CN100496994C - Thermal transfer receptive sheet, process for producing the same and method of image forming therewith - Google Patents

Abstract

A thermal transfer receiving sheet comprising a sheet-like support having sequentially formed on at least one surface thereof a hollow particle-containing intermediate layer and an image receiving layer, wherein the hollow particles have an average particle diameter of 0.2 to 35 m and a hollow percentage by volume of 30 to 97% and the printing smoothness (Rp value) on the surface of the thermal transfer receiving sheet, as measured by using a Microtopograph under an applied pressure of 0.1 MPa 10 m-seconds after the initiation of pressure application, is 1.5 m or less. A production method of the thermal transfer receiving sheet is also provided.

Description

Hot transfer printing receiver sheet, its preparation method and adopt the image forming method of this sheet material

Technical field

The present invention relates to hot transfer printing receiver sheet, its be used for by it is superimposed upon thermal transfer sheet (China ink band) is gone up and by thermal head make this China ink with on thermal dye transfer form image.More specifically, the present invention relates to be specially adapted to the thermal dye transfer printer and between sheet supporter and image receiving layer, have the hot transfer printing receiver sheet (hereinafter abbreviating " receiver sheet " sometimes as) in the intermediate layer that comprises hollow particle, the invention still further relates to the image forming method of preparation method and this hot transfer printing receiver sheet of employing of described hot transfer printing receiver sheet.

Background technology

Recently, thermal printer is noticeable, and it is especially noticeable to print the thermal dye transfer printer of full-colour image clearly.In the thermal dye transfer printer, the dye coating that contains dyestuff of China ink band is superimposed on the image receiving layer that contains the dye capable of dyeing resin (hereinafter abbreviating " receiving layer " sometimes as) of receiver sheet, by the first-class heat effect that provides of temperature-sensitive, to be transferred on the described receiving layer with predetermined concentration at the dyestuff of the dye coating of required part, thereby form image.In the China ink band, order provides four look dye coating zones of yellow, magenta, cyan three look dye coatings zone or these three kinds of colors and black.On receiver sheet, obtain coloured image by the corresponding color dye of order repetitive displacement.Under the situation of the printer of described thermal dye transfer system, receiver sheet generally infeeds with the flat sheet form.

Along with the development of digital image that adopts computer, the image quality in images by thermal dye transfer system record etc. is significantly improved, and the market of this system obtains enlarging.In addition, the technology of control thermal head temperature is improved, and is thereupon, growing to the demand of high speed high sensitivity print system.Therefore, how effectively the calorific value of firing equipment such as thermal head being applied to form image is one major issue to be solved is arranged.Equally, also require low, the designs simplification of printer cost, this will bring as reducing the squeegee pressure that is produced by thermal head and prolonging technical problem such as print head longevity.At present, can obtain in 30 seconds, to print the printer of an A6 sized sheets on the market, estimate that following demand to the more speed printing will increase.

In order to form high-quality and highdensity image effectively, the general receiver sheet that comprises the supporter that the receiving layer that mainly comprises the dye capable of dyeing resin is provided on it that adopts, but when adopting normal film as the substrate of supporter, although it has excellent smoothness, but the heat that is dispersed into this substrate from thermal head can cause the recording sensitivity deficiency, perhaps when film lacks gratifying shock-absorbing capacity, described China ink band is not satisfied with close contact the between the receiver sheet, and the result causes problems such as density unevenness is even.

In order to address these problems, proposed for example to adopt with foam films and core material floor such as the stacked supporter that obtains of papery sheet material (for example referring to Japanese unexamined patent publication No. open (kokai) 61-197282 number (the 1st page)), and the biaxially-stretched film (synthetic paper) that will mainly comprise thermoplastic resin (as vistanex) and gap structure and core material floor such as the stacked supporter that obtains of papery sheet material (for example disclosing (kokai) 62-198497 number (the 1st page) referring to Japanese unexamined patent publication No.) are as supporter.Adopt the receiver sheet of this supporter aspect heat-insulating property and smoothness, to show excellence, but weak point is that it has paper shape quality, perhaps costs an arm and a leg.

In addition, when adopting the papery sheet material as the supporter of described receiver sheet, similar with described film, its recording sensitivity deficiency, though shock-absorbing capacity is higher slightly than described film, but because the fibre density of paper is inhomogeneous, thereby described China ink band becomes inhomogeneous with close contact the between the receiving layer, and printed article has irregular depth effect easily.Therefore, in order to improve transfer printing density etc., disclose a kind of receiver sheet, the intermediate layer that comprises hollow particle (for example referring to open (kokai) 63-87286 number (the 1st, 2 page) of Japanese unexamined patent publication No. and 1-27996 number (1-3 page or leaf)) wherein is provided between described papery supporter and receiving layer.In this receiver sheet, by strengthening described heat-insulating property or the shock-absorbing capacity that comprises the layer of hollow particle, sensitivity is improved, but described hollow particle is easy to produce scrambling on the receiver sheet surface.

For the improvement of the lip-deep scrambling of described receiver sheet, the receiver sheet that the average particulate diameter of the hollow particle by being given for described intermediate layer or hollow rate have particular surface roughness for example or glossiness (for example referring to Japanese unexamined patent publication No. open (kokai) 9-99651 number (1-5 page or leaf) and 2001-39043 number (the 2nd, 3 page)) has been proposed.In addition, proposed to comprise the receiver sheet of substrate sheet, on this substrate sheet, be formed with the resin bed that comprises bubble layer and receiving layer, wherein described bubble layer and/or receiving layer carried out smoothing processing (for example referring to Japanese unexamined patent publication No. open (kokai) 6-210968 number (2-4 page or leaf)).

Yet, not necessarily have satisfied correlation at the surface roughness value of the receiving layer of measuring by the general measure method and between by the quality of the actual image that obtains of thermal dye transfer printer.Especially, be low squeegee pressure down by in the present high-speed printer printing, almost the picture quality that can not obtain.In addition, when the volume hollow rate of described hollow particle improved, the surface of described receiver sheet was drawn easily and is carved.That is to say, exist in when handling printed matter because nail, nib etc. are easy to generate the problem of cut to the collision of sheet surface, and commercial value seriously descends.

In addition, in order to improve the lip-deep smoothness of described receiver sheet, proposed to have the receiver sheet of the porous layer that comprises a plurality of layers, the laminate layers that forms by the coextrusion thermoplastic resin (for example referring to Japanese unexamined patent publication No. open (kokai) 2000-272259 number (the 2nd page)) wherein is provided on described porous layer.Yet, when will be by the resin solution that comprises bubble that stir to form or the heat-swellable resin that forms excessive hollow during as the porous layer of core material layer side, almost can not obtain enough smoothnesses, perhaps because heat effect, the formation of described laminate layers may for example cause the loose structure distortion of described porous layer and cave in, and the effect that improves described sensitivity and picture quality not necessarily reaches satisfied level.In addition, proposed to have the receiver sheet of receiving layer, wherein the different tiny hollow particle of two or more particle diameters is introduced in the described receiving layer (for example referring to Japanese unexamined patent publication No. open (kokai) 11-291647 number (the 2nd page)), but be present in the effect that the hollow particle in the receiving layer can not provide heat-insulating property or shock-absorbing capacity to strengthen satisfactorily, and can influence stainability of described receiving layer etc. unfriendly, therefore, image has not enough uniformity easily.

In addition, the partition wall that is used for the hollow particle of these receiver sheets with intermediate layer is to be formed by the low polymeric material of glass transition temperature, therefore, the hear resistance of described hollow particle is bad usually, heat in the time of may producing owing to receiver sheet or when printing are from the heat of thermal head and thermal deformation or cave in, make the control printing density difficulty that becomes, perhaps printing zone may since heat and indenture to cause appearance damage.Correspondingly, in by the printing of present high-speed printer, may can not get sufficiently high picture quality.

In addition, proposed to comprise the receiver sheet of the paper substrate of the layer that contains hollow particle that has on it order stack and dyestuff receiving layer, wherein the buffering deformation rate of whole receiver sheet is 10～30% (for example disclosing (kokai) 2002-200851 number (2-5 page or leaf) referring to Japanese unexamined patent publication No.).Although be used for the structural material of the partition wall of described hollow particle from the viewpoint selection that improves solvent resistance, because do not consider hear resistance at all, therefore the demand of improving still exists.

Summary of the invention

Finished the present invention under these circumstances, and one object of the present invention is by providing the hot transfer printing receiver sheet that is specially adapted to the thermal dye transfer printer and has an intermediate layer of containing hollow particle to solve the problems referred to above of traditional receiver sheet, wherein under the situation that does not adopt expensive synthetic paper or foam films, the equating and improvement image deflects such as irregular depth effect and white point when realizing low cost, high sensitivity and high image quality of the printing density that guarantees described receiver sheet and synthetic paper or foam films.Purpose of the present invention comprises preparation method that described receiver sheet is provided and the image forming method that adopts this receiver sheet.One preferred embodiment in, the invention provides above-mentioned hot transfer printing receiver sheet, it has fully high compression strength and the indenture phenomenon can not occur.In an embodiment that is more preferably, the invention provides above-mentioned hot transfer printing receiver sheet, it also has sufficiently high hear resistance.

The present invention includes following invention:

(1) a kind of hot transfer printing receiver sheet, it comprises and has on its at least one surface the intermediate layer of containing hollow particle that order forms and the sheet supporter of image receiving layer, the average particulate diameter of wherein said hollow particle is 0.2～35 μ m, the volume hollow rate is 30～97%, in the lip-deep printing smoothness of described hot transfer printing receiver sheet (Rp value) that is beginning under the exerting pressure of 0.1MPa to exert pressure after 10 milliseconds by adopting microstructure analysis to record is 1.5 μ m or littler, described intermediate layer comprises two kinds of different hollow particle A of average particulate diameter and B, and the average particulate diameter L of hollow particle separately _A(μ m) and L _B(μ m) satisfies following all relational expressions (1)～(3):

L _A＝2～35μm (1)

L _B＝0.2～9μm (2)

0.05≤L _B/L _A≤0.4 (3)。

(2) according to the hot transfer printing receiver sheet of (1), the thickness in wherein said intermediate layer is 20～90 μ m.

(3) according to the hot transfer printing receiver sheet of (1) or (2), all hollow particles in wherein said intermediate layer and the quality ratio of all solids content are 30～75 quality %.

(4) according to (1) to (3) each hot transfer printing receiver sheet, it has the barrier layer that is superimposed between described intermediate layer and the described image receiving layer.

(5) according to (1) to (4) each hot transfer printing receiver sheet, wherein said sheet supporter is the sheet supporter that mainly comprises cellulose slurry.

(6), wherein on that side that image receiving layer wherein is not provided of described sheet supporter, provide to comprise the back of the body superficial layer of fluoropolymer resin and organic and/or fine inorganic particles at least according to (1) to (5) each hot transfer printing receiver sheet.

(7) according to (1) to (6) each hot transfer printing receiver sheet, wherein said hot transfer printing receiver sheet is 30MPa or littler based on the elastic compression modulus of JIS K7220.

(8) according to (1) to (7) each hot transfer printing receiver sheet, it is the hollow particle that 130 ℃ or higher polymeric material form partition wall as described hollow particle by glass transition temperature that wherein said intermediate layer comprises.

(9), be that the polymeric material that 130 ℃ or higher polymeric material form the described hollow particle of partition wall is obtained by the component that mainly comprises the itrile group monomer wherein by glass transition temperature according to the hot transfer printing receiver sheet of (8).

(10) according to the hot transfer printing receiver sheet of (9), wherein said itrile group monomer is to be selected from least a in acrylonitrile, methacrylonitrile, α-Lv Daibingxijing, α-ethoxy propylene nitrile and the anti-maleic nitrile.

