is hydroxyl and (methyl) although the active energy ray-curable crylic acid acrylic ester resin of acryloyl group and/or active energy ray-curable urethane acrylate resin and polyisocyanate compounds and be not particularly limited with ratio, preferred is 7 ~ 25 parts by mass conversion, relative to above-mentioned active energy ray-curable resin nonvolatile component 100 parts.
In priming paint agent composition, except polyisocyanate compounds, composition further except active energy ray-curable acrylic acrylate and/or active energy ray-curable urethane acrylate resin, can be used together the thermoplastic acrylic resin, mylar, polyurethane resin etc. such as without active energy ray-curable.
As other any compositions, polymerization initiator, wax, silica, plasticizer, levelling agent, surfactant, dispersant, defoamer etc. can be contained.
Solvent can be illustrated as the fragrant family hydrocarbon such as toluene, dimethylbenzene; The aliphatic such as n-hexane, cyclohexane or ester ring type hydrocarbon; The ester such as ethyl acetate, propyl acetate class; The alcohols such as methyl alcohol, ethanol, isopropyl alcohol; The ketone such as acetone, MEK; The alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether.
The coating of priming paint agent composition, the object lesson of mode of printing can be illustrated as roller coat, heliogravure coating, dropping curtain coating, application mode such as spraying coating, extrusion coated etc., or the mode of printing such as photogravure, flexographic printing and serigraphy.
Active energy ray-curable resin in active energy ray-curable resin in hard coating material composition and priming paint agent composition, as long as can be then different materials in the scope of afore mentioned rules, if but hard coating material composition and priming paint agent composition both sides are all 200 ~ 2500g/eq containing acrylic double bond equivalent, weight average molecular weight is 50000 ~ 250000, glass transition temperature is 40 ~ 130 DEG C, hydroxyl value is the active energy ray-curable crylic acid acrylic ester resin of 5 ~ 300 (mgKOH/g), then can also by each layer of the hard conating that uses identical active energy ray-curable resin to be formed there is difference in functionality and prime coat.
The printing ink layer inserted as required in transfer sheet of the present invention, by printing or be coated with known printing-ink or coating is formed.The object lesson of printing-ink or coating can be illustrated as acrylic acid series, cellulose-based, ethene base system, chlorinated polyolefin system, chlorinated rubber system, carbamate system printing-ink or coating.
The printing process of printing-ink, the object lesson of coating and printing mode, can illustrate as the mode of printing such as application mode and photogravure, flexographic printing and serigraphy such as roller coat, heliogravure coating, dropping curtain coating, spraying coating, extrusion coated.
The bond layer of transfer sheet of the present invention can use acrylic acid series, polystyrene, ethene base system, ester system, carbamate system, chlorinated polyolefin hydrocarbon system, ethene-vinyl acetate system bonding agent to be formed.
The coating process of bonding agent, can illustrate as the mode of printing such as application mode and photogravure, flexographic printing and serigraphy such as roller coat, heliogravure coating, dropping curtain coating, spraying coating, extrusion coated.Coating weight is 1 ~ 2g/m preferably
2left and right.
Transfer sheet of the present invention, it is mode as described above, by containing as must operation, the coating to the hard coating material composition of base material film, drying, the coating of priming paint agent composition, drying, also have the coating of bonding agent, the manufacture of dry manufacturing process form.
Transfer sheet of the present invention, in order to after shaping, such as, after preferably this base material film being peeled off from the base material film after demoulding process, irradiating active energy beam is cured to the curing degree with the material composition of curability be included in sheet material saturated, is necessary be arranged at for reservation of shaping metal die stage curability.And the hard conating after shaping and prime coat must be closely sealed.The resistance to adhesive of hard conating and prime coat also wishes to improve.
Therefore, the 1st invention utilizes the solidification of the polyisocyanate compounds in priming paint agent composition, and the 2nd invention utilization makes active energy ray-curable resin solidify with retaining curability.
