CN102604504A - Aqueous dispersion type coating agent for printing and printing film - Google Patents
Aqueous dispersion type coating agent for printing and printing film Download PDFInfo
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- CN102604504A CN102604504A CN2012100082553A CN201210008255A CN102604504A CN 102604504 A CN102604504 A CN 102604504A CN 2012100082553 A CN2012100082553 A CN 2012100082553A CN 201210008255 A CN201210008255 A CN 201210008255A CN 102604504 A CN102604504 A CN 102604504A
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Abstract
The invention provides an aqueous dispersion type coating agent for printing a printing film. The aqueous dispersion type coating agent for printing form a film base material and a coating agent layer of excellent adhesion property and also excellent adhesion property for ultraviolet-curable ink. The aqueous dispersion type coating agent for printing comprises ethyl acrylate, methyl methacrylate and butyl methacrylate monomer mixture obtained by the emulsion polymerization of acrylic copolymer and is characterized in that the dynamic viscoelastic spectrum of energy storage modulus of the coating agent layer formed after being coated by the aqueous dispersion type coating agent and dried at 11 Hz is 5.0 * 105 pa or more at above 10 DEG C, 1.0 * 105 to 5.0 * 106 pa below 30 DEG C, and 8.0 * 103-5.0 * 105 pa below 50 DEG C, while the loss tangent peak temperature thereof is 30 DEG C to 80 DEG C.
Description
Technical field
The present invention relates to printing and use film with aqueous dispersion type coating agent and printing, in detail, the printing that relates to the film base material that also can be used for poor solvent resistance is used film with aqueous dispersion type coating agent and printing.
Background technology
All the time, use has the printing of various film base materials to be used in every field with film.In printing with China ink, use under the situation of the printing that the ultraviolet hardening China ink is arranged, the ultraviolet hardening China ink is poor to the adaptation on film base material surface, therefore, in order to improve the adaptation of ultraviolet hardening China ink, the coating agent layer need be set on the surface of film base material.
As the coating agent that is used to be provided with the coating agent layer in the past; Known aqueous coating or solvent are arranged is the coating agent, though aqueous coating is preferred aspect environment, has insufficient and so on the problem of the adaptation of film base material and coating agent layer; Therefore, using solvent mostly is the coating agent.
On the other hand, in recent years, consider, reclaiming the resin system cabinet of exhausted household electrical appliances and electronics and pulverize and recycling of utilization again from the viewpoint of saving resource.
Surface substrate for the pressure sensitive adhesion sheet of the resin system cabinet that is used for household electrical appliances and electronics recycles in order directly to be pasted on cabinet, and requiring it is the material identical with cabinet.
Therefore, these surface substrates use polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate resin etc. usually film (with reference to patent documentation 1.)。
Therefore but the poor solvent resistance of these resin moldings exists that can not to use solvent be the problem of coating agent.
Patent documentation 1: japanese kokai publication hei 11-237840 communique
Summary of the invention
The problem that invention will solve
The present invention accomplishes in view of the situation of above-mentioned prior art; Its purpose is; Provide printing use film with aqueous dispersion type coating agent and the printing of having used it to make, said printing can form film base material and coating agent layer with the aqueous dispersion type coating agent and have the also coating agent layer of excellence of the black adaptation of adaptation and the ultraviolet hardening of excellence.
Be used to solve the means of problem
The inventor finds in order to solve above-mentioned problem; Through the storage modulus that makes the dynamic viscoelastic spectrum of coating agent layer under 11Hz is specific scope; And the tangent raising peak, loss angle angle that makes dynamic viscoelastic spectrum is in specific scope; Can solve above-mentioned problem, wherein, said coating agent layer is coated with to comprise the aqueous dispersion type coating agent of acrylic copolymer and carry out drying and obtains; Said acrylic copolymer carries out letex polymerization with the monomer mixture that comprises specific acrylic monomer and obtains, and has accomplished the present invention based on above-mentioned opinion knowledge.
Promptly; The present invention provides printing to use the aqueous dispersion type coating agent; It is the aqueous dispersion type coating agent that comprises acrylic copolymer; Said acrylic copolymer obtains for the monomer mixture that will comprise ethyl propenoate, TEB 3K and NSC 20956 carries out letex polymerization, with this aqueous dispersion type coating agent coating, dry and coating agent layer that obtain is 5.0 * 10 under 10 ℃ at the storage modulus of the dynamic viscoelastic spectrum under the 11Hz
5Pa is above, be 1.0 * 10 under 30 ℃
5Pa～5.0 * 10
6Pa, be 8.0 * 10 under 50 ℃
3Pa～5.0 * 10
5Pa, and the temperature at the tangent raising peak, loss angle angle of dynamic viscoelastic spectrum is 30 ℃～80 ℃.
