CN1980798B - Thermal transfer receptive sheet and process for producing the same - Google Patents
Thermal transfer receptive sheet and process for producing the same Download PDFInfo
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- CN1980798B CN1980798B CN2005800230144A CN200580023014A CN1980798B CN 1980798 B CN1980798 B CN 1980798B CN 2005800230144 A CN2005800230144 A CN 2005800230144A CN 200580023014 A CN200580023014 A CN 200580023014A CN 1980798 B CN1980798 B CN 1980798B
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Abstract
This invention provides a thermal transfer receptive sheet comprising a sheet-like support composed mainly of a cellulose pulp and an empty particle-containing intermediate layer and an image receptive layer provided in that order on one side of the support, and a process for producing the thermal transfer receptive sheet. The thermal transfer receptive sheet is characterized in that the water content of the whole thermal transfer receptive sheet is 2 to 8% by mass and the moisture permeability of the whole receptive sheet is not more than 400 g/m<2>day. There is also provided a thermal transfer receptive sheet comprising a sheet-like support composed mainly of a cellulose pulp, an empty particle-containing intermediate layer and an image receptive layer provided in that order on one sideof the support, and a backside layer provided on the other side of the support. In this thermal transfer receptive sheet, the backside layer contains a resin filler composed mainly of an acrylic resin with a glass transition point (Tg) of 45 DEG C or below and having an average particle diameter of 5 to 22 [mu]m, and the Bekk smoothness of the surface of the backside layer based on JIS P 8119 is not more than 100 sec.
Description
Technical field
The present invention relates to a kind of thermal transfer image receiving sheet that in printer, uses (following abbreviate as sometimes " receiving sheet "), utilize hot transfer printing on image receiving layer, to form image thereby described printer is a dyestuff with thermal transfer dyesheet.More particularly, the present invention relates to a kind ofly to be suitable for thermo printer, particularly be suitable for the image receiving layer thermal dye transfer printer, that when printing, contain the dyeing resin and (followingly abbreviate " receiving layer bamboo sometimes as.) and the dye coating that contains dyestuff of thermal transfer dyesheet (followingly abbreviating " China ink band " sometimes as) is difficult for fusing and the receiving sheet of image excellent in uniformity.In addition, the present invention also relates under various environment, not have warpage curling, blank sheet of paper the back of the body small, the back side to print the suitable good receiving sheet of property.
Background technology
In recent years, among the thermo printer, the thermal dye transfer printer that especially can print distinct full-color image receives publicity.The thermal dye transfer printer is that the receiving layer of the dye coating that contains dyestuff of China ink band and receiving sheet is overlapped, and utilizes from the heat of the first-class supply of the temperature-sensitive dyestuff with the desired area of dye coating only to be transferred on the receiving layer with the concentration of defined, thereby forms image.The China ink band has the dye coating of Huang, magenta and blue or green three looks or adds the dye coating of four looks of black therein again.Full-color image can obtain on receiving sheet by the versicolor dyestuff reiteration transfer printing with the China ink band.
Along with the development of computer digital image treatment technology, the image quality of document image etc. improve extraordinarily, and thermal transfer mode has enlarged the market of document image, but people are just pursuing image quality and the reflecting feel equal with the silver salt photo.In addition, the raising along with the temperature control technique of thermal head improves the high speed of printer system, the requirement of high sensitivityization.Therefore, how the heat dissipation capacity of the first-class heater element of temperature-sensitive being applied to efficiently image forms and just becomes an important techniques problem.
Receiving sheet generally is made of supporter and the receiving layer that forms in its surface.If use common film as the supporter base material, though flatness excellence then, thus occurrence record sensitivity deficiency distributed from the heat of thermal head to base material, or because film does not have sufficient resiliency, therefore the adaptation deficiency of China ink band and receiving sheet takes place that density unevenness is spared etc.
In order to address these problems, to have proposed once that core laminating with foamed thin sheet and stationery etc. closes and the supporter (for example opening clear 61-197282 communique (the 1st page)) that obtains, will be principal component and the biaxially oriented film (synthetic paper) that contains hole (space) structure and the core laminating of stationery etc. closes (for example the opening clear 62-198497 communique (the 1st page) with reference to the spy) such as supporters that obtains with thermoplastic resins such as vistanexes with reference to the spy as supporter.Adopt its thermal insulation of receiving sheet and the flatness excellence of these supporters, but owing to during conveying in printer and heat and pressure during printing, have the problem that produces pit, infringement outward appearance on the receiving sheet.
In addition, foamed thin sheet price height, for the THICKNESS CONTROL with receiving sheet integral body is the thickness of defined, need to use thick foamed thin sheet, therefore also there be the texture problem different of disadvantageous economically problem and resulting receiving sheet with the photographic pape of silver salt photo.
When using stationery as the supporter base material of receiving sheet, distribute to base material from the heat of thermal head, there is the problem of recording sensitivity deficiency.Though the resiliency of stationery is more better than film because result from that the density of fiber of paper is uneven, the driving fit of China ink band and receiving layer is inhomogeneous, thereby the density unevenness that printing takes place is even.
In order to improve these problems, once disclosed a kind of receiving sheet that between paper supporter and receiving layer, is provided with the intermediate layer of containing hollow particle (for example with reference to the spy open clear 63-87286 communique (the 1st～2 page), the spy opens flat 1-27996 communique (the 1st～3 page)).This receiving sheet is by having the thermal insulation that improves the intermediate layer contain hollow particle and the effect of resiliency, sensitivity and image quality improve, but with the occasion of using supporter that core laminatings such as foamed thin sheet and stationery are closed etc. relatively, the release property of receiving layer and China ink band is bad during printing, and the phenomenon of fusion promptly takes place to cause easily.
Can think this be because, in order to prevent the fusion with the dye coating of China ink band, and, generally in receiving layer, be combined with PIC and (for example open flat 10-129128 communique (2-4 page or leaf) with reference to the spy for releasing agent, the three-dimensional cross-linked purpose of thermoplastic resin.), but since in the stationery moisture and the PIC that contain optionally react, thereby three-dimensional cross-linked for the expection of receiving layer resin can not obtain the anti-fully effect that fuses, expectation improves.
In addition, stipulated in certain humiture atmosphere to place moisture content after 1 day, receiving sheet, but for think roughly to reach balance, manufacture process or just made after moisture content still unclear.In addition, once disclosed and between paper base material and foaming layer, form watertight composition, substrate backside side and form non-curl backing etc. (reference example such as spy open flat 8-25811 communique (2-4 page or leaf).)。Yet, the fusion of receiving sheet during about the printing among the present invention and China ink band, mainly result from the receiving layer performance, can think that receiving layer composition, receiving layer such as the crosslinking agent intermediate layer of containing hollow particle or the formation on barrier layer etc. nearby has a significant impact the performance of receiving layer.
In addition, proposed as the adhesive resin that is used for the intermediate layer, (reference example such as spy open flat 1-27996 communique (1-3 page or leaf) to use organic solvent resistance resin (preferably polyethylene alcohol, casein, starch etc.).), to use minimum system film temperature be that (reference example such as spy open flat %17149 communique (the 2nd page) for resin more than 25 ℃.) etc., if but use these resins separately, can there be the problem that is difficult to evenly to form the intermediate layer and is difficult to form layer with flexibility, this is just being sought improve.
In addition, (reference example such as spy open flat 7-98510 communique (the 2nd page) about the distribution of pores of the surperficial coating layer that utilizes the transfer paper that the forced pore size determination instrument of mercury measures.) and the surface impacts hardness of hot transfer ink receiving layer (reference example such as spy open 2002-11969 communique (the 2nd page).) wait existing disclosing, but these mainly are to be used for fusion thermal transfer mode or electronic photo mode, are limited to the characteristic on receiving layer surface.
In addition, with the receiving sheet of paper base material as supporter, cost is lower, can form abundant high-density images by the intermediate layer is set, but then, also exist easy absorbing environmental moisture, the warpage that easily takes place to cause by moisture fluctuation, be so-called curling problem.Though be provided with coating layers such as intermediate layer and receiving layer on the one side of receiving sheet, general such coating layer is more few to absorption and the paper of moisture, becomes the curling factor that produces with the difference of the wettability of paper base material.That is, under high humidity environment,,, under low wet environment,, curl so the so-called back of the body takes place in the face side opposite with receiving layer because paper base material will shrink so produce so-called upsweeping in reception aspect side because paper base material absorption moisture will expand.
From improve printing various purposes such as mobility, on the side of the back side of receiving sheet (with intermediate layer, face that receiving layer is opposite), back layer is set.For example disclose for forming the resin that back layer is used, and with polyvinyl acetal resin and glass transition point the method for the acrylic resin more than 50 ℃ (reference example as, Te Kaiping 4-161383 communique (the 1st page)), but these be with improve non-dyeability, antistatic etc. be main purpose, anti-crimpiness may not be abundant.In order to form back layer, form elastomeric epithelium thereby need be coated with the good resin of fabric film with curling rectification effect.
In addition,, increase for the printing heat of receiving sheet, exist the easy back side that takes place to print bad tendency simultaneously by thermal head along with the high speed of hot tranfer recording mode, the continuous development of highly sensitiveization.The bad following problems that is meant is printed at the so-called back side, that is, when on thermal transfer printer receiving sheet being installed, installing, carry out under the situation of printing at the surperficial back side of making a mistake receiving sheet, and the heat of thermal head makes the back side fusion of China ink band and receiving sheet, thereby the paper obstruction takes place.Also do not fuse and arrange paper in order to print time China ink band and back layer overleaf, possess anti-fusion character for the back side requirement of receiving sheet.
Known in order to dock that the back layer that takes up gives that suitable property is printed at the back side and the scheme of adding various fillers.By adding filler, can improve the sliding of back layer, the heat of thermal head makes the back side fusion of China ink band and receiving sheet in the time of can preventing to print overleaf.As filler, micropowder, particulate, particulate latex of organic or inorganic etc. have been proposed.
For example, be purpose improve to print that mobility and anti-scratch wait, proposed to use resin and filler of the same race in the layer overleaf, do not expose filler and make its method that is covered by resin (reference example as, the spy opens flat 8-25814 communique (the 2nd page).); Contain organic filler that particle diameter is 0.5～30 μ m overleaf in the layer, make surface roughness be 0.3-3.0 μ m method (reference example as, the spy opens flat 9-123623 communique (the 2nd page).) etc.But without any about preventing the distinctive explanation of curling under high humidity environment of paper supporter.
