CN103847412A - Base film for liquid pressure transfer printing - Google Patents
Base film for liquid pressure transfer printing Download PDFInfo
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- CN103847412A CN103847412A CN201310634762.2A CN201310634762A CN103847412A CN 103847412 A CN103847412 A CN 103847412A CN 201310634762 A CN201310634762 A CN 201310634762A CN 103847412 A CN103847412 A CN 103847412A
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Abstract
The invention relates to a base film for liquid pressure transfer printing. A base film for liquid pressure transfer printing which can form a film for liquid pressure transfer printing that can completely prevent crimp when floating on the liquid level and is high in transfer printing efficiency, and a method for manufacturing the base film are provided. The invention relates to a base film for liquid pressure transfer printing which is composed of polyvinyl alcohol and a surfactant comprising secondary alkyl and a method for manufacturing the base film for liquid pressure transfer printing. The method comprises a process that film-manufacturing original fluid composed of the polyvinyl alcohol and the surfactant comprising the secondary alkyl are used to manufacture the film. In the base film for liquid pressure transfer printing, relative to 100 parts by mass of polyvinyl alcohol, preferably, 0.05-4 parts by mass of the surfactant comprising the secondary alkyl are selected, in addition, the arithmetic mean roughness (Ra) of at least one surface of the base film for liquid pressure transfer printing is preferably below 400nm.
Description
Technical field
The present invention relates to a kind of basement membrane for hydraulic-transfer, its manufacture method, by this hydraulic-transfer base film formed hydraulic-transfer film with use the liquid pressure transfer method of this hydraulic-transfer film, this hydraulic-transfer is used to form the hydraulic-transfer film using in the time that the irregular three-dimensional surface of tool, the transfer printing body such as formed body with curved surface are implemented to printing with basement membrane.
Background technology
As being formed for giving the irregular three-dimensional surface of tool, the surface of formed body with curved surface is with design or improve the method for the printed layers of surface physical property, known use is formed with the method for the hydraulic-transfer film of transfer printing printed layers on the film surface of water-soluble or water-swellable.For example, thus in patent documentation 1, recorded the printing surface that makes hydraulic-transfer film upward and after swimming on the liquid level of the liquid using water as representative, be pressed into as the various formed bodys of transfer printing body and utilize hydraulic pressure printed layers to be transferred to the surperficial method of transfer printing body from the upper side.
In liquid pressure transfer method, curling while importantly preventing from making hydraulic-transfer film swim on liquid level.For example, in patent documentation 2, record, in recent years, the printing of design is multi-sheet printed or when printing ink that useful life longevity is excellent, because hydraulic-transfer causes curling by the design and printing face of film and the water imbibition of non-printing surface generation difference etc., in order to prevent that this is curling, in the time that manufacture hydraulic-transfer is used basement membrane, the face of the opposition side to the face contacting with masking band or masking drum is heat-treated.
Prior art document
Patent documentation
Patent documentation 1: the clear 54-33115 communique of Japanese Patent Laid-Open
Patent documentation 2: Japanese Patent Laid-Open 2009-1009 communique.
Summary of the invention
Invent problem to be solved
But, in the method that patent documentation 2 is recorded, prevent that curling effect from still having deficiency, therefore transfer efficiency is poor.Therefore, the object of this invention is to provide a kind of basement membrane for hydraulic-transfer that can form curling, hydraulic-transfer film that transfer efficiency is excellent can fully prevent from swimming on liquid level time, its manufacture method, by this hydraulic-transfer base film formed hydraulic-transfer film with use the liquid pressure transfer method of this hydraulic-transfer use film.
For solving the means of problem
The inventor has carried out conscientiously research in order to achieve the above object repeatedly, found that, if use the masking stoste that contains polyvinyl alcohol (sometimes " polyvinyl alcohol " being abbreviated as to " PVA " below) and there is the surfactant of secondary alkyl, easily obtain the hydraulic-transfer basement membrane that surface roughness is little, use the hydraulic-transfer that this basement membrane forms to use film in the time of hydraulic-transfer, the inequality of the dissolution velocity on the liquid level of the liquid take water as representative is suppressed, the inequality of print pattern is suppressed, and use and contain PVA and there is hydraulic-transfer that the hydraulic-transfer of surfactant of secondary alkyl forms with basement membrane with in film, curling being subject to while making it swim on liquid level highly suppressed.The inventor further studies repeatedly based on these discoveries, thereby has completed the present invention.
, the present invention relates to:
[1] hydraulic-transfer basement membrane, it contains PVA and the surfactant containing secondary alkyl;
[2] the hydraulic-transfer basement membrane of above-mentioned [1], wherein, with respect to the PVA of 100 mass parts, the surfactant containing secondary alkyl that contains 0.05～4 mass parts;
[3] the hydraulic-transfer basement membrane of above-mentioned [1], wherein, the saponification degree of PVA is 80～98 % by mole;
[4] the hydraulic-transfer basement membrane of above-mentioned [1], the arithmetic mean roughness (Ra) of its at least one face is below 400nm;
[5] manufacture method of basement membrane for hydraulic-transfer, it comprises the operation that uses the masking stoste that contains PVA and contain the surfactant of secondary alkyl to be filmed;
[6] hydraulic-transfer film, it is that the surface of the hydraulic-transfer basement membrane to any one in above-mentioned [1]～[4] is implemented to print and formed;
[7] liquid pressure transfer method, it comprises: make the facing up of enforcement printing of the hydraulic-transfer film of above-mentioned [6] swim in the operation on liquid level; The operation of pressing transfer printing body with the top of film with the hydraulic-transfer from floating.
