CN102673211A - Active energy ray curing transfer sheet and manufacture method thereof - Google Patents
Active energy ray curing transfer sheet and manufacture method thereof Download PDFInfo
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- CN102673211A CN102673211A CN2011100588541A CN201110058854A CN102673211A CN 102673211 A CN102673211 A CN 102673211A CN 2011100588541 A CN2011100588541 A CN 2011100588541A CN 201110058854 A CN201110058854 A CN 201110058854A CN 102673211 A CN102673211 A CN 102673211A
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Abstract
The invention provides a transfer sheet for active energy ray curing intra-mold forming and a manufacture method thereof, wherein the transfer sheet has excellent adhesion resistance and sealing performance and heat resistance during forming. The transfer sheet for active energy ray curing intra-mold forming is characterized in that primer agent composites are used for half-curing, wherein the primer agent composites contain active energy ray curing crylic acid acrylic ester resin with hydroxyl and (methyl) acryloyl groups and/or active energy ray curing carbamic acid ester acrylic ester resin and polyisocyanate compounds; or active energy ray curing crylic acid acrylic ester resin and/or active energy ray curing carbamic acid ester acrylic ester resin curing hard coating and/or curing primer coating are used for half curing.
Description
Technical field
The hard conating that hear resistance when the present invention relates to have anti-adhesive, adaptation and moulding, mouldability are all excellent and the active energy ray-curable of prime coat are in-molded with transfer sheet (to call transfer sheet in the following text).
Background technology
At the substrate surface of paper, timber, plastics, metal, glass, inorganic material etc., be coated with to protect the surface in order to give multiple performances such as hardness, marresistance, rub resistance, chemical reagent resistance, organic solvent resistance.As coating agent, the most use with the active energy ray-curable composition is master's material.Because this compares with the situation of using thermoplastic resin or thermosetting resin, marresistance, the rub resistance on surface are more excellent.
The surface protection of the plastic shaping thing that is used for occasions such as household appliances, computer, mobile phone as purpose, the surface coated coating agent of the article shaped after moulding.In recent years, replace the method for coating and adopt make in advance sealer as transfer sheet, at this transfer sheet of configuration on the diaphragm capsule, use the method for molding resin through molding procedure transfer surface protective layer on article shaped.
In patent documentation 1; A kind of transfer materials that is formed by the heat cross-linking reaction product of actinic energy ray curable resion composition is disclosed, said actinic energy ray curable resion composition contain as active ingredient, (methyl) acrylic equivalent is that 100～300g/eq, hydroxyl value are 20～500, weight average molecular weight is 5000～50000 polymer and many functional group isocyanates.But, along with the propelling of cross-linking reaction, the problem of the adaptation of one deck priming paint down appears hindering.And many functional group isocyanates's composition makes adhesive that the tendency (with reference to patent documentation 1) of decline arranged.
In patent documentation 2; The transfer sheet that a kind of its ionizing radiation line style resin protective layer contains non-crosslinked thermoplastic acrylic resin and prepolymer is disclosed; The mean molecule quantity of said non-crosslinked thermoplastic acrylic resin is 50000～600000, glass transition temperature is 50～130 ℃, has acryloyl group or the methacryl more than 2 in said prepolymer 1 molecule.But,, be difficult to obtain sufficiently high case hardness (with reference to patent documentation 2) because contain the non-crosslinked thermoplastic acrylic resin.
In patent documentation 3; A kind of transfer foil that is coated with is firmly disclosed; It is characterized in that; It is on the surface of the one side of fissility substrate sheet, and the sequential laminating of hard conating that forms according to the ionizing radiation gel-type resin by hard and this record of hard conating that formed by soft ionizing radiation gel-type resin forms.But, because hard conating forms by 2 layers, the problem (with reference to patent documentation 3) that has cost to increase.In addition, in patent documentation 4, a kind of mean molecule quantity as prime coat disclosed be 20,000～200,000 polymethyl methacrylate.But, not enough as the hear resistance of prime coat, the hear resistance (with reference to patent documentation 4) when being difficult to obtain transfer printing.
In patent documentation 5, a kind of transfer sheet is disclosed, it is characterized in that between transfer sheet upper surface protective layer and decorative pattern printed layers, having the prime coat of the cementability that is used to improve sealer and decorative pattern printed layers.But, not as the hear resistance of prime coat, the hear resistance (with reference to patent documentation 5) in the time of can't obtaining abundant transfer printing.
In recent years, for the high design property that obtains and high rerum natura, carrying out the trial that overlapping coating coating agent, layer close always.But, because the active energy ray-curable composition generally at room temperature is aqueous, residual tack.For other masking liquids of coating on these active energy ray-curable compositions, need the irradiation active energy beam earlier the surface to be become solid-state (not having sticking state).That is to say, inviscid in order to obtain at present, before implementing overlapping coating, shine active energy beam in advance.But, the occasion that further is coated with on the surface of having shone active energy beam in advance, adaptation descends, and mouldability descends.And implementing repeatedly the occasion that layer closes, need a plurality of active energy beam irradiation units, cost increases, the problem on the initiation equipment.Therefore, need seek to have anti-adhesive etc., productivity ratio is good, the hard conating that adaptation and mouldability are all excellent and the active energy ray-curable transfer sheet of prime coat.Simultaneously, even also seek in order to obtain inviscid before implementing overlapping coating, to shine active energy beam in advance, adaptation does not also descend and can keep the active energy ray-curable transfer sheet of good mouldability.Aspect the coating agent of using in delustring, though knownly, hard conating carries out semi-solid preparation when forming, and do not know to have the active energy ray-curable transfer sheet (with reference to patent documentation 6) that the surface layer of gloss is used.
