CN102604504B - Printing water decentralized smears and printing film - Google Patents
Printing water decentralized smears and printing film Download PDFInfo
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- CN102604504B CN102604504B CN201210008255.3A CN201210008255A CN102604504B CN 102604504 B CN102604504 B CN 102604504B CN 201210008255 A CN201210008255 A CN 201210008255A CN 102604504 B CN102604504 B CN 102604504B
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Abstract
The present invention provides printing water decentralized smears and the printing film using it to manufacture, described printing water decentralized smears can form film base material and coating oxidant layer has the adaptation of excellence and the coating oxidant layer of the adaptation also excellence of ultraviolet hardening ink.Printing water decentralized smears and the printing film using it to manufacture are provided, described printing water decentralized smears comprises the acrylic acid series copolymer monomer mixture comprising ethyl acrylate, methyl methacrylate and butyl methacrylate being carried out emulsion polymerization and obtain, it is characterized in that, by this water-dispersion type coating agent, be dried and the storage modulus of the coating oxidant layer that the obtains dynamic viscoelastic spectrum under 11Hz is 5.0 × 10 at 10 DEG C5More than Pa, it is 1.0 × 10 at 30 DEG C5～5.0 × 106Pa, at 50 DEG C 8.0 × 103～5.0 × 105Pa, and the temperature at protruding peak is 30 DEG C～80 DEG C in the loss angle tangent of dynamic viscoelastic spectrum.
Description
Technical field
The present invention relates to printing water decentralized smears and printing film, specifically, relate to
The printing water decentralized smears and the printing that can be used for the film base material of poor solvent resistance are used
Film.
Background technology
All the time, use has the printing film of various film base material to be used in every field.Entering
In the case of row printing ink uses the printing having ultraviolet hardening black, ultraviolet hardening
Ink is poor to the adaptation on film base material surface, therefore, in order to improve the closely sealed of ultraviolet hardening ink
Property, need the surface configuration at film base material to be coated with oxidant layer.
As the conventional smears for arranging coating oxidant layer, it is known to aqueous coating or molten
, although aqueous coating is preferred in terms of environment, but there is film base material and coating in agent system smears
The problem that the adaptation of oxidant layer is insufficient etc, therefore, is used mostly solvent system smears.
On the other hand, in recent years, from the viewpoint of saving resource, carrying out recovery and using
Household electrical appliances and the resin-made cabinet of electronic equipment carry out pulverizing and the recycling that recycles.
Surface base for the pressure sensitive adhesion sheet of the resin-made cabinet for household electrical appliances and electronic equipment
Material, in order to be directly adhered to cabinet and recycle, it is desirable to it is the material identical with cabinet
Matter.
Therefore, these surface substrates generally use polystyrene resin, acrylonitrile-butadiene-benzene
The film of ethylene copolymer resin, polycarbonate resin etc. is (with reference to patent document 1.).
But, the poor solvent resistance of these resin moldings, therefore exist and solvent system can not be used to be coated with
The problem of agent.
Patent document 1: Japanese Unexamined Patent Publication 11-237840 publication
Summary of the invention
The problem that invention is to be solved
The present invention is the situation in view of above-mentioned prior art and completes, and its object is to, it is provided that
Printing water decentralized smears and employ it manufacture printing film, described printing water divides
Scattered type smears can form film base material and coating oxidant layer has excellent adaptation and ultraviolet
The coating oxidant layer of the adaptation of curing type ink also excellence.
For solving the means of problem
The present inventor finds to solve above-mentioned problem, by making coating oxidant layer moving under 11Hz
The storage modulus of state Viscoelastic Spectral is specific scope, and makes the loss angle of dynamic viscoelastic spectrum
On the tangent of angle, protruding peak is in specific scope, can solve above-mentioned problem, wherein, described coating
Oxidant layer is to be coated with the water-dispersion type smears comprising acrylic acid series copolymer and be dried and obtain
, described acrylic acid series copolymer is the monomer mixture by comprising specific acrylic monomer
Carry out emulsion polymerization and obtain, complete the present invention based on above-mentioned opinion knowledge.
That is, the present invention provides printing water decentralized smears, and it is for comprising acrylic copolymer
The water-dispersion type smears of thing, described acrylic acid series copolymer will be for will comprise ethyl acrylate, first
The monomer mixture of base methyl acrylate and butyl methacrylate carries out emulsion polymerization and obtains,
By this water-dispersion type coating agent, it is dried and the coating oxidant layer that obtains dynamically gluing under 11Hz
The storage modulus of elastic spectrum is 5.0 × 10 at 10 DEG C5More than Pa, be 1.0 at 30 DEG C ×
105Pa～5.0 × 106Pa, it is 8.0 × 10 at 50 DEG C3Pa～5.0 × 105Pa, and dynamically
On the loss angle angle tangent of Viscoelastic Spectral, the temperature at protruding peak is 30 DEG C～80 DEG C.