The film solidify to form with retaining curability, in the art, be also sometimes referred to as the film of such as " semi-solid preparation " state, but " partly " herein, have more than and mean the curing degree of the material composition with curability is reached capacity the situation of solidification as this 1 point of 50% curing degree during 100% curing degree, also mean that there is the state that its uncured state and curing degree reach the amplitude of saturation state.In the present invention, using the curing degree of the material composition with curability reach capacity solidification situation as 100% curing degree time, be preferably 10 ~ 80% curing degrees.For light source kind, exposure intensity, irradiation time, process (パ ス, the pass) number of times of active energy beam that irradiate, be preferably suitably adjusted to and can reach above-mentioned curing degree.
The manufacture method of transfer sheet of the present invention has following characteristics.The hard coating material composition that base material film after demoulding process is coated with, after coating, after passing through the dry coatings such as heat, wind, the state of evaporating solvent composition can form noncohesive film.Therefore, this layer not necessarily must pass through active energy ray-curable, can be coated with the priming paint agent composition of subsequent processing thereon.This is favourable in the occasion that the mode be particularly coated with by heliogravure is coated with, and reason also can overlapping not be coated with for each coater unit arranges active energy beam irradiation unit.In addition, so-called inviscid, refer to that the surface of film reaches by the methods such as finger touches the also imperceptible degree of drying be clamminess.In this occasion, after the priming paint agent composition of coating subsequent processing, by irradiating active energy beam, hard conating and prime coat both sides all can be solidified.
In the 2nd invention, in the operation (operation 3) of the operation (operation 2) of the coating operation (operation 1) of hard coating material composition, primer coating agent composition, coating adhesive, by between operation 1 and operation 2 and/or between operation 2 and operation 3 containing irradiating 10mJ/cm to improve resistance to adhesive further
2~ 100mJ/cm
2the operation of active energy beam, be cured with retaining curability.In the 1st invention, because also with polyisocyanate compounds, there is no need as the 2nd invention, active energy ray-curable resin to be solidified with retaining curability, but if necessary, also can the same with the 2nd invention active energy ray-curable resin be solidified with retaining curability.
The transfer sheet of the present invention of such acquisition, metal die diaphragm capsule is arranged at according to the mode making its release layer be in metal die side, by to its bonding agent aspect injection moulding molding resin, can obtain have required form, the adhesive linkage of transfer sheet of the present invention and the closely sealed products formed of molding resin.
Then, open mould diaphragm capsule, products formed is taken away from mould, irradiate the products formed that active energy beam can obtain finished product.As molding resin, as long as have thermoplasticity, can illustrate as acrylic resin, vistanex, mylar etc.
The irradiation of accurately machined active energy beam, can carry out front and back arbitrary time of base material film after peeling off demoulding process.In this fine finishining, 600mJ/cm can be become by accumulation
2~ 1000mJ/cm
2mode irradiate active energy beam.
Embodiment
Next, enumerating experimental example carries out more specifically bright to the present invention.In addition, unless otherwise specified, " part " and " % " is quality criteria to this description.Embodiment and comparative example film composition and evaluation result as shown in table 1.
(preparation of hard coating material composition (1))
Crylic acid acrylic ester resin (WHV-652:DIC Inc. is standby) 60 parts, urethane acrylate resin (UnidicV-4000BA:DIC Inc. is standby) 10 parts, polymerization initiator (gorgeous good solid 184: prepared by Ciba Specialty Chemicals) 3 parts, MEK 27 parts are used mixer mix and blend, makes hard coating material composition (1).
Here, the WHV-652 that DIC Inc. is standby is acrylic double bond equivalent is 200 ~ 2500g/eq, weight average molecular weight is 50000 ~ 250000, glass transition temperature is 40 ~ 130 DEG C, hydroxyl value is 5 ~ 300 (mgKOH/g), have (methyl) acryloyl group and do not have the active energy ray-curable crylic acid acrylic ester resin of carbamate bond structure.