[patent documentation 1] spy opens flat 10-58895 communique
[patent documentation 2] spy opens flat 7-314995 communique
[patent documentation 3] spy opens flat 3-130199 communique
[patent documentation 4] spy opens the 2001-180190 communique
[patent documentation 5] spy opens flat 9-24699 communique
[patent documentation 6] spy opens the 2006-198911 communique
Summary of the invention
The problem that invention will solve
It is in-molded with transfer sheet and manufacturing approach thereof that problem of the present invention provides the active energy ray-curable of all excellent hard conating of hear resistance when having anti-adhesive, adaptation and moulding, mouldability and prime coat.
The solution of problem
Therefore; In order to solve above-mentioned problem; The present invention has been expected in wholwe-hearted research finally, and it has the formation of acrylic acrylate resin and urethane acrylate resin for hard conating, and the transfer sheet of the structure relevant with the prime coat of cross-linking type of the hear resistance during moulding.
In other words, the present invention provides respectively:
The in-molded transfer sheet of using of a kind of active energy ray-curable; It forms for the polyisocyanate compounds with the active energy ray-curable sheet material solidifies; With regard to this active energy ray-curable sheet material; On the one side of the basement membrane with release layer, the transfer printing layer as peeling off from this basement membrane has: the curable hard conating; Said hard conating is formed by hard coating material composition, and said hard coating material composition comprises and has (methyl) acryloyl group and do not have the active energy ray-curable acrylic acrylate resin and the active energy ray-curable urethane acrylate resin of carbamate bond structure; Be the curable prime coat of contact condition with this hard conating; Said prime coat is formed by priming paint agent composition, and said priming paint agent composition comprises active energy ray-curable acrylic acrylate resin and/or active energy ray-curable urethane acrylate resin and the polyisocyanate compounds with hydroxyl and (methyl) acryloyl group; And, bond layer, (being called the 1st invention);
And; The in-molded transfer sheet of using of a kind of active energy ray-curable; It forms for curable hard conating and/or the ground curing of prime coat reservation curable with the active energy ray-curable sheet material, with regard to this active energy ray-curable sheet material, on the one side of the basement membrane with release layer; As the transfer printing layer that can peel off from this basement membrane; Have: the curable hard conating, said hard conating is formed by hard coating material composition, and said hard coating material composition comprises and has (methyl) acryloyl group and do not have the active energy ray-curable acrylic acrylate resin and the active energy ray-curable urethane acrylate resin of carbamate bond structure; Be the curable prime coat of contact condition with this hard conating; Said prime coat is formed by priming paint agent composition, and said priming paint agent composition comprises active energy ray-curable acrylic acrylate resin and/or the active energy ray-curable urethane acrylate resin with (methyl) acryloyl group; And, bond layer.(being called the 2nd invention).
The invention effect
In the 1st invention, with polyisocyanate compounds and use in the active energy ray-curable resin that contains hydroxyl and (methyl) acryloyl group, and this polyisocyanate compounds is solidified as the priming paint agent; On the other hand, in the 2nd invention, the active energy ray-curable resin that is included in hard paint or priming paint agent or both sides is kept curable ground solidify, thus, can obtain the in-molded transfer sheet of using of active energy ray-curable of remarkable quality separately.
Hear resistance that active energy ray-curable of the present invention is in-molded when having anti-adhesive, adaptation, moulding with transfer sheet and mouldability, hard conating and prime coat that case hardness is all excellent.Hard conating has excellent anti-adhesive, in manufacture process, gets final product the primer layer without curing process, and, in the coating hard conating stage on basement membrane, can also temporarily reel.In addition, through before priming paint coating, the arbitrary or both sides of priming paint after being coated with shine active energy beam constantly, can improve inviscidly, can also improve anti-adhesive.And, can provide the free degree of the exposure of the active energy beam when making also to become the big in-molded transfer sheet of using for the transfer sheet that has influence on suitable character such as the breaking of moulding article, adaptation.
So-called in-molded, the meaning is with the moulding of molding resin in injection moulding and the implementation method that integrated, moulding and transfer printing are carried out is simultaneously carried out in the transfer printing that is used to give the transfer paper of surface protection or design etc.This method is: use transfer sheet, with regard to this transfer sheet, on the one side of the basement membrane with release layer; As the transfer printing layer that can peel off from this basement membrane, have hard conating, be the prime coat and the bond layer of contact condition with this hard conating, be arranged on the metal die diaphragm capsule according to the mode that makes said release layer be in the metal die side; Through to the injection moulding of bond layer surface; Can obtain the moulding article, take away after the mould, through peeling off the method that release layer obtains the moulding article of finished product.The present invention utilizes active energy beam when implementing this forming method.
In-molded with regard to transfer sheet (to call transfer sheet in the following text) with regard to active energy ray-curable of the present invention, have aforesaid characteristic as the 1st invention and the 2nd invention.In the present invention, active energy beam refers to ultraviolet ray or electron ray.Have ultra-violet solidified, preferred in order to state hard coating material composition or priming paint agent composition after making also with known Photoepolymerizationinitiater initiater commonly used.Also can between prime coat and bond layer, have printing ink layer or vapor deposition layer.