In addition, proposed overleaf to contain in the layer method that average grain diameter is the spherical particle of 2～6 μ m and 8～15 μ m (reference example as, the spy opens flat 7-137464 communique (the 4th page).)。Yet such polyvinyl alcohol shown in the embodiment generally has the character of moisture absorption under high humidity environment, for common paper supporter, has the anti-extremely low shortcoming of effect of curling.In addition, proposed to use in the layer overleaf polyvinyl acetal resin and polyacrylate resin and Mohs' hardness be 1～4 particle method (reference example as, the spy opens flat 6-239036 communique (the 2nd page).), but because generally really up to the mark, thereby exist in the shortcoming of the portrait difference that the receiving layer that contact with back layer when receiving sheet overlapped each other abraded, exports by filler as filler.
As the method that improves the anti-performance of curling, proposed to use in the layer overleaf acrylic acid multielement alcohol ester resin and filler method (reference example as, the spy opens flat 8-118822 communique (the 2nd page).), but using polyester film as supporter, the acrylic acid multielement alcohol ester itself has the inadequate shortcoming of resistance to water.In addition, disclose the method (reference example as, the spy opens flat 11-34516 communique (the 2nd page)) of the water vapor barrier layer that vinylidene resin etc. is set at the back side of paper base material, but from considering the viewpoint of environment, chlorine is the resin existing problems.
Summary of the invention
The present invention provides to have overcome receiving sheet and the problem of the easy fusion of China ink band and the thermal transfer image receiving sheet of image excellent in uniformity when printing as first viewpoint, and described receiving sheet is to be the receiving sheet of the paper of principal component as supporter with the cellulose pulp.In addition, as mentioned above, as receiving sheet, require back layer and China ink band when printing overleaf can not fuse and do not exist and ambient humidity fluctuation curling together, therefore, the present invention's second viewpoint also provides the receiving sheet with the back layer that possesses anti-crimpiness and the suitable property of back side printing under wide in range environment, and described receiving sheet is to be supporter with the paper base material especially.
The present invention comprises following each mode in above-mentioned first viewpoint.
(1) a kind of thermal transfer image receiving sheet, it is characterized in that, be on the one side of sheet supporter that is principal component, to form in turn to contain the intermediate layer of hollow particle, the thermal transfer image receiving sheet of image receiving layer with the cellulose pulp, the moisture content of described thermal transfer image receiving sheet integral body is 2～8 quality %, and the moisture permeability of receiving sheet integral body is 400g/m
2Below it.
(2) as (1) described thermal transfer image receiving sheet, above-mentioned image receiving layer contains the dyeing resin and this resin is carried out the crosslinked crosslinking agent with water reactive functional groups as principal component.
(3) as (2) described thermal transfer image receiving sheet, above-mentioned crosslinking agent with water reactive functional groups is a polyisocyanate compounds.
(4) as each described thermal transfer image receiving sheets of (1)～(3), above-mentioned intermediate layer contain saponification degree be 65～90% and the degree of polymerization be 200～1000 polyvinyl alcohol resin.
(5) as each described thermal transfer image receiving sheet of (1)～(3), water soluble polymer and water-dispersed resin are contained in above-mentioned intermediate layer, and the minimum system film temperature of above-mentioned water-dispersed resin is below 0 ℃.
(6) as (5) described thermal transfer image receiving sheet, above-mentioned water soluble polymer be saponification degree be 65～90% and the degree of polymerization be 200～1000 polyvinyl alcohol resin.
(7) as each described thermal transfer image receiving sheet of (1)～(6), the impact hardness in above-mentioned intermediate layer is below 3.0.
(8) as each described thermal transfer image receiving sheets of (1)～(7), above-mentioned intermediate layer is that the scope of 0.01～10 μ m has the peak in pore diameter in the pore measure of spread that utilizes the forced pore size determination instrument of mercury to carry out.
(9) as each described thermal transfer image receiving sheet of (1)～(8), the pore volume in zone, above-mentioned peak is in the scope of 0.0l～0.7cc/g.
(10) as each described thermal transfer image receiving sheets of (1)～(9), between above-mentioned intermediate layer and image receiving layer, further form the barrier layer, swelling inorganic layered compounds and adhesive are contained as principal component in above-mentioned barrier layer.
(11) as each described thermal transfer image receiving sheet of (1)～(10), the another side of above-mentioned supporter is provided with back layer.
(12) as (11) described thermal transfer image receiving sheet, above-mentioned back layer is that acrylic resin below 45 ℃ is a principal component with glass transition point (Tg), and contain the resin extender that average grain diameter is 5～22 μ m, the Bake smoothness of measuring according to JIS P 8119 on back layer surface is below 100 seconds.
(13) a kind of manufacture method of thermal transfer image receiving sheet, it is the manufacture method that on the one side of sheet supporter that with the cellulose pulp principal component, forms the thermal transfer image receiving sheet of the intermediate layer contain hollow particle, image receiving layer in turn, on the one side of above-mentioned sheet supporter, form in turn and contain after the intermediate layer and image receiving layer of hollow particle, the moisture content of thermal transfer image receiving sheet integral body is adjusted to 1～8 quality %, wear out then, the moisture permeability of this thermal transfer image receiving sheet integral body is 400g/m
2Below it.
(14) as the manufacture method of (13) described thermal transfer image receiving sheet, above-mentioned image receiving layer contains the dyeing resin and this resin is carried out the crosslinked crosslinking agent with water reactive functional groups as principal component.
(15) as the manufacture method of (14) described thermal transfer image receiving sheet, above-mentioned crosslinking agent with water reactive functional groups is a polyisocyanate compounds.
(16) as the manufacture method of each described thermal transfer image receiving sheet of (13)～(15), be included between above-mentioned intermediate layer and the image receiving layer operation that further forms the barrier layer, swelling inorganic layered compounds and adhesive are contained as principal component in above-mentioned barrier layer.
(17) as the manufacture method of each described thermal transfer image receiving sheet of (13)～(16), on the one side of above-mentioned sheet supporter, form in turn and contain the intermediate layer of hollow particle, arbitrarily after barrier layer and the image receiving layer, further be included in the operation that back layer is set on another face of above-mentioned supporter.
(18) as the manufacture method of (17) described thermal transfer image receiving sheet, it is characterized in that, above-mentioned back layer is that acrylic resin below 45 ℃ is a principal component with glass transition point (Tg), and contain the resin extender that average grain diameter is 5～22 μ m, the Bake smoothness of measuring according to JIS P 8119 on back layer surface is below 100 seconds.
(19), the moisture permeability of above-mentioned sheet supporter integral body before aging is adjusted to 400g/m as the manufacture method of each described thermal transfer image receiving sheet of (13)～(18)
2Below it.
(20) a kind of thermal transfer image receiving sheet, be on the one side of sheet supporter that is principal component, to form intermediate layer, the image receiving layer that contains hollow particle in turn with the cellulose pulp, another face of above-mentioned supporter is provided with the thermal transfer image receiving sheet of back layer, above-mentioned back layer is that acrylic resin below 45 ℃ is a principal component with glass transition point (Tg), and contain the resin extender that average grain diameter is 5～22 μ m, the Bake smoothness of measuring according to JIS P 8119 on back layer surface is below 100 seconds.
(21) as (20) described thermal transfer image receiving sheet, the content of above-mentioned resin extender is more than the 2 quality % with respect to the total solid composition of back layer.
(22) as (20) or (21) described thermal transfer image receiving sheet, the principal component of above-mentioned resin extender is at least a kind that is selected from acrylic resin, polyvinyl resin, starch-resin, polyorganosiloxane resin and the nylon resin.
(23) as each described thermal transfer image receiving sheets of (20)～(22), between above-mentioned intermediate layer and image receiving layer, further form the barrier layer of containing the swelling inorganic layered compounds, the average major diameter of the particle of this swelling inorganic layered compounds is 0.5～100 μ m, and aspect ratio (ratio of the average major diameter/thickness of particle of lamellar compound) is 5～5000.
The specific embodiment
Present inventors further investigate in order to overcome following receiving sheet receiving sheet and the black problem of fusion easily of being with when printing, found that, and be that 2～8 quality % and the moisture permeability that makes receiving sheet integral body are 400g/m by the moisture content that makes receiving sheet integral body
2Below it, can access the receiving sheet of the release property excellence of receiving layer and China ink band.Described receiving sheet is to be that the paper of principal component is as supporter with the cellulose pulp, on the one side of this supporter, it is the intermediate layer of principal component, barrier layer and receiving layer arbitrarily that stacked above one another has with hollow particle and adhesive, is provided with back layer arbitrarily in the side that receiving layer is not set of above-mentioned supporter.
The release property of the dye coating of this receiving sheet and China ink band reduces, fuses when printing, can think that reason is, in order to prevent to be with the fusion of dye coating with China ink, for with remover, the three-dimensional cross-linked purpose of thermoplastic resin, generally in receiving layer, be combined with crosslinking agents such as PIC, but owing to be that moisture and the crosslinking agent that is contained in the paper of principal component optionally reacts,, can not get the anti-fully effect that fuses so can not get desired three-dimensional cross-linkedly with the cellulose pulp.
In order to prevent this fusion, the moisture content of the receiving sheet integral body before needing to wear out is adjusted to 1～8 quality %, preferably is adjusted to 2～6 quality %.In addition, it is important that making the moisture permeability of receiving sheet integral body is 400g/m
2. below day, be preferably 350g/m
2Below it.If the moisture content of the receiving sheet integral body before aging is less than 1 quality %, then because the contraction of cellulose tablet causes the concavo-convex change on receiving sheet surface big, the portrait uniformity worsens.In addition, if moisture content surpasses 8 quality %,, be 400g/m then even therefore make the moisture permeability of receiving sheet integral body because absolute amount of moisture is many
2Below it, the crosslinking agent that contains in the receiving layer also is vulnerable to the influence of moisture.For example, sometimes isocyanates can not with desirable functional group reactions, three-dimensional cross-linkedly become insufficient, reduce with the fissility of China ink band.
The moisture adjustment of receiving sheet integral body can be undertaken by for example adjusting conditions such as the coating drying condition in the formation operation of receiving sheet, for example temperature, time, air quantity.In addition, adjustment for the moisture permeability of receiving sheet integral body, can be by for example, the suitable selection that is used for the selection of adhesive resin such as the water-soluble resin (being also referred to as " water soluble polymer ") on intermediate layer, barrier layer and water-dispersed resin and pigment etc. or coating condition etc. realizes.