(11) a kind of employing according to (1) to (10) each the image forming method of hot transfer printing receiver sheet, it is included in by during the printing of thermal dye transfer printer and/or apply the step of 1.0MPa or bigger pressure treatment afterwards to described hot transfer printing receiver sheet surface.

(12) a kind of manufacturing comprises the method for the hot transfer printing receiver sheet of the sheet supporter that has on its at least one surface the intermediate layer of containing hollow particle that order forms and image receiving layer, this method comprise the following steps: on by at least one surface coating at described sheet supporter comprise average particulate diameter for 0.2～35 μ m and volume hollow rate for the intermediate layer coating solution of 30～97% hollow particle and make its dry described intermediate layer is provided after and/or after on described intermediate layer, providing described image receiving layer, carry out described sheet material by having the smoothing processing step of the cramping parts of forming by warm-up mill and pressure roller that become pair roller, thereby make that in the lip-deep printing smoothness of described hot transfer printing receiver sheet (Rp value) that is beginning under the exerting pressure of 0.1MPa to exert pressure after 10 milliseconds by adopting microstructure analysis to record be 1.5 μ m or littler, described intermediate layer comprises two kinds of different hollow particle A of average particulate diameter and B, and the average particulate diameter L of hollow particle separately _A(μ m) and L _B(μ m) satisfies following all relational expressions (1)～(3):

L _A＝2～35μm (1)

L _B＝0.2～9μm (2)

0.05≤L _B/L _A≤0.4 (3)。

(13) method of the hot transfer printing receiver sheet of manufacturing of basis (12), it also is included in described smoothing processing step heats described hot transfer printing receiver sheet afterwards subsequently by described sheet surface is contacted with warm-up mill caliper recovery treatment step.

Receiver sheet of the present invention is to have receiver sheet very one's best quality, that be applicable to the thermal dye transfer printer, it has the intermediate layer of containing hollow particle, the problems such as irregular depth effect and white point that guarantee improve, and the high sensitivity record that can have high image quality under low cost.In addition, according to image processing method of the present invention, can reduce the generation of the cut, scratch etc. of print surface.One preferred embodiment in, receiver sheet of the present invention has sufficiently high compression strength and indenture can not occur.In a preferred embodiment, receiver sheet of the present invention also has sufficiently high hear resistance.

Description of drawings

Fig. 1 represents that step (a) is used for the smoothing processing of receiver sheet of the present invention or the schematic diagram that step (b) smoothing processing+caliper recovery is handled.

The specific embodiment

Below with reference to preferred implementation, describe the present invention.

In order to obtain high sensitivity, high-quality image, described receiver sheet fully is with China ink is contacted closely, thereby and make it follow the shape of thermal head and be out of shape and fully the heat from thermal head be used to form image.Correspondingly, under the situation of exerting pressure, described receiver sheet need show high smoothness on this receiver sheet surface when printing.

In the present invention, as the result who investigates further, have been found that when in beginning under the exerting pressure of 0.1MPa to exert pressure after 10 milliseconds, can obtain high sensitivity, high-quality image by adopting printing smoothness (Rp value) on the described receiver sheet surface (receiving layer surface) that microstructure analysis records to be set to 1.5 μ m or more hour.The Rp value is essentially 0～1.5 μ m, is preferably 0～1.0 μ m.If the Rp value surpasses 1.5 μ m, owing to the smoothness deficiency on receiver sheet surface, described receiver sheet may descend aspect printing density and print image quality so.

Incidentally, being used for printing smoothness of the present invention (Rp value) measures with the proportional physical quantity of mean depth of indenture on the surface that contacts the sample that is connected to standard flat (prism) by measuring.Measuring principle for example is disclosed in Nippon Insatsu Gakkai Ronbun-Shu (JapanPrinting Society Articles) the 17th volume the 3rd phase (1978) and Nippon Insatsu GakkaiDai 60-Kai Shuki Kenkyu Happyo Kai (60 ^ThSpring Meeting for ReadingResearch Papers of Japan Printing Society) on (1978).On the other hand, in paper making industry, adopt the equipment that calculates smoothness by air leakage rate in many cases, represent the smoothness of paper product as Bekk smoothness instrument, Oken type smoothness instrument and Smoothter smoothness instrument.Yet, consider when printing by printer, found that printing smoothness (Rp value) under given conditions can successfully be reproduced in the actual print by the contact condition of China ink with described receiver sheet and thermal head.

When sublimation dye is transferred to the receiving layer of receiver sheet by the China ink band on, forming image, because the pressure that is applied on the described receiver sheet that the squeeze pressure between the air roll of thermal head and printer causes is generally about 0.1～0.5MPa, be generally 10 milliseconds or still less from the application time of the heat energy of thermal head.By this way, in the smoothness of in the very short time described receiver sheet of exerting pressure down, promptly contacting ratio between receiver sheet and the thermal head, is important.

For measuring in the equipment of lower-glass surface with the optical contact ratio of paper product of exerting pressure, minute surface reflection smoothness instrument (being also referred to as " Chapman smoothness instrument ") has been known traditionally.Exerting pressure when this minute surface reflection smoothness instrument can reproduce hot transfer printing, but reading of the contact ratio of measuring is to carry out initial several seconds in that initiation pressure applies, and this compares with the application time of heat energy in the hot transfer printing of reality is the very long time.Therefore, the actual print state almost can not reproduce.

On the other hand, printing smoothness (Rp value) can the optical contact ratio of prism surface and paper product calculates in initial 10 milliseconds by measuring after beginning to exert pressure, and, found that 10 milliseconds of Rp value and print image qualities that record have confidential relation after the prism to receiver sheet begins to apply 0.1MPa pressure as result of study to concerning between the Rp value that calculates by this contact ratio and the print image quality.For measurement device, for example can adopt printing smoothness measuring instrument (optical contact ratio microstructure analysis measuring instrument is made by Toyo Seiki Seisaku-Sho Ltd.).

In addition, the elastic compression modulus of the receiver sheet of measuring according to JIS K7220 of the present invention is preferably 30MPa or littler, 3～20MPa more preferably, even 4～16MPa more preferably.If the elastic compression modulus of receiver sheet is greater than 30MPa, picture quality may degenerate so, perhaps may produce banded gauffer on the surface of printing and causes commercial value to reduce.

Receiver sheet of the present invention has enough low elastic compression modulus, therefore when printing, when inserting described receiver sheet between thermal head and the air roll by the China ink band, described receiver sheet inside suitably is out of shape to strengthen receiver sheet and contacts with the close of thermal head, thereby can obtain the packing density and the high image quality of excellence.

Because the heat of thermal head China ink band can shrink by the experience localized heat, this can cause producing gauffer, but because the elastic compression modulus of described receiver sheet is enough low, receiver sheet can be followed reductus shape and is out of shape, therefore avoid China ink is transferred to print surface with going up the reductus shape that produces, thereby show good surface appearance.Yet if elastic compression modulus height, receiver sheet is out of shape unsatisfactorily so, thereby can not follow reductus shape, therefore China ink with on the reductus shape that produces be transferred to print surface, cause defective outward appearance.

For layer structure, receiver sheet of the present invention comprises sheet supporter, intermediate layer and receiving layer at least.In addition, preferably to receiver sheet of the present invention structure so that order forms intermediate layer and the receiving layer that contains two kinds of different hollow particle A of average particulate diameter and B on the sheet supporter.Certainly, can further provide other layer as the intermediate layer to take two-layer or more multi-layered sandwich construction.To describe these layers below in detail.

(sheet supporting layer)

The example that is suitable for the sheet supporter among the present invention comprises that (1) mainly comprises the papery sheet material of cellulose slurry, as does not have wooden paper, as acidic paper, neutralized paper, mean quality paper, coated paper, enamel paper, glassine paper, flow coat paper; The laminated paper of thermoplastic resin is provided on its at least one surface, as vistanex, synthetic resin impregnated paper, emulsion impregnated paper, synthetic rubber latex dipping paper, inner paper, the blistering paper that comprises the heat-swellable particle or the cardboard that adds synthetic resin, perhaps (2) comprise that plastic foil (mainly comprises thermoplastic resin, as polyolefin, as polyethylene, polypropylene; Polyester is as PETG; Polyamide, polyvinyl chloride or polystyrene) at interior film, molten mixture with the blend by will comprising above-mentioned resin and incompatible resin or inorganic pigment is extruded from extruder and extrudate is stretched forming the porous stretched film of the single or multiple lift structure that the space obtains, as synthetic paper, porous polyester film or by these films being piled up each other or lamination or with this film and other film or pile is folded or lamination obtains composite membrane.

In these sheet supporters, preferably mainly comprise the papery sheet material of cellulose slurry, because the of good quality and cost that their heat-shrinkable is low, heat-insulating property is good, paper is accepted in conduct is low.

Be used for sheet supporter of the present invention and can have following structure: wherein sequence stack is formed with first substrate layer, pressure sensitive adhesive layer, release agent layer and second substrate layer of receiving layer on it.As selection, certainly adopt sheet supporter with so-called sticker or sealed structure.

Be used for the thickness that sheet supporter of the present invention preferably has 100～300 μ m.If thickness may cause the mechanical strength deficiency less than 100 μ m, the receiver sheet that obtains thus has low rigidity and shows repulsion metamorphosis unsatisfactory, and the result can not avoid receiver sheet to take place to curl when printing fully.If thickness surpasses 300 μ m, the receiver sheet that obtains so can have excessive thickness, the quantity of receiver sheet of printer of packing into may reduce, perhaps under the situation of the receiver sheet of the scheduled volume of packing into, this need increase the capacity of printer, and may produce as being difficult to the problem of scaled down printer size.

(intermediate layer)

In the present invention, the intermediate layer is formed at least one surface of described sheet supporter.Described intermediate layer mainly comprises adhesive resin and hollow particle, and has loose structure realizing high shock-absorbing capacity, thereby even when using paper product as the sheet supporter, also can obtain highly sensitive receiver sheet.By hollow particle is joined in the intermediate layer, give described receiver sheet the suitable distortion free degree, be improved with close contact of printhead shape and black belt shape along toughness, described receiver sheet, even thereby printer port of printer also can be enhanced to the thermal efficiency of receiver sheet under low-energy state, printing density and picture quality can be improved.In addition, since also can avoid simultaneously in high-speed printer, applying high-octane operation the time China ink with on the printing trouble that causes of the banded gauffer that produces.

By hollow particle being joined in the described intermediate layer, the heat-insulating property of described receiver sheet is enhanced, so thermal head also is enhanced to the thermal efficiency of described receiving layer, therefore, printing density and picture quality are improved.In addition, even when the high pressure that will be produced by the thermal head or the delivery roll of printer is applied on the described receiver sheet, this stress also can be by the absorbed inside of described receiver sheet, therefore, described receiver sheet resistance is improved by the ability that forms nail shape mark or indenture on print surface that delivery roll causes.

The hollow particle that is used for intermediate layer of the present invention comprises housing that is formed by polymeric material and the one or more hollow spaces that surrounded by this housing.The preparation method of described hollow particle has no particular limits, but can select described hollow particle from the hollow particle (i) that is prepared as follows with (ii):

(i) by making the foaming hollow particle (hereinafter being referred to as " prefoam hollow particle " sometimes) of the thermoplastic, polymeric materials thermal expansion preparation that comprises the heat-swellable material; And

(ii) by making from making housing and form material and adopt volatile liquid to make the microencapsulated hollow particle that the hole of microcapsules that the hole forms the microcapsules polymerization preparation of material forms the material volatilization and disperses to obtain by adopting polymer to form material.