(preparation of hard coating material composition (2))
Crylic acid acrylic ester resin (WHV-652:DIC Inc. is standby) 50 parts, urethane acrylate resin (UnidicV-4000BA:DIC Inc. is standby) 20 parts, polymerization initiator (gorgeous good solid 184: prepared by Ciba Specialty Chemicals) 3 parts, MEK 27 parts are used mixer mix and blend, makes hard coating material composition (2).
(preparation of hard coating material composition (3))
Crylic acid acrylic ester resin (WHV-652:DIC Inc. is standby) 50 parts, urethane acrylate resin (UnidicV-4221:DIC Inc. is standby) 20 parts, polymerization initiator (gorgeous good solid 184: prepared by Ciba Specialty Chemicals) 3 parts, MEK 27 parts are used mixer mix and blend, makes hard coating material composition (3).
(preparation of hard coating material composition (4))
Crylic acid acrylic ester resin (WHV-652:DIC Inc. is standby) 40 parts, urethane acrylate resin (UnidicV-4221:DIC Inc. is standby) 30 parts, polymerization initiator (gorgeous good solid 184: prepared by Ciba Specialty Chemicals) 3 parts, MEK 27 parts are used mixer mix and blend, makes hard coating material composition (4).
(preparation of priming paint agent composition (1))
Crylic acid acrylic ester resin (WHV-652:DIC Inc. is standby) 35 parts, urethane acrylate resin (UnidicV-4221:DIC Inc. is standby) 15 parts, polymerization initiator (gorgeous good solid 184: prepared by Ciba Specialty Chemicals) 3 parts, polyisocyanate compounds (TakenateD-110N: Mitsui Chemicals polyurethane Inc. is standby) 10 parts, MEK 37 parts are used mixer mix and blend, makes priming paint agent composition (1).
(preparation of priming paint agent composition (2))
Crylic acid acrylic ester resin (WHV-652:DIC Inc. is standby) 35 parts, urethane acrylate resin (UnidicV-4221:DIC Inc. is standby) 15 parts, polymerization initiator (gorgeous good solid 184: prepared by Ciba Specialty Chemicals) 3 parts, MEK 47 parts are used mixer mix and blend, makes priming paint agent composition (2).
(preparation of ink)
Acrylic acid series photogravure ink (TRC-906805 ink: prepared by DIC) 70 parts, MEK 30 parts are used mixer mix and blend, makes ink (1).
(preparation of bonding agent)
The acrylic resin (ParaloidB-72: prepared by Rhom and Hass) 20 parts of Tg about 40 DEG C, MEK 80 parts are used mixer mix and blend, makes bonding agent (1).
(making of transfer sheet)
In PET film after carrying out demoulding process (thickness is 38 μm, Japan's textile company preparation), by described hard coating material composition (1) by heliogravure coating process with 5g/m
2be coated with.By hot blast mode at 160 DEG C after dry 30s, on the dry epithelium of described hard coating material composition (1), by described priming paint agent composition (1) by heliogravure coating process with 2g/m
2be coated with.By hot blast mode at 80 DEG C after dry 30s, on the dry epithelium with noncohesive described priming paint agent composition (1), described ink (1) is carried out overall printed by heliogravure coating process with 2g/m2, further, after heated-air drying, by described bonding agent (1) by heliogravure coating process with 2g/m
2be coated with, the transfer sheet of experimental example 1 can be obtained.
Similarly, form according to the mixing of table 1 ~ 3, prepare each hard coating material composition, priming paint agent composition, through coating drying condition, Ultraviolet radiation condition that this token carries, obtain each transfer sheet of each experimental example.As follows is the evaluation method of the evaluation method of the coating master of hard coating material composition, molding procedure condition and each transfer sheet.
(hard conating inviscid)
After at 160 DEG C, heated drying is about 30s, or with high-pressure mercury light irradiation 15mJ/cm after at 160 DEG C, heated drying is about 30s
2ultraviolet, by fingers-touch method evaluate tackiness.
(zero) inviscid, (△) has a little viscosity, (×) viscosity remarkable
(the resistance to adhesive of hard conating)
Coating material is arranged PET film (Japan's textile company prepare S5101,25 μm), with 1kg/cm
2, 40 DEG C place 24h, evaluate the state that the back side to PET film is shifted.