It addition, the present invention provides printing water decentralized smears, wherein at above-mentioned printing water
In decentralized smears, monomer mixture also comprises cationic acrylic monomer.
It addition, the present invention provides printing film, it is by above-mentioned printing water decentralized smears
The printing film coating film base material surface and obtain, is characterised by, is disperseed by this printing water
Type coating agent, it is dried and the storage of the coating oxidant layer that the obtains dynamic viscoelastic spectrum under 11Hz
Can modulus be 5.0 × 10 at 10 DEG C5More than Pa, it is 1.0 × 10 at 30 DEG C5Pa～5.0 ×
106Pa, it is 8.0 × 10 at 50 DEG C3Pa～5.0 × 105Pa, and the damage of dynamic viscoelastic spectrum
On the tangent of consumption angle, angle, the temperature at protruding peak is 30 DEG C～80 DEG C.
It addition, the present invention provides the printing film of foregoing invention, in the most above-mentioned printing film,
Above-mentioned film base material comprise polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin,
Polycarbonate resin or the mixture of more than two kinds in them.
It addition, the present invention provides printing film, in above-mentioned printing film, above-mentioned printing is for using
The printing of ultraviolet hardening ink.
It addition, the present invention provides printing film, in above-mentioned printing film, at above-mentioned film base material
Inner face is provided with pressure sensitive adhesive layer.
The printing water decentralized smears of the present invention can form film base material and coating oxidant layer has
The coating oxidant layer of the adaptation of excellent adaptation and ultraviolet hardening ink also excellence.
Detailed description of the invention
The printing water decentralized smears of the present invention is comprise acrylic acid series copolymer water-dispersible
Type smears, described acrylic acid series copolymer will be for will comprise ethyl acrylate, methyl methacrylate
The monomer mixture of ester and butyl methacrylate carries out emulsion polymerization and obtains.
Acrylic acid series copolymer is will to comprise ethyl acrylate, methyl methacrylate and methyl-prop
The monomer mixture of olefin(e) acid butyl ester carries out emulsion polymerization and obtains, but with regard in monomer mixture
For the content ratio of each monomer, relative to the total amount of whole monomers, ethyl acrylate is preferably
10～35 mass %, more preferably 12～30 mass %；Methyl methacrylate be preferably 15～
50 mass %, more preferably 20～35 mass %；And butyl methacrylate is preferably 15～40
Quality %, more preferably 25～35 mass %.It is above-mentioned by the content ratio making these each monomers
Scope, can make film base material and the excellent adhesion of coating oxidant layer, alternatively, it is also possible to make coating
Oxidant layer and the excellent adhesion of ultraviolet hardening ink.
It should be noted that can be containing other copolymerizable monomer in above-mentioned monomer mixture.
As other copolymerizable monomer, can enumerate: methyl acrylate, propyl acrylate, third
Olefin(e) acid butyl ester, Hexyl 2-propenoate, lauryl acrylate, EMA, metering system
Propyl propionate, hexyl methacrylate, lauryl methacrylate etc. (wherein, remove acrylic acid second
Ester, methyl methacrylate, butyl methacrylate.) carbon atom of alkyl of alkylester moieties
Number is (methyl) alkyl acrylate of 1～20；With acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-
Hydroxypropyl acrylate, acrylic acid-3-hydroxypropyl acrylate, acrylic acid-3-hydroxy butyl ester, acrylic acid-4-hydroxy butyl ester, first
Base acrylic acid-2-hydroxyl ethyl ester, Hydroxypropyl methacrylate, methacrylic acid-3-hydroxypropyl acrylate,
The alkyl of the alkylester moieties such as methacrylic acid-3-hydroxy butyl ester, methacrylic acid-4-hydroxy butyl ester
Carbon number is that (methyl) alkyl acrylate etc. of the hydroxyl of 1～10, preferably the latter are containing hydroxyl
(methyl) alkyl acrylate of base.These copolymerizable (methyl) alkyl acrylates or containing hydroxyl
The content ratio of (methyl) alkyl acrylate of base is relative to the total amount of whole monomers, the most excellent
Elect 1～20 mass %, more preferably 5～15 mass % as.
Additionally, it is preferred that make in above-mentioned monomer mixture containing copolymerizable cationic acrylic compounds
Monomer or there is the acrylic monomer of acetoacetyl.These monomers can improve and film base material
Adaptation, furthermore it is possible to improve and the adaptation of ink.Particularly cationic acrylic compounds list
Body can improve and the adaptation of ink further.