Preparation for hollow particle, it is also conceivable that to adopt and comprise the particle (hereinafter being referred to as " expanded beads " sometimes) that contains with the thermoplastic of the heat-swellable material of non-foamed state, because heating steps such as the heat effect in the drying steps in the receiver sheet preparation process make this granule foaming, thereby form the foaming hollow particle.Yet, when the thermoplastic that contains the heat-swellable material in the preparation process in receiver sheet foams by heating, it is difficult obtaining the homogeneous granules diameter by foaming, and can not strictly control the particle diameter after the thermal expansion, therefore, interlayer surfaces may have the scrambling of big degree to cause bad smoothness.In the receiver sheet with such intermediate layer, the receiving layer surface also can have the scrambling of big degree, and the uniformity of heat transfer image can reduce, and causes bad picture quality.Correspondingly, in the present invention, the preferred employing provides the feasible prefoam hollow particle that comprises the particle thermal expansion in advance of the thermoplastic that contains the heat-swellable material and make.

The for example following prefoam hollow particle that obtains by making that the thermoplastic thermal expansion contain the heat-swellable material makes.To by will be (for example as the volatility low boiling hydrocarbon of described heat-swellable core substance, normal butane, iso-butane, pentane and/or neopentane) in the thermoplastic of packing into and adopt the homopolymers of vinylidene chloride, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, (methyl) acrylate etc. or copolymer to make housing (wall) material of described capsule and the particle for preparing is handled in advance as described thermoplastic, as heat treated, thereby make its thermal expansion arrive predetermined particle size to form the prefoam hollow particle.

As above the prefoam hollow particle for preparing by the feasible thermoplastic thermal expansion that comprises the heat-swellable material has low-gravity usually, therefore, in order to improve operability and dispersibility biglyyer, can be by the hot melt effect with inorganic powder such as calcium carbonate, talcum, titanium dioxide surface attached to this foaming hollow particle.The surface that obtains by this way is coated with the compound hollow particle of foaming of inorganic powder and also can uses in the present invention.

Be used for microencapsulated hollow particle of the present invention, have housing that forms by polymeric material (as styrene-propene acidic group copolymer) or animi resin (as melmac) and the microcapsules drying that comprises volatile liquid (as water) in the core by making, thereby make the water volatilization and disperse to form described hollow core part.These microcapsules can form polymerization, form material (housing forms material) and volatile liquid (hole forms material) obtains by polymer by microcapsules.

The average particulate diameter that is used for hollow particle of the present invention is 0.2～35 μ m, is preferably 0.5～10 μ m, more preferably 0.8～8 μ m.If the average particulate diameter of hollow particle is less than 0.2 μ m, the hollow particle that obtains so has low volume hollow rate, and this can cause low heat-insulating property or shock-absorbing capacity usually, so cause obtaining the effect of sufficiently high raising sensitivity and picture quality.If average particulate diameter surpasses 35 μ m, the surface smoothness in the intermediate layer that obtains so may reduce, and the lip-deep scrambling of described receiver sheet may increase, and causes the lack of uniformity and the poor image quality of heat transfer image.

Be used for hollow particle of the present invention and preferably have 25 μ m or littler, more preferably 20 μ m or littler the largest particles diameter.If the largest particles diameter of hollow particle surpasses 25 μ m,, in heat transfer image, may produce because uneven printing depth effect or the white point that coarse granule causes, make image quality decrease.In order to make described hollow particle not contain the coarse granule that the largest particles diameter surpasses 25 μ m, can realize this purpose by the setting (it is usually expressed as the standard profile state) of in the preparation process of hollow particle, regulating average particulate diameter.In addition, not comprising coarse grained hollow particle can also be by providing the step of gradation and successfully obtain.

Incidentally, the particle diameter that is used for hollow particle of the present invention can be measured by adopting general particle diameter measuring instrument, described particle diameter is the value that adopts laser diffraction type particle size distribution analysis instrument (SALD2000, trade name are made by Shimadzu company) to measure.

The volume hollow rate that is used for hollow particle of the present invention is 30～97%, is preferably 75～95%.Less than 30%, it is bad that picture quality may become as the fruit volume hollow rate, and surpass 97% as the fruit volume hollow rate, and the intensity variation of coating may be caved in and causes the reduction of surface smoothness at hollow particle described in coating or the dry run.

In the measurement of the volume hollow rate of hollow particle, adopt (the sensitivity: 1mg), measuring bottle (volume 100ml) and screen cloth (12 order) be as measurement device of direct-reading chemical balance, isopropyl alcohol (IPA) is as reagent, and the sample that is used to measure is dry 48 hours a hollow particle in advance under 45 ℃.True specific gravity is measured through the following steps:

(1) accurately take by weighing the weight (W1) of measuring bottle,

(2) about 0.5 gram sample is packed in the measuring bottle, and accurately weigh (W2: measuring bottle+sample),

(3) add IPA to mark line, and accurate weigh (W3: measuring bottle+sample+IPA), and

(4) add in contrast IPA to measuring bottle until mark line, and accurate weigh (W4).True specific gravity and hollow rate are calculated according to following formula:

True specific gravity=A/B

Condition is

A=(W2-W1) * (W4-W1)/100} and

B＝{(W4-W1)-(W3-W2)}

Hollow rate (%)={ 1-1/ (membrane material proportion/true specific gravity) } * 100

Based on the hollow particle quality in whole intermediate layer and the ratio of total solid content quality, the combined amount of described hollow particle in the intermediate layer is preferably 30～75%, and more preferably 35～70%.If the ratio of the hollow particle quality in whole intermediate layer and total solid content quality is less than 30%, it is not enough that the heat-insulating property in so described intermediate layer or shock-absorbing capacity become, the effect of sensitivity and the picture quality of can not being improved satisfactorily, if and the quality ratio of hollow particle is greater than 75%, the be coated with ability of the coating solution that is used for the intermediate layer that obtains so can descend, so that sufficiently high strength of coating can't be provided and can not realize required effect.

Contain in described intermediate layer under the situation of two kinds of different hollow particle A of above-mentioned average particulate diameter and B, hollow particle with specific small particle diameters is filled between the hollow particle with specific bulky grain diameter playing the effect of enhancing, and the resistance against compression in described intermediate layer is enhanced.Therefore, described receiver sheet has the structure that can destroy hardly as a whole.In addition, by means of this structure, the scrambling on the described interlayer surfaces reduces, and surface uniformity and the picture quality that causes thus all are improved.

Correspondingly, even when described receiver sheet is subjected to the high pressure of thermal head, delivery roll etc. from printer, have the receiver sheet of improving resistance against compression and be absorbed at stress and enter in the receiver sheet and also can restore immediately after being eliminated, thereby can avoid on the print surface of described receiver sheet, producing nail shape mark, indenture etc.

Be included in the average particulate diameter L of the hollow particle A in the intermediate layer of the present invention _ABe preferably 2～35 μ m, 3～30 μ m more preferably, even 3～25 μ m more preferably.If average particulate diameter L _ALess than 2 μ m, so because the low particle size of hollow particle A, the volume deficiency of hollow space causes heat-insulating property or the shock-absorbing capacity can not be satisfactory, almost can not obtain the effect of sufficiently high raising sensitivity and picture quality.On the other hand, if average particulate diameter L _AGreater than 35 μ m, the intensity in intermediate layer reduces so, is easy to generate indenture on the described receiver sheet during printing by thermal head.In addition, the scrambling on the interlayer surfaces may increase, and the uniformity of image and picture quality etc. are tended to descend.

The average particulate diameter L of hollow particle B _BBe preferably 0.2～9 μ m, 0.3～8 μ m more preferably, even 0.4～7 μ m more preferably.If average particulate diameter L _BLess than 0.2 μ m, because its excessive little average particulate diameter, hollow particle B almost can not fill up the gap between the hollow particle A so, and if average particulate diameter L _BGreater than 9 μ m, the gap of getting into so between the hollow particle A becomes difficult.Under any situation, all obtain the effect that resistance against compression strengthens unsatisfactorily.

The average particulate diameter that is included in hollow particle A in the intermediate layer of the present invention and hollow particle B is than (L _B/ L _A) be preferably 0.05≤L _B/ L _A≤ 0.4,0.1≤L more preferably _B/ L _A≤ 0.4, even 0.15≤L more preferably _B/ L _A≤ 0.3.If L _B/ L _A0.4, so because the excessive average particulate diameter of hollow particle B, thereby it can't get into the gap of hollow particle A, and when clamp-on, described gap can be extended, result, the resistance against compression of the described receiver sheet deficiency that becomes.In addition, smoothness on the described interlayer surfaces reduces, and causes the picture quality or the sensitivity meeting of the receiver sheet that obtains to reduce thus.On the other hand, if L _B/ L _A＜0.05, because the too small average particulate diameter of hollow particle B, it can not fill up the gap between the particle and the effect of the resistance against compression of the receiver sheet that causes being improved unsatisfactorily.

The variation coefficient of the particle diameter separately of hollow particle A and hollow particle B is preferably 35% or littler, and more preferably 30% or littler, even more preferably 25% or littler.The variation coefficient of used here particle diameter is the percentage by the value that the standard deviation of described particle diameter is obtained divided by average particulate diameter.

Incidentally, the average particulate diameter of hollow particle A and B and the standard deviation of described particle diameter can adopt general particle diameter measurement mechanism to measure, can adopt for example laser diffraction type particle size distribution analysis instrument (SALD2000, trade name is made by Shimadzu company) measure.

If the variation coefficient of the particle diameter of hollow particle A surpasses 35%, so owing to have the number increase of the hollow particle A that is in the particle diameter in the low limit area, the hollow percentage descends, thereby causes unsafty heat-insulating property or shock-absorbing capacity and can not obtain sufficiently high sensitivity or picture quality.Perhaps, because having the number of the hollow particle A that is in the particle diameter in the higher limit area increases, it is not enough that the intensity in intermediate layer becomes, thereby the time produce indenture on described receiver sheet in printing easily, the scrambling on the perhaps described interlayer surfaces can increase so that declines such as the uniformity of image, picture quality.

If the variation coefficient of the particle diameter of hollow particle B surpasses 35%, have the hollow particle B that is in the particle diameter in the low limit area so and fill up gap between the hollow particle A unsatisfactorily, perhaps have the hollow particle B that is in the particle diameter in the higher limit area and can not get into gap between the hollow particle A, owing to this reason or other reason, it is not enough that the resistance against compression of described receiver sheet becomes sometimes.

The volume hollow rate of hollow particle A is preferably 60～97%, and more preferably 65～95%.If described volume hollow rate is less than 60%, can not obtain well balanced between the raising of the resistance against compression in intermediate layer and sensitivity and picture quality so, if and described volume hollow rate is greater than 97%, described coating material may have bad stability, and the intermediate layer that perhaps obtains can be subjected to the influence of strength of coating deficiency.

The volume hollow rate of hollow particle B is preferably 30～97%, and more preferably 35～95%.If the volume hollow rate of described hollow particle is less than 30%, sensitivity and picture quality can reduce so, and if described volume hollow rate greater than 97%, the stability of coating material can descend so.

Incidentally, the volume hollow rate of hollow particle A or B is represented the volume of hollow space and the ratio of particle volume.Particularly, can obtain described volume hollow rate by mass fraction in this liquid dispersion of the proportion of the hollow particle liquid dispersion that comprises hollow particle and poor solvent, hollow particle, the true specific gravity of fluoropolymer resin of housing (wall) that constitutes hollow particle and the proportion of described poor solvent.Poor solvent is not dissolve and/or swelling constitutes the solvent of the resin of hollow particle wall, and described example comprises water and isopropyl alcohol.The volume hollow rate of described hollow particle also can be determined by the photo of the cross section in intermediate layer by for example adopting small angle X ray scattering measurement mechanism (Rigaku company makes for RU-200, trade name).