In addition, the present invention provides printing to use the aqueous dispersion type coating agent, wherein above-mentioned printing with the aqueous dispersion type coating agent in, in monomer mixture, also comprise the cationic acrylic monomer.
In addition; The present invention provides printing to use film; It is that above-mentioned printing is coated film base material surface with the aqueous dispersion type coating agent and film is used in the printing that obtains; Be characterised in that, aqueous dispersion type coating agent coating, dry and coating agent layer that obtain is 5.0 * 10 at the storage modulus of the dynamic viscoelastic spectrum under the 11Hz is used in this printing under 10 ℃
5Pa is above, be 1.0 * 10 under 30 ℃
5Pa～5.0 * 10
6Pa, be 8.0 * 10 under 50 ℃
3Pa～5.0 * 10
5Pa, and the temperature at the tangent raising peak, loss angle angle of dynamic viscoelastic spectrum is 30 ℃～80 ℃.
In addition, the present invention provides the printing of foregoing invention to use film, and wherein above-mentioned printing is with in the film, and above-mentioned film base material comprises polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate resin or the mixture more than 2 kinds in them.
In addition, the present invention provides printing to use film, and above-mentioned printing is with in the film, and above-mentioned being printed as used the black printing of ultraviolet hardening.
In addition, the present invention provides printing to use film, and above-mentioned printing is with in the film, is provided with pressure sensitive adhesive layer at the inner face of above-mentioned film base material.
Printing of the present invention can form film base material with the aqueous dispersion type coating agent and the coating agent layer has excellent adaptation and the black also excellent coating agent layer of adaptation of ultraviolet hardening.
Embodiment
It is the aqueous dispersion type coating agent that comprises acrylic copolymer that the aqueous dispersion type coating agent is used in printing of the present invention, and letex polymerization obtains said acrylic copolymer for the monomer mixture that will comprise ethyl propenoate, TEB 3K and NSC 20956 carries out.
Acrylic copolymer carries out letex polymerization with the monomer mixture that comprises ethyl propenoate, TEB 3K and NSC 20956 and obtains; But with regard in the monomer mixture each monomeric contain proportional with regard to; With respect to whole monomeric total amounts; Ethyl propenoate is preferably 10～35 quality %, more preferably 12～30 quality %; TEB 3K is preferably 15～50 quality %, more preferably 20～35 quality %; Reach NSC 20956 and be preferably 15～40 quality %, more preferably 25～35 quality %.Through make these each monomericly contain the proportional above-mentioned scope that is, can make the adaptation of film base material and coating agent layer excellent, in addition, also can make the black adaptation excellence of coating agent layer and ultraviolet hardening.
Need to prove, but can contain other monomer of copolymerization in the above-mentioned monomer mixture.
But other monomer as copolymerization; Can enumerate: methyl acrylate, propyl acrylate, Bing Xisuandingzhi, NSC 11786, lauryl acrylate, Jia Jibingxisuanyizhi, propyl methacrylate, N-Hexyl methacrylate, lauryl methacrylate(LMA) etc. (wherein, are removed ethyl propenoate, TEB 3K, NSC 20956.) carbonatoms of alkyl of alkyl ester part is (methyl) alkyl acrylate of 1～20; And the carbonatoms of the alkyl of vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-2-hydroxypropyl acrylate, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-3-hydroxy butyl ester, vinylformic acid-4-hydroxy butyl ester, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, methylacrylic acid-3-hydroxypropyl acrylate, methylacrylic acid-3-hydroxy butyl ester, methylacrylic acid-alkyl esters such as 4-hydroxy butyl ester part is (methyl) alkyl acrylate of 1～10 hydroxyl etc., (methyl) alkyl acrylate of preferred latter's hydroxyl.But containing of (methyl) alkyl acrylate of (methyl) alkyl acrylate of these copolymerization or hydroxyl is proportional with respect to whole monomeric total amounts, is preferably 1～20 quality %, 5～15 quality % more preferably respectively.
In addition, but preferably make cationic acrylic monomer that contains copolymerization in the above-mentioned monomer mixture or acrylic monomer with acetoacetyl.These monomers can improve the adaptation with film base material, in addition, can improve the adaptation with China ink.Particularly the cationic acrylic monomer can further improve and black adaptation.
As the cationic acrylic monomer; For example can preferably enumerate: have the amino vinyl monomer of quaternary ammonium salt root and/or uncle; Special preferable methyl vinylformic acid dimethylamino ethyl ester, further preferred cationic property acrylic monomer and acrylic monomer with acetoacetyl and usefulness.