As cationic acrylic monomer, such as, can preferably enumerate: there is quaternary ammonium salt root
And/or the vinyl monomer of tertiary amino, particularly preferred dimethylaminoethyl methacrylate, enter
One step preferred cationic acrylic monomer and the acrylic monomer two with acetoacetyl
Person also uses.
As having the acrylic monomer of acetoacetyl, such as, can preferably enumerate: propylene
Acid acetoacetoxy groups methyl esters, acetoacetoxyethyl methyl esters, acrylic acid acetyl second
Acyloxy ethyl ester, acetoacetoxyethyl methacrylate etc., particularly preferred methacrylic acid
Acetoacetoxyethyl.
Cationic acrylic monomer or there is the containing of acrylic monomer of acetoacetyl
Ratio relative to the total amount of whole monomers, be respectively preferably 0.1～20 mass %, more preferably 3～
10 mass %.
And with cationic acrylic monomer and the acrylic monomer with acetoacetyl
In the case of, both be preferably by quality ratio containing ratio 1: 5～5: 1 scope, more
It is preferably the scope of 1: 2～2: 1.
In the present invention, aforesaid propylene acid based copolymer is polymerized by emulsion and obtains.Breast
Liquid polymerization can be carried out by various emulsion polymerizations, but general emulsion polymerization.
Specifically, such as can enumerate following method: in reactor add comprise ethyl acrylate,
The monomer of methyl methacrylate and butyl methacrylate and other monomer as required mixes
Compound, and then put into surfactant, polymerization initiator etc., internal with non-active gas such as nitrogen
After portion replaces, under reflux, with water for decentralized medium warming while stirring, 40～
The temperature range of about 100 DEG C carries out emulsion and is polymerized about 1～8 hour.
The emulsion polymerization of above-mentioned monomer mixture can be carried out in the presence of surfactant, but makees
For surfactant, preferred cationic surfactant.
As cationic surfactant, such as, can enumerate: cetyl trimethyl chlorination
The alkyl trimethyl chlorinations such as ammonium, lauryl trimethyl ammonium chloride, OTAC
Ammonium；Varisoft 432PPG, bis-lauryl alkyl dimethyl ammonium chloride, double octadecyl
The Dialkyl dimethyl ammonium chlorides such as alkyl dimethyl ammonium chloride；Benzalkonium chloride (benzalkonium
Chloride) etc..Surfactant can be used alone a kind, it is also possible to is applied in combination 2 kinds
Above.
The mixing ratio of surfactant is not particularly limited, but relative to the total amount of whole monomers,
It is preferably generally 0.001～1.0 mass %, more preferably 0.005～0.05 mass %.
The emulsion polymerization of above-mentioned monomer mixture can be carried out in water-medium, but is situated between as water system
Matter, can enumerate: water, comprise the water etc. of a small amount of organic solvent, and preferably water, more preferably ion are handed over
Change water.
In the water-dispersion type smears of the present invention, in order to make acrylic copolymer by crosslinking agent
Thing cross-links, and preferably coordinates crosslinking agent.By coordinating crosslinking agent can improve the intensity of coating oxidant layer.
As the crosslinking agent for cross-linked acrylic acid based copolymer, preferably epoxy crosslinking agent.Make
For epoxy crosslinking agent, it is possible to use such as: neopentylglycol diglycidyl ether, polyethylene glycol
Diglycidyl ether, bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, adjacent benzene two
Formic acid 2-glycidyl ester, dimer acid diglycidyl ether, triglycidyl isocyanurate,
Two T 55s, trimethylolpropane polyglycidylether, D-sorbite four shrink
Glycerin ether, N, N, N ', N '-four glycidyl group m-xylene diamine, 1,3-is double, and (N, N-bis-contracts
Water glyceryl amino methyl) hexamethylene, N, N, N ', N '-four glycidyl group diamino-diphenyl
The epoxy crosslinking agents such as methane.
Crosslinking agent can be used singly or in combination of two or more.
Relative to acrylic acid series copolymer 100 mass parts for the consumption of crosslinking agent, it is preferably
0.01～5 mass parts, more preferably 0.1～3 mass parts.
The water-dispersion type smears of the present invention, except aforesaid propylene acid based copolymer and as required
Outside other compositions such as contained crosslinking agent, possibly together with water-medium.
The water system that this water-medium is used when can be polymerized by acrylic acid series copolymer emulsion is situated between
Matter, it is also possible to for other water-medium.In order to be replaced into water-medium when being polymerized with emulsion
Different water-mediums, can be by separating from the emulsion polymer fluid of acrylic acid series copolymer
After going out acrylic acid series copolymer, the acrylic acid series copolymer separated is made to be dispersed in other water system
Medium is carried out.