(zero) there is vestige without vestige, (△) but have the back side to shift without back side transfer, (×)
(storage stability of priming paint agent composition)
Priming paint agent composition is put into vial, by the mobility after visual valuation 24h.
(zero) mobility, (△) poor fluidity is had
(adaptation of the hard conating before shaping)
In film coated surface, sticking glass paper adhesive tape, when evaluation is peeled off, film is residual.
(zero) all residual, (△) part film peel off, (×) almost all film peel off
(shaping and Ultraviolet radiation operation)
Use high-pressure mercury-vapor lamp, 15mJ/cm
2the occasion of irradiating, irradiates once (1 パ ス, 1pass) with 80W/cm, 1 lamp, 30m/min.30mJ/cm
2the occasion of irradiating, irradiates once with 140W/cm, 1 lamp, 30m/min.60mJ/cm
2the occasion of irradiating, irradiates once with 140W/cm, 1 lamp, 15m/min.
As for the Ultraviolet radiation in the operation obtaining transfer sheet, using the curing degree of the material composition with curability reach capacity solidification situation as 100% curing degree time, be the scope (above-mentioned semi-cured state) of 10 ~ 50% curing degrees.
(adaptation of the hard conating after shaping)
Being transferred to the laminating of the film coated surface on acrylic panel glassine paper adhesive tape, evaluate the residual of film when peeling off.
(zero) all residual, (△) part film peel off, (×) almost all film peel off
(cast gate current mark (ゲ mono-ト flows れ, gateflow))
The injection (mo(u)lding) machine (model J55AD: JSW produces) that use is provided with 45mm × 75mm, R angle is the metal die of 20 °, the transfer sheet of above-mentioned gained is arranged according to the mode making its bonding agent aspect contact with the molding resin of melting, at 250 DEG C, injection moulding is carried out to acrylic resin (Plexiglaszk5BR that Daicel-Ying Chuan Inc. is standby).By the outward appearance of visual valuation article shaped.
(crackle)
By the outward appearance of visual valuation article shaped.
(zero) there are crackle in flawless, (×)
(woolliness of resistance to steel wire)
After transfer printing, peel off the PET film after carrying out demoulding process, to the hard conating irradiation ultraviolet radiation exposed until curing degree reaches capacity.Film coated surface steel wool (#0000,100g load) two friction (ダ Block Le ラ PVC Application グ, doublerubbing) of transfer printing on shaping acrylic panel obtained thus, by the degree of impairment of visual valuation film coated surface.
(zero) not damaged, (△) have slight damage, (×) have damage
The experimental example 1 ~ 4 and 6 ~ 8 of following table is equivalent to embodiments of the invention, and experimental example 5 and experimental example 9 ~ 12 are equivalent to comparative example.
[table 1]
[table 2]
[table 3]
In addition, as follows shown in each raw material in table 1,2.
● WHV-652: acrylic acrylate (DIC Inc. is standby)
● UnidicV-4000BA: urethane acrylate (DIC Inc. is standby)
● UnidicV-4221: urethane acrylate (DIC Inc. is standby)
● gorgeous good solid 184: Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals's preparation)
● TRC-906805 ink: acrylic acid series photogravure ink (DIC Inc. is standby)
● the acrylic resin (Rhom and Hass's preparation) that ParaloidB-72:Tg is about 40 DEG C
● TakenateD-110N: PIC (Mitsui Chemicals polyurethane Inc. is standby)
From table 1 ~ 3, by after the coating drying of hard coating material composition and or priming paint agent composition coating drying after irradiation ultraviolet radiation, isocyanates can be saved from priming paint agent composition, the storage stability of priming paint agent composition can be improved.In addition, according to the hard coating material composition (1) forming transfer sheet of the present invention, be 15 ~ 60mJ/cm at ultraviolet irradiation amount
2wide region in do not crack.That is, the deviation of the exposure in manufacturing process can be absorbed, be easy to adjust manufacturing process, can boost productivity.Further, by the dry epithelium both sides irradiation ultraviolet radiation of the dry epithelium to hard coating material composition, priming paint agent composition, resistance to adhesive and shaping front adaptation can be improved further.