The effect of invention
By the present invention, can provide a kind of basement membrane for hydraulic-transfer that can form curling, hydraulic-transfer film that transfer efficiency is excellent can fully prevent from swimming on liquid level time, its manufacture method, by this hydraulic-transfer base film formed hydraulic-transfer film with use the liquid pressure transfer method of this hydraulic-transfer use film.
The specific embodiment
Below, the present invention is described in detail.
Hydraulic-transfer of the present invention contains PVA with basement membrane.As this PVA, can use the PVA that the polyvinylesters saponification being obtained by one or more polymerizations of the vinyl esters such as vinyl acetate, vinyl formate, propionate, vinyl butyrate, new vinyl acetate acid, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, methylvinyl acetate is obtained.In above-mentioned vinyl esters, from the complexity of the manufacture of PVA, the viewpoint such as complexity, cost obtaining, preferably vinyl acetate.
Above-mentioned polyvinylesters, the vinyl esters that preferably only uses one or more as monomer and polyvinylesters, more preferably the polyvinylesters that only uses a kind of vinyl esters as monomer and obtain, but as long as not damaging in the scope of effect of the present invention, can be also one or more vinyl esters and can with the copolymer of other monomer of its copolymerization.
As above-mentioned can with other monomer of vinyl esters copolymerization, can exemplify the alpha-olefin of the carbon numbers 2～30 such as such as ethene, propylene, 1-butylene, isobutene; (methyl) acrylic acid or its salt; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl; (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, (methyl) acrylamide derivatives such as N-dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) acrylamide propane sulfonic acid or its salt, (methyl) acrylamide propyl dimethylamine or its salt, N-methylol (methyl) acrylamide or derivatives thereof; The N-vinylamides such as N-vinyl formamide, N-vinyl acetamide, NVP; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers; The vinyl cyanides such as (methyl) acrylonitrile; The vinyl halides such as vinyl chloride, vinylidene chloride, PVF, vinylidene; The allyl compound such as allyl acetate, allyl chloride; Maleic acid or its salt, ester or acid anhydrides; Itaconic acid or its salt, ester or acid anhydrides; The vinyl silanes based compounds such as vinyltrimethoxy silane; Unsaturated sulfonic acid etc.Above-mentioned polyvinylesters can have the construction unit that derives from one or more above-mentioned other monomers.
The construction unit that derives from above-mentioned other monomer in above-mentioned polyvinylesters shared ratio take the molal quantity of entire infrastructure unit that forms polyvinylesters as benchmark, be preferably below 25 % by mole, more preferably below 15 % by mole, more preferably below 5 % by mole.If this ratio is greater than 25 % by mole, the tendency that has the compatibility etc. of hydraulic-transfer basement membrane and printed layers to reduce.
Above-mentioned PVA is as long as damaging in the scope of effect of the present invention, also can by one or more can graft copolymerization monomer modified.As the monomer of this energy graft copolymerization, can exemplify for example unsaturated carboxylic acid or derivatives thereof; Unsaturated sulfonic acid or derivatives thereof; The alpha-olefin of carbon number 2～30 etc.The ratio of the construction unit that derives from monomer that can graft copolymerization in PVA, take the molal quantity of entire infrastructure unit that forms PVA as benchmark, is preferably below 5 % by mole.
A part for the hydroxyl of above-mentioned PVA can be cross-linked also and can not be cross-linked.In addition, a part for the hydroxyl of above-mentioned PVA both can be reacted with the aldehyde compound such as acetaldehyde, butyraldehyde etc. and form ethylidene ether structure, also can not react with these compounds, did not form ethylidene ether structure.
The degree of polymerization of above-mentioned PVA is preferably in 500～3000 scope, more preferably in 700～2800 scope, further preferably in 1000～2500 scope.The degree of polymerization of PVA is lower than in 500 situation, and the hydraulic-transfer of gained is not enough sometimes by the mechanical strength of basement membrane.On the other hand, if the production efficiency when degree of polymerization of PVA higher than 3000, is manufactured hydraulic-transfer basement membrane reduces sometimes, in addition, for hydraulic-transfer, basement membrane, the even water-soluble reduction sometimes of film for hydraulic-transfer, be difficult to carry out hydraulic-transfer with the operation speed of economy.In addition, in this description, the degree of polymerization of said PVA refers to the average degree of polymerization that benchmark records that is recited as with JIS K6726-1994.
The saponification degree of above-mentioned PVA is preferably in the scope of 80～98 % by mole, more preferably in the scope of 83～96 % by mole, further preferably in the scope of 85～90 % by mole.The saponification degree of PVA is lower than in the situation of 80 % by mole, and for hydraulic-transfer, basement membrane, the even water-soluble reduction sometimes of film for hydraulic-transfer, be difficult to carry out hydraulic-transfer with the operation speed of economy.On the other hand, the saponification degree of PVA is higher than in the situation of 98 % by mole, and for hydraulic-transfer, basement membrane, hydraulic-transfer also reduce sometimes with the water-soluble of film, are difficult to carry out hydraulic-transfer with the operation speed of economy.In addition, the saponification degree of the PVA in this description refer to have with respect to PVA can by saponification change into the shared ratio of the molal quantity of the construction unit (being typically vinyl ester units) of vinyl alcohol units and the total mole number of vinyl alcohol units, this vinyl alcohol units (% by mole).Saponification degree can be measured with the benchmark that is recited as of JIS K6726-1994.
From guaranteeing as viewpoints such as the hydraulic-transfer basic physical properties of basement membrane, more than hydraulic-transfer is preferably 50 quality % with the containing ratio of the PVA in basement membrane, more preferably more than 80 quality %, more preferably more than 85 quality %.The upper limit of this containing ratio is not particularly limited, and this containing ratio is preferably below 99 quality %, more preferably below 98 quality %.