The content regulation of the water-medium in the water-dispersion type smears of the present invention can pass through water system
The removing of medium or add etc. is carried out.
Containing of the resin solid content such as the acrylic acid series copolymer of the water-dispersion type smears of the present invention
Proportional preferably 0.5～10 mass %, more preferably 1～7 mass %.
In the water-dispersion type smears of the present invention, scattered acrylic acid series copolymer particle is average
Particle diameter is preferably 10～500nm, more preferably 50～300nm.Acrylic acid series copolymer particle
Average grain diameter within the range time, the excellent adhesion of coating oxidant layer and film base material can be made.
It addition, in the water-dispersion type smears of the present invention, in order to improve lubricity or obtain nothing
Light sensation, can coordinate the various filler such as organic filler, inorganic filler.
As organic filler, can enumerate: polystyrene resin, acrylonitrile-butadiene-benzene second
Alkene copolymer resin (ABS resin), polycarbonate resin or the resin-oatmeal of their mixture etc.
End etc..
As inorganic filler, can enumerate: the inorganic oxide such as silica, aluminum oxide；Gold
The metal powder such as powder, silver powder etc..
In the present invention, it is coated with above-mentioned water-dispersion type smears and is dried and the coating that obtains
The storage modulus of oxidant layer dynamic viscoelastic spectrum under 11Hz is 5.0 × 10 at 10 DEG C5Pa with
Above, 8.0 × 10 it are preferably5～3.0 × 106Pa, is 1.0 × 10 at 30 DEG C5～5.0 × 106Pa、
It is preferably 1.2 × 105～2.5 × 106Pa, is 8.0 × 10 at 50 DEG C3～5.0 × 105Pa、
It is preferably 1.0 × 104～4.0 × 105Pa.By make storage modulus in these scopes, can be with shape
Film base material and coating oxidant layer is become to have adaptation and the adaptation of ultraviolet hardening ink of excellence
Also excellent coating oxidant layer.When storage modulus is less than these scopes, the cohesiveness of smears becomes
Insufficient, sometimes cause the cohesional failure of coating oxidant layer, when storage modulus exceedes these scopes,
Being become by film-strength of coating oxidant layer is superfluous, and the adaptation of coating oxidant layer and ink may reduce.
It should be noted that storage modulus measures according to JIS K7244-4.
In the present invention, in the painting being coated with above-mentioned water-dispersion type smears and be dried and obtain
On the loss angle angle tangent of the dynamic viscoelastic spectrum of cloth oxidant layer the temperature at protruding peak be 30 DEG C～
80 DEG C, preferably 40 DEG C～75 DEG C.When the temperature at protruding peak is less than above-mentioned scope, smears
Cohesiveness becomes insufficient, may cause the cohesional failure of coating oxidant layer, on the contrary, exceed
When stating scope, being become by film-strength of coating oxidant layer is superfluous, and the adaptation of coating oxidant layer and ink can
Can be able to reduce.
The printing film of the present invention is at film base material by above-mentioned printing water decentralized coating agent
Surface and obtain.
For above-mentioned printing water decentralized smears in the coating weight of film base material, it is often preferred that
0.01～5g/m2, more preferably 0.05～2g/m2。
As film base material, it is possible to use various plastic foils.As the object lesson of film base material, can
Enumerate such as: the vistanex such as polyvinyl resin, acrylic resin；Poly terephthalic acid second
Terephthalate resin, PEN resin, polybutylene terephthalate (PBT) resin
In polyester resin；Corvic, polystyrene resin, acrylonitrile-butadiene-styrene (ABS)
Copolymer resin (ABS resin), polycarbonate resin, polyamide, polyimide resin,
The film of the various synthetic resin such as the mixture of more than two kinds in fluorine resin and these resins or this
Stacked films more than of the same race or the most of the same race 2 layer of a little films, particularly preferably uses and household appliances
The material that the resin-phase used in resin-made cabinet with electronic equipment is same.As these film bases
Material, can enumerate by polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS
Resin), the film that constitutes of polycarbonate resin or the mixture of more than two kinds in them.
The thickness of film base material is not particularly limited, but preferably generally 10～350 μm, more preferably
It is 15～300 μm, particularly preferably 20～250 μm.
As the coating process in the above-mentioned printing water decentralized smears of film base material coating, such as
Can enumerate: bar type rubbing method, scraper plate rubbing method, print roll coating method, scraper for coating method, mould
The known methods such as pressure rubbing method.
It is dried and generally preferably carries out at 60～130 DEG C, more preferably carry out at 80～120 DEG C.
Drying time is not particularly limited, and within usual 10 seconds～5 minutes, is sufficient for.