As acrylic monomer with acetoacetyl; For example can preferably enumerate: vinylformic acid acetoacetoxy groups methyl esters, methylacrylic acid acetoacetoxy groups methyl esters, vinylformic acid acetoacetoxy groups ethyl ester, acetoacetoxyethyl methacrylate etc., special preferable methyl vinylformic acid acetoacetoxy groups ethyl ester.
The cationic acrylic monomer or have acetoacetyl acrylic monomer contain proportionally with respect to whole monomeric total amounts, be preferably 0.1～20 quality %, 3～10 quality % more preferably respectively.
And with the cationic acrylic monomer with have under the situation of acrylic monomer of acetoacetyl, both ratios that contains are preferably 1: 5～5: 1 scope, more preferably 1: 2～2: 1 scope by quality ratio.
In the present invention, aforesaid propylene acid based copolymer obtains through letex polymerization.Letex polymerization can be carried out through various emulsion polymerizations, but general emulsion polymerization gets final product.Particularly; For example can enumerate following method: in reactor drum, add and comprise ethyl propenoate, TEB 3K and NSC 20956 and other monomeric monomer mixture as required; And then input table surface-active agent, polymerization starter etc., after with non-active gas such as nitrogen inside being replaced, under refluxing; With water is the dispersion medium warming while stirring, carries out letex polymerization about 1～8 hour in the TR about 40～100 ℃.
The letex polymerization of above-mentioned monomer mixture can be carried out in the presence of tensio-active agent, but as tensio-active agent, the preferred cationic surfacant.
As cationic surfactant, for example can enumerate: alkyl trimethyl ammonium chlorides such as palmityl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, OTAC; Two alkyl-dimethyl ammonium chlorides such as Varisoft 432PPG, two lauryl alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride; Benzalkonium chloride (benzalkonium chloride) etc.Tensio-active agent can use a kind separately, also can make up and use more than 2 kinds.
The cooperation ratio of tensio-active agent is not special to be limited, but with respect to whole monomeric total amounts, is preferably 0.001～1.0 quality % usually, more preferably 0.005～0.05 quality %.
The letex polymerization of above-mentioned monomer mixture can be carried out in water-medium, but as water-medium, can enumerate: water, comprise the water of a small amount of organic solvent etc., preferably water, more preferably ion exchanged water.
In aqueous dispersion type of the present invention coating agent,, preferably cooperate linking agent in order to make acrylic copolymer crosslinked through linking agent.Through cooperating linking agent can improve the intensity of coating agent layer.
As the linking agent that is used for the cross-linked acrylic acid based copolymer, preferred epoxy is a linking agent.As epoxy is linking agent; For example can use: neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, bisphenol A diglycidyl ether, Bisphenol F diglycidylether, o-phthalic acid diglycidyl ester, dimeracid diglycidylether, triglycidyl isocyanurate, two T 55s, trimethylolpropane polyglycidylether, Sorbitol Powder four glycidyl ethers, N, N, N '; N '-four glycidyl group m-xylene diamine, 1; Two (N, the N-diglycidyl amino methyl) hexanaphthenes of 3-, N, N; N ', N '-epoxies such as four glycidyl group diaminodiphenyl-methane are linking agent.
Linking agent can use a kind separately, also can make up and use more than 2 kinds.
The consumption of linking agent is preferably 0.01～5 mass parts with respect to acrylic copolymer 100 mass parts, more preferably 0.1～3 mass parts.
Aqueous dispersion type of the present invention coating agent except aforesaid propylene acid based copolymer reaches other compositions such as linking agent that contained as required, also contains water-medium.
Employed water-medium when this water-medium can be for the acrylic copolymer letex polymerization also can be other water-medium.The different water-medium of water-medium in order to be replaced into letex polymerization, can through after from the letex polymerization liquid of acrylic copolymer, isolating acrylic copolymer, the acrylic copolymer that has separated is dispersed in the other water-medium carry out.
The content of the water-medium in the aqueous dispersion type of the present invention coating agent is regulated can removing or appending to wait and carry out through water-medium.
The resin solid compositions such as acrylic copolymer of aqueous dispersion type of the present invention coating agent contain proportional 0.5～10 quality %, 1～7 quality % more preferably of being preferably.
The median size of dispersive acrylic copolymer particle is preferably 10～500nm, 50～300nm more preferably in aqueous dispersion type of the present invention coating agent.The median size of acrylic copolymer particle can make the adaptation of coating agent layer and film base material excellent in this scope the time.
In addition, in aqueous dispersion type of the present invention coating agent,, can cooperate various fillers such as organic filler, mineral filler in order to improve oilness or to obtain not having light sensation.
As organic filler, can enumerate: the toner of polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin or their mixture etc. etc.
As mineral filler, can enumerate: inorganic oxides such as silicon-dioxide, aluminum oxide; Metal powder such as bronze, silver powder etc.