And then, in manufacturing process, form back, as to wear out preceding receiving sheet moisture permeability about receiving layer, be preferably 400g/m
2Below it, 350g/m more preferably
2Below it.Moisture permeability surpasses 400g/m
2. during the sky, the crosslinking agent that contains in the receiving layer in aging is subjected to moisture effects, quality instability easily sometimes.The moisture permeability of the receiving sheet before aging is roughly the same with for example moisture permeability after forming the barrier layer on the sheet supporter, also can measure the moisture permeability after the barrier layer forms.
(represent for moisture content with %; Be also referred to as " moisture rate ".) mensuration, carry out according to JIS P 8127, for moisture permeability, can be according to JIS K 7129, measure machine (trade name: L80-4000, リ Star シ one system) automatically with moisture permeability and measure.
As aging condition,, generally, can obtain effect of sufficient in aging about 50 hours aging more than 24 hours under the temperature about 40～60 ℃ so long as the NA temperature range of receiving layer gets final product.
In addition, when the adhesive that is used for the intermediate layer is water soluble polymer and water-dispersed resin etc.,, find that then the moisture permeability of receiving layer reduces more, avoid fusion easily if the minimum system film temperature of water-dispersed resin is below 0 ℃.This can think therefore can reduce the cause of the transit dose of moisture because minimum system film temperature is made uniform epithelium when low easily in the intermediate layer.
Also finding in addition, is principal component by making the barrier layer with swelling inorganic layered compounds and adhesive, and effect improves more.This can think because swelling inorganic layered compounds crystallinity height, and is multilayer laminated in the barrier layer, so moisture there is the cause of circuitous effect.
Below the formation layer of receiving sheet of the present invention is elaborated.
(sheet supporter)
As the sheet supporter that is used for receiving sheet of the present invention, be to be the stationery of principal component with the cellulose pulp.As the object lesson of stationery, at least one surface that can enumerate coated papers such as uncoated paper, coated paper, art paper, cast-coated paper such as full slurry paper, middle matter paper, body paper is provided with the laminated paper of thermoplastic resins such as vistanex, synthetic resin impregnated paper, cardboard etc.In addition, for high smoothing, can implement press polish and handle.
Be used for the thickness that sheet supporter of the present invention preferably has 50～250 μ m.If thickness is less than 50 μ m, then its mechanical strength is insufficient, and the rigidity of receiving sheet therefrom is little, and is insufficient to the repulsion of distortion, the curling of the receiving sheet that produces in the time of can not fully preventing printing sometimes.In addition, if thickness surpasses 250 μ m,, therefore cause the number that holds of the receiving sheet in the printer to reduce then because the thickness of the receiving sheet that obtains is excessive, or desire to hold defined hold number the time cause the increase of printer volume, produce the problem that printer is difficult to densification etc. sometimes.
(intermediate layer)
In the present invention, be arranged at the intermediate layer on the sheet supporter, contain the hollow particle and the adhesive that possess specific rerum natura.
By in the intermediate layer, disperseing the distribution hollow particle, can reduce the modulus of elasticity in comperssion of receiving sheet, give the distortion free degree of receiving sheet with appropriateness, improved receiving sheet for the tracing ability of thermal head shape and black belt shape, adaptation etc., even so under low-energy state, also can improve the thermal efficiency of thermal head to receiving layer, improve the printing concentration of the image that is printed, improve image quality.In addition, under the high-octane state of adding of high-speed printer, can prevent from simultaneously also to result from that China ink is bad with the printing of going up the China ink band fold that produces.
(hollow particle)
As the hollow particle that is used for intermediate layer of the present invention, be to comprise the shell that forms by polymeric material and the hollow particle of the hollow more than 1 (pore) portion that surrounded by this shell.Its manufacture method is not particularly limited, but can be from for example selecting following such hollow particle of making.
(I) thus the foaming hollow particle (being designated hereinafter simply as " hollow particle has foamed ") that the thermoplastic, polymeric materials foamable that contains the thermal expansivity material is made.
(II) use polymer formation property material to become to use material as hull shape, and use volatile liquid to form and use material as pore, utilize the microcapsules polymerization to prepare microcapsules, thereby make pore form the microencapsulated hollow particle (being designated hereinafter simply as " microencapsulated hollow particle ") that from microcapsules, volatilizees and disperse and obtain with material.
In intermediate layer of the present invention, preferably use the above-mentioned hollow particle that foamed.Hollow particle has foamed, followingly obtain like that: for example, will be as the normal butane of thermal expansivity material, iso-butane, pentane, and/or be wrapped in the thermoplastic, polymeric materials in the volatility low boiling hydrocarbon of neopentane and so on, will be as the vinylidene chloride of thermoplastic, polymeric materials, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, (methyl) acrylic acid, homopolymers of (methyl) acrylate etc. or their copolymer etc. are used as shell (wall) thereby material obtains particle, this particle is implemented in advance processing such as heating, make it the particle diameter of thermal expansion thus, thereby obtain to defined.
In addition, the above-mentioned hollow particle that foamed, usually proportion is less, therefore be purpose to improve dispersiveness etc., to improve operation task, also can use in the present invention inorganic powders such as calcium carbonate, talcum, titanium dioxide by on the surface of heat fused attached to the hollow particle that foams, thus the compound hollow particle of foaming that the surface is covered by inorganic powder.
In addition, the hollow particle of the preferred microencapsulated of using in intermediate layer of the present invention, can form polymerization by microcapsules obtains, to polymer formation property material (hull shape becomes material) is carried out drying as the microcapsules that shell (wall), core contain volatile liquid (pore forms and uses material), it is discrete that pore is formed with the material volatilization, thereby form hollow core.Form the property material as polymer, preferably use the animi resin of styrene-(methyl) acrylate based copolymer, melmac etc.,, for example use water etc. as volatile liquid.
The average grain diameter that is used for hollow particle of the present invention (hollow particle that foamed, microencapsulated hollow particle) is preferably 0.5～10 μ m, and more preferably 1～9 μ m most preferably is 2～8 μ m.Under the situation of average grain diameter less than 0.5 μ m of foaming hollow particle,, improve effect so can not give full play to the sensitivity of receiving sheet sometimes because the volume hollow rate of hollow particle is generally lower.In addition, if average grain diameter surpasses 10 μ m, the flatness of the intermediate surface that then obtains sometimes reduces, and the uniformity of heat transfer image is bad, and manifesting property of gloss is insufficient.
In addition, the average grain diameter of hollow particle can use general particle size determination device to measure.For example use laser diffraction formula particle size distribution machine (trade name: SALD2000, Shimadzu Seisakusho Ltd.'s system) to wait and measure.
The volume hollow rate that is used for hollow particle of the present invention (hollow particle that foamed, microencapsulated hollow particle) is preferably 50～97%, and more preferably 55～95%.The volume hollow rate of hollow particle less than 50% situation under, the sensitivity that can not give full play to receiving sheet integral body improves effect, in addition, surpass 97%, the problem that coating strength reduces, the intermediate layer is injured easily, outward appearance worsens in intermediate layer then occurs as the fruit volume hollow rate.
In addition, the volume hollow rate of so-called hollow particle is meant the ratio of the volume of hollow space with respect to particle volume, particularly can from the proportion of the hollow particle dispersion liquid that comprises hollow particle and poor solvent, above-mentioned dispersion liquid hollow particle mass fraction and form the true specific gravity of fluoropolymer resin of shell (wall) of hollow particle and the proportion of poor solvent is obtained.In addition, so-called poor solvent is meant the resin dissolves of the wall that can not make the formation hollow particle and/or the solvent of swelling, can enumerate for example water, isopropyl alcohol etc.In addition,, can use for example small angle X ray scattering determinator (trade name: RU-200, リ ガ Network society system) etc., obtain from the cross-section photograph in the intermediate layer of containing hollow particle for the average grain diameter and the volume hollow rate of hollow particle.
For intermediate layer of the present invention, with respect to intermediate layer all solids composition, the quality ratio of hollow particle is preferably 20～80 quality %, more preferably 25～70 quality %.If the quality ratio of hollow particle is less than 20 quality %, it is insufficient that then the sensitivity of receiving sheet sometimes improves effect, in addition, if the quality ratio of hollow particle surpasses 80 quality %, then worsen with the coating of coating fluid in the intermediate layer, can not get good coated face, in addition, the coating strength in intermediate layer reduces sometimes.
(adhesive)
In order to improve the coating strength in intermediate layer, need in the intermediate layer, cooperate adhesive resin.As adhesive resin, there is not particular determination, from film forming, stable on heating viewpoint, preferably for example use water soluble polymers such as polyvinyl alcohol resin, casein, soybean protein, synthetic protein class, starch, cellulose-based resin and derivative thereof.In addition, water-dispersed resin, water-borne acrylic resin, waterborne polyurethane resin, aqueous polyester resin etc. such as vinyl based copolymer latex such as SB, methyl methacrylate butadi ene copolymer equiconjugate diene polymer latex, styrene-vinyl acetate base ester copolymer and other general public in the coated paper field various adhesive resins can use as the water-dispersed resin of low viscosity higher-solid.In addition, above-mentioned water soluble polymer and water-dispersed resin can be distinguished separately and use, and also can will also use more than 2 kinds.
The water soluble polymer of using as the intermediate layer, among above-mentioned resin, preferred use polyvinyl alcohol (PVA) is a resin, saponification degree is 65～90%, the degree of polymerization is 200～1000 polyvinyl alcohol resin, from the moisture permeability that reduces receiving sheet more, prevent and the also excellent viewpoint of effect of the fusion of China ink band, more preferably use.For the preferred reason of using this polyvinyl alcohol resin in the intermediate layer, can think because, for example making in the intermediate layer uses coating also being fit to aspect the viscosity with favorable dispersibility, this intermediate layer of the hollow particle in the coating, so when the coating intermediate layer, the formation excellence of filming, intermediate layer more uniformly can be formed, the transit dose of moisture can be reduced more.
In addition, as the water-dispersed resin that the intermediate layer is used, preferred minimum system film temperature is below 0 ℃.If minimum system film temperature surpasses 0 ℃, then in the intermediate layer, can not fully form epithelium, and become uneven epithelium, result's moisture sometimes moves, and promptly poisture-penetrability rises.On the other hand, if minimum system film temperature is low excessively, then the bleeding of image sometimes worsens.As minimum system film temperature is water dispersible acrylic resin below 0 ℃, for example can enumerate FK4025 (trade name) of the E-377 (trade name) of JSR society system, central physics and chemistry society system etc.