For the printing film of the present invention, the preferably inner face at film base material arranges contact adhesive
Layer.By arranging pressure sensitive adhesive layer, can easily be pasted onto household electrical appliances and electronic equipment etc.
On resin-made cabinet.
For the inner face of film base material, in order to improve the closing force with pressure sensitive adhesive layer further,
Easy adhesion process can be implemented.As easy adhesion process, it is not particularly limited, such as, can lift
Go out Corona discharge Treatment etc..
As the adhesive for pressure sensitive adhesive layer, it is possible to use various contact adhesives.Make
For the object lesson of contact adhesive, such as, can enumerate: natural rubber system contact adhesive,
Synthetic rubber system contact adhesive, acrylic resin system contact adhesive, polyvingl ether tree
Fat system contact adhesive, polyurethane resin system contact adhesive, the pressure-sensitive adhesion of organic siliconresin system
Agent etc., preferably enumerate acrylic resin contact adhesive, rubber series contact adhesive, organic
Silicones system contact adhesive etc..It addition, contact adhesive can be solvent-borne type contact adhesive,
Can also be water type contact adhesive, it is also possible to for suppressing quick adhesion type, the most exfoliated pressure-sensitive
Any one in adhesive.
Alternatively, it is also possible to arrange stripping on the face with opposition side, base material film side of pressure sensitive adhesive layer
From sheet.
As stripping film, it is not particularly limited.As the base material of stripping film, such as, can enumerate:
Paper, synthetic paper, synthetic resin film etc..As paper, such as, can enumerate: wood-free
The paper base materials such as paper, glassine paper, art paper；At these paper base material laminated polyethylene, polypropylene etc.
The paper base material of the laminated paper of thermoplastic resin etc and with cellulose, starch, polyvinyl alcohol,
The paper of wood-free, glassine paper, art paper etc. are filled out by acrylic-styrene resins etc.
The paper base material etc. that seam processes.As plastic synthetic resin film, such as, can enumerate by poly-second
The vistanex such as olefine resin, acrylic resin, polybutylene terephthalate (PBT) resin, poly-
Film that the polyester resin such as ethylene glycol terephthalate resin is constituted and real to these synthetic resin films
Execute the film etc. of easy adhesion process, be preferably coated with the film of remover at these films.
For remover, can enumerate fluorine resin, silicon-type resin, containing chain alkyl
Carbamate etc..
The printing ink used to carry out printing in the coating oxidant layer of the printing film of the present invention
The various ink such as ultraviolet hardening ink can be used.As ultraviolet hardening ink, can use various
Ultraviolet hardening ink, but optimization polypropylene acid esters system ultraviolet hardening ink.
The printing film of the present invention can be used as the base material film of the pressure sensitive adhesion sheet of printing, its purposes
Do not limit, but can be especially useful for being recycled by clung body and carrying out the purposes recycled.
The base material film of the printing pressure sensitive adhesion sheet of the present invention preferably applies the material at film base material
In the case of identical with the material constituting clung body.
As constitute clung body material, can enumerate by polystyrene resin, ABS resin,
The clung body that polycarbonate resin or the mixture of more than two kinds in them are constituted is as specifically
Example.
The shape of clung body is not particularly limited, and can make variously-shaped.
Embodiment
Below, by embodiment, the present invention is carried out more specific description.It should be noted that
The present invention is not by any restriction of these examples.
(embodiment 1)
(1) preparation of water-dispersion type smears
In advance by ion exchange water 75.9 mass parts, lauryl trimethyl ammonium chloride in beaker
(Kao Corp's system, trade name " U one タ ミ Application 24P ", solid constituent 27 mass %) 3.7
Mass parts, ethyl acrylate 24 mass parts, methyl methacrylate 24 mass parts, methyl-prop
Olefin(e) acid butyl ester 32 mass parts, dimethylaminoethyl methacrylate 5 mass parts, metering system
Acid acetoacetoxyethyl 5 mass parts and HEMA 10 mass parts coordinate,
Homomixer is used to be stirred making monomer mixture.
In the reaction unit being provided with agitator, reflux condenser, thermometer, nitrogen ingress pipe,
Put into ion exchange water 67.9 mass parts, be warming up to 70 DEG C, at 70 DEG C, add as poly-
Closing the 2 of initiator, 2-azo two (2-amino two propane) dihydrochloride is (with Wako Pure Chemical Industries strain formula
Commercial firm's system, trade name " V-50 ") the 10 mass % aqueous solution 2 mass parts, immediately after with 3
Hour drip pre-prepd above-mentioned monomer mixture make it carry out polymerisation.Completion of dropwise addition
After, cure 3 hours at 70 DEG C further, be then cooled to room temperature.After cooling, add ice
Acetic acid 1.2 mass parts, obtains the waterborne cation acrylic acid series for cationic charge of yellow
Copolymer.The solid constituent of this copolymer be 40.0 mass %, viscosity be 300mPa s/30 DEG C,
PH is 4.8, average grain diameter is 150nm.