The basement membrane with peel ply that constitutes transfer printing layer of the present invention is made up of plastic foil/releasing agent layer.As base material film, generally use commercially available plastics.Concrete example as, can use PETG, PTT, polybutylene terephthalate (PBT) etc., preferred PETG.
Releasing agent layer is the layer to the good non-transfer printing property of the driving fit of basement membrane.It is the high occasion of temperature when transfer printing, and the perhaps inadequate occasion of the performance of peeling agent layer has and prevents that transfer printing layer is not transferred and the effect that remains in the basement membrane side, peel off transfer printing layer, improve operability from basement membrane easily.Releasing agent as forming releasing agent layer can use known material.Concrete example is like, releasing agents such as urea system, melamine system, benzoguanamine system.
Constitute the curable hard conating of transfer sheet of the present invention; All be to have (methyl) acryloyl group by comprising and do not have the active energy ray-curable acrylic acrylate resin of carbamate bond structure and the hard coating material composition of active energy ray-curable urethane acrylate resin forms in the 1st invention is invented with the 2nd.
The preferred acrylic double bond equivalent of active energy ray-curable acrylic acrylate resin that hard coating material composition contains is that 200～2500g/eq, weight average molecular weight are 50000～250000, glass transition temperature is 40～130 ℃ active energy ray-curable acrylic acrylate resin.
The two the ratio of components of active energy ray-curable acrylic acrylate resin and active energy ray-curable urethane acrylate resin that does not have the carbamate bond structure about having (methyl) acryloyl group is preferably the having (methyl) acryloyl group of 50～99 quality % and does not have the active energy ray-curable acrylic acrylate resin of carbamate bond structure, the active energy ray-curable urethane acrylate resin of 1～50 quality %.The having (methyl) acryloyl group of 60～90 quality % and do not have the active energy ray-curable acrylic acrylate resin of carbamate bond structure, the active energy ray-curable urethane acrylate resin of 10～40 quality % more preferably.
For hard coating material composition; Further as required, also can contain be selected from the active energy ray-curable monomer, do not have active energy ray-curable and have the resin combination of carbamate bond structure and do not have active energy ray-curable and have in the resin combination of ester bond structure more than a kind.
Constituting the monomer component have (methyl) acryloyl group and not have an active energy ray-curable acrylic acrylate resin of carbamate bond structure can give an example like simple function group monomer and polyfunctional monomers such as ethyl (methyl) acrylic acid ester, ethylhexyl (methyl) acrylic acid ester, styrene, methyl styrene, N-vinyl pyrrolidones; For example; Trimethylolpropane (methyl) acrylic acid ester, hexylene glycol (methyl) acrylic acid ester, tripropylene glycol two (methyl) acrylic acid ester, diethylene glycol (DEG) (methyl) acrylic acid ester, pentaerythrite three (methyl) acrylic acid ester, dipentaerythritol six (methyl) acrylic acid ester, 1,6-hexylene glycol two (methyl) acrylic acid ester, neopentyl glycol (methyl) acrylic acid ester etc.
Constitute the composition of active energy ray-curable urethane acrylate resin, can give an example like the compound, the polyisocyanate compounds that have more than one alcoholic extract hydroxyl group and more than one (methyl) acrylic acid ester or (methyl) acrylamide in multi-group alcohol's composition, the molecule.
Constitute multi-group alcohol's composition of active energy ray-curable urethane acrylate resin, can use more than one compounds that are selected from the following illustrative compound separately or can mix the two or more of use arbitrary proportion as required.
Ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, 1,2-propane diols, two (1, the 2-propane diols), three (1, the 2-propane diols), 1, ammediol, 1; 2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl isophthalic acid, ammediol, neopentyl glycol, 2-butyl-2-ethyl-1; Ammediol, 1,5-pentanediol, 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, 1, two (methylol) cyclohexanes, 1 of 2-, two (methylol) cyclohexanes, 1 of 3-, two (methylol) cyclohexanes of 4-, two (methylol) tristane, 1; Two (methylol) adamantane, 2 of 3-, two (methylol) norbornanes, 2 of 3-, two (methylol) norbornanes, 2 of 5-, two (methylol) norbornanes of 6-, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, bisphenol-A epoxy ethane addition product,
Neopentyl glycol single 3-hydroxypivalic acid ester, the spiroglycol (3; 9-two (1; 1-dimethyl-2-hydroxyethyl)-2; 4; 8,10-four oxa-volution [5.5] hendecanes), trimethylolethane, trimethylolpropane, oxirane modification trimethylolpropane, three (hydroxyethyl) isocyanuric acid, glycerine, oxirane modified glycerol, epoxy pronane modification glycerine, pentaerythrite, oxirane modification pentaerythrite, epoxy pronane modification pentaerythrite, two trimethylolpropanes, oxirane modification two trimethylolpropanes, epoxy pronane modification two trimethylolpropanes, dipentaerythritol, oxirane modification dipentaerythritol, epoxy pronane modification dipentaerythritol, refined caster oil etc.
In the constituent of active energy ray-curable urethane acrylate resin, the compound that is used for giving terminal free-radical polymerised unsaturated bond is exemplified below that the molecule of enumerating has an above alcoholic extract hydroxyl group and the compound of (methyl) acrylic acid ester or (methyl) acrylamide more than.