The surfactant that hydraulic-transfer of the present invention contains secondary alkyl with basement membrane.By the surfactant that makes hydraulic-transfer basement membrane contain secondary alkyl, can fully prevent curling when the hydraulic-transfer film being formed by it swims on liquid level.The present invention is not formed to any restriction, think that its reason is, while making hydraulic-transfer film swim on liquid level, containing the surfactant stripping of secondary alkyl, cover liquid level, by this, with film, the expansion on liquid level is suppressed hydraulic-transfer, and curling is hindered.
Surfactant containing secondary alkyl refers to the surfactant in its structure with at least 1 secondary alkyl.Here, secondary alkyl (the 2nd Grade ア Le キ Le (base)) refers to the alkyl (ア Le キ Le (base)) with at least 1 secondary carbon.Curling owing to can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time, therefore the carbon number of secondary alkyl is preferably in 3～20 scope, more preferably in 5～18 scope.
As the surfactant containing secondary alkyl, can exemplify the alkyl ether type surfactant that for example contains secondary alkyl, fatty acid ester type surfactant, the sulfuric acid (sodium salt, sylvite, ammonium salt etc.) of secondary alcohol etc. that contains secondary alkyl.Surfactant containing secondary alkyl both can use separately one, also can two or more and use.Curling owing to can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time, therefore preferably contain the alkyl ether type surfactant of secondary alkyl and/or the fatty acid ester type surfactant containing secondary alkyl containing the surfactant of secondary alkyl, more preferably contain the alkyl ether type surfactant of secondary alkyl.
Refer to there is alkyl and the organic group beyond it that containing the alkyl ether type surfactant in the alkyl ether type surfactant of secondary alkyl hydrophilic radicals such as (etc.) such as polyoxyalkylenes forms the surfactant of the structure of ehter bond ((C)-O-(C)) by oxygen atom.Containing in the alkyl ether type surfactant of secondary alkyl, the position of secondary alkyl is not particularly limited, curling etc. owing to can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time, therefore preferably has secondary alkyl and the organic group beyond it hydrophilic radicals such as (etc.) such as polyoxyalkylenes and forms by oxygen atom the structure of ehter bond ((C)-O-(C)) containing the alkyl ether type surfactant of secondary alkyl.
In addition, refer to there is the surfactant that forms the acyl group of aliphatic acid and the organic group beyond it hydrophilic radicals such as (etc.) such as polyoxyalkylenes and form by oxygen atom the structure of ester bond ((acyl group)-O-(C)) containing the fatty acid ester type surfactant in the fatty acid ester type surfactant of secondary alkyl.Containing in the fatty acid ester type surfactant of secondary alkyl; the position of secondary alkyl is not particularly limited; curling etc. owing to can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time, therefore preferably has the acyl group of the structure that is equivalent to secondary alkyl and carbonyl bonding and the organic group beyond it hydrophilic radicals such as (etc.) such as polyoxyalkylenes and forms by oxygen atom the structure of ester bond ((acyl group)-O-(C)) containing the fatty acid ester type surfactant of secondary alkyl.
As the alkyl ether type surfactant containing secondary alkyl, can exemplify the secondary alkyl ethers of polyoxyalkylene such as the secondary alkyl ether of such as polyoxyethylene, the secondary alkyl ether of polyoxypropylene, the secondary alkyl ether of polyoxy butylene, the secondary alkyl ether of polyoxy octene; The secondary alkyl ether sulfates of polyoxyalkylene such as the secondary alkyl ether sulfate of polyoxyethylene, the secondary alkyl ether sulfate of polyoxypropylene, the secondary alkyl ether sulfate of polyoxy butylene, the secondary alkyl ether sulfate of polyoxy octene; The secondary alkyl ether phosphates of polyoxyalkylene such as the secondary alkyl ether phosphate of polyoxyethylene, the secondary alkyl ether phosphate of polyoxypropylene, the secondary alkyl ether phosphate of polyoxy butylene, the secondary alkyl ether phosphate of polyoxy octene; The secondary alkyl ether carboxy acid salts of polyoxyalkylene such as the secondary alkyl ether acetate of polyoxyethylene, the secondary alkyl ether acetate of polyoxypropylene, the secondary alkyl ether acetate of polyoxy butylene, the secondary alkyl ether acetate of polyoxy octene; The secondary alkyl sulfo succinates of polyoxyalkylene such as the secondary alkyl sulfo succinate of polyoxyethylene, the secondary alkyl sulfo succinate of polyoxypropylene, the secondary alkyl sulfo succinate of polyoxy butylene, the secondary alkyl sulfo succinate of polyoxy octene etc.In addition, be in the situation of salt containing the alkyl ether type surfactant of secondary alkyl, can exemplify such as sodium salt, sylvite, ammonium salt etc.
In addition,, as the fatty acid ester type surfactant containing secondary alkyl, can exemplify the secondary fatty acid esters of polyoxyalkylene such as the secondary fatty acid ester of such as polyoxyethylene, the secondary fatty acid ester of polyoxypropylene, the secondary fatty acid ester of polyoxy butylene, the secondary fatty acid ester of polyoxy octene; The secondary fatty acid esters of polyoxyalkylene glycerine such as the secondary fatty acid ester of polyoxyethylene glycerine, the secondary fatty acid ester of polyoxypropylene glycerine, the secondary fatty acid ester of polyoxy butylene glycerine, the secondary fatty acid ester of polyoxy octene glycerine etc.
Curling owing to can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time, therefore these contain alkyl ether type surfactants of secondary alkyl and contain the surfactant that in the fatty acid ester type surfactant of secondary alkyl, all preferably nonionic is, more preferably the secondary alkyl ether of polyoxyalkylene and/or the secondary fatty acid ester of polyoxyalkylene, the secondary alkyl ether of further preferred polyoxyalkylene.