Relative to solid constituent 100 mass parts of above-mentioned copolymer, add and cross-link as epoxy
The glycerol polyglycidyl ether of agent (Na ガ セ ケ system テ ツク ス Co., Ltd. system, trade name " デ
Na U one Le EX-313 ") 1.0 mass parts, and then be diluted with ion exchange water so that
Solid constituent is 5 mass %, prepares water-dispersion type smears (coordinating 1).
(2) making of printing film
On the surface of polystyrene resin film (thickness 65 μm), so that coating weight is 0.2g/m2(dry
After dry) mode be coated with in above-mentioned (1) the water-dispersion type smears (coordinate 1) obtained, with 70 DEG C
Air drier be dried 2 minutes, make printing film.
(3) with the making of printing film of pressure sensitive adhesive layer
With roll-type scraper plate coating machine, in the way of making respective dried coating thickness be 20 μm,
Quick adhesion type acrylic pressure-sensitive adhesive (リ ンテツク company system, trade name will be suppressed
" PA-T1 ") and the most exfoliated acrylic pressure-sensitive adhesive (リ ンテツク company system, commodity
Name " MF ") (リ ンテツク company system, is shelled with organic siliconresin to be coated on stripping film
From process glassine paper, trade name " SP-8K ア オ ") lift-off processing face on, at 90 DEG C
It is dried 2 minutes, forms pressure sensitive adhesive layer.After drying, the printing made in above-mentioned (2) is used
The inner face of the polystyrene resin film of film pastes the pressure sensitive adhesive layer on stripping film, and making is suppressed
Quick adhesion type printing pressure sensitive adhesion sheet and the most exfoliated printing pressure sensitive adhesion sheet.
(embodiment 2)
In (2) of embodiment 1, the coating weight making water-dispersion type smears (coordinate 1) is
0.4g/m2(after drying), in addition, make printing by method same as in Example 1 and use
Film, suppress quick adhesion type printing pressure sensitive adhesion sheet and the most exfoliated printing pressure sensitive adhesion sheet.
(embodiment 3)
In (2) of embodiment 1, the coating weight making water-dispersion type smears (coordinate 1) is
0.6g/m2(after drying), in addition, make printing by method same as in Example 1 and use
Film, suppress quick adhesion type printing pressure sensitive adhesion sheet and the most exfoliated printing pressure sensitive adhesion sheet.
(embodiment 4～9)
In (1) of embodiment 1, preparation is containing the cooperation 2 shown in table 1 or the cooperation of cooperation 3
Water-dispersion type smears (coordinating 2) or the water-dispersion type smears (coordinating 3) of composition replace coordinating
1；In (2) of embodiment 1, make the coating weight such as table 2 of water-dispersion type smears (coordinating 1)
Shown in be 0.2g/m2(after drying), 0.4g/m2(after drying) or 0.6g/m2(after drying), remove
Outside this, make printing film by method same as in Example 1, suppress quick adhesion type print
Brush pressure sensitive adhesion sheet and the most exfoliated printing pressure sensitive adhesion sheet.
(embodiment 10～12)
In (2) of embodiment 1, use by ABS resin film (ABS), polycarbonate resin adipose membrane
Or hybrid resin (mixing quality ratio 1: the 1) structure of polycarbonate resin-polystyrene resin (PC)
Become film (PC-PS mixture) replace polystyrene resin film (PS), in addition, with reality
Execute the identical method of example 1 to make printing film, to suppress quick adhesion type printing pressure sensitive adhesion sheet
And the most exfoliated printing pressure sensitive adhesion sheet.
(comparative example 1～3)
In (1) of embodiment 1, preparation is containing the cooperation 4 shown in table 1, cooperation 5 or joins
Close the water-dispersion type smears (coordinating 4) of the gradation composition of 6, water-dispersion type smears (coordinating 5)
Or water-dispersion type smears (coordinating 6) replaces cooperation 1, in addition, with same as in Example 1
Method make printing film.