Preferably also with water soluble polymer and water-dispersed resin.The match ratio of water soluble polymer and water-dispersed resin is not subjected to particular restriction, but preferably with respect to 100 mass parts water soluble polymers, cooperates the water-dispersed resin of 100～800 mass parts.If water-dispersed resin is less than 100 mass parts, then the viscosity of coating rises, and can not get fully level and smooth face sometimes, on the other hand, if surpass 800 mass parts, then film forming and poor heat resistance sometimes.
Can in the intermediate layer, suitably select as required, add in the various auxiliary agents such as defoamer, colouring agent, fluorescent whitening agent, antistatic additive, anticorrisive agent, dispersant, tackifier, resin cross-linking agent more than a kind or 2 kinds.
In order to bring into play the desirable performance that improves thermal insulation, resiliency, glossiness etc., the thickness in intermediate layer is preferably 20～90 μ m, more preferably 25～85 μ m.If the thickness in intermediate layer is less than 20 μ m, then thermal insulation, resiliency deficiency sometimes, the effect that sensitivity and image quality improve is insufficient.In addition, if thickness surpasses 90 μ m, then the effect of thermal insulation and resiliency is saturated, can not get higher performance, and is also unfavorable economically, so not preferred.
In addition, the thickness in intermediate layer is preferably the thickness more than 3 times of the average grain diameter of the hollow particle that contains, the more preferably thickness more than 4 times in the intermediate layer.If the thickness in intermediate layer is less than 3 times of the average grain diameter of the hollow particle that contains in the intermediate layer, then thick hollow particle is outstanding from intermediate surface, causes image uniformity and glossiness to reduce sometimes, so not preferred.
In the present invention, the intermediate layer of containing hollow particle has high thermal insulation and resiliency, and this resiliency can be stipulated with " impact hardness ".The hardness of general film can be obtained in the strain when vertically applying static load with material surface.In the present invention, the impact hardness in intermediate layer is to use for example value of the little hardometer of ultra micro (trade name: DUH-201H, society of Shimadzu Seisakusho Ltd. system) mensuration.Pyrometric cone pressure head to 115 ° is given load, from the compression distance of load and pressure head, can obtain impact hardness by following formula.
Impact hardness DHT
115=3.7838 * P/h
2
P: load (mN), h: compression distance (μ m)
This assay method is that the micro-displacement with the needle-like pressure head is converted to the method that the signal of telecommunication is measured, and by adjusting load, can obtain the hardness under required compression distance.Method as the impact hardness of measuring the intermediate layer in the receiving sheet, comprise: with the receiving layer of lamination in advance with razor etc. eliminate, directly method for measuring under method for measuring under the state in intermediate layer that exhumes out and former state state at stacked receiving layer, arbitrary method is all applicable to the present invention.For example directly method for measuring under the former state state of stacked receiving layer waits the coating layer thickness of measuring the receiving layer side by the observation of tomography enlarged photograph in advance, sets load and makes compression distance reach more than the thickness of receiving layer, gets final product thereby measure hardness.
In the present invention, the impact hardness in intermediate layer is preferably below 3.0, more preferably 0.1～1.0 scope.If impact hardness surpasses 3.0, then as the resiliency deficiency in intermediate layer, the adaptation difference owing to receiving sheet and thermal head causes image quality to reduce sometimes when printing.On the other hand, if impact hardness is excessively little, for example less than 0.1, then scratch easily sometimes, operability is bad.
In the present invention, for the impact hardness that makes the intermediate layer below 3.0, can enumerate following method, but be not limited to these methods.
(1) hollow particle of the thin thickness in use next door is as the method for the hollow particle that is contained in the intermediate layer.Hollow particle is kept the state of hollow and is out of shape when bearing load.The thickness in the next door of hollow particle is preferably below the 10 μ m, more preferably below the 2 μ m.
(2) in the intermediate layer, contain in the hollow particle, add the method for the resin of softening point below normal temperature.Soft resin has the effect of the hardness of the layer integral body that reduces the intermediate layer.The softening point of resin is preferably below 30 ℃, more preferably below 10 ℃.
Intermediate layer of the present invention, preferably in the pore measure of spread that utilizes the forced pore size determination instrument of mercury to carry out, be that the scope of 0.01～10 μ m has the peak in pore diameter, also can in this scope, have the peak more than 2.In addition, preferably the pore volume of the accumulation in zone, above-mentioned peak in the scope of 0.01～0.7cc/g.
It is generally acknowledged that pore volume is big more, the thermal insulation in intermediate layer and resiliency increase more, and recording sensitivity improves more.But, under the situation of pore diameter greater than 10 μ m at the peak in the pore in intermediate layer distributes, or the accumulation pore volume in the zone, peak is than under the big situation of 0.7cc/g, when on the intermediate layer, forming receiving layer (or barrier layer etc.), sometimes coating fluid excessive permeation in the intermediate layer, becoming is difficult to make film, can not get uniform coating layer.On the other hand, under the situation of pore diameter less than 0.01 μ m at peak, or under the situation of pore volume less than 0.01cc/g of accumulation, coating fluid can not moderately infiltrate the intermediate layer, sometimes become inhomogeneous and adhesive strength deficiency of coating layer is for example sometimes because coating layer takes place in the fusion that China ink is with etc. peels off.
The method that the pore that utilizes the forced pore size determination instrument of mercury to measure the intermediate layer distributes is as follows, but the present invention is not limited by these methods.(1) for the cellulose pulp being these 2 kinds of the sheet supporter of principal component and the intermediate layer coated articles till being applied to the intermediate layer on the above-mentioned supporter, use the forced pore size determination instrument of mercury to measure pore and distribute, the method that the difference that distributes from 2 pores of gained comes the pore of specific intermediate layer coating layer to distribute.(2) coating layer of the intermediate layer coated articles till being applied to the intermediate layer on the sheet supporter that with the cellulose pulp is principal component, utilize cuttings such as razor and obtain powder, for this powder, use the forced pore size determination instrument of mercury to measure the method that pore distributes.(3) for stacked above one another on the sheet supporter that with the cellulose pulp is principal component intermediate layer, barrier layer as required, the receiving sheet of the present invention of receiving layer are arranged, utilize razor etc. to remove receiving layer, each coating layer of barrier layer, exhumed out in the intermediate layer.The intermediate layer coating layer that strips out for cuttings such as utilizing razor and the powder that obtains uses the forced pore size determination instrument of mercury to measure the method that pore distributes.At this moment, can pass through cross section enlarged photograph observation etc., confirm that receiving layer and barrier layer are removed, exhume out in the intermediate layer.
In intermediate layer of the present invention, as the method that the peak scope of pore diameter and the pore volume in the zone, peak is adjusted in the required scope, be not subjected to particular restriction, but can be by for example, the selection of the material of the hollow particle that contains in the intermediate layer and average grain diameter (being preferably internal diameter) etc., the selection of adhesive or the quality ratio of suitably setting hollow particle and adhesive wait to be adjusted.
In addition, with in the preparation of coating fluid, the proportion of coating fluid preferably is modulated to 0.8g/cm usually in the intermediate layer of containing hollow particle
3Below, more preferably be modulated to 0.7g/cm
3Below.
(barrier layer)
In the present invention, preferably between intermediate layer and receiving layer, the barrier layer is set.Usually, use organic solvents such as toluene, MEK with the solvent of coating fluid as receiving layer, therefore, the distortion that cause as the hollow particle swelling in the intermediate layer that is used to prevent caused by the organic solvent infiltration, by dissolving on the barrier layer, to destroy be effective.
As the resin that is used for the barrier layer, can use the filming performance excellence, can prevent the resin that organic solvent permeates, has elastic force and flexibility.More particularly, can use starch; modified starch; hydroxyethylcellulose; methylcellulose; carboxymethyl cellulose; gelatin; casein; gum arabic; fully saponified polyvinyl alcohol; partly-hydrolysed polyvinyl alcohol; carboxy-modified polyvinyl alcohol; acetoacetyl modified polyethylene alcohol; ethylene-vinyl alcohol copolymer; diisobutylene-copolymer-maleic anhydride salt; styrene-maleic anhydride copolymer salt; styrene-propene acid copolymer salt; ethylene-acrylic acid copolymer salt; urea resin; polyurethane resin; melmac; the water-soluble resin of amide resin etc.In addition, also can use styrene-butadiene based copolymer latex, acrylate is water-dispersed resins such as latex, methacrylate ester copolymer resins latex, vinyl-vinyl-acetic ester copolymer emulsion, polyester-polyurethane ionomer, polyether-polyurethane ionomer.
In above-mentioned resin, general preferred use water soluble polymer more preferably uses polyvinyl alcohol, ethylene-vinyl alcohol copolymer, styrene-propene acid copolymer salt etc. such as for example fully saponified polyvinyl alcohol, partly-hydrolysed polyvinyl alcohol.
And then, in the barrier layer, can contain various pigment, preferably use the swelling inorganic layered compounds, this not only can prevent to be coated with the infiltration with solvent, and also can obtain excellent effect for the bleeding that prevents hot transfer printing colored graph picture etc.As the swelling inorganic layered compounds, can enumerate natural clays such as montmorillonite family, mica family, vermiculite family is mineral.In addition, except that the clay of natural product is mineral, the also arbitrary substance in composite, the processing item for disposal (for example surface treatment product of silane coupling agent).
As the synthetic swelling inorganic layered compounds, more preferably for example use fluorophologopite (KMg
3AlSi
3O
10F, fusion method or solid reaction process), four silicon muscovite (KMg
2.5Si
4O
10F
2, fusion method), four silicon paragonite (NaMg
2.5Si
4O
10F
2, fusion method), sodium taincolite (NaMg
2LiSi
4O
10F
2, fusion method), lithium taincolite (LiMg
2LiSi
4O
10F
2, fusion method) etc. synthetic mica or hectorite sodium (Na
0.33Mg
2.67Li
0.33Si
4.0O
10(OH or F)
2, hydro-thermal reaction method or fusion method), hectorite lithium (Na
0.33Mg
2.67Li
0.33Si
4.0O
10(OH or F)
2, hydro-thermal reaction method or fusion method), saponite (Na
0.33Mg
2.67AlSi
4.0O
10(OH)
2, the hydro-thermal reaction method) etc. synthetic montmorillonite.
Wherein preferred especially four silicon paragonites utilize flux synthesis procedure to access and have needed particle diameter, aspect ratio, crystalline four silicon paragonites.