Be included in of the variations such as average particulate diameter of the mixing ratio of two kinds of different hollow particle A of average particulate diameter in the described intermediate layer and B, but supposition is included in hollow particle A in the described intermediate layer and the quality of B is respectively W according to packed density level, apparent density and the hollow particle of hollow particle _AAnd W _B, mass ratio (W _B/ W _A) be preferably 0.001～1, more preferably 0.003～0.8.

The partition wall that intermediate layer of the present invention comprises scheduled volume at least is preferably 130 ℃ or bigger, more preferably 140 ℃ or the bigger even hollow particle (hereinafter, this hollow particle abbreviates " Tg is 130 ℃ or bigger hollow particle " sometimes as) that forms of 150～200 ℃ polymeric material more preferably by glass transition temperature (Tg).Because this intermediate layer has loose structure, described receiver sheet is improved aspect heat-insulating property, the result, and printing density increases, and picture quality improves.The formation in this intermediate layer can be given the suitable distortion free degree of described receiver sheet and be caused the raising of shape flowability and close contact of receiver sheet and printing head or China ink band, thereby even printing head can be improved to printing density and the picture quality that the thermal efficiency of receiving layer also can be enhanced and print image under low-energy state.In addition, also can avoid simultaneously in high-speed printer when applying high-octane operation since China ink with on the printing trouble that causes of the China ink band gauffer of generation.

If described glass transition temperature (Tg) is less than 130 ℃, the hear resistance of hollow particle is low and because the heat effect in the drying steps of production period so, the distortion of hollow particle may take place and caves in.Because heating indenture occurs in the image after the printing and obtains bad outward appearance, this is not preferred in addition.On the other hand, if described glass transition temperature (Tg) is too high, making in the production process of hollow particle foaming of non-foaming that excessively a large amount of heats causes foaming so, this is disadvantageous economically.

Incidentally, the Tg of described hollow particle is the value of measuring according to the method employing difference formula scanning calorimeter (the Seiko electronic enterprise is made for SSC5200, trade name) of JIS K 7121 regulations.

The polymerisable monomer that is used to produce Tg and is 130 ℃ or bigger hollow particle mainly comprises the itrile group monomer, in order to improve heat-swellable, hear resistance and solvent resistance etc., if desired, suitably adopts for example non-itrile group monomer and cross-linking monomer.

The example of described itrile group monomer comprises acrylonitrile, methacrylonitrile, α-Lv Daibingxijing, α-ethoxy propylene nitrile, anti-maleic nitrile and any mixture thereof.In these monomers, preferred acrylonitrile and/or methacrylonitrile.The homopolymers of acrylonitrile or methacrylonitrile has high glass-transition temperature (Tg), and performance is excellent aspect hear resistance, chemical-resistant and gas barrier property, so especially preferably adopts acrylonitrile or methacrylonitrile among the present invention.

The example of non-itrile group monomer comprises acrylate, methacrylate, styrene, vinylacetate, vinyl chloride, vinylidene chloride, butadiene, vinylpyridine, AMS, chlorobutadiene, neoprene and any mixture thereof.Wherein, preferred methyl acrylate, methyl methacrylate and EMA.The consumption of described non-itrile group monomer is preferably counted 25 mass parts or still less with per 100 mass parts itrile group monomers.If the consumption of non-itrile group monomer surpasses 25 mass parts, the glass transition temperature of the hollow particle that obtains so can reduce and cause the disappearance of stable on heating decline or gas barrier property, and can not obtain required quality.

For the cross-linking monomer that in monomer molecule, has two or more polymerizable double bonds, the monomer that preferably adopts the polyfunctional vinyl monomer and/or have interior ethylene linkage.Its instantiation comprises divinylbenzene, GDMA, dimethacrylate triethyleneglycol ester, triacryl formal, trihydroxy methyl propane trimethyl acrylate, ALMA, dimethacrylate 1,3-butanediol ester and isocyanic acid triallyl ester.Wherein, be preferably the trifunctional cross-linking monomer, for example triacryl formal and trihydroxy methyl propane trimethyl acrylate.The consumption of described cross-linking monomer is preferably counted 3 mass parts with per 100 mass parts itrile group monomers.If the consumption of described cross-linking monomer surpasses 3 mass parts, the degree of cross linking becomes excessive so, may cause bad dilatancy.

If desired, being used for Tg is that the wall material of 130 ℃ or bigger hollow particle prepares by further mixing suitable polymerization initiator to said components.The example of described polymerization initiator comprises azodiisobutyronitrile and benzoyl peroxide.

The example that is used to make Tg and is the low boiling point organic solvent of 130 ℃ or bigger hollow particle comprises low molecular weight hydrocarbon, for example ethane, ethene, propane, propylene, butane, iso-butane, butylene, isobutene, pentane, neopentane, isopentane, hexane and heptane; Chlorofluorocarbon is as CCl ₃F, CCl ₂F ₂And CClF ₃And silane compound, as tetramethylsilane and trimethyl ethylsilane.Wherein, be preferably low molecular weight hydrocarbon, as butylene, iso-butane, isobutene, pentane, isopentane and neopentane with 20～50 ℃ of boiling points.Can use one of these low boiling point organic solvents separately, perhaps can be used in combination wherein two or more.

To by using above-mentioned polymerizable material that the method for heat-swellable material microencapsulation is had no particular limits, can use conventional method.For example the method for describing in Japan's unexamined patent open (Kokoku) 42-26524 number is particularly preferred, wherein polymerisable monomer is mixed with heat-swellable material and polymerization initiator, with the mixture suspension polymerisation in the water-bearing media that contains suitable emulsifying dispersant etc. that obtains.

Under the temperature of the boiling point that is higher than described low boiling point organic solvent, carry out external heat to containing low boiling point organic solvent therein as heat-swellable material, the described non-expanded beads that obtains by suspension polymerisation subsequently, thereby described heat-swellable material generation thermal expansion, with the particle diameter that obtains being scheduled to, thereby obtain being in the hollow particle of prefoam state.Adopt centrifugal separator that this hollow particle is repeated to filter and washing, the material of the similar cake shape that obtains is carried out drying, to obtain prefoam hollow particle of the present invention.

Tg is that the average particulate diameter of 130 ℃ or bigger described prefoam hollow particle is preferably 2～10 μ m, 2.5～9 μ m more preferably, even 3～8 μ m more preferably.

If Tg is that the average particulate diameter of 130 ℃ or bigger described prefoam hollow particle is less than 2 μ m, so because described average particulate diameter is little, thereby the volume of the hollow space of described hollow particle is little, heat-insulating property or shock-absorbing capacity are bad usually, as a result, can not obtain the effect of sufficiently high raising sensitivity and picture quality.

If described average particulate diameter is greater than 10 μ m, the scrambling on the interlayer surfaces of gained becomes excessive so, and described image can be subjected to the influence of the not enough and poor image quality of uniformity.

Tg is that the volume hollow rate of 130 ℃ or bigger hollow particle is preferably 60～90%, more preferably 65～85%.

As the fruit volume hollow rate less than 60%, the receiver sheet that obtains so may be relatively poor unfriendly aspect sensitivity and picture quality, and as the fruit volume hollow rate greater than 90%, the stability of coating material or the strength of coating in the intermediate layer that obtains may descend so, and this is not preferred.

In described intermediate layer, also can in not damaging the scope that Tg is 130 ℃ or bigger hollow particle effect, unite and use other hollow particles.For other hollow particle of uniting use, average particulate diameter is preferably about 0.3～10 μ m, and it is about 30～90% that the volume hollow rate is preferably, but these can change and can not stipulate clearly according to purpose.

Hollow particle of the present invention is preferably at least about 70 quality % with the quality ratio of gross mass that is included in the hollow particle of the present invention in the described intermediate layer and unites other hollow particle of use.If the quality ratio that is included in the hollow particle of the present invention in the described intermediate layer is less than about 70 quality %, the problem of hear resistance deficiency can appear in so described intermediate layer, become big, result, the effect of the picture quality that can not be improved satisfactorily owing to be printed on the indenture that produces on the receiver sheet.

In addition, but in order to improve coating or smoothness or to improve caving in or, also can being used in combination hollow particle of intermediate layer with different average particulate diameters for other purposes.

In order to make described intermediate layer bring into play desirable performance, as heat-insulating property and shock-absorbing capacity, the thickness in described 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, can cause heat-insulating property or shock-absorbing capacity deficiency so, the effect that sensitivity and picture quality improve can not be satisfactory, if and the thickness in intermediate layer is greater than 90 μ m, make that so thermal insulation or buffering effect are saturated, and not only because described performance can not be improved again but also this is disadvantageous from the angle of profit.

Intermediate layer of the present invention comprises hollow particle and adhesive resin.Consider the solvent resistance of described hollow particle, the coating material that is used for intermediate layer of the present invention is preferably aqueous coating material.Correspondingly, adhesive resin is preferably water-base resin, but water-base resin and organic solvent soluble resin can use.Used adhesive resin is had no particular limits, consider filming performance, hear resistance and flexibility, for example preferably adopt the hydrophilic polymeric resin, as polyvinyl alcohol based resins, cellulose base resin or derivatives thereof, casein and starch derivatives.Equally, also can use various kinds of resin to have the water-base resin of low viscosity and high solids content as the emulsion conduct of (methyl) acrylate, SB resin, polyurethane resin, mylar and ethylene-vinyl acetate copolymer resin.But consider strength of coating, cohesive and the coating in intermediate layer, preferred compositions uses the emulsion of hydrophilic polymeric resin and above-mentioned various kinds of resin to be used for described intermediate layer as adhesive resin.

If desired, described intermediate layer can comprise multiple additives.For example, can use suitably to be selected from a kind of with in crosslinking agent, defoamer, dispersant, illuminating colour, interleaving agent and the lubricant of antistatic additive, inorganic pigment, organic pigment, resin, perhaps can select and use two or more.

(barrier layer)

In the present invention, if desired, can on described intermediate layer, provide barrier layer, and on this barrier layer, provide receiving layer.The solvent that is used for the coating solution of receiving layer is generally organic solvent, and as toluene and MEK, described barrier layer is effective as barrier and is used for preventing that hollow particle in the intermediate layer from avoiding swelling or dissolution that the infiltration owing to organic solvent causes and caving in.In addition, owing to the hollow particle that is included in the intermediate layer, described interlayer surfaces has scrambling, and provide receiving layer thereon also to have scrambling in some cases, the result, the image that obtains usually has white point or irregular depth effect, thereby causes the problem of image uniformity or resolution ratio aspect.In order to address this problem, effectively provide to comprise barrier layer and improve picture quality thus with pliability and flexible resin glue.

With regard to the resin that is used for barrier layer, adopt the filming performance excellence, can prevent the organic solvent infiltration and have elasticity and flexible resin.More specifically; use the water-soluble polymeric resin with aqueous solution form, as 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; isobutene-copolymer-maleic anhydride salt; styrene-maleic anhydride copolymer salt; styrene-propene acid copolymer salt; ethylene-acrylic acid copolymer salt; Lauxite; polyurethane resin; melmac or amide resin.Equally, can adopt water-dispersed resin, as styrene-butadiene base co-polymer latex, acrylate base latex, methacrylate based copolymer resin latex, ethylene-vinyl acetate copolymer latex, polyester-polyurethane ionomer or polyether-polyurethane ionomer.Can use a kind of in these resins separately, perhaps can be used in combination its two or more.

In described intermediate layer and barrier layer, can add inorganic pigment such as inorganic Chinese white (for example calcium carbonate, titanium dioxide, zinc oxide, aluminium hydroxide, barium sulfate, silica, aluminium oxide, talcum, kaolin, diatomite, satin white) or fluorescent dye etc. to give receiver sheet screening performance or whiteness, perhaps improve the quality of receiver sheet.For inorganic pigment, preferably use the swelling inorganic layered compounds, this compound is not only effective to the permeated height that prevents the coating solvent, and to preventing that it also is highly effective being taken place fuzzy etc. by the image of hot transfer printing and dyeing.The instantiation of described swelling inorganic layered compounds comprises graphite, phosphate base derivative type compound (for example basic zirconium phosphate based compound), chalcogenide product, hydrotalcite compound, compound lithium hydroxide aluminium, and clay-based mineral, for example synthetic mica, synthetic montmorillonite, montmorillonite family, vermiculite family, mica family.