By method shown below to the coating storage modulus of dynamic viscoelastic spectrum of oxidant layer, film base
Material and the adaptation of coating oxidant layer and printing adaptation are evaluated.The results are shown in table 1～
4。
(1) storage modulus and the mensuration of loss angle tangent of the dynamic viscoelastic spectrum of oxidant layer it are coated with
The water-dispersion type containing acrylic acid series copolymer obtained in embodiment and comparative example is coated with
Cloth agent is coated on the surface of stripping film, is dried 2 minutes at 90 DEG C, will be coated with oxidant layer from stripping
Sheet peels, and makes the coating oxidant layer of thickness 20 μm.The coating oxidant layer obtained is cut into wide 8mm,
Measured length 20mm makes sample, uses Measurement of Dynamic Viscoelasticity device (TA イ Application ス Star Le
メ ンツ company system, device name " DMA Q800 "), by stretching determination method, frequency 11Hz,
Under conditions of amplitude 5 μm, 3 DEG C/min of programming rate, measure the energy storage mould of-30 DEG C～100 DEG C
Amount and loss angle tangent, read 10 DEG C, 30 DEG C, storage modulus at 50 DEG C.
(2) mensuration of the temperature at protruding peak in the loss angle tangent of dynamic viscoelastic spectrum
The chart of the loss angle tangent obtained from above-mentioned (1) reads the temperature at protruding peak.
(3) evaluation of the adaptation of film base material and coating oxidant layer
The coating oxidant layer surface obtained in embodiment and comparative example is drawn lattice is chessboard wide for 1mm
Trellis, this by draw lattice be tessellated coating oxidant layer surface mount adhesive tape (ニ チ Application バ Application
Company's system, trade name " セ ロ テ mono-プ "), according to the chess of JISK5600-5-6 (cross-hatching)
Dish lattice adhesive tape method carries out セ ロ テ mono-プ disbonded test, according to following benchmark to film base material and coating
The adaptation of oxidant layer is evaluated.
0: cutting-up edge is the most smooth, all grid eyes the most do not peel off.
1: the film in cutting-up crosspoint has slight peeling.Affected part in drawing lattice part
Clearly less than 5%.
2: film peels off along cutting-up edge and/or drawing lattice point.Impacted drawing in lattice part
Part clearly more than 5% but less than 15%.
3: film is along ground, cutting-up marginal portion or produces each of big peeling and/or eye by entire surface
Part partly or is by entire surface peeled off.In drawing lattice part, affected part exceedes clearly
15% but less than 35%.
4: film is along ground, cutting-up marginal portion or produces big peeling and/or many places eye by entire surface
Partly or by entire surface peel off.Draw in lattice part affected part clearly more than 35% but
Less than 65%.
5: the degree of peeling exceedes the situation of classification 4.
(4) evaluation of the printing adaptation of coating oxidant layer
It is coated with water-dispersion type smears on the surface of film base material, is dried 2 minutes at 70 DEG C, system
Become coating oxidant layer.Surface coating and printing ultraviolet hardening ink (TOKA in coating oxidant layer
UV101 ink), carry out ultraviolet irradiation so that ink solidification, form the printing of thickness 0.5 μm
Layer.Printing layer surface is drawn lattice is chessboard eye wide for 1mm, is chessboard eye at this stroke of lattice
Adhesive tape (ニ チ バ Application society system, trade name " セ ロ テ mono-プ ") is sticked on the surface of printing layer,
Gridiron pattern adhesive tape method according to JIS K5600-5-6 (cross-hatching) carries out セ ロ テ mono-プ and peels off examination
Test, according to following benchmark, the printing adaptation of coating oxidant layer is evaluated.
0: cutting-up edge is the most smooth, all grid eyes the most do not peel off.
1: the film in cutting-up crosspoint has slight peeling.Drawing, the affected part of lattice part is bright
Really less than 5%.
2: film peels off along cutting-up edge and/or drawing lattice point.Impacted drawing in lattice part
Part clearly more than 5% but less than 15%.
3: film is along ground, cutting-up marginal portion or produces big peeling and/or lattice eye by entire surface
Each several part partly or by entire surface peels off.In drawing lattice part, affected part clearly exceedes
15% but less than 35%.
4: film is along ground, cutting-up marginal portion or produces big peeling and/or many places eye by entire surface
Partly or by entire surface peel off.Drawing in lattice part affected part clearly more than 35% but not
More than 65%.
5: the degree of peeling exceedes the situation of classification 4.
[table 1]
It should be noted that in table 1 above, the use level of gradation composition represents with mass parts.
[table 2]
[table 3]
[table 4]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Film base material | PS | PS | PS |
| Smears coordinates | 4 | 5 | 6 |
| Coating agent amount (g/m2) | 0.2 | 0.2 | 0.2 |
| Film base material adaptation | 5 | 5 | 0 |
| Printing adaptation | 3 | 3 | 2 |
(5) disbonded test
As clung body, the following 4 kinds of films of preparation: polystyrene resin film (オ mono-ジ mono-strain formula meeting
Society's system, trade name " Ha イ ス チ レ Application PS 65 ", thickness 65 μm), ABS resin film (letter
More Polymer Company's system, trade name " PSZ980 ", thickness 80 μm), polycarbonate resin adipose membrane
(Di Ren company system, trade name " ピ ユ ア エ mono-ス C-110-100 ", thickness 100 μm),
By polycarbonate resin-polystyrene resin hybrid resin (PC-PS, mixing quality ratio 1:
1) film (thickness 100 μm) constituted.This film is fixed on plate as clung body.