In the present invention, be coated with above-mentioned aqueous dispersion type coating agent and carry out drying and the storage modulus of the dynamic viscoelastic spectrum of coating agent layer under 11Hz that obtain is 5.0 * 10 under 10 ℃
5Pa is above, be preferably 8.0 * 10
5～3.0 * 10
6Pa is 1.0 * 10 under 30 ℃
5～5.0 * 10
6Pa, be preferably 1.2 * 10
5～2.5 * 10
6Pa is 8.0 * 10 under 50 ℃
3～5.0 * 10
5Pa, be preferably 1.0 * 10
4～4.0 * 10
5Pa.Through making storage modulus, can form the also excellent coating agent layer of adaptation that film base material and coating agent layer have excellent adaptation and ultraviolet hardening China ink in these scopes.When storage modulus was lower than these scopes, the cohesive force of coating agent became insufficient, caused the cohesive failure of coating agent layer sometimes, and when storage modulus surpassed these scopes, being become by film toughness of coating agent layer was superfluous, and the coating agent layer may reduce with the adaptation of China ink.
Need to prove that storage modulus is measured according to JIS K7244-4.
In the present invention, in coating above-mentioned aqueous dispersion type coating agent and carry out drying and the temperature at the tangent raising peak, loss angle angle of the dynamic viscoelastic spectrum of the coating agent layer that obtains is 30 ℃～80 ℃, is preferably 40 ℃～75 ℃.When the temperature at protruding peak was lower than above-mentioned scope, the cohesive force of coating agent became insufficient, possibly cause the cohesive failure of coating agent layer; On the contrary; When surpassing above-mentioned scope, being become by film toughness of coating agent layer is superfluous, and the coating agent layer may reduce with the adaptation of China ink.
Printing of the present invention is coated on film base material surface with above-mentioned printing with the aqueous dispersion type coating agent with film and obtains.
With the glue spread of aqueous dispersion type coating agent, be preferably 0.01～5g/m for above-mentioned printing usually at film base material
2, 0.05～2g/m more preferably
2
As film base material, can use various plastic films.As the object lesson of film base material, for example can enumerate: polyolefin resines such as polyvinyl resin, acrylic resin; Vibrin such as pet resin, PEN resin, polybutylene terephthalate resin; The film of the various synthetic resins such as mixture more than 2 kinds in PVC RESINS, polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, polyamide resin, polyimide resin, fluorine resin and these resins or the stacked film more than 2 layers of the same race or not of the same race of these films, employed resin identical materials in the resin system cabinet of preferred especially use and household appliances and electronics.As these film base materials, can enumerate the film that constitutes by polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin or the mixture more than 2 kinds in them.
The not special restriction of the thickness of film base material, but be preferably usually 10～350 μ m, more preferably 15～300 μ m, be preferably 20～250 μ m especially.
As be coated with the coating process of above-mentioned printing with the aqueous dispersion type coating agent at film base material, for example can enumerate: bar type coating method, scraper plate coating method, print roll coating method, scraper coating method, mold pressing coating method etc. are known method in the past.
Drying is preferably carried out under 60～130 ℃ usually, more preferably under 80～120 ℃, carries out.Not special restriction time of drying, common 10 second～5 are minute just enough.
With regard to film, preferably the inner face at film base material is provided with pressure sensitive adhesive layer with regard to printing of the present invention.Through pressure sensitive adhesive layer is set, can easily stick on the resin system cabinet of household electrical appliances and electronics etc.
For the inner face of film base material,, can implement to be prone to adhesion process for the closing force of further raising with pressure sensitive adhesive layer.As easy adhesion process, not special restriction for example can be enumerated Corona discharge Treatment etc.
As the tackiness agent that is used for pressure sensitive adhesive layer, can use various pressure sensitive adhesives.Object lesson as pressure sensitive adhesive; For example can enumerate: tree elastomer is that pressure sensitive adhesive, viton are that pressure sensitive adhesive, acrylics are that pressure sensitive adhesive, polyvingl ether resin system pressure sensitive adhesive, urethane resin are that pressure sensitive adhesive, silicone resin are pressure sensitive adhesive etc., preferably enumerates the acrylic resin pressure sensitive adhesive, rubber is that pressure sensitive adhesive, silicone resin are pressure sensitive adhesive etc.In addition, pressure sensitive adhesive can be the solvent-borne type pressure sensitive adhesive, also can be water type pressure sensitive adhesive, also can be for suppressing quick adhesion type, any in the exfoliated pressure sensitive adhesive again.
In addition, also can on pressure sensitive adhesive layer and face base material film side opposition side, stripping film be set.