Wherein, be preferably synthetic montmorillonite, more preferably sodium four silicon micas.Compound with required particle diameter, draw ratio and degree of crystallinity can obtain by flux synthesis procedure.

The draw ratio of described swelling inorganic layered compounds is preferably 5～5, and 000.This draw ratio more preferably 100～5,000, even more preferably 500～5,000.If draw ratio is less than 5, image may blur so, and if draw ratio greater than 5,000, image may have bad uniformity so.Draw ratio (Z) is represented with the following relationship formula: Z=L/a, and wherein L is that the long diameter of the average grain of swelling inorganic layered compounds in water is (by adopting the particle size distribution instrument LA-910 that made by Horiba Ltd., measuring by laser diffractometry; Volume distributed median is 50% o'clock a median particle diameter), a is the thickness of swelling inorganic layered compounds.

The thickness a of described swelling inorganic layered compounds is to the observable value of the photograph of the cross section of barrier layer by ESEM (SEM) or transmission electron microscope (TEM).The long diameter of the average grain of described swelling inorganic layered compounds is 0.1～100 μ m, is preferably 0.3～50 μ m, more preferably 0.5～20 μ m.If the long diameter of average grain is less than 0.1 μ m, draw ratio diminishes so, simultaneously this compound almost can not be on the intermediate layer parallel sprawling, it is fuzzy to cause preventing fully that image from taking place.If the long diameter of average grain is greater than 100 μ m, so described swelling inorganic layered compounds is outstanding producing scrambling on the barrier layer surface from barrier layer, the result, and the lip-deep smoothness of receiving layer descends, and picture quality may worsen.

In the present invention, preferably adopt moisture coating solution to form barrier layer.For swelling and the dissolving that prevents hollow particle, described moisture coating solution does not preferably contain organic solvent, as ketone-based solvent, as MEK; The ester group solvent is as ethyl acetate; The lower alcohol based solvent is as methyl alcohol, ethanol; The alkyl solvent is as toluene, dimethylbenzene; And the high polar solvent of higher boiling, as DMF or cellosolve.Coating weight in the barrier layer solid content is preferably 0.5～10g/m ², 1～8g/m more preferably ²If in the coating weight of barrier layer solid content less than 0.5g/m ², described so in some cases barrier layer can not cover interlayer surfaces fully, prevents that the effect of organic solvent infiltration may be insufficient.On the other hand, if in the coating weight of barrier layer solid content greater than 10g/m ², therefore so not only the coating effect is saturated, is disadvantageous aspect profit, and the thickness of barrier layer can become excessive, and the result can not demonstrate the insulation effect or the buffering effect in intermediate layer fully, and picture quality can descend.

(receiving layer)

In receiver sheet of the present invention, on the intermediate layer or by barrier layer, provide receiving layer.Described receiving layer itself can be known thermal dye transfer receiving layer.For the resin that constitutes receiving layer, adopt the dyestuff from the migration of China ink band is had high affinity and correspondingly has the resin of good dye capable of dyeing.The example of described dye capable of dyeing resin comprises thermoplastic resin and active energy beam curable resin, as mylar, polycarbonate resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl acetal resin, polyvinyl butyral resin, polystyrene resin, polyacrylate resin, cellulose derivative base resin (as acetobutyryl cellulose) and polyamide.Described resin preferably has with used crosslinking agent and is reactive functional group (for example, functional groups such as hydroxyl, amino, carboxyl and epoxy radicals).

The described receiving layer that causes for the heating that prevents owing to thermal head is melt bonded with the China ink band, and one or more of preferably sneaking into crosslinking agent, interleaving agent or slip agent etc. in receiving layer are as additive.In addition, if desired, can in receiving layer, add one or more of plasticizer, antioxidant, pigment, filler, ultra-violet absorber, antistatic additive etc.Described additive can mix with the formation component of receiving layer before coating, perhaps can be coated on the receiving layer and/or under receiving layer conduct be different from the independent coating of receiving layer.

Coating weight in the solid content of receiving layer is preferably 1～12g/m ², 3～10g/m more preferably ²If in the coating weight of the solid content of receiving layer less than 1g/m ², receiving layer can not cover the barrier layer surface fully so in some cases, picture quality may reduce, and perhaps causes melt bonded problem, promptly since the heating of thermal head to make receiving layer and China ink be with bonding.On the other hand, if in the coating weight of the solid content of receiving layer greater than 12g/m ², so not only described effect is saturated, thereby is disadvantageous aspect profit, and receiving layer can have not enough strength of coating, and perhaps coating thickness is excessive, and the result can not give play to the insulation effect of sheet supporter fully, and picture quality may descend.

(back of the body superficial layer)

In receiver sheet of the present invention, can on the back of the body surface of sheet supporter (with providing receiving layer that side facing surfaces), provide back of the body superficial layer.Described back of the body superficial layer consists predominantly of imitates the resin of ground as adhesive, and can comprise crosslinking agent, conductive agent, melt bonded inhibitor, inorganic and/or organic pigment etc.

For back of the body superficial layer of the present invention, use the back of the body superficial layer that is effective as adhesive to form resin.This resin can be used to improve the adhesion strength between described back of the body superficial layer and the supporter on chip effectively, guarantees the printing transfer performance of receiver sheet, prevents the scraping on the receiving layer surface, and prevents when contact support or oppose migration of superficial layer of dyestuff during receiving layer.For described resin, for example can use the reaction cured product of acrylic resin, epoxy resin, mylar, phenol resin, alkyd resins, polyurethane resin, melmac, polyvinyl acetal resin or described resin.

In back of the body superficial layer of the present invention,, can in back of the body superficial layer coating material, suitably sneak into crosslinking agent, for example polyisocyanate compounds and epoxide in order to strengthen the bonding between sheet supporter and the back of the body superficial layer.Based on the total solid content of back of the body superficial layer, its blending ratio generally is preferably about 1～30 quality %.

In back of the body superficial layer of the present invention, in order to improve the printing transfer performance or, can to add conductive agent, as conducting polymer and conduction inorganic pigment in order to prevent electrostatic charge.Described conducting polymer comprises cation, anion and nonionic conducting polymer compounds.Described cationic polymer examples for compounds comprises polymine, comprises the acrylic acid based polymer of cationic monomer, cation-modified acrylamide polymer and cationic starch.Described anionic polymer examples for compounds comprises polyacrylate, poly styrene sulfonate and styrene-maleic acid copolymer.Usually, the blending ratio of conductive agent is preferably about 5～50 quality % based on the total solid content of back of the body superficial layer.

Described conduction inorganic pigment comprises for example compound semiconductor pigment, as oxide and/or sulfide, and the inorganic pigment that scribbles compound semiconductor pigment.The example of described compound semiconductor comprises cuprous oxide (I), zinc oxide, zinc sulphide and carborundum.The described example that scribbles the inorganic pigment of compound semiconductor comprises titanium oxide and the potassium titanate that scribbles semiconductor oxide tin respectively.For shape, needle-like or spherical conduction inorganic pigment are can get on the market.

In back of the body superficial layer of the present invention, if desired, can sneak into the organic or inorganic filler as the coefficient of friction conditioning agent.The example of operable organic filler comprises nylon gasket, cellulose wadding, Lauxite filler, styrene resin filler and acrylic resin filler.The example of operable inorganic filler comprises silica, barium sulfate, kaolin, clay, talcum, calcium bicarbonate, winnofil, titanium oxide and zinc oxide.For example, under the situation of using nylon gasket, average particulate diameter is preferably about 1～25 μ m, and its mixed volume changes according to particle diameter, and is preferably about 2～30 quality % based on the total solid content of back of the body superficial layer.

If desired, described back of the body superficial layer also can comprise melt bonded inhibitor, as lubricant and interleaving agent.The example of melt bonded inhibitor comprises siloxy group compound (as unmodified or modified silicon oil, silicone block copolymer and silicone rubber), phosphate compound, fatty acid ester compound and fluorine compounds.In addition, can suitably select and use conventional known defoamer, dispersant, coloring pigment, fluorescent dye, fluorescent pigment and ultra-violet absorber etc.

The coating weight of solid content in back of the body superficial layer is preferably 0.3～10g/m ², 1～8g/m more preferably ²If in the coating weight of solid content of back of the body superficial layer less than 0.3g/m ², the anti-scraping performance when the friction receiver sheet may not fully show so, may produce coating defects in addition and increase to cause surface resistivity; And if in the coating weight of solid content greater than 10g/m ², so described effect is saturated, thereby is disadvantageous on profit.

(priming coat)

In receiver sheet of the present invention, can between described supporter and intermediate layer, provide the priming coat that mainly comprises fluoropolymer resin.By means of this priming coat, even when the coating solution that will be used for the intermediate layer is coated on the supporter, this coating solution can not infiltrate in the described supporter yet and can reach desired thickness so that the intermediate layer forms.The example that is used for the fluoropolymer resin of priming coat comprises acrylic resin, polyurethane resin, mylar, vistanex and its modified resin.

Be used as under the situation of supporter of the present invention in for example paper substrate, when coating comprises the priming coat of moisture coating solution, because the uneven water imbibition in paper substrate surface may produce gauffer or fluctuating in paper substrate, it can influence quality or impressionability unfriendly.Correspondingly, in this case, the coating solution that is used for priming coat preferably is not moisture coating solution, but by with fluoropolymer resin dissolving or be dispersed in the coating solution for preparing in the organic solvent.The example of operable organic solvent comprises common organic solvents, as toluene, MEK, isopropyl alcohol and ethyl acetate.

In addition, can in priming coat, add inorganic white pigments,, but, strengthen the cohesive force between described supporter and the intermediate layer, improve the whiteness of receiver sheet to improve the coating of priming coat coating solution itself as titanium dioxide, calcium carbonate and barium sulfate.Coating weight in the solid content of priming coat is preferably 1～20g/m ²If in the coating weight of solid content less than 1g/m ², the effect that may not realize adding priming coat so; And if in the coating weight of solid content greater than 20g/m ², the effect of priming coat can reach capacity so, thereby is disadvantageous aspect profit, and perhaps receiver sheet may lose the papery quality.

The method that is used to make receiver sheet of the present invention comprises the following step at least.

That is to say, manufacture method may further comprise the steps: comprise by coating on (a) at least one surface at the sheet supporter average particulate diameter provide described intermediate layer for 0.2～35 μ m and volume hollow rate for the intermediate layer coating solution of 30～97% hollow particle and make its dry after and/or (b) provides image receiving layer on the intermediate layer after, (c) with this sheet material by having the smoothing processing step of the cramping parts of forming by warm-up mill and pressure roller that become pair roller, wherein will be adjusted to 1.5 μ m or littler by what adopt that microstructure analysis records in the lip-deep printing smoothness of receiver sheet (Rp value) in beginning under the exerting pressure of 0.1MPa to exert pressure after 10 milliseconds.

In addition, after step (a) provides the intermediate layer, preferably on this intermediate layer, provide barrier layer, and on this barrier layer, provide receiving layer.In addition, this manufacture method can be included in the step that back of the body superficial layer is provided on that side that receiving layer wherein is not provided of sheet supporter.

In the present invention, form intermediate layer, barrier layer, receiving layer, back of the body superficial layer and other coating according to conventional methods, can by preparation comprise required component coating solution, by use known coating machine as spreading rod, notch board coating machine, comma coating machine, knife type coater, Kohler coater, braking club formula coating machine, pattern coating machine, curtain type coating machine, flanging coating machine and sliding pearl coating machine with as described in coating solution be applied on the predetermined surface of sheet supporter and be dried and if necessary to as described in the coating heat cure form each layer.