As the swelling inorganic layered compounds, preferably using its aspect ratio is 5～5,000, and further preferred aspect ratio is 100～5, in 000 scope, particularly preferably in 500～5, in 000 the scope.If aspect ratio less than 5, the image bleeding takes place sometimes then, on the other hand, if aspect ratio surpasses 5,000, then the uniformity of image is bad sometimes.Aspect ratio (Z) is to represent with the relation of Z=L/a, and wherein L is that the average major diameter of the particle of swelling inorganic layered compounds in water (is measured with laser diffractometry.Use the size distribution meter LA-910 of hole Games making manufacturing, the median particle diameter of 50% volume distributed median), a is the thickness of swelling inorganic layered compounds.
The thickness a of swelling inorganic layered compounds observes the value of trying to achieve by utilizing ESEM (SEM) or transmission electron microscope (TEM) that photo is carried out in the cross section on barrier layer.The average major diameter of the particle of swelling inorganic layered compounds is 0.1～100 μ m, is preferably 0.3～50 μ m, more preferably 0.5～20 μ m.Less than 0.1 μ m, then aspect ratio diminishes as the average major diameter of fruit granule, is difficult to simultaneously sprawl abreast on the intermediate layer comprehensively, can not prevent the bleeding of image fully.Become big as the average major diameter of fruit granule, surpassed 100 μ m, then the swelling inorganic layered compounds is outstanding from the barrier layer, takes place concavo-convexly on the surface on barrier layer, and the smoothness on receiving layer surface reduces, sometimes image quality aggravation.
In addition, in order to give disguised and white, to improve the texture of receiving sheet, in the barrier layer, can contain white inorganic pigment such as calcium carbonate as inorganic pigment, titanium dioxide, zinc oxide, aluminium hydroxide, barium sulfate, silica, aluminium oxide, talcum, kaolin, diatomite, satin white and fluorescent dye etc.
Barrier layer of the present invention preferably uses the water system coating fluid to form.For swelling and the dissolving that prevents hollow particle, preferred water system coating fluid does not contain the organic solvent of high polarity series solvents of higher boiling such as hydrocarbon system solvents such as lower alcohol series solvent, toluene, dimethylbenzene such as ester series solvent, methyl alcohol, ethanol such as ketone series solvent, ethyl acetate, dimethyl formamide (DMF), cellosolve such as MEK etc. not superfluously.
The solid constituent coating weight on barrier layer is preferably 0.5～8g/m
2Scope, and then be preferably 1～7g/m
2, be preferably 1～6g/m especially
2If barrier layer solid constituent coating weight is less than 0.5g/m
2, then the barrier layer can not cover interlayer surfaces fully sometimes, prevents that sometimes the effect of organic solvent infiltration is insufficient.On the other hand, if barrier layer solid constituent coating weight surpasses 8g/m
2, it is saturated, uneconomical then not only to be coated with effect, and because the thickness on barrier layer is excessive, can not give full play to the insulation effect and the resiliency in intermediate layer sometimes, causes image color and reduces.
(receiving layer)
In receiving sheet of the present invention, on above-mentioned barrier layer, receiving layer is set.Receiving layer itself can be known thermal dye transfer receiving layer.As the resin that forms receiving layer, thereby adopt the good resin of affinity height dyeing from the next dyestuff of China ink band migration.As such dyeing resin, for example can enumerate thermoplastic resin, active energy ray cured resins etc. such as the cellulose-derived system resin of mylar, polycarbonate resin, Corvic, vinyl chloride vinyl acetate copolymer resin, polyvinyl acetal resin, polyvinyl butyral resin, polystyrene resin, polyacrylate resin, cellulose acetate-butyrate etc., polyamide.These resins preferably contain used crosslinking agent are had reactive functional group (for example, functional groups such as hydroxyl, amino, carboxyl, epoxy radicals).
In receiving layer of the present invention,, and, be combined with crosslinking agents such as polyisocyanate compounds for making the three-dimensional cross-linked purpose of above-mentioned dyeing resin for the fusion that prevents from when printing, to cause receiving layer and China ink to be with by the heating of thermal head.In addition, in receiving layer, also can cooperate as among crosslinking agent additive, beyond the polyisocyanate compounds, releasing agent, the lubricant etc. more than a kind.And then, as required, also can in above-mentioned receiving layer, add among fluorescent dye, plasticizer, antioxidant, pigment, filler, ultra-violet absorber, light stabilizer, the antistatic additive etc. more than a kind.These additives both can mix with the formation composition of receiving layer before coating, also can be used as the coat different with receiving layer be coated on the top of receiving layer and/or below.
The formation of receiving layer, can be with the additive of necessity of dyeing resin and releasing agent etc., for example amino modified or hydroxyl modification silicone oil, the siloxane-based resin of acrylic acid silica alkane resin etc., silicone oil, releasing agent with fatty acid ester compound etc., the crosslinking agent of isocyanates based compound and epoxy based compound etc., phthalic acid ester system, fatty group dibasic acid system, trimellitate system, phosphate system, epoxy system, plasticizer with polyester system etc., ultra-violet absorber etc., suitably dissolve or be dispersed in and modulate the receiving layer coating fluid in the organic solvent, use known coating machine, be coated with being provided with on the sheet supporter on barrier layer, after the drying, carry out heat ageing as required, thereby form.
The solid constituent coating weight of receiving layer is 1～12g/m
2, 3～10g/m more preferably
2Scope.If the solid constituent coating weight of receiving layer is less than 1g/m
2, then sometimes receiving layer fully the covering barrier layer surface, cause image quality to reduce, or since the heating of thermal head that receiving layer and China ink are with is bonding, the fusion fault takes place.On the other hand, if the solid constituent coating weight surpasses 12g/m
2, it is saturated, uneconomical then not only to be coated with effect, and the coating strength deficiency or the coating thickness of receiving layer are excessive, thereby can not give full play to the insulation effect in intermediate layer, and the concentration that causes drawing a portrait reduces.
(back layer)
Receiving sheet of the present invention, can go up setting at the back side (surface of a side opposite with the side that receiving layer is set) of sheet supporter is the back layer of principal component with the macromolecule resin.This macromolecule resin can effectively improve back layer and supporter bonding strength, guarantee that the printing of receiving sheet carries property, prevents that the reception aspect is injured, prevents that dyestuff from moving to the back layer that contact with receiving layer.As such resin, can use the reaction solidfied material of acrylic resin, epoxy resin, mylar, phenol resin, alkyd resins, polyurethane resin, melmac, polyvinyl acetal resin etc. and these resins.In addition, in order to improve the cohesive of sheet supporter and back layer, suitably contain the crosslinking agent of polyisocyanate compounds, epoxide etc. overleaf in the layer.
Back layer preferably cooperates organic or inorganic filler is adjusted agent as coefficient of friction.As organic filler, can use nylon gasket, cellulose wadding, urea resin filler, styrene resin filler, acrylic resin filler etc.As inorganic filler, can use silica, barium sulfate, kaolin, clay, talcum, powdered whiting, precipitated calcium carbonate, titanium oxide, zinc oxide etc.
In the layer, print conveying property, antistatic overleaf, can add conductive agents such as electroconductive polymer and electric conductivity inorganic pigment in order to improve.As electroconductive polymer, preferably use cationic electroconductive polymer compound (for example, polymine, the acrylic acid series polymeric compounds that contains cationic monomer, cation-modified acrylamide polymer and cationic starch etc.).
Can contain anti-fusion agent such as releasing agent, lubricant as required in the layer overleaf.For example,, the siloxane-based compounds such as silicone oil, silicone block copolymer and silicon rubber of non-modification and modification can be enumerated,, phosphate compound, fatty acid ester compound, fluorine compounds etc. can be enumerated as lubricant as releasing agent.In addition, can suitably select, use existing known defoamer, dispersant, colored pigment, fluorescent dye, fluorescent pigment, ultra-violet absorber etc.
For will being that the paper base material of principal component is as the thermal transfer image receiving sheet sheet supporter, that have back layer with the cellulose pulp, about curling further investigation that prevents to cause by the ambient humidity fluctuation, the result distinguishes that the glass transition point (Tg) of the adhesive that uses in the layer has a significant impact the curling of receiving sheet overleaf.
Usually, acrylic resin, hear resistance, resistance to water excellence also can be used as the back layer adhesive, but in back layer of the present invention, and the acrylic resin that contains Tg and be below 45 ℃ is important as adhesive.The Tg of acrylic resin is more preferably below 30 ℃, and then is preferably-10～30 ℃.If the Tg of acrylic resin surpasses 45 ℃, then exist coating back layer time system film insufficient, be difficult to form high resiliency and tough epithelium, can not demonstrate fully the problem of the anti-curling effect that epithelium has.On the other hand, if Tg is low excessively, then receiving sheet is being overlapped each other, when the back layer surface contacts with the receiving layer surface, sticking together easily sometimes.
Acrylic resin of the present invention, be as principal component and synthetic polymer with various acrylic ester monomers, as this monomer, can be from acrylate, suitably select in the various acrylic ester monomers such as methacrylic acid, for example can enumerate methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, isodecyl methacrylate, lauryl methacrylate, methacrylic acid tridecyl ester, the methacrylic acid stearyl ester, cyclohexyl methacrylate, methacrylic acid benzyl ester etc.In addition, can in acrylic resin of the present invention, introduce reactive base.As reactive base, for example can enumerate amino, carboxyl, hydroxyl etc.
Adjusting for the Tg of acrylic resin, can be chosen in suitable academic documents, for example macromolecule association compiles " lecture 4 is learned in high molecular rerum natura II, macromolecule experiment ", uprightly altogether publishes, the Tg of the various monomers of record among the p51 (1959), by Fox formula (1/Tg=∑ w
i/ Tg
i" w in the formula
i" represent the mass fraction of each composition; " Tg
i" represent the Tg of each composition) can suitably design acrylic resin with required Tg.
As the concrete example of acrylic resin of the present invention, can enumerate the trade name FK420 (acrylic copolymer, Tg are 40 ℃) etc. of trade name AT510 (acrylate copolymer, Tg are 28 ℃), SEK301 (methacrylate polymers latex, Tg are 18 ℃), ET410 (acrylate copolymer, Tg are 44 ℃) and the central physics and chemistry system of the trade name Port リ ヅ-Le AT731 (methacrylate copolymer, Tg are 0 ℃) of clear and macromolecule system, Japanese pure medicine system.
In addition, the glass transition point of acrylic resin of the present invention (Tg) is according to the method for regulation among the JIS K 7121, the value of using differential heat scan type calorimeter (trade name: SSC5200, セ イ コ Application electronics industry society system) to measure.