For example, as the secondary alkyl ether of above-mentioned polyoxyalkylene and the secondary fatty acid ester of polyoxyalkylene, the compound that can use following formula (I) to represent.
[changing 1]
In formula (I), R
1and R
2represent respectively the alkyl of carbon number 1～18, R
3represent the alkylidene of singly-bound or carbon number 1～10, f represents 0 or 1, R
4the alkylidene that represents carbon number 1～4, n represents 1～20 integer.
In formula (I), R
1and R
2represented alkyl can be both straight chain shape, can be also a chain.The carbon number of this alkyl is in 1～18 scope, preferably in 1～16 scope, more preferably in 1～14 scope.In addition, R
1and R
2can be mutually the same also can be different.
In formula (I), R
3the carbochain of represented alkylidene both can straight chain shape, can be also a chain.The carbon number of this alkylidene is in 1～10 scope, preferably in 1～8 scope, more preferably in 1～6 scope.Curling from can more effectively prevent from making the hydraulic-transfer film of gained to swim in liquid level time and the viewpoint such as easily obtain, R
3preferably singly-bound.
In formula (I), f is 0 or 1.F is 0 o'clock, and the compound that formula (I) represents is the secondary alkyl ether of polyoxyalkylene, and f is 1 o'clock, and the compound that formula (I) represents is the secondary fatty acid ester of polyoxyalkylene.
In formula (I), R
4the carbochain of represented alkylidene both can straight chain shape, can be also a chain.As this alkylidene, for example can exemplify 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene etc., curling from can more effectively prevent from making the hydraulic-transfer film of gained to swim in liquid level time and the viewpoint such as easily obtain, preferably 1,2-ethylidene.
In formula (I), n is any in 1～20 integer.Wherein, curling from can more effectively prevent from making the hydraulic-transfer film of gained to swim in liquid level time and the viewpoint such as easily obtain, n is preferably any in 3～18 integer, more preferably any in 5～12 integer.In addition, because the method for making of the secondary alkyl ether of polyoxyalkylene and the secondary fatty acid ester of polyoxyalkylene etc. causes n to have in the situation of distribution, the surfactant containing secondary alkyl using in the present invention as mentioned above both can a kind ofly use separately, also can be two or more and use, therefore, both can use separately n is single integer and do not have the compound of distribution, or also can use n to have the compound (, by mutually different n compound with) of distribution.
In formula (I), by the carbon number of secondary moieties entirety, the carbon number of part-structure entirety that following formula (I ') represents is while being made as m, if the relation of this m and said n meets m>n, curling can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time.From this viewpoint, m and n preferably meet the relation of 1≤m-n≤9, more preferably meet the relation of 2≤m-n≤7.
[changing 2]
Formula (I ') in, R
1, R
2and R
3implication with above identical.
Hydraulic-transfer with respect to the PVA of 100 mass parts, preferably contains 0.05～4 mass parts with basement membrane, more preferably contain 0.1～3.5 mass parts, further preferably contain the surfactant containing secondary alkyl of 0.5～3 mass parts.By make containing the surfactant of secondary alkyl with respect to the content of the PVA of 100 mass parts more than above-mentioned lower limit, curling can more effectively prevent from making the hydraulic-transfer film of gained to swim on liquid level time, on the other hand, by below the above-mentioned upper limit, can effectively suppress ooze out (the bleed out) of surfactant.
By making hydraulic-transfer with containing plasticizer in basement membrane, can give flexibility.As plasticizer preferred polyol, as concrete example, can exemplify ethylene glycol, glycerine, propane diols, diethylene glycol, diglycerol, triethylene glycol, TEG, trimethylolpropane etc.Hydraulic-transfer is preferably below 20 mass parts with respect to the PVA of 100 mass parts with the content of the plasticizer in basement membrane, more preferably below 15 mass parts.If the content of plasticizer is more than 20 mass parts, hydraulic-transfer sticks together sometimes with basement membrane.
In addition, the objects such as the complexity of the distortion in required time, the hydraulic-transfer operation of the ductility on speed, the liquid level of the softness being caused by the absorption of liquid when giving the moisture-proof of hydraulic-transfer basement membrane forming mechanical strength required when printed layers, while maintaining operation hydraulic-transfer basement membrane or to regulate the hydraulic-transfer film that makes to be formed with printed layers to swim on liquid level, the diffusion in liquid, preferably contain starch and/or PVA water soluble polymer in addition for above-mentioned hydraulic-transfer in basement membrane.
As starch, can exemplify the native starch classes such as such as cornstarch, farina, sweet potato starch, wheaten starch, rice starch, tapioca, sago starch; Implement the producing starch class of etherificate processing, esterification processing, oxidation processing etc. etc., particularly preferably producing starch class.Hydraulic-transfer is preferably below 15 mass parts with respect to the PVA of 100 mass parts with the content of the starch in basement membrane, more preferably below 10 mass parts.If the content of starch is more than 15 mass parts, for hydraulic-transfer, basement membrane, hydraulic-transfer reduce by the resistance to impact of film, become fragile, and operation trafficability characteristic reduces sometimes.
As the water soluble polymer beyond PVA, can exemplify the copolymer, polyvinylpyrrolidone, cellulose, acetyl group cellulose, acetyl group butyl cellulose, carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethylcellulose, sodium alginate of copolymer, vinyl acetate and the itaconic acid of such as dextrin, gelatin, animal glue, casein, lac, Arabic gum, polyacrylamide, Sodium Polyacrylate, polyvinyl methyl ether, methyl vinyl ether and maleic anhydride etc.Hydraulic-transfer is preferably below 15 mass parts with respect to the PVA of 100 mass parts with the content of the water soluble polymer beyond the PVA in basement membrane, more preferably below 10 mass parts.If the content of the water soluble polymer beyond PVA is more than 15 mass parts, hydraulic-transfer when hydraulic-transfer reduces sometimes by dissolubility and the dispersiveness of film.