At room temperature, the band obtained in embodiment 1～12 is made to suppress quick adhesion type and peel off
The film base material resin of the printing film of the pressure sensitive adhesive layer of type is same with the resin-phase constituting clung body
The printing film with pressure sensitive adhesive layer of combination and clung body paste, then, 60 DEG C,
Placing in the environment of 95%RH 7 days, then, recover to room temperature, quick adhesion type suppressed by result band
And the printing film of the most exfoliated pressure sensitive adhesive layer does not all occur being attached to floating peeling be glued
Body.It addition, the printing film of pressure sensitive adhesive layer the most exfoliated for band, at room temperature from quilt
When viscous body is peeled off, pasty state is not had to remain on clung body surface.
Industrial utilizability
The printing film of the present invention can be attached to the resin-made cabinet etc. of household appliances and electronic equipment
Various clung bodies.
Claims (5)
1. printing film, is characterised by, it is in film by printing water decentralized coating agent
Substrate surface makes coating weight be 0.01～5g/m2And the printing film obtained, by this printing water
Decentralized coating agent, it is dried and the coating oxidant layer that the obtains dynamic viscoelastic spectrum under 11Hz
Storage modulus be 5.0 × 10 at 10 DEG C5More than Pa, it is 1.0 × 10 at 30 DEG C5Pa～
5.0×106Pa, it is 8.0 × 10 at 50 DEG C3Pa～5.0 × 105Pa, and dynamic viscoelastic
In the loss angle tangent of spectrum, the temperature at protruding peak is 30 DEG C～80 DEG C,
Wherein said printing water decentralized smears comprises acrylic acid series copolymer, described propylene
Acid based copolymer is will to comprise ethyl acrylate 10～35 matter relative to the total amount of whole monomers
Amount %, methyl methacrylate 15～50 mass %, butyl methacrylate 15～40 mass %,
And the monomer mixture of cationic acrylic monomer 0.1～20 mass % carries out emulsion and gathers
Close and obtain,
Described film base material comprises polystyrene resin, acrylonitrile-butadiene-styrene copolymer
Resin, polycarbonate resin or the mixture of more than two kinds in them.
2. the printing film described in claim 1, described cationic acrylic monomer is tool
There is the vinyl monomer of quaternary ammonium salt group and/or tertiary amino.
3. the printing film described in claim 1 or 2, the described sun in described monomer mixture
The content ratio of ionic acrylic monomer is 3～10 matter relative to the total amount of whole monomers
Amount %.
4. the printing film described in claim 1 or 2, described printing is solid for employing ultraviolet
The printing of change type ink.
5. the printing film described in claim 1 or 2, the inner face at described film base material is provided with
Pressure sensitive adhesive layer.
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 |
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| Publication Number | Publication Date |
|---|---|
| CN102604504A CN102604504A (en) | 2012-07-25 |
| CN102604504B true CN102604504B (en) | 2016-09-07 |
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|---|---|---|---|
| CN201210008255.3A Active CN102604504B (en) | 2011-01-12 | 2012-01-12 | Printing water decentralized smears and printing film |
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| JP (1) | JP2012144632A (en) |
| CN (1) | CN102604504B (en) |
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| CN112373214B (en) * | 2020-09-17 | 2022-09-23 | 上海当纳利印刷有限公司 | Film coating method for ink-jet proofing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11158453A (en) * | 1997-11-27 | 1999-06-15 | Sekisui Chem Co Ltd | Pressure-sensitive acrylic adhesive composition and pressure-sensitive processed article |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5367965B2 (en) * | 2007-07-31 | 2013-12-11 | スリーエム イノベイティブ プロパティズ カンパニー | Molded body and manufacturing method thereof |
| JP5485503B2 (en) * | 2007-08-10 | 2014-05-07 | 株式会社日本触媒 | Damping emulsion |
| KR101454183B1 (en) * | 2007-11-12 | 2014-10-27 | 린텍 코포레이션 | Adhesive sheet |
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2011
- 2011-01-12 JP JP2011003654A patent/JP2012144632A/en active Pending
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11158453A (en) * | 1997-11-27 | 1999-06-15 | Sekisui Chem Co Ltd | Pressure-sensitive acrylic adhesive composition and pressure-sensitive processed article |
| 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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| JP2012144632A (en) | 2012-08-02 |
| CN102604504A (en) | 2012-07-25 |
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