(methyl) esters of acrylic acid or (methyl) acrylic amide of having an alcoholic extract hydroxyl group in the molecule can be given an example like 2-hydroxyethyl (methyl) acrylic acid ester; 2-hydroxypropyl (methyl) acrylic acid ester; 2-hydroxybutyl (methyl) acrylic acid ester; 3-hydroxypropyl (methyl) acrylic acid ester; 4-hydroxybutyl (methyl) acrylic acid ester; 6-hydroxyl hexyl (methyl) acrylic acid ester; 4-hydroxymethyl cyclohexyl methyl (methyl) acrylic acid ester; The Alpha-hydroxy methyl methacrylate; The Alpha-hydroxy EMA; 6-caprolactone modification 2-hydroxyethyl (methyl) acrylic acid ester; Gamma-butyrolacton modification 2-hydroxyethyl (methyl) acrylic acid ester;
Gather (ethylene glycol) single (methyl) acrylic acid ester; Gather (propane diols) single (methyl) acrylic acid ester; Trimethylolpropane two (methyl) acrylic acid ester; Pentaerythrite three (methyl) acrylic acid ester; Two trimethylolpropane tris (methyl) acrylic acid ester; Dipentaerythritol five (methyl) acrylic acid ester; 2-hydroxyl-3-phenoxy propyl (methyl) acrylic acid ester; Glycerine (methyl) acrylic acid ester stearate; Glycerine (methyl) acrylic acid ester oleate; Glycerine two (methyl) acrylic acid ester; Glycerine acrylate acrylic acid ester; Two [(methyl) acrylyl oxy-ethyl] isocyanuric acid; N-(2-hydroxyethyl) (methyl) acrylamide etc.
In addition; (methyl) esters of acrylic acid with two above alcoholic extract hydroxyl groups can be given an example like: trimethylolpropane (methyl) acrylic acid ester, trimethylolpropane two (methyl) acrylic acid ester, pentaerythrite two (methyl) acrylic acid ester, two trimethylolpropane two (methyl) acrylic acid ester, dipentaerythritol four (methyl) acrylic acid ester, two (hydroxyethyl) isocyanuric acids of (methyl) acrylyl oxy-ethyl etc. except glycerine (methyl) acrylic acid ester.
In addition; Can use through ethylene glycol diglycidylether, propylene glycol diglycidylether, 1; 4-butanediol diglycidyl ether, 1, gathers (ethylene glycol) diglycidyl ether, gathers aliphatic diglycidylether such as (propane diols) diglycidyl ether and (methyl) acrylic acid reaction compound group that obtain, that be commonly referred to as epoxy acrylate at the 6-hexanediol diglycidyl ether.Also can more than one compound utilizations works of selecting thus be imported free-radical polymerised unsaturated bond at the compound that 2 ends have 2-hydroxyl (methyl) acrylate structural in the carbamate resins skeleton.
Can contain polymerization initiator, wax, silica, plasticizer, levelling agent, surfactant, dispersant, antifoaming agent etc. as other any compositions.
Solvent can be given an example like fragrant family hydrocarbon such as toluene, xylenes; Aliphatic such as n-hexane, cyclohexane or ester ring type hydrocarbon; Ester such as ethyl acetate, propyl acetate class; Alcohols such as methyl alcohol, ethanol, isopropyl alcohol; Ketone such as acetone, MEK; 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 given an example like application modes such as roller coat, heliogravure coating, the curtain that falls coating, spraying coating, extrusion coated, or mode of printings such as photogravure, flexographic printing and serigraphy.About drying, be to carry out the evaporation drying about 5～30s with 60～180 ℃ hot blast.Coating thickness under the preferred drying regime is about 3～7 μ m.
The curable prime coat of transfer sheet of the present invention is formed by priming paint agent composition, and this priming paint agent composition contains active energy ray-curable acrylic acrylate resin and/or the active energy ray-curable urethane acrylate resin with hydroxyl and (methyl) acryloyl group as neccessary composition.
In the 1st invention; As for the curable prime coat; Can with the active energy ray-curable acrylic acrylate resin with 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 the curable prime coat; Can only use active energy ray-curable acrylic acrylate resin and/or active energy ray-curable urethane acrylate resin, keep curable ground by following mode and solidify with (methyl) acryloyl group.
Therefore; In the 1st invention; As being comprised in active energy ray-curable acrylic acrylate resin and/or active energy ray-curable urethane acrylate resin in the priming paint agent composition that is used to form the curable prime coat, that have (methyl) acryloyl group; Through utilizing the material that further contains hydroxyl, the reaction of the NCO of initiation and polyisocyanate compounds can be solidified thus.
From this viewpoint; As the active energy ray-curable resin that priming paint agent composition contains, preferred hydroxyl value is active energy ray-curable acrylic acrylate resin and/or an active energy ray-curable urethane acrylate resin 5～300 (mgKOH/g), that have (methyl) acryloyl group.
The monomer component that constitutes the acrylic acrylate resin can use and the identical monomer of monomer component that is formed in the acrylic acrylate resin that utilizes when forming hard conating.
The monomer component that constitutes urethane acrylate resin can use and the identical monomer of monomer component that is formed in the urethane acrylate resin of utilizing when forming hard conating.
As polyisocyanate compounds, for example,, hexamethylene diisocyanate, IPDI, XDI, double-hexyl methane vulcabond, hydrogenation of benzene dimethyl vulcabond are arranged as fatty family; Then have 2 as fragrant family, 4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenylene PIC, dimethyl diphenyl vulcabond etc.