As stripping film, not special the qualification.As the base material of stripping film, for example can enumerate: paper, synthetic paper, synthetic resin film etc.As paper, for example can enumerate: paper base materials such as the paper of wood-free, zellglas, enamelled paper; The paper base material of laminated paper that forms at thermoplastic resins such as these paper base material laminated polyethylenes, Vestolen PP 7052 and so on and with Mierocrystalline cellulose, starch, Z 150PH, acrylic acid or the like-styron etc. the paper of wood-free, zellglas, enamelled paper etc. are carried out joint filling and handle the paper base material that forms etc.As the plastic synthetic resin film; The films that for example can enumerate the film that is made up of vibrin such as polyolefin resines such as polyvinyl resin, acrylic resin, polybutylene terephthalate resin, pet resins and these synthetic resin films have been implemented to be prone to adhesion process etc. preferably are coated with the film of stripper at these films.
With regard to stripper, can enumerate fluorine resin, silicon-type resin, contain the carbamate of chain alkyl etc.
For the printing of printing with the coating agent layer of film in printing of the present invention and using can be used various China inks such as ultraviolet hardening China ink with China ink.As the ultraviolet hardening China ink, can use various ultraviolet hardening China inks, but the optimization polypropylene acid esters is the ultraviolet hardening China ink.
Printing of the present invention can be used as the base material film of the pressure sensitive adhesion sheet that prints usefulness with film, and its purposes is unqualified, but particularly can be used for clung body is recycled and the purposes utilized again.
But printing of the present invention with the base material film advantageous applications of pressure sensitive adhesion sheet under the material of the film base material situation identical with the material that constitutes clung body.
As the material that constitutes clung body, can enumerate the clung body that constitutes by polystyrene resin, ABS resin, polycarbonate resin or the mixture more than 2 kinds in them as concrete example.
The not special restriction of the shape of clung body can be made different shape.
Embodiment
Below, through embodiment the present invention is explained more specifically.Need to prove that the present invention does not receive any restriction of these examples.
(embodiment 1)
(1) preparation of aqueous dispersion type coating agent
In advance in beaker with ion exchanged water 75.9 mass parts, lauryl trimethyl ammonium chloride (Kao Corp's system; Trade(brand)name " コ one タ ミ Application 24P "; Solids component 27 quality %) 3.7 mass parts, ethyl propenoate 24 mass parts, TEB 3K 24 mass parts, NSC 20956 32 mass parts, dimethylaminoethyl methacrylate 5 mass parts, acetoacetoxyethyl methacrylate 5 mass parts and methylacrylic acid 2-hydroxyl ethyl ester 10 mass parts cooperate, and use homomixer to stir and make monomer mixture.
In the reaction unit that is provided with whisking appliance, reflux exchanger, TM, nitrogen ingress pipe; Drop into ion exchanged water 67.9 mass parts, be warming up to 70 ℃, under 70 ℃; Interpolation is as 2 of polymerization starter; The 10 quality % aqueous solution, 2 mass parts of 2-azo two (amino two propane of 2-) dihydrochloride (Wako Pure Chemical Industries, Ltd.'s system, trade(brand)name " V-50 ") dripped pre-prepd above-mentioned monomer mixture and made it carry out polyreaction with 3 hours immediately then.After dripping end, further, be cooled to room temperature then 70 ℃ of following slakings 3 hours.After the cooling, add Glacial acetic acid min. 99.5 1.2 mass parts, obtaining xanchromatic is the waterborne cation property acrylic copolymer of cationic charge.The solids component of this multipolymer is that 40.0 quality %, viscosity are that 300mPas/30 ℃, pH are 4.8, median size is 150nm.
Solids component 100 mass parts with respect to above-mentioned multipolymer; Interpolation is glycerine polyglycidyl ether (Na ガ セ ケ system テ Star Network ス Co., Ltd. system of linking agent as epoxy; Trade(brand)name " デ Na コ one Le EX-313 ") 1.0 mass parts; And then thereby use ion exchanged water to dilute to make solids component be 5 quality %, preparation aqueous dispersion type coating agent (cooperating 1).
(2) printing is with the making of film
On the surface of polystyrene resin film (thickness 65 μ m), so that glue spread is 0.2g/m
2The mode of (dry back) is coated with the aqueous dispersion type coating agent (cooperating 1) that obtains in above-mentioned (1), with dry 2 minutes of 70 ℃ hot air dryers, makes to print and uses film.