For example, when the coating intermediate layer, molded surface be can use, height smooth surface such as metallic plate, metal drum and plastic foil perhaps can be used with good dimensional stability.If desired, in order to help that described intermediate layer is separated from molded surface, can on molded surface, be coated with higher fatty acids base interleaving agent (as calcium stearate and zinc stearate), polyvinyl interleaving agent (as polyethylene emulsion) or interleaving agent (as paraffin and silicone).

The method that is used to make receiver sheet of the present invention preferably includes the smoothing processing step.

Smoothing processing is preferably carried out in the following manner: receiver sheet is become pair roller by what have a fixed interval (FI) by what warm-up mill and pressure roller were formed, thereby be reduced in the lip-deep scrambling of receiver sheet, carry out the calender process of smooth surface subsequently.At this moment, can between described one-tenth pair roller, apply heat and pressure.

If become 1.5 μ ms or littler by what adopt that microstructure analysis records in the final lip-deep printing smoothness of receiver sheet (Rp value) that obtains in beginning under the exerting pressure of 0.1MPa to exert pressure after 10 milliseconds, so described smoothing processing may be enough.Described smoothing processing can be applied to any one in sheet supporting body surface, interlayer surfaces, barrier layer surface, the receiving layer surface etc.Especially, described smoothing processing preferably is applied on described interlayer surfaces or the receiving layer surface.In addition, described smoothing processing certainly is applied on two or more surfaces.

Have no particular limits for the calender apparatus that is used for smoothing processing and multiple treatment conditions such as nip pressure, the number of cramping parts, the surface temperature of warm-up mill, but for calender apparatus, can suitably use normally used calender apparatus in paper industry, as supercalender, soft calender, gloss calender, mechanical calender and gap calender.

In smoothing processing, nip pressure condition preference is as being 0.2～150MPa, more preferably 0.3～100MPa.The time of staying of described receiver sheet in the cramping parts is subjected to the significant impact of the line pressure of hardness, calender of pressure roller and processing speed etc., but is preferably 5～500 milliseconds.For the temperature conditions of warm-up mill, preferably, promptly for example be 20～150 ℃, more preferably 30～120 ℃ in the temperature of room temperature melting range of adhesive in the coating that stands smoothing processing.In addition, for the surface roughness of warm-up mill, be preferably 0.01～5 μ m based on the Ra value of JIS B 0601 standard, more preferably 0.02～1 μ m.

The method that is used to make receiver sheet of the present invention can comprise, as shown in Figure 1, heats the caliper recovery treatment step of receiver sheet subsequently by described sheet material is contacted with warm-up mill after the smoothing processing step under the pressure release conditions.When under the pressurized state that between the one-tenth pair roller of forming by warm-up mill and pressure roller, forms described receiver sheet being carried out smoothing processing by the cramping parts, smoothness is improved, but the inside of receiver sheet, particularly intermediate layer are compressed and thickness descends.When under the pressure release conditions, described receiver sheet being contacted with warm-up mill immediately by after the cramping parts, expand especially in described intermediate layer and thickness increases, thereby can be so that the printing density that the density in whole intermediate layer reduces and can improve receiver sheet.

The temperature of warm-up mill can be identical with the condition of warm-up mill in above-mentioned smoothing processing in the caliper recovery treatment step, is preferably 20～150 ℃, more preferably 30～120 ℃.Equally, be preferably 0.5 second or bigger the time of contact of receiver sheet and warm-up mill, more preferably 1 second or bigger.

(image forming method)

In at present commercially available distillation thermal transfer printer, but the receiving layer that is transferred to receiver sheet from China ink band heat when sublimation dye is when forming image, owing to the thermal head of printer and the nip pressure between the air roll, apply the pressure of about 0.1～0.5MPa to receiver sheet.

Receiver sheet of the present invention preferably during printing and/or experience the pressure treatment that applies 1.0MPa or bigger pressure to described receiver sheet surface afterwards, thereby improve the intensity on printing item surface.The more preferably pressure treatment of 1.5～5MPa.

The example that is used for the pressure treatment on receiver sheet surface comprises following method (1)～(4):

(1) under normal operation after the printing, by adjustable clamp pressure roller pressure receiver sheet is carried out predetermined pressure and handle;

(2) under normal operation after the printing, by the squeeze pressure of regulating air roll receiver sheet is carried out predetermined pressure and cross paper and handle;

(3) be under the situation of three loop jump processes of yellow, magenta and cyan, in printing process by regulating the squeeze pressure of air roll and receiver sheet is carried out predetermined pressure and transfer processing in final transfer place of cyan; With

(4) be under the situation of four loop jump processes of yellow, magenta, cyan and protective clear layer in printing process,, receiver sheet carried out predetermined pressure and transfer processing by regulate the squeeze pressure of air roll in final transfer place of protective clear layer.

Suitably select these systems by cost, processing speed and the control easiness of considering equipment.

Embodiment

Below by reference example the present invention is explained in more detail, but scope of the present invention is not limited to this.In an embodiment, except as otherwise noted, " % " and " part " expression is in " the quality % " and " mass parts " of solid content (except the solvent).

Embodiment 1

[formation of back of the body superficial layer]

(by Oji PaperCo., Ltd. makes, 174.4g/m for OK Kinfuji N, trade name to adopt the thick enamel paper of 150 μ m ²) as the sheet supporter, thus the back of the body superficial layer coating solution 1 that will have following composition is coated on the 3g/m that has on the one surface in solid content ²Dry-coated amount, dry to form back of the body superficial layer.

Back of the body superficial layer coating solution 1

Polyvinyl acetal resin (ESLEC KX-1,40 parts

By Sekisui Chemical Co., Ltd. makes)

Polyacrylate resin (JURYMER AT613,20 parts

Trade name, by Nihon Junyaku Co., Ltd. makes)

Nylon resin particle (MW330, trade name, 10 parts

By Shinto Toryo Co., Ltd. makes)

Zinc stearate (Z-7-30, trade name, 10 parts

By Chukyo Yushi Co., Ltd. makes)

Cationic electroconductive resin (CHEMISTAT9800, trade name, 20 parts

By Sanyo Chemical Industries Co., Ltd. makes)

400 parts of 2/3 (quality) mixed solutions of water/isopropyl alcohol

[formation in intermediate layer]

Coating has the intermediate layer coating solution 1 of following composition so that its dried thickness is 43 μ m on the sheet supporting body surface relative with that side that back of the body superficial layer wherein is provided, and dry to form the intermediate layer.In addition, for smooth surface, to this sheet material carry out calender process (roll surface temperature: 80 ℃, nip pressure: 2.5MPa).

Intermediate layer coating solution 1

35 parts of polyvinylidene chloride base prefoam hollow particles

(the volume hollow rate: 93%, average particulate diameter:

4 μ m, the largest particles diameter: 20 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 50 parts

Make by Nippon ZEON Corporation)

200 parts in water

[preparation of receiver sheet]

Thereby being coated with the barrier layer coating solution 1 feasible coating weight in solid content with following composition on described intermediate layer is 2g/m ², and dry to form barrier layer.Subsequently, thus the receiving layer coating solution 1 that coating has a following composition on barrier layer makes that the coating weight in solid content is 5g/m ², and dry.Under 50 ℃, the coating that forms is solidified 48 hours to form receiving layer then.By this way, preparation receiver sheet.

Barrier layer coating solution 1

Polyvinyl alcohol (PVA420, trade name, 100 parts

By Kuraray Co., Ltd. makes)

1,000 part in water

Receiving layer coating solution 1

Mylar (VYLON200, trade name, 100 parts

By Toyobo Co., Ltd. makes)

Silicone oil (KF393, trade name, 3 parts

By Shin-Etsu Chemical Co., Ltd makes)

PIC (TAKENATE D-140N, trade name, 5 parts

Make by Mitsui Takeda chemical industry Co., Ltd)

400 parts of 1/1 (quality) mixed solutions of toluene/MEK

[image forming course]

Adopt commercially available hot transfer printing video printer (UP-DR100, trade name, make by Sony), but three ink and color layers of the polyester film that the 6 μ m that will comprise the black layer that the sublimation dye that contains yellow, magenta or cyan respectively is provided on it are thick and the China ink band of adhesive contact with the order receiver sheet, and it is carried out the heat effect progressively controlled by thermal head, so that predetermined picture heat is transferred to described receiver sheet, thereby print partly the mix colours monochrome image or the color mix image of each color.The image web that obtains (is contacted with print surface from metallic roll under the exerting pressure of 1.5MPa; Diameter: 30mm) (contact with the back side with rubber rollers; Diameter: pass through 30mm).

Embodiment 2

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 2 of following composition so that dried thickness is 25 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 2

Mainly comprise acrylonitrile and acrylate copolymer based 35 parts

The prefoam hollow particle (the volume hollow rate: 79%,

Average particulate diameter: 3.6 μ m,

The largest particles diameter: 19 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 50 parts

Make by Nippon ZEON Corporation)

200 parts in water

Embodiment 3

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 3 of following composition so that dried thickness is 40 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 3

Mainly comprise acrylonitrile and acrylate copolymer based 55 parts

The prefoam hollow particle (the volume hollow rate: 79%,

Average particulate diameter: 3.6 μ m,

The largest particles diameter: 19 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 30 parts

Make by Nippon ZEON Corporation)

200 parts in water

Embodiment 4

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 4 of following composition so that dried thickness is 50 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 4

Mainly comprise acrylonitrile and acrylate copolymer based 35 parts

The prefoam hollow particle (the volume hollow rate: 80%,

Average particulate diameter: 8.0 μ m,

The largest particles diameter: 25 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 50 parts

Make by Nippon ZEON Corporation)

200 parts in water

Embodiment 5

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 5 of following composition so that dried thickness is 65 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 5

Mainly comprise acrylonitrile and acrylate copolymer based 55 parts

The prefoam hollow particle (the volume hollow rate: 88%,

Average particulate diameter: 4.4 μ m,

The largest particles diameter: 20 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 30 parts

Make by Nippon ZEON Corporation)

200 parts in water

Embodiment 6

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 6 of following composition so that dried thickness is 33 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 6

Mainly comprise acrylonitrile and acrylate copolymer based 45 parts

The prefoam hollow particle (the volume hollow rate: 77%,

Average particulate diameter: 5.2 μ m,

The largest particles diameter: 24 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 40 parts

Make by Nippon ZEON Corporation)

200 parts in water

Embodiment 7

After adopting following printing of receiver sheet for preparing with embodiment 1 same way as, when forming protective layer, carry out pressure treatment.

[image forming course]

Adopt commercially available hot transfer printing video printer (thermal head/air roll pressure: 0.8MPa), but three ink and color layers of the polyester film that the 6 μ m that will comprise the black layer that the sublimation dye that contains yellow, magenta or cyan respectively is provided on it are thick and the China ink band of adhesive contact with the receiver sheet order, and it is carried out the heat effect progressively controlled by thermal head, so that predetermined picture heat is transferred to described receiver sheet, thereby print partly the mix colours monochrome image or the color mix image of each color.

After the pressure between thermal head and the air roll is adjusted to 4.5MPa, the image web that obtains is passed through therebetween.At this moment, will comprise on thick its of 6 μ m providing the sheet material of the polyester film of transparent resin layer to contact with described receiver sheet, and by the thermal head heating, thereby protective layer heat is transferred to receiver sheet.

Embodiment 8

Carry out image forming course in the mode identical with embodiment 7; except after printing, protective layer heat is transferred to receiver sheet by not changing the pressure (0.8MPa) between thermal head and the air roll by the receiver sheet that adopts the mode identical to prepare with embodiment 1.