Have hydroxyl and (methyl) though the active energy ray-curable acrylic acrylate resin of acryloyl group and/or active energy ray-curable urethane acrylate resin and polyisocyanate compounds and do not limit especially with ratio, preferably by mass conversion, be 7～25 parts for 100 parts with respect to above-mentioned active energy ray-curable resin nonvolatile component.
In priming paint agent composition; Except polyisocyanate compounds; Further except active energy ray-curable acrylic acrylate and/or the composition the active energy ray-curable urethane acrylate resin, can and with the thermoplastic acrylic resin that does not for example have active energy ray-curable, mylar, polyurethane resin etc.
As other any compositions, can contain polymerization initiator, wax, silica, plasticizer, levelling agent, surfactant, dispersant, antifoaming agent etc.
Solvent can be given an example like fragrant family hydrocarbon such as toluene, xylenes; Aliphatic such as n-hexane, cyclohexane or ester ring type hydrocarbon; Ester such as ethyl acetate, propyl acetate class; Alcohols such as methyl alcohol, ethanol, isopropyl alcohol; Ketone such as acetone, MEK; 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 given an example like application modes such as roller coat, heliogravure coating, the curtain that falls coating, spraying coating, extrusion coated, or mode of printings such as photogravure, flexographic printing and serigraphy.
Active energy ray-curable resin in active energy ray-curable resin in the hard coating material composition and the priming paint agent composition; As long as then can be different materials in the scope of afore mentioned rules; If but hard coating material composition and priming paint agent composition both sides are all contained that the acrylic double bond equivalent is that 200～2500g/eq, weight average molecular weight are 50000～250000, glass transition temperature is that 40～130 ℃, hydroxyl value are the active energy ray-curable acrylic acrylate resin of 5～300 (mgKOH/g), then can also be through the hard conating that uses identical active energy ray-curable resin to form to have difference in functionality and each layer of prime coat.
The printing ink layer that in transfer sheet of the present invention, inserts as required can or be coated with known printing-ink or coating forms through printing.It is printing-ink or coating that the object lesson of printing-ink or coating can be given an example like acrylic acid series, cellulose-based, ethene base system, chloro polyolefin, chlorinated rubber system, carbamate.
The object lesson of the printing process of printing-ink, coating and printing mode can be given an example like application mode and mode of printings such as photogravure, flexographic printing and serigraphy such as roller coat, heliogravure coating, the curtain that falls coating, spraying coating, extrusion coated.
It is that bonding agent forms that the bond layer of transfer sheet of the present invention can use acrylic acid series, polystyrene, ethene base system, ester system, carbamate system, chloridized polyolefin system, ethene-vinyl acetate.
The coating process of bonding agent can be given an example like application mode and mode of printings such as photogravure, flexographic printing and serigraphy such as roller coat, heliogravure coating, the curtain that falls coating, spraying coating, extrusion coated.Preferred 1～the 2g/m of coating weight
2About.
Transfer sheet of the present invention; Be by aforesaid mode; Through contain as must operation, to coating, the drying of the hard coating material composition of base material film, coating, the drying of priming paint agent composition also have the coating of bonding agent, dry manufacturing process to make and form.
Transfer sheet of the present invention; For after moulding; After for example preferably this base material film being peeled off on the base material film after the demoulding is handled; The irradiation active energy beam is cured to the curing degree that is included in the material composition with curable in the sheet material saturated, is necessary the metal die stage reservation curable that is used for moulding being arranged at.And hard conating after the moulding and prime coat must driving fits.The anti-adhesive of hard conating and prime coat also hopes to improve.
Therefore, the 1st invention utilizes the curing of the polyisocyanate compounds in the priming paint agent composition, and the 2nd invention utilization is solidified the active energy ray-curable resin with keeping curable.
What solidify to form films with keeping curable; In the art; Sometimes for example also be called as filming of " semi-solid preparation " state; But " partly " here has more than and means the situation of solidifying this 1 point of 50% curing degree during as 100% curing degree that reaches capacity of the curing degree with material composition of curable, also means to have the state that its uncured state and curing degree reach the amplitude of saturation state.In the present invention, reach capacity the situation of solidifying to the curing degree of material composition during, be preferably 10～80% curing degrees as 100% curing degree with curable.(パ ス, pass) number of times preferably suitably are adjusted into and can reach above-mentioned curing degree for the light source kind of the active energy beam that is used to shine, exposure intensity, irradiation time, process.
The manufacturing approach of transfer sheet of the present invention has following characteristic.The hard coating material composition that is coated with on the base material film after the demoulding is handled, after the coating, the state of evaporating solvent composition can form noncohesive filming after through dry coatings such as heat, wind.Therefore, this layer not necessarily must solidify through active energy beam, can be coated with the priming paint agent composition of subsequent processing above that.This is favourable in the occasion that the mode that particularly is coated with through heliogravure is coated with, and reason is also can overlappingly to be coated with for each coater unit is provided with the active energy beam irradiation unit.In addition, so-called inviscid, be meant that the surface of filming reaches with the also imperceptible degree of drying that is clamminess of method such as referring to touch.In this occasion, behind the priming paint agent composition of coating subsequent processing, through the irradiation 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 operation (operation 1), the primer agent composition of coating hard coating material composition, coating adhesive, through shining 10mJ/cm containing between operation 1 and the operation 2 and/or between operation 2 and the operation 3 for the anti-adhesive of further raising
2～100mJ/cm
2The operation of active energy beam, be cured with keeping curable.In the 1st invention; Because also use polyisocyanate compounds; There is no need as the 2nd invention, the active energy ray-curable resin to be kept curable ground and solidify, but if necessary, also can the same with the 2nd invention the active energy ray-curable resin be kept curable ground and solidify.