In the present invention, the fusion of back layer and China ink band contains the resin extender that average grain diameter is 5～22 μ m in the layer overleaf in order to prevent to print overleaf.The average grain diameter of resin extender is preferably 8～20 μ m, is more preferably 8～15 μ m.If average grain diameter is less than 5 μ m, then the sliding deficiency of back layer can not fully prevent the fusion when print at the back side, if surpass 22 μ m, when then receiving sheet being overlapped each other, the impression with having large particle size filler on the receiving layer that back layer contacts causes bad influence to print image.
The content of the resin extender in the back layer need be preferably 2～20 quality % with respect to the total solid composition of back layer more than 2 quality %.If the addition of resin extender is less than 2 quality %, then sliding is insufficient sometimes.On the other hand, when the addition of resin extender is superfluous, because the reduction of the ratio of the acrylic resin in the back layer, so can not demonstrate fully the anti-effect of curling that epithelium has sometimes.
In addition, the average grain diameter of resin extender is to use particle size determination device (trade name: SALD2000, Shimadzu Seisakusho Ltd.) to measure.
As the composition of above-mentioned resin extender, can enumerate acrylic resin, polyvinyl resin, acrylic resin, starch, polyorganosiloxane resin, nylon resin, fluorine resin (for example TFE), benzoguanamine resin, polyurethane resin, SB resin etc.Wherein, the preferred filler that comprises acrylic resin, polyvinyl resin, starch, polyorganosiloxane resin and nylon resin etc. that uses, the preferred especially filler that comprises acrylic resin, polyvinyl resin, starch, polyorganosiloxane resin etc. that uses.
For the smoothness on back layer surface, the Bake smoothness of measuring according to JIS P 8119 need be below 100 seconds, preferably 5～50 seconds scope, and 5～30 seconds scope more preferably.If the Bake smoothness on back layer surface surpasses 100 seconds, then with receiving sheet coincidence each other, when back layer contact with receiving layer, receiving layer abrades easily, and the printing blank takes place sometimes.
The solid constituent coating weight of back layer is preferably at 0.3～10g/m
2Scope in.1～8g/m more preferably
2If back layer solid constituent coating weight is less than 0.3g/m
2, the anti-injured property in the time of then can not giving full play to receiving sheet and rubbed, the mobility that receiving sheet might take place in addition is bad.On the other hand, if the solid constituent coating weight surpasses 10g/m
2, then effect is saturated, and is uneconomical.
In the present invention, also can implement press polish, calendering (cast) and handle receiving sheet, this can reduce the receiving layer surface concavo-convex, make it smoothing.Press polish, calendering are handled, and can carry out in the arbitrary stage after intermediate layer, barrier layer or the receiving layer coating.Do not have particular restriction for the surface temperature that is used for calendering device that press polish handles, nip pressure, nip number, metallic roll etc., but the pressure condition when implementing press polish and handle is preferably 0.5～50MPa, more preferably 1～30MPa.Surface temperature for the calender device that is used to roll processing, nip pressure, stack does not have particular restriction yet, but as the preferred room temperature～hollow particle of temperature conditions do not destroy and the intermediate layer with below the fusing point of adhesive, be preferably 20～150 ℃, more preferably 30～130 ℃.As calendering device, can suitably use for example general calendering device that in paper making industry, uses such as supercalender, soft calender, gloss calender, gap calender.
In addition, the thickness of receiving sheet integral body is preferably 100～300 μ m.If this thickness is less than 100 μ m, then its mechanical strength becomes insufficient, and the rigidity of receiving sheet is also insufficient, can not fully prevent curling of the receiving sheet that takes place when printing sometimes.In addition, if thickness surpasses 300 μ m, thereby then cause the number of open ended receiving sheet in printing to reduce or if hold the number of defined and then need to increase the problem that the volume of accommodation section is difficult to realize the densification etc. of printer.
(manufacture method of thermal transfer image receiving sheet)
In the present invention, comprise intermediate layer, barrier layer, receiving layer and back layer, and other coating layer, can form according to conventional method, modulation contains the coating fluid of required composition respectively, use rod to be coated with that machine, gravure roll coating machine, comma (comma) coating machine, scraper plate coating machine, Kohler coater, door roll coater, mould are coated with machine, curtain is coated with known coating machines such as machine, labial lamina coating machine and sliding pearl coating machine, coating, drying on the surface of the defined of sheet supporter, thus form.
Embodiment
Describe the present invention in detail by following embodiment, but scope of the present invention is not limited by these embodiment.In addition, in an embodiment, unless otherwise specified, except the material of relevant solvent, " the quality % " and " mass parts " of " % " and " part " expression solid constituent.
Embodiment 1
[formation in intermediate layer]
As the sheet supporter, the art paper of used thickness 150 μ m (trade name: OK gold rattan N, 174.4g/m
2, Oji Paper system), to use thickness after the gravure roll coating machine forms the intermediate layer on its one side be the 51 μ m intermediate layer that is coated with following composition like that with coating fluid-1, thereby form the intermediate layer.
Intermediate layer coating fluid-1
With the polyacrylonitrile is the hollow particle of foaming of principal component
(average grain diameter 3.5 μ m, volume hollow rate 70%) 60 parts
20 parts of water dispersible acrylic resins (trade name: AE337, JSR system, minimum system film temperature are below 0 ℃)
20 parts of partly-hydrolysed polyvinyl alcohol (trade name: PVA205, Network ラ レ system, saponification degree 88%, the degree of polymerization 500)
1000 parts in water
[formation on barrier layer]
And then, the barrier layer coating fluid-1 of the following composition of coating on above-mentioned intermediate layer, making the solid constituent coating weight is 2g/m
2, drying, thus the barrier layer formed.
Moisture permeability after the barrier layer forms is 341g/m
2My god.
Barrier layer coating fluid-1
100 parts of ethylene-vinyl alcohol copolymers (trade name: RS4103, Network ラ レ system)
100 parts of styrene acrylic copolymer resinses (trade name: Port リ マ ロ Application 326, waste river chemistry system)
1000 parts in water
[formation of receiving layer]
And then, the receiving layer coating fluid-1 of the following composition of coating on above-mentioned barrier layer, making the solid constituent coating weight is 5g/m
2, carry out drying then.
Receiving layer coating fluid-1
100 parts in mylar (trade name: バ イ ロ Application 200, Japan's spinning)
3 parts of silicone oil (trade name: KF393, SHIN-ETSU HANTOTAI's chemical industry system)
5 parts of PICs (trade name: タ ケ ネ-ト D-140N, the military field of Mitsui ケ ミ カ Le system)
400 parts of toluene/MEK=1/1 (mass ratio) mixed liquors
[formation of back layer]
Then, on the face of the side that receiving layer is not set of sheet supporter the back layer of the following composition of coating to make the solid constituent coating weight with coating fluid-1 be 3g/m
2, and carrying out drying, to make the receiving sheet moisture rate be 5%, thus form back layer.And then, this sheet was worn out 48 hours down at 50 ℃, thereby obtain receiving sheet.The moisture permeability of gained receiving sheet integral body is 314g/m
2My god, the results are shown in table 1.
Back layer coating fluid-1
40 parts of polyvinyl acetal resins (trade name: worker ス レ Star Network KX-1, ponding chemical industry system)
20 parts of polyacrylate resins (trade name: ジ ユ リ マ-AT613, Japanese pure medicine system)
10 parts of nylon resin particles (trade name: MW330, refreshing eastern coating system)
10 parts of zinc stearates (trade name: Z-7-30, Zhong jing grease system)
20 parts of cationic electroconductive resins (trade name: ケ ミ ス タ Star ト 9800, Sanyo's system of changing into)
400 parts of water/isopropyl alcohol=2/3 (mass ratio) mixed liquors
Embodiment 2
In the formation in intermediate layer, except using following intermediate layer with the coating fluid-2, operation obtains receiving sheet similarly to Example 1.In addition, the moisture permeability behind the formation barrier layer is 323g/m
2My god.
[formation in intermediate layer]
Intermediate layer coating fluid-2
With the polyacrylonitrile is the hollow particle of foaming of principal component
(average grain diameter 3.5 μ m, volume hollow rate 70%) 60 parts
20 parts of water dispersible acrylic resins (trade name: FK402S, central physics and chemistry system, minimum system film temperature are below 0 ℃)
20 parts of partly-hydrolysed polyvinyl alcohol (trade name: PVA205, Network ラ レ system)
1000 parts in water
Embodiment 3
In the formation on barrier layer,, operate similarly to Example 1, thereby obtain receiving sheet except using following barrier layer with the coating fluid-2.In addition, the moisture permeability behind the formation barrier layer is 232g/m
2My god.
Barrier layer coating fluid-2
100 parts of ethylene-vinyl alcohol copolymers (trade name: RS4103L, Network ラ レ system)
100 parts of styrene acrylic copolymer resinses (trade name: Port リ マ ロ Application 326, waste river chemistry system)
Swelling inorganic layered compounds four silicon paragonites
(trade name: NTO-5, ト ピ-industry system) 100 parts
1000 parts in water
Embodiment 4
In the formation on barrier layer,, operate similarly to Example 1, thereby obtain receiving sheet except using following barrier layer with the coating fluid-3.In addition, the moisture permeability behind the formation barrier layer is 320g/m
2My god.
Barrier layer coating fluid-3
100 parts of fully saponified polyvinyl alcohol (trade name: PVA110, Network ラ レ system, saponification degree 98.5%, the degree of polymerization 1000)
100 parts of styrene acrylic copolymer resinses (trade name: Port リ マ ロ Application 326, waste river chemistry system)
1000 parts in water
Embodiment 5
In the formation in intermediate layer,, operate similarly to Example 1, thereby obtain receiving sheet except using following intermediate layer with the coating fluid-3.In addition, the moisture permeability behind the formation barrier layer is 315g/m
2My god.
Intermediate layer coating fluid-3
With the polyacrylonitrile is the hollow particle of foaming of principal component
(average grain diameter 3.5 μ m, volume hollow rate 70%) 60 parts
20 parts of water dispersible acrylic resins (trade name: AE337, JSR system, minimum system film temperature are below 0 ℃)
20 parts of low saponified polyvinyl alcohols (trade name: PVA505, Network ラ レ system, saponification degree 73%, the degree of polymerization 500)
1000 parts in water
Embodiment 6
In the formation in intermediate layer, use above-mentioned intermediate layer coating fluid-3 (in embodiment 5, modulating), and then in the formation on barrier layer, use above-mentioned barrier layer coating fluid-2 (in embodiment 3, modulating), in addition, operation obtains receiving sheet similarly to Example 1.In addition, the moisture permeability behind the formation barrier layer is 220g/m
2My god.