In addition, the objects such as the time that the ductility on speed, the liquid level of the softness that the hydraulic-transfer film that makes to be formed with printed layers in order to regulate is caused by the absorption of liquid while swimming on liquid level, the diffusion in liquid are required, above-mentioned hydraulic-transfer is with preferably containing borate compounds in basement membrane.
As borate compounds, preferred boric acid, borax.Hydraulic-transfer is preferably below 5 mass parts with respect to the PVA of 100 mass parts with the content of the borate compounds in basement membrane, more preferably below 1 mass parts.If the content of borate compounds is more than 5 mass parts, for hydraulic-transfer, basement membrane, hydraulic-transfer reduce sometimes with the water-soluble of film, are difficult to carry out hydraulic-transfer with the operation speed of economy.
In addition, hydraulic-transfer can contain one or more in other surfactant beyond the above-mentioned surfactant containing secondary alkyl with basement membrane.The kind of this other surfactant is not particularly limited, and can use known anion is that surfactant, cation are that surfactant, nonionic are surfactant etc.In the situation that hydraulic-transfer contains this other surfactant with basement membrane, hydraulic-transfer is preferably below 4 mass parts with respect to the PVA of 100 mass parts with the total content (content of all surfactants) including the surfactant containing the surfactant of secondary alkyl in basement membrane.If the total content of surfactant, more than 4 mass parts, oozes out sometimes, operability reduces.
In hydraulic-transfer use basement membrane, except mentioned component, also can contain other compositions such as heat stabilizer, ultra-violet absorber, antioxidant, colouring agent, filler.The content of these other compositions also depends on its kind, is conventionally preferably below 10 mass parts with respect to the PVA of 100 mass parts, more preferably below 5 mass parts.If the content of other composition is more than 10 mass parts, hydraulic-transfer worsens sometimes by the resistance to impact of basement membrane.
Hydraulic-transfer of the present invention uses the moisture rate of basement membrane preferably in the scope of 2～6 quality %, more preferably in the scope of 3～5 quality %.If moisture rate is lower than 2 quality %, the hydraulic-transfer of gained also easily reduces with the moisture rate of film, the tendency that while having hydraulic-transfer, amount of crimp increases.On the other hand, if moisture rate higher than 6 quality %, has the tendency of the unfavorable conditions such as the precision reduction of easy generation printing.
Hydraulic-transfer of the present invention can consider that with the thickness of basement membrane water-soluble and balance operation trafficability characteristic suitably selects, conventionally in the scope of 10～100 μ m, preferably in the scope of 20～80 μ m, more preferably in the scope of 30～50 μ m.If thickness is less than 10 μ m,, there is the reduction of operation trafficability characteristic in the undercapacity of basement membrane for hydraulic-transfer sometimes.On the other hand, if thickness is greater than 100 μ m, hydraulic-transfer reduces sometimes with basement membrane or the water-soluble of hydraulic-transfer film, is difficult to carry out hydraulic-transfer with the operation speed of economy.
Can easily form the print pattern of fine when hydraulic-transfer of the present invention is implemented to printing by least one face side of basement membrane and make the hydraulic-transfer film of gained swim on liquid level time, can suppress hydraulic-transfer dissolution velocity on liquid level with film inequality, can suppress the inequality of print pattern, therefore the arithmetic mean roughness (Ra) of this face is preferably below 400nm, more preferably, below 350nm, be particularly preferably below 300nm.As the lower limit of this arithmetic mean roughness (Ra), can exemplify for example 100nm.The hydraulic-transfer with such arithmetic average roughness (Ra) is as described below with basement membrane, and the masking stoste that can be contained PVA and be contained the surfactant of secondary alkyl by use is manufactured the method for hydraulic-transfer basement membrane and easily manufactured.The present invention is not formed to any restriction, think that its reason is, the surfactant containing secondary alkyl using is difficult for separating out on the face of the hydraulic-transfer making basement membrane.
In addition,, in order to improve the objects such as the hydraulic-transfer sliding of membrane surface, also preferably hydraulic-transfer is implemented to delustring processing with the surface of basement membrane.As the method for delustring processing, can exemplify in the time of masking roller or the frosting brought are transferred to online delustring facture on film, the film making are temporarily batched to method of implementing embossing processing etc. after roller.More than the surface roughness that enforcement delustring is after treatment is preferably 0.5 μ m in arithmetic average roughness (Ra), more preferably more than 1 μ m.As the upper limit of this arithmetic mean roughness (Ra), can exemplify for example 10 μ m.In addition, more than being preferably 1 μ m with maximum height roughmeter, more preferably more than 3 μ m.As the upper limit of this maximum height roughness (Rz), can exemplify for example 20 μ m.Use one of preferred configuration of basement membrane as hydraulic-transfer of the present invention, a face that can exemplify film is that face, another face of having implemented above-mentioned delustring processing are the hydraulic-transfer basement membrane of its arithmetic mean roughness (Ra) for the face of 400nm following (being preferably below 350nm, more preferably below 300nm).
In this description, arithmetic mean roughness (Ra) and maximum height roughness (Rz) can be used as respectively each arithmetic mean roughness (Ra) of recording at 5 places arbitrarily on determined film surface and the mean value of each maximum height roughness (Rz) is tried to achieve.Here, each arithmetic mean roughness (Ra) and each maximum height roughness (Rz) can be measured according to JIS B0601:2001.