The transfer sheet of the present invention that obtains like this; Be arranged at the metal die diaphragm capsule according to the mode that makes its release layer be in the metal die side; Through to its bonding agent aspect injection moulding molding resin, can obtain to have the moulding article of adhesive linkage required form, transfer sheet of the present invention and molding resin driving fit.
Then, open the mould diaphragm capsule, the moulding article that active energy beam can obtain finished product are taken away, shone to the moulding article from mould.As molding resin,, can give an example like acrylic resin, vistanex, mylar etc. as long as have thermoplasticity.
The irradiation of accurately machined active energy beam can be carried out in arbitrary time of front and back of peeling off the base material film after the demoulding is handled.In this fine finishining, can become 600mJ/cm by accumulation
2～1000mJ/cm
2Mode shine active energy beam.
Embodiment
Next, enumerating experimental example carries out bright more specifically to the present invention.In addition, the short of special instruction of this specification, " part " and " % " is quality criteria.The filming of embodiment and comparative example form and evaluation result as shown in table 1.
(preparation of hard coating material composition (1))
(gorgeous good solid 184: 27 parts of the preparation of Ciba company) 3 parts, MEK mix with mixer and stir, and process hard coating material composition (1) with 60 parts of acrylic acrylate resins (preparation of WHV-652:DIC company), 10 parts of urethane acrylate resin (preparation of Unidic V-4000BA:DIC company), polymerization initiator.
Here, the WHV-652 of DIC company preparation is that the acrylic double bond equivalent is that 200～2500g/eq, weight average molecular weight are 50000～250000, glass transition temperature is that 40～130 ℃, hydroxyl value are 5～300 (mgKOH/g), have (methyl) acryloyl group and do not have the active energy ray-curable acrylic acrylate resin of carbamate bond structure.
(preparation of hard coating material composition (2))
(gorgeous good solid 184: 27 parts of the preparation of Ciba company) 3 parts, MEK mix with mixer and stir, and process hard coating material composition (2) with 50 parts of acrylic acrylate resins (preparation of WHV-652:DIC company), 20 parts of urethane acrylate resin (preparation of Unidic V-4000BA:DIC company), polymerization initiator.
(preparation of hard coating material composition (3))
(gorgeous good solid 184: 27 parts of the preparation of Ciba company) 3 parts, MEK mix with mixer and stir, and process hard coating material composition (3) with 50 parts of acrylic acrylate resins (preparation of WHV-652:DIC company), 20 parts of urethane acrylate resin (preparation of Unidic V-4221:DIC company), polymerization initiator.
(preparation of hard coating material composition (4))
(gorgeous good solid 184: 27 parts of the preparation of Ciba company) 3 parts, MEK mix with mixer and stir, and process hard coating material composition (4) with 40 parts of acrylic acrylate resins (preparation of WHV-652:DIC company), 30 parts of urethane acrylate resin (preparation of Unidic V-4221:DIC company), polymerization initiator.
(preparation of priming paint agent composition (1))
(gorgeous good solid 184: (Takenate D-110N: 37 parts of the preparation of Mitsui Chemicals polyurethane company) 10 parts, MEK mix with mixer and stir, and process priming paint agent composition (1) for the preparation of Ciba company) 3 parts, polyisocyanate compounds with 35 parts of acrylic acrylate resins (preparation of WHV-652:DIC company), 15 parts of urethane acrylate resin (preparation of Unidic V-4221:DIC company), polymerization initiator.
(preparation of priming paint agent composition (2))
(gorgeous good solid 184: 47 parts of the preparation of Ciba company) 3 parts, MEK mix with mixer and stir, and process priming paint agent composition (2) with 35 parts of acrylic acrylate resins (preparation of WHV-652:DIC company), 15 parts of urethane acrylate resin (preparation of Unidic V-4221:DIC company), polymerization initiator.
(preparation of printing ink)
30 parts of 70 parts of acrylic acid series photogravure inks (TRC-906 805 China inks: DIC preparation), MEK mixed with mixer stir, process printing ink (1).
(preparation of bonding agent)
80 parts of 20 parts of the acrylic resins that Tg is about 40 ℃ (Paraloid B-72: Rhom and Hass preparation), MEK mix with mixer and stir, and process bonding agent (1).
(making of transfer sheet)
On the PET film (thickness is 38 μ m, Japan's textile company preparation) that carries out after the demoulding is handled, said hard coating material composition (1) is passed through the heliogravure coating process with 5g/m
2Be coated with.Behind dry 30s under 160 ℃, on the dry epithelium of said hard coating material composition (1), said priming paint agent composition (1) is passed through the heliogravure coating process with 2g/m through the hot blast mode
2Be coated with.Through the hot blast mode at 80 ℃ down behind the dry 30s; On dry epithelium with noncohesive said priming paint agent composition (1); Said printing ink (1) is printed with 2g/m2 through the heliogravure coating process comprehensively; Further, after the heated-air drying, said bonding agent (1) is passed through the heliogravure coating process with 2g/m
2Be coated with, can obtain the transfer sheet of experimental example 1.