[utilizability in industry]
There is the active energy ray-curable transfer sheet of the present invention of specific hard conating and prime coat, be easy to the active energy beam adjusted in manufacturing process and irradiate, contribute to thus boosting productivity.Further, in the molding procedure after transfer printing, adaptation and heat resistance are also excellent.There is the possibility of extensively developing in the surface protection purposes of the plastic shaping thing for occasions such as household appliances, computer, mobile phones.
Claims (10)
1. the in-molded transfer sheet of active energy ray-curable, it is the solidification of the polyisocyanate compounds of active energy ray-curable sheet material formed,
With regard to this active energy ray-curable sheet material, in the one side of basement membrane with release layer, as the transfer printing layer can peeled off from this basement membrane, have: curability hard conating, described curability hard conating is formed by hard coating material composition, and described hard coating material composition comprises and has (methyl) acryloyl group and active energy ray-curable crylic acid acrylic ester resin and the active energy ray-curable urethane acrylate resin without carbamate bond structure; With the curability prime coat that this curability hard conating is contact condition, described curability prime coat is formed by priming paint agent composition, and described priming paint agent composition comprises the active energy ray-curable crylic acid acrylic ester resin with hydroxyl and (methyl) acryloyl group and/or the active energy ray-curable urethane acrylate resin with hydroxyl and (methyl) acryloyl group and polyisocyanate compounds; And, bond layer.
2. the in-molded transfer sheet of active energy ray-curable, it is the curability hard conating of active energy ray-curable sheet material and/or prime coat are solidified with retaining curability to form,
With regard to this active energy ray-curable sheet material, in the one side of basement membrane with release layer, as the transfer printing layer can peeled off from this basement membrane, have: curability hard conating, described curability hard conating is formed by hard coating material composition, and described hard coating material composition comprises and has (methyl) acryloyl group and active energy ray-curable crylic acid acrylic ester resin and the active energy ray-curable urethane acrylate resin without carbamate bond structure; With the curability prime coat that this curability hard conating is contact condition, described curability prime coat is formed by priming paint agent composition, and described priming paint agent composition comprises the active energy ray-curable crylic acid acrylic ester resin with (methyl) acryloyl group and/or the active energy ray-curable urethane acrylate resin with (methyl) acryloyl group; And, bond layer.
3. the in-molded transfer sheet of active energy ray-curable as claimed in claim 1 or 2, it has printing ink layer between described curability prime coat and bond layer.
4. the in-molded transfer sheet of active energy ray-curable as claimed in claim 1 or 2; wherein, the hard coating material composition forming described curability hard conating contains: 50 ~ 99 quality % have (methyl) acryloyl group and do not have the active energy ray-curable crylic acid acrylic ester resin of carbamate bond structure, the active energy ray-curable urethane acrylate resin of 1 ~ 50 quality %.
5. the in-molded transfer sheet of active energy ray-curable as claimed in claim 1 or 2, wherein, form the active energy ray-curable crylic acid acrylic ester resin contained in the hard coating material composition of described curability hard conating, be acrylic double bond equivalent be 200 ~ 2500g/eq, weight average molecular weight is 50000 ~ 250000, glass transition temperature is the active energy ray-curable crylic acid acrylic ester resin of 40 ~ 130 DEG C.
6. the in-molded transfer sheet of active energy ray-curable as claimed in claim 1 or 2, wherein, form the active energy ray-curable crylic acid acrylic ester resin contained in the priming paint agent composition of described curability prime coat, be acrylic double bond equivalent be 200 ~ 2500g/eq, weight average molecular weight is 50000 ~ 250000, glass transition temperature is 40 ~ 130 DEG C, active energy ray-curable crylic acid acrylic ester resin that hydroxyl value is 5 ~ 300mgKOH/g.