The situation of the existing rectangular film of basement membrane for general hydraulic-transfer, also there is the situation of rectangular membrane, in the situation of rectangular film, can on one side the film that is rolled into roller shape be emitted continuously, printing is implemented in its surface on one side, make hydraulic-transfer film, again emit after directly or temporarily coiling into roller shape, continuously for hydraulic-transfer.Hydraulic-transfer of the present invention is with in basement membrane, its shape can be both that rectangular film can be also long short (for example the length on one side is all less than 1m) rectangular membrane, it can also be the polygon-shaped or toroidal such as triangle, pentagon, the viewpoints such as the operability during from hydraulic-transfer, preferred rectangular film and rectangular membrane, if consider can print continuously, the aspect such as hydraulic-transfer, preferred rectangular film.
In rectangular film, its length and width are not particularly limited, and the viewpoint of the productivity ratio during from printing, more than length is preferably 1m, more preferably more than 100m, more preferably more than 1000m.In addition,, as the upper limit of length, can exemplify for example 10000m.On the other hand, the viewpoint of the productivity ratio while printing from improving, more than width is preferably 50cm, more preferably more than 80cm, more preferably more than 100cm.In addition, owing to having, the hydraulic-transfer production of basement membrane of thickness of homogeneous is easy etc., and therefore this width is preferably below 4m, more preferably below 3m.
Utilize hydraulic-transfer basement membrane of the present invention, can form the curling hydraulic-transfer film can fully prevent from swimming on liquid level time.Hydraulic-transfer can carry out pattern by the amount of crimp of evaluation hydraulic-transfer basement membrane itself by the amount of crimp of film and evaluate.Method as evaluation hydraulic-transfer by the amount of crimp of basement membrane, adopts curling area occupation ratio in this description.After curling area occupation ratio refers to and swims on the water surface because the area of the end part curling and that do not contact with the water surface of hydraulic-transfer basement membrane with respect to the ratio of area that swims in the hydraulic-transfer use basement membrane that the water surface goes forward, measure by following method.The value of curling area occupation ratio is less, just represents more can prevent curling, and hydraulic-transfer is better with the transfer efficiency of film, is particularly preferably below 7%, more preferably below 6%, more preferably below 5%.
Hydraulic-transfer of the present invention is not particularly limited with the film-forming method of basement membrane, and owing to easily manufacturing the hydraulic-transfer basement membrane that surface roughness is little, therefore the preferred masking stoste that contains PVA and contain the surfactant of secondary alkyl of using is carried out masking.As the concrete example of such masking stoste, can exemplify PVA and containing the surfactant dissolves of secondary alkyl in liquid medium and masking stoste, contain PVA, containing the surfactant of secondary alkyl and the masking stoste of liquid medium and PVA melting etc.
The liquid medium using in preparation as masking stoste, such as water, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, ethylene glycol, glycerine, propane diols, diethylene glycol, triethylene glycol, TEG, trimethylolpropane, ethylenediamine, diethylenetriamines etc. can be exemplified, wherein one or more can be used.Wherein, preferably make water from the burden that environment is caused, the viewpoint of recyclability.
The volatile ingredient rate of masking stoste (volatile ingredient of the liquid medium being removed by volatilization, evaporation in the time of masking etc. containing proportional) is according to film-forming method, film forming condition etc. and different, be in general preferably 50～95 quality %, more preferably 55～90 quality %, be particularly preferably 60～85 quality %.If the volatile ingredient rate of masking stoste is too low, the viscosity of masking stoste is too high, and filtration time prepared by masking stoste, deaeration become difficulty, has the tendency that is difficult to manufacture foreign matter, hydraulic-transfer basement membrane that defect is few.On the other hand, if the volatile ingredient rate of masking stoste is too high, the concentration of masking stoste is too low, has the manufacture of payable hydraulic-transfer basement membrane to become difficult tendency.
Film-forming method when manufacturing hydraulic-transfer basement membrane by above-mentioned masking stoste, for example, can adopt film by wet method, gel masking method, casting film method, extrude masking method etc.In addition, also can adopt method of being combined by them etc.In above film-forming method, owing to obtaining the thickness of film and width homogeneous, the good hydraulic-transfer basement membrane of physical property, therefore preferably adopt casting film method or extrude masking method.
As concrete film-forming method, can preferably adopt with the following method industrial: use T-shaped slit die, hopper plate (hopper plate), I-mould, lip coating machine mould etc., masking stoste is spued equably or be cast on the periphery of the roller through heating (or band) of the rotation that is positioned at upstream side, make volatile ingredient evaporation from the face spuing or be cast to the film this roller (or band), dry, then further dry on the periphery of the roller through heating of one or more rotations that is disposed at its downstream, or make it by being further dried in hot-air drying device, then batch with devices for taking-up.Use dry and the dry of use hot-air drying device of the roller through heating appropriately combinedly to implement.
Hydraulic-transfer after masking both can be without stretching with basement membrane, and transfer printing condition that also can be when coordinating hydraulic-transfer etc. is improved the object of mechanical property and implements uniaxial tension or biaxial stretch-formed.
By hydraulic-transfer of the present invention is implemented to printing with the surface of basement membrane, can become hydraulic-transfer film.This printing process is not particularly limited, and can by adopting known mode of printing to form printed layers, for example, can adopt intaglio printing, serigraphy, hectographic printing, rolling method etc.This printing both can be at hydraulic-transfer with directly carrying out by printing-ink on basement membrane, also can on other film, temporarily form after printed layers, be printed by being transferred to hydraulic-transfer basement membrane.As described in the former at hydraulic-transfer with directly print by printing-ink on basement membrane in the situation that, problem of misalignment while there is sometimes problem, the polychrome printing of restriction, the drying process of the composition of printing-ink etc., therefore preferably as described in the latter, temporarily on other film form after printed layers, printed by being transferred to hydraulic-transfer basement membrane.As the printing-ink using in printing, can use existing known printing-ink.