Likewise, form, prepare each hard coating material composition, priming paint agent composition,, obtain each transfer sheet of each experimental example through coating drying condition, the ultraviolet illuminate condition that this souvenir carries according to the mixing of table 1～3.As follows is the evaluation method of evaluation method, molding procedure condition and each transfer sheet of the coating master of hard coating material composition.
(hard conating inviscid)
Behind 160 ℃ of about 30s of following heated drying, perhaps behind 160 ℃ of about 30s of following heated drying with high-pressure mercury light irradiation 15mJ/cm
2Ultraviolet ray, through the fingers-touch method evaluate tackiness.
(zero) inviscid, (△) has a little viscosity, (*) viscosity remarkable
(the anti-adhesive of hard conating)
PET film (S5101, the 25 μ m of Japan's textile company preparation) is set, with 1kg/cm on the coating thing
2, 40 ℃ place 24h, estimate the state that shifts to the back side of PET film.
(zero) no vestige, (△) have vestige but do not have that shift at the back side, (*) has the back side to shift
(storage stability of priming paint agent composition)
Priming paint agent composition is put into vial, through the flowability behind the visual valuation 24h.
(zero) there are flowability, (△) mobile poor
(adaptation of the hard conating before the moulding)
In film coated surface, sticking glass paper adhesive tape is estimated film when peeling off residual.
(zero) all residual, (△) part is filmed and is peeled off, (*) almost all film and peel off
(moulding and ultraviolet irradiation process)
Use high-pressure mercury-vapor lamp, 15mJ/cm
2The occasion of irradiation is shone once (1 パ ス, 1 pass) with 80W/cm, 1 lamp, 30m/min.30mJ/cm
2The occasion of irradiation is shone once with 140W/cm, 1 lamp, 30m/min.60mJ/cm
2The occasion of irradiation is shone once with 140W/cm, 1 lamp, 15m/min.
As for until obtain the ultraviolet ray irradiation in the operation of transfer sheet, reach capacity the situation of curing to the curing degree of material composition during as 100% curing degree with curable, be the scope (above-mentioned semi-cured state) of 10～50% curing degrees.
(adaptation of the hard conating after the moulding)
In the film coated surface applying glassine paper adhesive tape that is transferred on the acrylic panel, estimate when peeling off film residual.
(zero) all residual, (△) part is filmed and is peeled off, (*) almost all film and peel off
(cast gate current mark (ゲ one ト flows れ, gate flow))
Use is provided with 45mm * 75mm, the R angle is the injection (mo(u)lding) machine (model J55AD: JSW produces) of 20 ° metal die; The transfer sheet of above-mentioned gained according to its bonding agent aspect is provided with the mode that the molding resin of fusion contacts, is carried out injection moulding to acrylic resin (the Plexiglas zk5BR of Daicel-win wound company preparation) under 250 ℃.Outward appearance through the visual valuation article shaped.
(crackle)
Outward appearance through the visual valuation article shaped.
(zero) there are crackle in flawless, (*)
(woolliness of anti-the steel wire)
After the transfer printing, peel off the PET film that carries out after the demoulding is handled, the hard conating irradiation ultraviolet radiation that exposes is reached capacity until curing degree.The film coated surface of transfer printing is with steel wool (#0000,100g load) two frictions (ダ Block Le ラ PVC Application グ, double rubbing), through the degree of impairment of visual valuation film coated surface on the acrylic panel of resulting moulding thus.
(zero) not damaged, (△) have slight damage, (*) that damage is arranged
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, shown in each raw material in the table 1,2 as follows.
● WHV-652: acrylic acrylate (preparation of DIC company)
● Unidic V-4000BA: urethane acrylate (preparation of DIC company)
● Unidic V-4221: urethane acrylate (preparation of DIC company)
● gorgeous good solid 184: Photoepolymerizationinitiater initiater (preparation of Ciba company)
● TRC-906 805 China inks: acrylic acid series photogravure ink (preparation of DIC company)
● the acrylic resin that Paraloid B-72:Tg is about 40 ℃ (Rhom and Hass's preparation)
● Takenate D-110N: PIC (preparation of Mitsui Chemicals polyurethane company)
Can know from table 1～3, through after the coating drying of hard coating material composition and or the coating drying of priming paint agent composition after irradiation ultraviolet radiation, can from priming paint agent composition, save isocyanates, can improve the storage stability of priming paint agent composition.In addition, according to the hard coating material composition (1) that constitutes transfer sheet of the present invention, be 15～60mJ/cm at ultraviolet irradiation amount
2Wide region in do not crack.That is to say, can absorb the deviation of the exposure in the manufacturing process, be easy to adjust manufacturing process, can boost productivity.And,, can further improve the preceding adaptation of anti-adhesive and moulding through to the dry epithelium of hard coating material composition, the dry epithelium both sides irradiation ultraviolet radiation of priming paint agent composition.
[utilizability on the industry]
Active energy ray-curable transfer sheet of the present invention with specific hard conating and prime coat is easy to adjust the active energy beam irradiation in the manufacturing process, helps thus to boost productivity.Further, adaptation and hear resistance are also excellent in the molding procedure after transfer printing.In the possibility that has extensive developing aspect the surface protection purposes of the plastic shaping thing that is used for occasions such as household appliances, computer, mobile phone.