Embodiment 9

[formation of back of the body superficial layer]

(OK Kinfuji N, trade name is by Oji PaperCo., Ltd., 174.4g/m to adopt the thick enamel paper of 150 μ m ²) as the sheet supporter, be 3g/m in 1 (in embodiment 1, preparing) of coating back of the body superficial layer coating solution on the one surface so that in the coating weight of solid content ², and dry to form back of the body superficial layer.

[formation in intermediate layer]

On the sheet supporting body surface relative with that side that back of the body superficial layer wherein is provided, coating intermediate layer coating solution 2 (preparing in embodiment 2) is so that dried thickness is 53 μ m, and is dry to form the intermediate layer.

[preparation of receiver sheet]

On the intermediate layer, coating barrier layer coating solution 1 (preparation in embodiment 1) is so that be 2g/m in the coating weight of solid content ², and dry to form barrier layer.Subsequently, on barrier layer, coating receiving layer coating solution 1 (preparation in embodiment 1) is so that be 5g/m in the coating weight of solid content ², and dry.The coating that solidify to form under 50 ℃ subsequently 48 hours is to form receiving layer.In addition, for smooth surface, to described sheet material carry out calender process (roll surface temperature: 78 ℃, nip pressure: 2.5MPa).By this way, preparation receiver sheet.

[image forming course]

By adopting the receiver sheet that obtains above, print in the mode identical with embodiment 7, when forming protective layer, exert pressure subsequently, thereby finish image forming course.

Embodiment 10

Carry out image forming course in the mode identical, except preparing receiver sheet by " preparation of receiver sheet " that changes as follows in embodiment 9 with embodiment 9.

[preparation of receiver sheet]

On the intermediate layer that the formation of superficial layer " back of the body " and " formation in intermediate layer " obtains afterwards in embodiment 9, coating barrier layer coating solution 1 (preparing in embodiment 1) is so that be 2g/m in the coating weight of solid content ², and to its drying to form barrier layer.Subsequently, on barrier layer, coating receiving layer coating solution 1 (preparation in embodiment 1) is so that be 5g/m in the coating weight of solid content ², and dry.The coating that solidify to form under 50 ℃ subsequently 48 hours is to form receiving layer.In addition, for level and smooth receiving layer surface, to sheet material carry out calender process (roll surface temperature: 78 ℃, nip pressure: 2.5MPa).Immediately under the pressure release conditions, be that 78 roller contacts 2 seconds with receiving layer surface and surface temperature, to carry out the caliper recovery processing.By this way, obtain receiver sheet.

[image forming course]

By adopting the receiver sheet that obtains above, print in the mode identical with embodiment 7, when forming protective layer, exert pressure subsequently, thereby finish image forming course.

Embodiment 11

[formation of back of the body superficial layer]

(OK Kinfuji N, trade name is by Oji PaperCo., Ltd., 174.4g/m to adopt the thick enamel paper of 150 μ m ²) as the sheet supporter, be 3g/m in 1 (in embodiment 1, preparing) of coating back of the body superficial layer coating solution on the one surface so that in the coating weight of solid content ², dry to form back of the body superficial layer.

[formation in intermediate layer]

On the sheet supporting body surface relative with that side that back of the body superficial layer wherein is provided, coating intermediate layer coating solution 5 (preparing in embodiment 5) is so that dried thickness is 65 μ m, and is dry to form the intermediate layer.

[preparation of receiver sheet]

On the intermediate layer, coating barrier layer coating solution 1 (preparation in embodiment 1) is so that be 2g/m in the coating weight of solid content ², dry to form barrier layer.Subsequently, on barrier layer, coating receiving layer coating solution 1 (preparation in embodiment 1) is so that be 5g/m in the coating weight of solid content ², and dry.The coating that solidify to form under 50 ℃ subsequently 48 hours is to form receiving layer.In addition, for level and smooth receiving layer surface, to sheet material carry out calender process (roll surface temperature: 78 ℃, nip pressure: 2.5MPa).Immediately under the pressure release conditions, be that 78 ℃ roller contacts 2 seconds with receiving layer surface and surface temperature, to carry out the caliper recovery processing.By this way, preparation receiver sheet.

[image forming course]

By adopting the receiver sheet that obtains above, print in the mode identical with embodiment 7, when forming protective layer, exert pressure subsequently, thereby finish image forming course.

The comparative example 1

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 7 of following composition so that dried thickness is 35 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 7

Mainly comprise acrylonitrile and acrylate copolymer based 35 parts

The prefoam hollow particle (the volume hollow rate: 97%,

Average particulate diameter: 4.4 μ m,

The largest particles diameter: 20 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 50 parts

Make by Nippon ZEON Corporation)

200 parts in water

The comparative example 2

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 8 of following composition so that dried thickness is 20 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 8

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 85 parts

Make by Nippon ZEON Corporation)

200 parts in water

The comparative example 3

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, adopts the intermediate layer coating solution 9 with following composition.

Intermediate layer coating solution 9

Mainly comprise acrylonitrile and acrylate copolymer based 35 parts

The prefoam hollow particle (the volume hollow rate: 77%,

Average particulate diameter: 15.0 μ m,

The largest particles diameter: 35 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 50 parts

Make by Nippon ZEON Corporation)

200 parts in water

The comparative example 4

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 1, difference is the formation in intermediate layer, coating has the intermediate layer coating solution 10 of following composition so that dried thickness is 60 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 10

Mainly comprise acrylonitrile and acrylate copolymer based 30 parts

The prefoam hollow particle (the volume hollow rate: 65%,

Average particulate diameter: 5.2 μ m,

The largest particles diameter: 24 μ m)

(PVA205, trade name is by 15 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 55 parts

Make by Nippon ZEON Corporation)

200 parts in water

The comparative example 5

Prepare receiver sheet and the receiver sheet after the printing is carried out pressure treatment in the mode identical with embodiment 4.

Yet, when forming the intermediate layer, be not used for the calender process of smooth surface.

Estimate

By following method the receiver sheet that obtains in embodiment and comparative example is respectively estimated, the result who obtains is as shown in table 1.

[printing smoothness]

Measure in the printing smoothness (Rp value) that is beginning under the exerting pressure of 0.1MPa to exert pressure after 10 milliseconds by adopting printing smoothness tester (microstructure analysis, by Toyo SeikiSeisaku-Sho, Ltd. makes).

[elastic compression modulus]

Measure the elastic compression modulus of receiver sheet according to JIS K 7220 standards (method of testing that is used for the compression property of rigidity porous plastics).Yet the height of sample (thickness) is the thickness (about 200 μ m) of the receiver sheet of test.In addition, compression speed is 20 μ m/min.

[printing quality (1)] (printing density, image uniformity)

The printed matter that employing obtains in embodiment and comparative example applies energy with respect to each and measures the reflection density of transferring to the document image on the receiver sheet by Macbeth reflection densitometer (RD-914, trade name are made by Kollmorgen).In " printing density " that be shown as corresponding to density the table 1 from the high tone part on lowest side the 15th rank that apply energy.

In addition, in tone part, whether exist irregular depth effect and white point to estimate the uniformity of document image by visualization corresponding to optical density (OD) 0.3 (deceiving).

Evaluation result is graded as follows, when excellence, with " excellence " expression, uses " good " expression when good, with " common " expression, represents with " poor " when irregular depth effect and white point are serious when observing irregular depth effect and white point a little.

[evaluation of scraping]

The printed matter surface that obtains respectively in embodiment and comparative example is swiped with nail, and form the easy degree of scraping vestige by visual valuation.Evaluation result is graded as follows, when excellence, with " excellence " expression, represents with " good " when good, with " common " expression, represents with " poor " when the vestige of perhaps swiping is serious when observing the scraping vestige a little.

From table 1, can be clear that, consider that from aspects such as printing density, image uniformities the receiver sheet that obtains in embodiments of the present invention is suitable for practical application.Printed matter is not being carried out among the embodiment 8 of pressure treatment, when scraping is estimated, observe the scraping vestige a little, but this is being in the level that can not cause problem in practice.

On the other hand, the receiver sheet that obtains among the comparative example 1～5 is not enough aspect printing density or the image uniformity and be not suitable for practical application.

Embodiment 12

[formation in intermediate layer]

(by Oji PaperCo., Ltd. makes, 174.4g/m for OK Kinfuji N, trade name to adopt the thick enamel paper of 150 μ m ²) as the sheet supporter, coating has the intermediate layer coating solution 11 of following composition so that dried thickness is 48 μ m on one surface, and is dry to form the intermediate layer.

Intermediate layer coating solution 11

Hollow particle A: mainly comprise 65 parts of the prefoam of polyacrylonitrile

Hollow particle (average particulate diameter: 3.8 μ m, particle

The diameter variation coefficient: 14%, volume hollow rate: 75%)

Hollow particle B: microencapsulated hollow particle (0.5 part of Nipol

MH-5055, trade name is by Nippon ZEON Corporation

Make average particulate diameter: 0.55 μ m, particle diameter

Variation coefficient: 15%, volume hollow rate: 55%)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 24.5 parts

Make by Nippon ZEON Corporation)

200 parts in water

[preparation of hot transfer printing receiver sheet]

Coating has the barrier layer coating solution 2 of following composition so that be 2g/m in the coating weight of solid content on the intermediate layer ², and dry to form barrier layer.Subsequently, be 5g/m at coating receiving layer coating solution 1 (in embodiment 1, preparing) on the barrier layer so that in the coating weight of solid content ², and dry.The coating that solidify to form under 50 ℃ then 72 hours is to form receiving layer.In addition, with the surperficial relative sheet supporting body surface of coating receiving layer on be coated with back of the body superficial layer coating solution 2 so that be 3g/m in the coating weight of solid content with following composition ², and dry to form back of the body superficial layer.By this way, obtain receiver sheet.

Barrier layer coating solution 2

Swelling inorganic layered compounds (sodium four silicon micas, 30 parts

The long diameter of average grain: 6.3 μ m,

Draw ratio: 2,700)

(PVA105, trade name is by 50 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (L-1537, trade name, 20 parts

Make by Asahi Kasei Corporation)

1,100 part in water

Back of the body superficial layer coating solution 2

Polyvinyl acetal resin (ESLEC KX-1,45 parts

By Sekisui Chemical Co., Ltd. makes)

Polyacrylate resin (JURYMER AT613,25 parts

Trade name, by Nihon Junyaku Co., Ltd. makes)

Nylon resin particle (MW330, trade name, 10 parts

By Shinto Toryo Co., Ltd. makes)

Zinc stearate (Z-7-30, trade name, 10 parts

By Chukyo Yushi Co., Ltd. makes)

(CHEMISTAT 9800, trade name, 10 parts for the cationic electroconductive resin

By Sanyo Chemical Industries Co., Ltd. makes)

400 parts of 2/3 (quality) mixed solutions of water/isopropyl alcohol

Embodiment 13

Obtain receiver sheet in the mode identical, except changing " formation in intermediate layer " step as follows with embodiment 12.

[formation in intermediate layer]

(by Oji PaperCo., Ltd. makes, 174.4g/m for OK Kinfuji N, trade name to adopt the thick enamel paper of 150 μ m ²) as the sheet supporter, coating has the intermediate layer coating solution 12 of following composition so that dried thickness is 48 μ m on one surface, and is dry to form the intermediate layer.

Intermediate layer coating solution 12

Hollow particle A: mainly comprise 65 parts of the prefoam of polyacrylonitrile

Hollow particle (average particulate diameter: 3.8 μ m, particle

The diameter variation coefficient: 14%, volume hollow rate: 75%)

Hollow particle B: microencapsulated hollow particle (3 parts of ROHPAKE

HP-1055, trade name is by Rohm ﹠amp; Haas makes,

Average particulate diameter: 1.0 μ m, particle diameter

Variation coefficient: 12%, volume hollow rate: 55%)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 22 parts

Make by Nippon ZEON Corporation)

200 parts in water

Estimate

Estimate the receiver sheet that obtains respectively among the embodiment in the above by following method, the result who obtains is as shown in table 2.