Swim on the liquid level of the liquid such as water by the facing up of enforcement printing that makes above-mentioned hydraulic-transfer film, press from the upper side the transfer printing bodies such as various formed bodys, can carry out hydraulic-transfer.As more detailed liquid pressure transfer method, can exemplify the liquid pressure transfer method that for example comprises following each operation: the facing up of enforcement printing of hydraulic-transfer film swum on liquid level, and ink jet activator etc. makes the first operation of printed layers activation; Make transfer printing body from the top that swims in the hydraulic-transfer film liquid level to be transferred second operation of falling, pressing facing to the mode of below; Hydraulic-transfer is fully bonded to behind the surface of transfer printing body by the printed layers of film, the 3rd operation that this hydraulic-transfer is removed by the basement membrane of the hydraulic-transfer in film part; The 4th operation that on face, transfer printing has the transfer printing body of printed layers to be fully dried will be transferred.
The kind of transfer printing body is not particularly limited, and can exemplify the wood substrates such as for example wood, glued board, particieboard; Various Plastics; Plasterboard; The fiber cement boards such as paper pulp cement plate, slabstone, cement asbestos board; Calcium silicate board; Magnesium silicate plate; Glass fiber reinforced cement; Concrete; The metallic plates such as iron, stainless steel, copper, aluminium; Their compound etc.The surperficial shape of transfer printing body both can be smooth, can be also matsurface, also can have concaveconvex shape, can be any, owing to more effectively utilizing the advantage of hydraulic-transfer, therefore preferably the irregular three-dimensional surface of tool, there is the transfer printing body of curved surface.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is not subject to their any restriction.In addition, hydraulic-transfer is recorded in below by the kind of each assay method of moisture rate, arithmetic average roughness (Ra) and the curling area occupation ratio of basement membrane and the surfactant that uses.
the mensuration of the moisture rate of basement membrane for hydraulic-transfer
Use Ka Er Fischer moisture meter to measure.
the mensuration of the arithmetic average roughness (Ra) of basement membrane for hydraulic-transfer
Use KEYENCE company measuring shape laser microscope processed " VK-X200 " to measure.Particularly, at hydraulic-transfer with at random determining on a face of basement membrane that (area respectively locating is 20mm as locating at 5 places
2), in the mensuration arithmetic mean roughness (Ra) separately that respectively locates, calculate the arithmetic mean roughness (Ra) of its mean value as hydraulic-transfer basement membrane.In addition, hydraulic-transfer is calculated respectively to arithmetic mean roughness (Ra) with two faces of basement membrane, wherein less value is judged to be "○" (well) below 300nm time, be greater than 300nm and be judged to be " △ " (better) below 400nm time, while being greater than 400nm, be judged to be "×" (bad).
the mensuration of the curling area occupation ratio of basement membrane for hydraulic-transfer
In the container of long 420mm × wide 320mm × high 160mm, add 10 premium on currency, be adjusted to after 30 ℃, the basement membrane for hydraulic-transfer (size: 200mm × 200mm) of manufacturing in following examples or comparative example is swum on the water surface in said vesse, and the face of the opposition side of the face that stainless steel band while making with the masking supporter of casting film stoste (spue or) contacts contacts with water.By this operation, hydraulic-transfer upsweeps with respect to the water surface conventionally with the end of basement membrane.Floating beginning, after 25 seconds, is measured the area (Amm of the part contacting with the water surface
2), calculate curling area occupation ratio (%) by following formula.In addition, above-mentioned area (Amm
2) be with a series of operation of camera, the view data of gained computer is carried out to image processing measure.
Curling area occupation ratio (%)=(1-A/ (200 × 200)) × 100
By curling area occupation ratio below 7%, be judged to be "○" (well), by be greater than 7% be judged to be "×" (bad).
the kind of surfactant
In following examples or comparative example, use following table surface-active agent.
[surfactant A]
The secondary alkyl ether of polyoxyethylene.Have and be equivalent on the secondary alcohol of carbon number 12 addition and have the structure of the structure of oxirane.Quantity=9 of oxygen ethylene unit., R
1and R
2in a side be that amyl group, the opposing party are hexyl, R
3for singly-bound, f are 0, R
4it is the compound (the carbon number m of secondary moieties entirety is 12) that 1,2-ethylidene, the n formula (I) that is 9 represents.
[surfactant B]
The secondary alkyl ether of polyoxyethylene.Have and be equivalent on the secondary alcohol of carbon number 12 addition and have the structure of the structure of oxirane.Quantity=7 of oxygen ethylene unit., R
1and R
2in a side be that amyl group, the opposing party are hexyl, R
3for singly-bound, f are 0, R
4it is the compound (the carbon number m of secondary moieties entirety is 12) that 1,2-ethylidene, the n formula (I) that is 7 represents.
[surfactant C]
The secondary alkyl ether of polyoxyethylene.Have and be equivalent on the secondary alcohol of carbon number 14 addition and have the structure of the structure of oxirane.Quantity=9 of oxygen ethylene unit., R
1and R
2in a side be that hexyl, the opposing party are heptyl, R
3for singly-bound, f are 0, R
4it is the compound (the carbon number m of secondary moieties entirety is 14) that 1,2-ethylidene, the n formula (I) that is 9 represents.
[surfactant D]
The secondary alkyl ether of polyoxyethylene.Have and be equivalent on the secondary alcohol of carbon number 16 addition and have the structure of the structure of oxirane.Quantity=9 of oxygen ethylene unit., R
1and R
2in a side be that heptyl, the opposing party are octyl group, R
3for singly-bound, f are 0, R
4it is the compound (the carbon number m of secondary moieties entirety is 16) that 1,2-ethylidene, the n formula (I) that is 9 represents.