Comparative example 1
Except using following intermediate layer with the coating fluid-4 in the formation in intermediate layer, operation obtains receiving sheet similarly to Example 1.In addition, the moisture permeability behind the formation barrier layer is 450g/m
2My god.
[formation in intermediate layer]
Intermediate layer coating fluid-4
With the polyacrylonitrile is the hollow particle of foaming of principal component
(average grain diameter 3.5 μ m, volume hollow rate 70%) 60 parts
20 parts of water dispersible acrylic resins (trade name: SX1706, Japanese ゼ ォ Application system, minimum system film temperature〉0 ℃)
20 parts of partly-hydrolysed polyvinyl alcohol (trade name: PVA505, Network ラ レ system)
100 parts in water
Comparative example 2
In the formation of layer overleaf, adjust the dry moisture rate that makes the dried receiving sheet of coating and be 10%, operation similarly to Example 1, thus obtain receiving sheet.
Comparative example 3
In the formation of layer overleaf, adjust the dry moisture rate that makes the receiving sheet after the burin-in process and be 1%, operation similarly to Example 1, thus obtain receiving sheet.
Estimate
For the receiving sheet that in each above-mentioned embodiment and comparative example, obtains, to estimate by following method respectively, gained the results are shown in table 1.
[determination of moisture]
As the determination of moisture of the receiving sheet before and after the burin-in process, measure moisture content (%) according to JIS P 8127.Directly measure the quality of the test film before dry with container under the state that the container of test film is added a cover, then directly put under test film is put into the state of container and be adjusted to 105 ℃ drying machine, take off the lid of container, drying is more than 60 minutes.After the drying, in drying machine, add a cover, it is transferred in the drier, be chilled to till the room temperature, measure the quality of test film then.Water content (%) utilizes following formula to calculate:
[(quality of the quality-dried test film of the test film before dry)/(quality of the test film before dry)] * 100
[moisture permeability mensuration]
The moisture permeability of receiving sheet is according to JIS K 7129, uses moisture permeability to measure machine (trade name: L80-4000, リ Star シ one system) automatically, adopts sense wet sensor method to measure.The moisture permeability of the receiving sheet integral body after aging is shown in table 1.
[image uniformity]
Use commercially available heat transfer image printer (trade name: UP-DR100, Sony system), under 23 ℃, the atmosphere of 50%RH, to on the polyester film of thickness 6 μ m, be provided with the ink lay of all kinds of China ink band of ink lay that adhesive together contains the sublimable dye separately of Huang, magenta, blue or green three looks and contact with receiving sheet in turn, by implement the heating of ladder ground control with thermal head, the thermal image transfer printing of defined to receiving sheet, has been printed the image of folded look.And then the uniformity that optical concentration (deceiving) is equivalent to the print image of 0.3 tonal gradation part is carried out visual valuation from gradation unequal evenness and blank having or not.
The outstanding note of evaluation result is done " good ", is had the even or blank note of some gradation unequals to do " generally ", and the note that the even blank of gradation unequal is many is done " bad ".If be evaluated as, then fully be suitable for practicality.
[China ink is with cold peeling force]
Make and on the polyester film of thickness 6 μ m, be provided with the China ink band that contains the ink lay of yellow sublimable dye with adhesive, use commercially available heat transfer image printer (trade name: UP-DR100, Sony system) that the China ink band is transferred on the receiving sheet.The China ink band that is transferred is cut into width 100mm, China ink band speed with 30mm/ second under 23 ℃, 50%RH atmosphere is peeled off in the horizontal direction, the electricity consumption sub-spring claims to measure peeling force.
According to this assay method, if peeling force less than 100gf, then can not fuse when actual printing, if but more than 100gf, then have receiving sheet and China ink band that the possibility of fusion takes place in the seal iseikonia under hot and humid etc.
[impact hardness in intermediate layer]
Use the little hardometer of ultra micro (trade name: DUH-21H, society of Shimadzu Seisakusho Ltd. system), measure the impact hardness in the intermediate layer of receiving sheet.Pressure head uses 115 ° of pyrometric cone pressure heads, sets the feasible compression distance apart from the receiving layer surface of load and surpasses receiving layer thickness, reaches till the intermediate layer.
[pore diameter in intermediate layer, pore volume]
Use the forced pore size determination instrument of mercury (trade name: Port ア サ イ ザ-9320, society of Shimadzu Seisakusho Ltd. system), this pore of 2 kinds of article of measuring sheet supporter and formation intermediate layer distributes.By both sides' result relatively, the peak of the pore of specific based intermediate layer coating layer, thus obtain the value of the pore volume of the value of pore diameter and based intermediate layer coating layer.
Table 1
| Before the receiving sheet moisture burin-in process (%) | After the receiving sheet moisture burin-in process (%) | Blank film moisture permeability g/m 2My god | Cold peeling force gf/100m | The image uniformity | The intermediate layer impact hardness | Intermediate layer pore diameter μ m | Intermediate layer pore volume cc/g | |
| Embodiment 1 | 5.0 | 4.5 | 314 | 90 | Good | 0.50 | 0.28 | 0.13 |
| Embodiment 2 | 5.0 | 4.5 | 290 | 72 | Good | 0.55 | 0.82 | 0.48 |
| Embodiment 3 | 5.0 | 4.5 | 217 | 53 | Good | 0.51 | 0.28 | 0.13 |
| Embodiment 4 | 5.0 | 4.5 | 305 | 80 | Good | 0.50 | 0.28 | 0.13 |
| Embodiment 5 | 5.0 | 4.5 | 288 | 68 | Good | 0.48 | 0.31 | 0.15 |
| Embodiment 6 | 5.0 | 4.5 | 205 | 50 | Good | 0.48 | 0.31 | 0.15 |
| Comparative example 1 | 5.0 | 4.5 | 432 | 297 | Good | 3.30 | 0.05 | 0.06 |
| Comparative example 2 | 10.0 | 9.5 | 314 | 150 | Good | 0.50 | 0.28 | 0.13 |
| Comparative example 3 | 0.5 | 1.0 | 314 | 48 | Bad | 0.50 | 0.28 | 0.13 |
Embodiment 7
(making of intermediate layer coated sheets)
70 parts of the aqueous dispersions (solid component concentration is 30%) of hollow particle (principal component: polyacrylonitrile, average grain diameter 5.4 μ m, volumetric porosity 75%) that will foam, 15 parts of the aqueous solution (solid component concentration is 10%), the SB latex (trade name: L-1537, solid component concentration 50%, Asahi Chemical Industry's system) of polyvinyl alcohol (trade name: PVA217, Network ラ レ system) mix stirring for 15 parts, obtain the intermediate layer coating fluid.Then, use art paper (trade name: OK gold rattan N, weight per unit area 186g/m
2, Oji Paper system) as supporter, on its one side, use mould to be coated with machine coating and dry, making dried coating weight is 20g/m
2Thereby, make the intermediate layer coated sheets.
(making of barrier-coated sheet)
4 parts of 100 parts of the aqueous solution (solid component concentration 10%) of mixing pva in 100 parts of the aqueous dispersions (the average major diameter 6.3 μ m of particle, aspect ratio are 2700,5% aqueous dispersions) of swelling inorganic layered compounds four silicon paragonites (trade name: PVA105, the degree of polymerization about 500, Network ラ レ system), SB latex (trade name: L-1537, solid component concentration are 50%, Asahi Chemical Industry's system) also stir, and obtain the barrier layer coating fluid.Then, on the intermediate layer of above-mentioned intermediate layer coated sheets, use メ イ ヤ one rod to be coated with machine, barrier-coating is also dry with coating fluid, and making dried coating weight is 3g/m
2Thereby, make the barrier-coated sheet.
(making of back layer coated sheets)
70 parts of acrylate copolymers (trade name: AT731, clear and macromolecule system, Tg are 0 ℃, solid component concentration 50%), 10 parts of acrylic resin fillers (trade name: MA1013, Japanese catalyst system, average grain diameter 13 μ m), 10 parts of kayexalates (trade name: CS6120, the Sanyo system of changing into), 10 parts of zinc stearates (trade name: Z-8-36, solid component concentration 30%, Zhong jing grease system) are mixed stir, thereby obtain the back layer coating fluid.Then on the back side of above-mentioned barrier-coated sheet, use メ イ ヤ one rod to be coated with machine, making dried coating weight is 5g/m
2Be coated with the back layer coating fluid like that, drying, thus make the back layer coated sheets.
(making of receiving sheet)
バ イ ロ Application 200, Japan spinning), 2 parts of silicone oil (trade name: KF393, SHIN-ETSU HANTOTAI's chemistry system), 6 parts of isocyanate compounds (trade name: タ ケ ネ one ト D-110N, military field medicine system) are dissolved in 200 parts the mixed solvent of toluene/MEK=1/1 (mass ratio) with 100 parts of mylar (trade name:, mix and stir, thereby obtain the receiving layer coating fluid.Then, on the barrier layer of above-mentioned back layer coated sheets, use the gravure roll coating machine, making dried coating weight is 6g/m
2Be coated with the receiving layer coating fluid like that, drying, thus obtain receiving sheet.
Embodiment 8
Except in the making of the back layer coated sheets of embodiment 7, using 70 parts of acrylate copolymer (trade names: AT510, the pure medicine system of Japan, Tg is 28 ℃, solid component concentration 30%), 10 parts of silicone powder (trade names: KPM601, SHIN-ETSU HANTOTAI's chemistry system, average grain diameter 12 μ m) replace 70 parts of acrylate copolymer (trade names: AT731, clear and macromolecule system, Tg is 0 ℃, solid component concentration 50%) and 10 parts of acrylic resin filler (trade names: MA1013, Japan's catalyst system, average grain diameter 13 μ m) outside, operation obtains receiving sheet similarly to Example 7.
Embodiment 9
Except in the making of the back layer coated sheets of embodiment 7, using 65 parts acrylate copolymer (trade name: SEK301, the pure medicine system of Japan, Tg is 18 ℃, solid component concentration 40%), 15 parts of polyethylene emulsion (trade names: SN コ-ト 950, サ Application ノ プ コ system, average grain diameter 10 μ m) replace 70 parts of acrylate copolymer (trade names: AT731, clear and macromolecule system, Tg is 0 ℃, solid component concentration 50%) and 10 parts of acrylic resin filler (trade names: MA1013, Japan's catalyst system, average grain diameter 13 μ m) in addition, operation obtains receiving sheet similarly to Example 7.
Estimate
For the receiving sheet that in the various embodiments described above and comparative example, obtains, carry out the quality evaluation of following project.Evaluation result is shown in table 2.