7. the in-molded transfer sheet of active energy ray-curable as claimed in claim 1 or 2, wherein, described hard coating material composition comprises and is selected from active energy ray-curable monomer and does not have active energy ray-curable and have more than a kind in the resin combination of ester bond structure.
8. the in-molded transfer sheet of active energy ray-curable as claimed in claim 7, wherein, described do not have active energy ray-curable and the resin combination with ester bond structure is do not have the resin combination that active energy ray-curable has carbamate bond structure.
9. the manufacture method of the in-molded transfer sheet of active energy ray-curable, it is characterized in that, it is the manufacture method of the in-molded transfer sheet of active energy ray-curable according to claim 1, when obtaining the active energy ray-curable sheet material as precursor, there is the operation 1 being coated with hard coating material composition on release layer, according to the operation 2 of the mode primer coating agent composition contacted with this curability hard conating, and the operation 3 of coating adhesive, arbitrary or both sides between described operation 1 and operation 2 and between operation 2 and operation 3 have irradiation 10mJ/cm
2~ 100mJ/cm
2the operation of active energy beam.
10. the manufacture method of the in-molded transfer sheet of active energy ray-curable, it is characterized in that, it is the manufacture method of the in-molded transfer sheet of active energy ray-curable according to claim 2, when obtaining the active energy ray-curable sheet material as precursor, there is the operation 1 being coated with hard coating material composition on release layer, according to the operation 2 of the mode primer coating agent composition contacted with this curability hard conating, and the operation 3 of coating adhesive, arbitrary or both sides between described operation 1 and operation 2 and between operation 2 and operation 3 have irradiation 10mJ/cm
2~ 100mJ/cm
2the operation of active energy beam.
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| CN201110058854.1A CN102673211B (en) | 2011-03-09 | 2011-03-09 | Active energy ray-curable transfer sheet and manufacture method thereof |
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| CN104129189B (en) * | 2013-05-02 | 2017-09-29 | 荒川化学工业株式会社 | Transfer decorating film |
| JP6344999B2 (en) | 2014-06-30 | 2018-06-20 | 株式会社ブリヂストン | LAMINATE, CONDUCTIVE ROLLER, AND METHOD FOR PRODUCING LAMINATE |
| JP2021062580A (en) * | 2019-10-16 | 2021-04-22 | 凸版印刷株式会社 | Transfer sheet and method for producing melamine decorative panel |
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|---|---|---|---|---|
| JPS58120626A (en) * | 1982-01-12 | 1983-07-18 | Mitsubishi Rayon Co Ltd | Composition curable with actinic energy radiation |
| JP2006305795A (en) * | 2005-04-27 | 2006-11-09 | Yoshida Industry Co Ltd | Resin molded product |
| CN101045347A (en) * | 2006-03-28 | 2007-10-03 | 日东电工株式会社 | Hard-coated film, method of manufacturing the same, optical device, and image display |
| CN101080431A (en) * | 2004-10-15 | 2007-11-28 | 帝斯曼知识产权资产管理有限公司 | Radiation curable coating composition |
| JP2010248426A (en) * | 2009-04-20 | 2010-11-04 | Nippon Kayaku Co Ltd | Transfer material excellent in fingerprint-proof property and method for producing the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58120626A (en) * | 1982-01-12 | 1983-07-18 | Mitsubishi Rayon Co Ltd | Composition curable with actinic energy radiation |
| CN101080431A (en) * | 2004-10-15 | 2007-11-28 | 帝斯曼知识产权资产管理有限公司 | Radiation curable coating composition |
| JP2006305795A (en) * | 2005-04-27 | 2006-11-09 | Yoshida Industry Co Ltd | Resin molded product |
| CN101045347A (en) * | 2006-03-28 | 2007-10-03 | 日东电工株式会社 | Hard-coated film, method of manufacturing the same, optical device, and image display |
| JP2010248426A (en) * | 2009-04-20 | 2010-11-04 | Nippon Kayaku Co Ltd | Transfer material excellent in fingerprint-proof property and method for producing the same |
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