Claims (9)
1. in-molded transfer sheet of using of active energy ray-curable, it forms for the polyisocyanate compounds with the active energy ray-curable sheet material solidifies,
With regard to this active energy ray-curable sheet material; On the one side of basement membrane with release layer; As the transfer printing layer that can peel off from this basement membrane; Have: the curable hard conating, said curable hard conating is formed by hard coating material composition, and said hard coating material composition comprises and has (methyl) acryloyl group and do not have the active energy ray-curable acrylic acrylate resin and the active energy ray-curable urethane acrylate resin of carbamate bond structure; Be the curable prime coat of contact condition with this hard conating; Said curable prime coat is formed by priming paint agent composition, and said priming paint agent composition comprises active energy ray-curable acrylic acrylate resin and/or active energy ray-curable urethane acrylate resin and the polyisocyanate compounds with hydroxyl and (methyl) acryloyl group; And, bond layer.
2. in-molded transfer sheet of using of active energy ray-curable, it solidifies and forms for the curable hard conating of active energy ray-curable sheet material and/or prime coat being kept curable ground,
With regard to this active energy ray-curable sheet material; On the one side of basement membrane with release layer; As the transfer printing layer that can peel off from this basement membrane; Have: the curable hard conating, said curable hard conating is formed by hard coating material composition, and said hard coating material composition comprises and has (methyl) acryloyl group and do not have the active energy ray-curable acrylic acrylate resin and the active energy ray-curable urethane acrylate resin of carbamate bond structure; Be the curable prime coat of contact condition with this hard conating; Said curable prime coat is formed by priming paint agent composition, and said priming paint agent composition comprises active energy ray-curable acrylic acrylate resin and/or the active energy ray-curable urethane acrylate resin with (methyl) acryloyl group; And, bond layer.
3. according to claim 1 or claim 2 the in-molded transfer sheet of using of active energy ray-curable, it has printing ink layer between said curable prime coat and bond layer.
4. like the in-molded transfer sheet of using of each described active energy ray-curable in the claim 1～3; Wherein, the hard coating material composition that forms said curable hard conating contains: the having (methyl) acryloyl group of 50～99 quality % and do not have the active energy ray-curable acrylic acrylate resin of carbamate bond structure, the active energy ray-curable urethane acrylate resin of 1～50 quality %.
5. like the in-molded transfer sheet of using of each described active energy ray-curable in the claim 1～4; Wherein, Form the active energy ray-curable acrylic acrylate resin that contains in the hard coating material composition of said curable hard conating, be that the acrylic double bond equivalent is that 200～2500g/eq, weight average molecular weight are 50000～250000, glass transition temperature is 40～130 ℃ active energy ray-curable acrylic acrylate resin.
6. like the in-molded transfer sheet of using of each described active energy ray-curable in the claim 1～5; Wherein, Form the active energy ray-curable acrylic acrylate resin that contains in the priming paint agent composition of said curable prime coat, be that the acrylic double bond equivalent is that 200～2500g/eq, weight average molecular weight are 50000～250000, glass transition temperature is that 40～130 ℃, hydroxyl value are the active energy ray-curable acrylic acrylate resin of 5～300 (mgKOH/g).
7. like the in-molded transfer sheet of using of each described active energy ray-curable in the claim 1～6; Wherein, said hard coating material composition comprise be selected from the active energy ray-curable monomer, do not have active energy ray-curable and have the resin combination of carbamate bond structure and do not have active energy ray-curable and have in the resin combination of ester bond structure more than a kind.
8. in-molded manufacturing approach of active energy ray-curable with transfer sheet; It is characterized in that; It is the in-molded manufacturing approach with transfer sheet of the described active energy ray-curable of claim 1; When the active energy ray-curable sheet material that obtains as precursor; Have on release layer the operation (operation 1) of coating hard coating material composition, according to the operation (operation 2) of the mode primer agent composition that contacts with this hard conating and the operation (operation 3) of coating adhesive, between said (operation 1) and (operation 2) and the arbitrary or both sides between (operation 2) and (operation 3) have irradiation 10mJ/cm
2～100mJ/cm
2The operation of active energy beam.
9. in-molded manufacturing approach of active energy ray-curable with transfer sheet; It is characterized in that; It is the in-molded manufacturing approach with transfer sheet of the described active energy ray-curable of claim 2; When the active energy ray-curable sheet material that obtains as precursor; Have on release layer the operation (operation 1) of coating hard coating material composition, according to the operation (operation 2) of the mode primer agent composition that contacts with this hard conating and the operation (operation 3) of coating adhesive, between said (operation 1) and (operation 2) and the arbitrary or both sides between (operation 2) and (operation 3) have irradiation 10mJ/cm
2～100mJ/cm
2The operation of active energy beam.
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| CN104129189A (en) * | 2013-05-02 | 2014-11-05 | 荒川化学工业株式会社 | Decorative film for transfer printing |
| CN106457802A (en) * | 2014-06-30 | 2017-02-22 | 株式会社普利司通 | Laminate, conductive roller, and method for producing laminate |
| CN114502388A (en) * | 2019-10-16 | 2022-05-13 | 凸版印刷株式会社 | Transfer sheet and method for manufacturing melamine decorative board |
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| CN104129189A (en) * | 2013-05-02 | 2014-11-05 | 荒川化学工业株式会社 | Decorative film for transfer printing |
| CN106457802A (en) * | 2014-06-30 | 2017-02-22 | 株式会社普利司通 | Laminate, conductive roller, and method for producing laminate |
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| CN114502388B (en) * | 2019-10-16 | 2023-10-27 | 凸版印刷株式会社 | Transfer sheet and method for producing melamine decorative board |
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| CN102673211B (en) | 2016-01-20 |
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