[warpage of receiving sheet, printing mobility]
(I) under the high humidity environment
With receiving sheet be cut into the postcard of certain specification size (100mm * 148mm) under 20 ℃, 90%RH environment, placed 3 hours on horizontal plane, measure then four jiaos of receiving sheets, from the height of horizontal plane warpage, calculate mean value, as curling numerical value.Under same environmental condition, 10 receiving sheets are positioned in the heat of sublimation transferred image printer (trade name: NV-AP1, Matsushita Electric Industries industry society system) print black solid images, the mobility of evaluation receiving sheet.
(II) under the low wet environment
Then, under 20 ℃, the environment of 10%RH,, measure curling of receiving sheet, in addition, estimate the mobility of receiving sheet with above-mentioned same operation.
＜evaluation criterion 〉
Excellent: under the low wet environment of high humidity, the back of the body of receiving sheet curls or upsweeps to below the 3mm, does not almost have warpage, and printing mobility and row's paper are also excellent.
Good: under the low wet environment of high humidity, the back of the body of receiving sheet curls or upsweeps above 3mm but below 5mm, some warpages are arranged, and printing mobility and row's paper are also good.
Generally: under the low wet environment of high humidity, the back of the body of receiving sheet curls or upsweeps above 5mm but below 10mm, some warpages are arranged, but the printing mobility do not have problems, and row's paper is also smooth, and is no problem in the practicality.
Bad: under any environment of high humidity low humidity, upsweeping or carrying on the back to curl all surpasses 10mm, when printing generation by warpage cause mobile bad, in practicality, have problems.
[suitable property is printed at the back side]
In heat of sublimation transferred image printer (trade name: NV-AP1, Matsushita Electric Industries industry society system), be placed to 10 receiving sheets opposite with common positive and negative, under 23 ℃, 50%RH environment, the print black solid images is estimated the back side of receiving sheet and is printed suitable property according to following standard.
＜metewand 〉
Good: the fusion that does not have back side coating layer and China ink to be with fully, normally arrange paper.
Generally: a little fusion of back side coating layer and China ink band, but can arrange paper in no problem ground, be realistic scale.
Bad: back side coating layer fuses with black being with, and has taken place to stop up and the black fault that ruptures of being with in printer, has problems in practicality.
[receiving the concavo-convex of aspect]
Concavo-convex for the receiving layer surface of gained receiving sheet estimated by following standard is visual.
＜evaluation criterion 〉
Good: do not have fully concavo-convex, the outward appearance excellence.
Generally: a little concavo-convex, do not have problems in the practicality.
Bad: concavo-convex obvious, outward appearance is bad.
Table 2
Can confirm from the result of table 2, the receiving sheet of embodiment 7～9, even the environmental change warpage is also little, the printing mobility is good, does not also exist the back side to print suitable property problem, print image is also good.Utilizability on the industry
The invention provides a kind of thermal transfer image receiving sheet that has overcome receiving sheet and China ink band are easy to fuse when printing problem and image excellent in uniformity, practical aspect excellence, described thermal transfer image receiving sheet is to be that the paper of principal component is as supporter with the cellulose pulp.The present invention so provide a kind of warpage that causes by environmental fluctuating little, in printer, do not have the fusion, the yet good thermal transfer image receiving sheet of mobility that stop up paper and overlapping paper feeding etc., printing mobility excellence and do not have back side coating layer and China ink band when printing overleaf.
Claims (17)
1. thermal transfer image receiving sheet, it is characterized in that, be on the one side of sheet supporter that is principal component, to form in turn to contain the intermediate layer of hollow particle, the thermal transfer image receiving sheet of image receiving layer with the cellulose pulp, above-mentioned intermediate layer contain saponification degree be 65～90% and the degree of polymerization be 200～1000 polyvinyl alcohol resin, the moisture content of described thermal transfer image receiving sheet integral body is 2～8 quality %, and the moisture permeability of receiving sheet integral body is 400g/m
2Below it.
2. thermal transfer image receiving sheet as claimed in claim 1, above-mentioned image receiving layer contain the dyeing resin and this resin are carried out the crosslinked crosslinking agent with water reactive functional groups as principal component.
3. thermal transfer image receiving sheet as claimed in claim 2, above-mentioned crosslinking agent with water reactive functional groups is a polyisocyanate compounds.
4. thermal transfer image receiving sheet as claimed in claim 1, water soluble polymer and water-dispersed resin are contained in above-mentioned intermediate layer, and the minimum system film temperature of above-mentioned water-dispersed resin is below 0 ℃.
5. thermal transfer image receiving sheet as claimed in claim 1, the impact hardness in above-mentioned intermediate layer are below 3.0.
6. thermal transfer image receiving sheet as claimed in claim 1, above-mentioned intermediate layer are that the scope of 0.01～10 μ m has the peak in pore diameter in the pore measure of spread that utilizes the forced pore size determination instrument of mercury to carry out.
7. thermal transfer image receiving sheet as claimed in claim 6, the pore volume in zone, above-mentioned peak is in the scope of 0.01～0.7cc/g.
8. thermal transfer image receiving sheet as claimed in claim 1 further is formed with the barrier layer between above-mentioned intermediate layer and image receiving layer, swelling inorganic layered compounds and adhesive are contained as principal component in above-mentioned barrier layer.
9. thermal transfer image receiving sheet as claimed in claim 1, the another side of above-mentioned supporter is provided with back layer.
10. thermal transfer image receiving sheet as claimed in claim 9, above-mentioned back layer is that acrylic resin below 45 ℃ is a principal component with glass transition point (Tg), and contain the resin extender that average grain diameter is 5～22 μ m, the Bake smoothness that records according to JIS P 8119 on back layer surface is below 100 seconds.
11. the manufacture method of a thermal transfer image receiving sheet, be on the one side of sheet supporter that is principal component, to be formed with in turn to contain hollow particle and saponification degree is 65～90% with the cellulose pulp, and the degree of polymerization is the intermediate layer of 200～1000 polyvinyl alcohol resin, the manufacture method of the thermal transfer image receiving sheet of image receiving layer, on the one side of above-mentioned sheet supporter, form in turn and contain after the intermediate layer and image receiving layer of hollow particle, the moisture content of thermal transfer image receiving sheet integral body is adjusted to 1～8 quality %, wear out then, the moisture permeability of this thermal transfer image receiving sheet integral body is 400g/m
2Below it.
12. the manufacture method of thermal transfer image receiving sheet as claimed in claim 11, above-mentioned image receiving layer contain the dyeing resin and this resin are carried out the crosslinked crosslinking agent with water reactive functional groups as principal component.
13. the manufacture method of thermal transfer image receiving sheet as claimed in claim 12, above-mentioned crosslinking agent with water reactive functional groups is a polyisocyanate compounds.
14. the manufacture method of thermal transfer image receiving sheet as claimed in claim 11 is included between above-mentioned intermediate layer and the image receiving layer operation that further forms the barrier layer, swelling inorganic layered compounds and adhesive are contained as principal component in above-mentioned barrier layer.
15. the manufacture method of thermal transfer image receiving sheet as claimed in claim 11, on the one side of above-mentioned sheet supporter, form in turn and contain the intermediate layer of hollow particle, arbitrarily after barrier layer and the image receiving layer, further be included in the operation that back layer is set on another face of above-mentioned supporter.
16. the manufacture method of thermal transfer image receiving sheet as claimed in claim 15, it is characterized in that, above-mentioned back layer is that acrylic resin below 45 ℃ is a principal component with glass transition point (Tg), and contain the resin extender that average grain diameter is 5～22 μ m, the Bake smoothness that records according to JIS P 8119 on back layer surface is below 100 seconds.
17. the manufacture method of thermal transfer image receiving sheet as claimed in claim 11 is adjusted into 400g/m with the above-mentioned moisture permeability that wears out preceding sheet supporter integral body
2Below it.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004201552A JP4341491B2 (en) | 2004-07-08 | 2004-07-08 | Thermal transfer receiving sheet |
| JP201552/2004 | 2004-07-08 | ||
| JP2004208402 | 2004-07-15 | ||
| JP208402/2004 | 2004-07-15 | ||
| JP264392/2004 | 2004-09-10 | ||
| JP2004264392 | 2004-09-10 | ||
| PCT/JP2005/012973 WO2006006639A1 (en) | 2004-07-08 | 2005-07-07 | Thermal transfer receptive sheet and process for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101619792A Division CN101856925B (en) | 2004-07-08 | 2005-07-07 | Thermal transfer receiving sheet and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1980798A CN1980798A (en) | 2007-06-13 |
| CN1980798B true CN1980798B (en) | 2011-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2005800230144A Expired - Fee Related CN1980798B (en) | 2004-07-08 | 2005-07-07 | Thermal transfer receptive sheet and process for producing the same |
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| Country | Link |
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| JP (1) | JP4341491B2 (en) |
| CN (1) | CN1980798B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009083298A (en) * | 2007-09-28 | 2009-04-23 | Dainippon Printing Co Ltd | Heat transfer image receiving sheet |
| US20100311296A1 (en) * | 2009-06-09 | 2010-12-09 | Boehmer Brian E | Dyed cellulose comminution sheet, dyed nonwoven material, and processes for their production |
| JP2013010662A (en) * | 2011-06-29 | 2013-01-17 | Asahi Kasei Corp | Dispersion liquid of layered inorganic compound |
| WO2014168784A1 (en) * | 2013-04-08 | 2014-10-16 | Kodak Alaris Inc. | Thermal image receiver elements prepared using aqueous formulations |
| JP6163925B2 (en) * | 2013-07-12 | 2017-07-19 | 凸版印刷株式会社 | Matte-like transfer film and molded product using the same |
| CN108944109B (en) * | 2018-06-29 | 2020-11-13 | 浙江真爱时尚家居有限公司 | Rainbow blanket manufacturing process |
| CN112622469A (en) * | 2020-12-29 | 2021-04-09 | 福州艾瑞数码影像有限公司 | Ink-jet printing heat transfer film capable of preventing sublimation dye ink from migrating |
| CN115635786A (en) * | 2022-09-28 | 2023-01-24 | 湖南鼎一致远科技发展有限公司 | High-concentration and high-uniformity coated paper coating suitable for thermal sublimation soft label printing |
-
2004
- 2004-07-08 JP JP2004201552A patent/JP4341491B2/en not_active Expired - Fee Related
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2005
- 2005-07-07 CN CN2005800230144A patent/CN1980798B/en not_active Expired - Fee Related
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| JP2006021431A (en) | 2006-01-26 |
| CN1980798A (en) | 2007-06-13 |
| JP4341491B2 (en) | 2009-10-07 |
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