[surfactant E]
The secondary alkyl ether of polyoxyethylene.Have and be equivalent on the secondary alcohol of carbon number 14 addition and have the structure of the structure of oxirane.Quantity=5 of oxygen ethylene unit., R
1and R
2in a side be that hexyl, the opposing party are heptyl, R
3for singly-bound, f are 0, R
4it is the compound (the carbon number m of secondary moieties entirety is 14) that 1,2-ethylidene, the n formula (I) that is 5 represents.
[surfactant F]
The secondary fatty acid ester of polyoxyethylene.Have and be equivalent on the secondary aliphatic acid of carbon number 12 addition and have the structure of the structure of oxirane.Quantity=9 of oxygen ethylene unit., R
1and R
2be amyl group, R
3for singly-bound, f are 1, R
4it is the compound (the carbon number m of secondary moieties entirety is 11) that 1,2-ethylidene, the n formula (I) that is 9 represents.
[surfactant G]
The secondary sodium alkylether sulphate of polyoxyethylene.Quantity=9 of oxygen ethylene unit.There is formula: CH (C
5h
11) (C
6h
13)-O-(CH
2cH
2o)
9-SO
3the structure of Na.
[surfactant H]
Polyoxyethylene lauryl ether.Have and be equivalent on n-dodecane alcohol addition and have the structure of the structure of oxirane.Quantity=9 of oxygen ethylene unit.
[surfactant I]
Polyoxyethylene sorbitan monolaurate.Quantity=9 of oxygen ethylene unit.
[embodiment 1]
It is that (the particle mean size 20 μ m) concentration of 5 mass parts and surfactant A 2 mass parts, PVA are that the aqueous solution of 18 quality % is as masking stoste for 88 % by mole and the degree of polymerization PVA that is 2400 (homopolymers of vinyl acetate saponified), 100 mass parts, glycerine 3 mass parts, cornstarch that use contains saponification degree, be cast on the stainless steel band of 95 ℃ of temperature dry 2 minutes.After dry, the face of the opposition side to the face contacting with band with 8 seconds of Heat treating roll heat treatment of 80 ℃, obtains the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 2]
Except replacing surfactant A by surfactant B, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 3]
Except the consumption of surfactant A is changed into 1 mass parts from 2 mass parts, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 4]
Except the consumption of surfactant A is changed into 5 mass parts from 2 mass parts, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 5]
Except replacing surfactant A with surfactant C, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 6]
Except replacing surfactant A by surfactant D, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 7]
Except replacing surfactant A with surfactant E, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 8]
Except replacing surfactant A with surfactant F, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[embodiment 9]
Except replacing surfactant A with surfactant G, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[comparative example 1]
Except replacing surfactant A with surfactant H, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[comparative example 2]
Except replacing surfactant A with surfactant I, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[comparative example 3]
Except not using surfactant A, operate similarly to Example 1, obtain the basement membrane for hydraulic-transfer (moisture rate 4.0 quality %) of thick 40 μ m.
For the hydraulic-transfer basement membrane of gained, measure according to the method described above arithmetic mean roughness (Ra) and curling area occupation ratio.The results are shown in table 1.
[table 1]
* 1) with respect to the mass parts of 100 mass parts PVA
* 2) less value in the arithmetic average roughness of two faces (Ra).
Known in embodiment 1～9, contain PVA and be filmed containing the masking stoste of the surfactant of secondary alkyl by use, can easily obtain the hydraulic-transfer basement membrane that surface roughness is little, in addition, this hydraulic-transfer due to the surfactant that contains secondary alkyl, is therefore that the value of curling area occupation ratio is little with basement membrane, curling, hydraulic-transfer film that transfer efficiency is excellent can fully prevent from swimming on liquid level time.On the other hand, in comparative example 1～3, owing to not using the surfactant containing secondary alkyl, therefore surface roughness is large, and the value of curling area occupation ratio is large.
Industrial usability
Hydraulic-transfer of the present invention can form curling, the hydraulic-transfer film that transfer efficiency is excellent can fully prevent from swimming on liquid level time with basement membrane, the hydraulic-transfer can be preferred for forming printed layers on the irregular three-dimensional surface of tool, the surface with the transfer printing body of curved surface time.
Claims (7)
1. hydraulic-transfer basement membrane, it contains polyvinyl alcohol and the surfactant containing secondary alkyl.
2. hydraulic-transfer basement membrane claimed in claim 1, wherein, with respect to the polyvinyl alcohol of 100 mass parts, the surfactant containing secondary alkyl that contains 0.05～4 mass parts.
3. hydraulic-transfer basement membrane claimed in claim 1, wherein, the saponification degree of polyvinyl alcohol is 80～98 % by mole.
4. hydraulic-transfer basement membrane claimed in claim 1, the arithmetic mean roughness (Ra) of its at least one face is below 400nm.
5. the manufacture method of basement membrane for hydraulic-transfer, it comprises the operation that uses the masking stoste that contains polyvinyl alcohol and contain the surfactant of secondary alkyl to be filmed.
6. hydraulic-transfer film, it is printing to be implemented in the surface of the basement membrane of the hydraulic-transfer described in any one in claim 1～4 form.
7. liquid pressure transfer method, it comprises: make the facing up of enforcement printing of hydraulic-transfer claimed in claim 6 film swim in the operation on liquid level; The operation of pressing transfer printing body with the top of film with the hydraulic-transfer from floating.
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| CN105038054A (en) * | 2015-07-02 | 2015-11-11 | 嘉善宏瑞包装材料有限公司 | Water transfer membrane |
| CN107635791A (en) * | 2015-06-15 | 2018-01-26 | 株式会社可乐丽 | Hydraulic-transfer basement membrane |
| JP2019171810A (en) * | 2018-03-29 | 2019-10-10 | 大日本印刷株式会社 | Water pressure transfer film and method of manufacturing it |
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| TWI622501B (en) | 2018-05-01 |
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