(3) have the making of the printing of pressure sensitive adhesive layer with film
With roll-type scraper plate coating machine; So that the mode that dried separately coating thickness is 20 μ m; To suppress quick adhesion type acrylic pressure-sensitive adhesive (リ Application テ Star Network corporate system, trade(brand)name " PA-T1 ") and exfoliated again acrylic pressure-sensitive adhesive (リ Application テ Star Network corporate system, trade(brand)name " MF ") and be coated on stripping film (リ Application テ Star Network corporate system; Carried out the zellglas of lift-off processing with silicone resin; Trade(brand)name " SP-8K ア オ ") on the lift-off processing face, drying is 2 minutes under 90 ℃, forms pressure sensitive adhesive layer.After the drying, the printing of in above-mentioned (2), making is pasted the pressure sensitive adhesive layer on the stripping film with the inner face of the polystyrene resin film of film, and making is suppressed quick adhesion type printing and used pressure sensitive adhesion sheet with pressure sensitive adhesion sheet and exfoliated again printing.
(embodiment 2)
In (2) of embodiment 1, making the glue spread of aqueous dispersion type coating agent (cooperating 1) is 0.4g/m
2(dry back), in addition, use with embodiment 1 identical method make printing with film, suppress quick adhesion type printing and reach exfoliated again printing with pressure sensitive adhesion sheet and use pressure sensitive adhesion sheet.
(embodiment 3)
In (2) of embodiment 1, making the glue spread of aqueous dispersion type coating agent (cooperating 1) is 0.6g/m
2(dry back), in addition, use with embodiment 1 identical method make printing with film, suppress quick adhesion type printing and reach exfoliated again printing with pressure sensitive adhesion sheet and use pressure sensitive adhesion sheet.
(embodiment 4～9)
In (1) of embodiment 1, preparation contains the cooperation 2 shown in the table 1 or cooperates the aqueous dispersion type coating agent of 3 gradation composition (cooperating 2) or aqueous dispersion type coating agent (cooperating 3) replaces cooperating 1; In (2) of embodiment 1, make the glue spread 0.2g/m of being as shown in table 2 of aqueous dispersion type coating agent (cooperating 1)
2(dry back), 0.4g/m
2(dry back) or 0.6g/m
2(dry back), in addition, use with embodiment 1 identical method make printing with film, suppress quick adhesion type printing and reach exfoliated again printing with pressure sensitive adhesion sheet and use pressure sensitive adhesion sheet.
(embodiment 10～12)
In (2) of embodiment 1; Use replaces polystyrene resin film (PS) by the film (PC-PS mixture) of hybrid resin (mixing quality was than 1: the 1) formation of ABS resin film (ABS), polycarbonate resin adipose membrane (PC) or polycarbonate resin-polystyrene resin; In addition, use with embodiment 1 identical method make printing with film, suppress quick adhesion type printing and reach exfoliated again printing with pressure sensitive adhesion sheet and use pressure sensitive adhesion sheet.
(comparative example 1～3)
In (1) of embodiment 1; Preparation contains the cooperation 4 shown in the table 1, cooperate 5 or cooperate aqueous dispersion type coating agent (cooperating 4), aqueous dispersion type coating agent (cooperating 5) or the aqueous dispersion type coating agent (cooperating 6) of 6 gradation composition to replace cooperating 1; In addition, use and make printing with embodiment 1 identical method and use film.
Method with shown in following is estimated the adaptation and the printing adaptation of storage modulus, film base material and the coating agent layer of the dynamic viscoelastic spectrum of coating agent layer.Its result is shown in table 1～4.
(1) mensuration of the storage modulus of the dynamic viscoelastic spectrum of coating agent layer and loss tangent
The aqueous dispersion type coating agent that contains acrylic copolymer that will in embodiment and comparative example, obtain is coated on the surface of stripping film, and drying is 2 minutes under 90 ℃, and the coating agent layer is peeled from stripping film, processes the coating agent layer of thickness 20 μ m.With the coating agent layer that obtains cut into wide 8mm, measured length 20mm processes sample; Use Measurement of Dynamic Viscoelasticity device (TA イ Application ス Star Le メ Application Star corporate system; Device name " DMA Q800 "), through the stretching assay method, under the condition of frequency 11Hz, amplitude 5 μ m, 3 ℃/min of heat-up rate; Measure-30 ℃～100 ℃ storage modulus and loss tangent, read the storage modulus under 10 ℃, 30 ℃, 50 ℃.
(2) mensuration of the temperature at the loss tangent raising peak of dynamic viscoelastic spectrum
The chart of the loss tangent that from above-mentioned (1), obtains reads the temperature at protruding peak.
(3) evaluation of the adaptation of film base material and coating agent layer
It is the wide chessboard trellis of 1mm that the coating agent laminar surface that will in embodiment and comparative example, obtain is drawn lattice; Drawing lattice at this quilt is that tessellated coating agent laminar surface is pasted sealing tape (ニ チ Application バ Application corporate system; Trade(brand)name " セ ロ テ one プ "); Carry out セ ロ テ one プ stripping test according to the checker adhesive tape method of JISK5600-5-6 (cross-hatching), the adaptation of film base material and coating agent layer is estimated according to following benchmark.
0: the cutting-up edge is level and smooth fully, and all grid eyes all do not peel off.
1: slight the peeling off of filming in cutting-up point of crossing.Affected part is no more than 5% clearly in drawing the lattice part.
2: film and peel off along the cutting-up edge and/or at a stroke lattice point.Affected part surpasses 5% but be no more than 15% clearly in drawing the lattice part.
3: film along cutting-up edge section ground or whole ground produce big peel off and/or the each several part of eye partly or whole ground peel off.Affected part surpasses 15% but be no more than 35% clearly in drawing the lattice part.
4: film along cutting-up edge section ground or whole ground produces big peel off and/or many places eye portion ground or whole ground peel off.Affected part surpasses 35% but be no more than 65% clearly in drawing the lattice part.
5: the degree of peeling off surpasses the situation of classification 4.
(4) evaluation of the printing adaptation of coating agent layer
In the surface coated aqueous dispersion type coating agent of film base material, drying is 2 minutes under 70 ℃, processes the coating agent layer.The surface coated printing of layer solidifies China ink with ultraviolet hardening China ink (TOKA UV101 China ink) thereby carry out uviolizing in the coating agent, forms the printed layers of thickness 0.5 μ m.It is the wide chessboard eye shape of 1mm that lattice are drawn on the printed layers surface; At this stroke lattice is that sealing tape (ニ チ バ Application society system is sticked on the surface of the printed layers of chessboard eye shape; Trade(brand)name " セ ロ テ one プ "); Carry out セ ロ テ one プ stripping test according to the checker adhesive tape method of JIS K5600-5-6 (cross-hatching), the printing adaptation of coating agent layer is estimated according to following benchmark.
0: the cutting-up edge is level and smooth fully, and all grid eyes all do not peel off.
1: slight the peeling off of filming in cutting-up point of crossing.Clearly be no more than 5% in stroke affected part of lattice part.
2: film and peel off along the cutting-up edge and/or at a stroke lattice point.Affected part clearly surpasses 5% but be no more than 15% in drawing the lattice part.
3: film along cutting-up edge section ground or whole ground produce big peel off and/or the each several part of lattice eye partly or whole ground peel off.Affected part clearly surpasses 15% but be no more than 35% in drawing the lattice part.
4: film along cutting-up edge section ground or whole ground produces big peel off and/or many places eye portion ground or whole ground peel off.Affected part clearly surpasses 35% but be no more than 65% in drawing the lattice part.
5: the degree of peeling off surpasses the situation of classification 4.
[table 1]
Need to prove that in above-mentioned table 1, the use level of gradation composition is represented with mass parts.
[table 2]
[table 3]
[table 4]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Film base material | PS | PS | PS |
| The coating agent cooperates | 4 | 5 | 6 |
| Coating agent glue spread (g/m 2) | 0.2 | 0.2 | 0.2 |
| The film base material adaptation | 5 | 5 | 0 |
| The printing adaptation | 3 | 3 | 2 |
(5) stripping test
As clung body; Prepare following 4 kinds of films: polystyrene resin film (オ one ジ one Co., Ltd.'s system; Trade(brand)name " Ha イ ス チ レ Application PS 65 ", thickness 65 μ m), ABS resin film (Shin-Estu Polymer Co., Ltd.'s system, trade(brand)name " PSZ980 "; Thickness 80 μ m), polycarbonate resin adipose membrane (Supreme Being people's corporate system; Trade(brand)name " ピ ユ ア エ one ス C-110-100 ", thickness 100 μ m), the film (thickness 100 μ m) that constitutes by the hybrid resin (PC-PS, mixing quality ratio 1: 1) of polycarbonate resin-polystyrene resin.This film is fixed in plate as clung body.
At room temperature; Make printing that the band that in embodiment 1～12, obtains suppresses quick adhesion type and exfoliated again pressure sensitive adhesive layer with the printing that has pressure sensitive adhesive layer of the film base material resin of the film combination identical with the resin of formation clung body with film and clung body stickup; Then, 60 ℃, the environment held of 95%RH 7 days, then; Return to room temperature, the band printing of suppressing quick adhesion type and exfoliated again pressure sensitive adhesive layer does not as a result all occur floating with film and is attached to clung body with peeling off.In addition, for band again the printing of exfoliated pressure sensitive adhesive layer use film, at room temperature when clung body is peeled off, do not have pasty state residual on the clung body surface.
Utilizability in the industry
Printing of the present invention can be attached to the various clung bodies such as resin system cabinet of household appliances and electronics with film.
Claims (6)
1. the aqueous dispersion type coating agent is used in printing; It is the aqueous dispersion type coating agent that comprises acrylic copolymer; Said acrylic copolymer obtains for the monomer mixture that will comprise ethyl propenoate, TEB 3K and NSC 20956 carries out letex polymerization, with this aqueous dispersion type coating agent coating, dry and coating agent layer that obtain is 5.0 * 10 under 10 ℃ at the storage modulus of the dynamic viscoelastic spectrum under the 11Hz
5Pa is above, be 1.0 * 10 under 30 ℃
5Pa～5.0 * 10
6Pa, be 8.0 * 10 under 50 ℃
3Pa～5.0 * 10
5Pa, and the temperature at the loss tangent raising peak of dynamic viscoelastic spectrum is 30 ℃～80 ℃.
2. the aqueous dispersion type coating agent is used in the described printing of claim 1, in monomer mixture, also comprises the cationic acrylic monomer.
3. film is used in printing; It is that claim 1 or 2 described printings are coated the film base material surface with the aqueous dispersion type coating agent and film is used in the printing that obtains; It is characterized in that, aqueous dispersion type coating agent coating, dry and coating agent layer that obtain is 5.0 * 10 at the storage modulus of the dynamic viscoelastic spectrum under the 11Hz is used in this printing under 10 ℃
5Pa is above, be 1.0 * 10 under 30 ℃
5Pa～5.0 * 10
6Pa, be 8.0 * 10 under 50 ℃
3Pa～5.0 * 10
5Pa, and the temperature at the loss tangent raising peak of dynamic viscoelastic spectrum is 30 ℃～80 ℃.
4. film is used in the described printing of claim 3, and said film base material comprises polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate resin or the mixture more than 2 kinds in them.
5. film is used in claim 3 or 4 described printings, and said being printed as used the black printing of ultraviolet hardening.
6. film is used in each described printing in the claim 3～5, is provided with pressure sensitive adhesive layer at the inner face of said film base material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-003654 | 2011-01-12 | ||
| JP2011003654A JP2012144632A (en) | 2011-01-12 | 2011-01-12 | Water dispersion-type coating agent for printing, and printing film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604504A true CN102604504A (en) | 2012-07-25 |
| CN102604504B CN102604504B (en) | 2016-09-07 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210008255.3A Active CN102604504B (en) | 2011-01-12 | 2012-01-12 | Printing water decentralized smears and printing film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2012144632A (en) |
| CN (1) | CN102604504B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112373214A (en) * | 2020-09-17 | 2021-02-19 | 上海当纳利印刷有限公司 | Glue film mixture for ink-jet proofing and film coating scheme |
Citations (5)
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| JPH11158453A (en) * | 1997-11-27 | 1999-06-15 | Sekisui Chem Co Ltd | Pressure-sensitive acrylic adhesive composition and pressure-sensitive processed article |
| US20090123746A1 (en) * | 2007-11-12 | 2009-05-14 | Lintec Corporation | Adhesive sheet |
| US20090286933A1 (en) * | 2007-11-02 | 2009-11-19 | Nippon Shokubai Co., Ltd. | Emulsion for vibrating damping materials |
| CN101717467A (en) * | 2009-11-18 | 2010-06-02 | 北京高盟化工有限公司 | Aqueous acrylic emulsion, aqueous adhesive for pearlized film composite materials and preparation method thereof |
| US20100316872A1 (en) * | 2007-07-31 | 2010-12-16 | Yorinobu Takamatsu | Adhesive film, production methods of shaped body |
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2011
- 2011-01-12 JP JP2011003654A patent/JP2012144632A/en active Pending
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2012
- 2012-01-12 CN CN201210008255.3A patent/CN102604504B/en active Active
Patent Citations (5)
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|---|---|---|---|---|
| JPH11158453A (en) * | 1997-11-27 | 1999-06-15 | Sekisui Chem Co Ltd | Pressure-sensitive acrylic adhesive composition and pressure-sensitive processed article |
| US20100316872A1 (en) * | 2007-07-31 | 2010-12-16 | Yorinobu Takamatsu | Adhesive film, production methods of shaped body |
| US20090286933A1 (en) * | 2007-11-02 | 2009-11-19 | Nippon Shokubai Co., Ltd. | Emulsion for vibrating damping materials |
| US20090123746A1 (en) * | 2007-11-12 | 2009-05-14 | Lintec Corporation | Adhesive sheet |
| CN101717467A (en) * | 2009-11-18 | 2010-06-02 | 北京高盟化工有限公司 | Aqueous acrylic emulsion, aqueous adhesive for pearlized film composite materials and preparation method thereof |
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|---|---|---|---|---|
| CN112373214A (en) * | 2020-09-17 | 2021-02-19 | 上海当纳利印刷有限公司 | Glue film mixture for ink-jet proofing and film coating scheme |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604504B (en) | 2016-09-07 |
| JP2012144632A (en) | 2012-08-02 |
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