[printing quality (2)] (printing density, image uniformity)

Adopt commercially available hot transfer printing video printer (DPP-SV55, trade name, make by Sony company), but each colors of ink layer of the polyester film that the 6 μ m that will comprise the three colors of ink layers that the sublimation dye that contains yellow, magenta or cyan respectively is provided on it are thick and the China ink band of adhesive contacts with the receiver sheet surface, and it is carried out the heat effect progressively controlled by thermal head, so that predetermined picture heat is transferred to receiver sheet, thereby print the halftoning monochrome image or the color mix image of each color.

Apply energy for each, measure the reflection density of transferring to the document image on the receiver sheet by Macbeth reflection densitometer (RD-914, trade name are made by Kollmorgen).Be shown as " printing density " the table 2 corresponding to density from the high tone part that applies energy lowest side the 15th rank.When printing density is 2.0 or when bigger, described receiver sheet fully is suitable for practical application.

In addition, whether exist irregular depth effect and white point to estimate corresponding to the document image uniformity in the tone of optical density (OD) 0.3 (deceiving) part by visualization.Evaluation result is graded as follows, when excellence, uses " excellence " expression, uses " good " expression when good, use when observing irregular depth effect and white point a little " in " expression, represent with " poor " when perhaps irregular depth effect and white point are serious.

[indenture of receiver sheet]

By the commercially available hot transfer printing video printer of conversion (M1, trade name are made by Sony company), the nip pressure of delivery roll is improved.The nip pressure that records by employing pressure test film (by Fuji Photo Film Co., Ltd. makes for PRESCALE, trade name) is 50kg/cm ²The indenture of the receiver sheet that visual valuation is caused by the delivery roll of this tester.

With " excellence " expression, with " good " expression, and indenture is represented with " poor " when serious in the time of seldom observing indenture when observing indenture at all.

When these evaluation results were " good " or higher level, this receiver sheet fully was suitable for practical application.

Embodiment 14

[formation in intermediate layer]

(by Oji PaperCo., Ltd. makes, 174.4g/m for OK Kinfuji N, trade name to adopt the thick enamel paper of 150 μ m ²) as the sheet supporter, coating has the intermediate layer coating solution 13 of following composition so that dried thickness is 51 μ m on one surface, and is dry to form the intermediate layer.

Intermediate layer coating solution 13

By 45 parts of the copolymers that mainly comprises acrylonitrile and methacrylonitrile

The prefoam hollow particle that forms (average particulate diameter:

3.2 μ m, the volume hollow rate: 76%, the partition wall resin

Tg:152 ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 45 parts

Make by Nippon ZEON Corporation)

250 parts in water

[formation of barrier layer and receiving layer]

On the intermediate layer, coating barrier layer coating solution 2 (preparation in embodiment 12) is so that be 2g/m in the coating weight of solid content ², and dry to form barrier layer.Subsequently, on barrier layer, coating receiving layer coating solution 1 (preparation in embodiment 1) is so that be 5g/m in the coating weight of solid content ², and dry to form receiving layer.

[preparation of receiver sheet layer]

On the sheet supporting body surface relative with that side that receiving layer wherein is provided, coating back of the body superficial layer coating solution 1 (preparation in embodiment 1) is so that be 3g/m in the dry-coated amount of solid content ², and to its drying to form back of the body superficial layer.Afterwards, solidified this sheet material 48 hours down, to form receiving layer at 50 ℃.In addition, for level and smooth receiving layer surface, to this sheet material carry out calender process (roll surface temperature: 80 ℃, nip pressure: 2.5MPa).By this way, obtain receiver sheet.

Embodiment 15

Obtain receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 14 of following composition so that dried thickness is 52 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 14

By 45 parts of the copolymers that mainly comprises acrylonitrile and methacrylonitrile

The prefoam hollow particle that forms (average particulate diameter:

8 μ m, the volume hollow rate: 76%,

The Tg:152 of partition wall resin ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 45 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 16

Obtain receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 15 of following composition so that dried thickness is 45 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 15

By 55 parts of the copolymers that mainly comprises acrylonitrile and methacrylonitrile

The prefoam hollow particle that forms (average particulate diameter:

3.4 μ m, the volume hollow rate: 65%,

The Tg:152 of partition wall resin ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 35 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 17

Obtain receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 16 of following composition so that dried thickness is 65m, and is dry to form the intermediate layer.

Intermediate layer coating solution 16

By 40 parts of the copolymers that mainly comprises acrylonitrile and methacrylonitrile

The prefoam hollow particle that forms (average particulate diameter:

3.3 μ m, the volume hollow rate: 85%,

The Tg:152 of partition wall resin ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 50 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 18

Obtain receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 17 of following composition so that dried thickness is 51m, and is dry to form the intermediate layer.

Intermediate layer coating solution 17

By 45 parts of the copolymers that mainly comprises acrylonitrile and methacrylonitrile

The prefoam hollow particle that forms (average particulate diameter:

3.5 μ m, the volume hollow rate: 78%,

The Tg:131 of partition wall resin ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 45 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 19

Obtain hot transfer printing receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 18 of following composition so that dried thickness is 54 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 18

By mainly comprising 40 parts that acrylonitrile and methacrylonitrile copolymers form

The prefoam hollow particle (average particulate diameter: 3.2 μ m,

The volume hollow rate: 76%, the Tg:152 of partition wall resin ℃)

Microencapsulated hollow particle (ROHPAKE HP-1055, trade name, 5 parts

By Rohm ﹠amp; Haas makes, average particulate diameter:

1.0 μ m, the volume hollow rate: 55%, the partition wall resin

Tg:100 ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 45 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 20

Obtain hot transfer printing receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 19 of following composition so that dried thickness is 58 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 19

By mainly comprising 34 parts that acrylonitrile and methacrylonitrile copolymers form

The prefoam hollow particle (average particulate diameter: 3.2 μ m,

The volume hollow rate: 76%, the Tg:152 of partition wall resin ℃)

Microencapsulated hollow particle (ROHPAKE HP-1055, trade name, 11 parts

By Rohm ﹠amp; Haas makes, average particulate diameter:

1.0 μ m, the volume hollow rate: 55%, the partition wall resin

Tg:100 ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 45 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 21

Obtain hot transfer printing receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 13 of following composition so that dried thickness is 29 μ m, and is dry to form the intermediate layer.

Embodiment 22

Obtain hot transfer printing receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating intermediate layer coating solution 13 is so that dried thickness is 72 μ m, to its drying to form the intermediate layer.

Embodiment 23

Obtain hot transfer printing receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 20 of following composition so that dried thickness is 40 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 20

By mainly comprising 35 parts that acrylonitrile and methacrylonitrile copolymers form

The prefoam hollow particle (average particulate diameter: 3.2 μ m,

The volume hollow rate: 76%, the Tg:152 of partition wall resin ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 55 parts

Make by Nippon ZEON Corporation)

250 parts in water

Embodiment 24

Obtain hot transfer printing receiver sheet in the mode identical with embodiment 14, except in the formation in the intermediate layer of embodiment 14, coating has the intermediate layer coating solution 21 of following composition so that dried thickness is 74 μ m, and is dry to form the intermediate layer.

Intermediate layer coating solution 21

By mainly comprising 65 parts that acrylonitrile and methacrylonitrile copolymers form

The prefoam hollow particle (average particulate diameter: 3.2 μ m,

The volume hollow rate: 76%, the Tg:152 of partition wall resin ℃)

(PVA205, trade name is by 10 parts for polyvinyl alcohol

Kuraray Co., Ltd. makes)

Styrene-butadiene latex (PT1004, trade name, 25 parts

Make by Nippon ZEON Corporation)

250 parts in water

Estimate

Estimate the receiver sheet that obtains respectively among the embodiment in the above by following method, the result who obtains is as shown in table 3.

[printing quality (3)] (printing density, image uniformity, heat resistance)

Adopt commercially available hot transfer printing video printer (UP-DR100, trade name, make by Sony company), but three ink and color layers of the polyester film that the 6 μ m that will comprise the three colors of ink layers that the sublimation dye that contains yellow, magenta or cyan respectively is provided on it are thick and the ink sheet material of adhesive contact in proper order with receiver sheet to be tested, subsequently it is carried out the heating progressively controlled by thermal head, so that predetermined picture heat is transferred to receiver sheet, thereby print the halftoning monochrome image or the color mix image of each color.

Apply energy with respect to each, measure the reflection density of transferring to the document image on the receiver sheet by Macbeth reflection densitometer (RD-914, trade name are made by Kollmorgen).Be shown as " printing density " the table 3 corresponding to reflection density from the high tone part on lowest side the 15th rank that apply energy.When printing density is 2.0 or when bigger, described receiver sheet fully is suitable for practical application.

In addition, whether exist irregular depth effect and white point to estimate the picture uniformity of kymogram in corresponding to the tone part of optical density (OD) 0.3 (deceiving) by visualization.Evaluation result is graded as follows, when excellence, with " excellence " expression, uses " good " expression when good, with " common " expression, represents with " poor " when the defective of perhaps irregular depth effect and white point is serious when observing irregular depth effect and white point.

When evaluation result is " good " or when more high-grade, described receiver sheet fully is applicable to practical application.

Whether produce the heat resistance that indenture is estimated receiver sheet by near the document image part of visualization maximal density 2.1 because of thermal head.Evaluation result is graded as follows, when excellence, with " excellence " expression, with " good " expression, with " common " expression, represents with " poor " when indenture is serious in the time of can observing the indenture of document image part when good.When evaluation result is " good " or when more high-grade, described receiver sheet fully is applicable to practical application.

Industrial applicability

Receiver sheet of the present invention has the intermediate layer of containing hollow particle, and be set to specific or littler value by printing smoothness, can improve at aspects such as irregular depth effect and white points, be suitable as the receiver sheet that has high image quality, is used for the high sensitivity record.In addition, printing and processing method of the present invention can be guaranteed to produce aspects such as scraping or scratch and improve on print surface, be adapted to pass through the thermal dye transfer printer and form image.One preferred embodiment in, receiver sheet of the present invention also has sufficiently high compression strength, can not produce indenture.In an embodiment that is more preferably, receiver sheet of the present invention also has sufficiently high hear resistance.

Claims (13)

1. hot transfer printing receiver sheet, it comprises and has on its at least one surface the intermediate layer of containing hollow particle that order forms and the sheet supporter of image receiving layer, the average particulate diameter of wherein said hollow particle is 0.2～35 μ m, the volume hollow rate is 30～97%, in beginning to exert pressure the lip-deep printing smoothness of described hot transfer printing receiver sheet by adopting microstructure analysis to record after 10 milliseconds under the exerting pressure of 0.1MPa, be that the Rp value is 1.5 μ m or littler, described intermediate layer comprises two kinds of different hollow particle A of average particulate diameter and B, and the average particulate diameter L of hollow particle separately _AAnd L _BSatisfy following all relational expressions (1)～(3):

L _A＝2～35μm (1)

L _B＝0.2～9μm (2)

0.05≤L _B/L _A0.4 (3)。

2. hot transfer printing receiver sheet as claimed in claim 1, the thickness in wherein said intermediate layer are 20～90 μ m.

3. hot transfer printing receiver sheet as claimed in claim 1, all hollow particles in wherein said intermediate layer and the quality ratio of all solids content are 30～75 quality %.

4. hot transfer printing receiver sheet as claimed in claim 1, it has the barrier layer that is superimposed between described intermediate layer and the described image receiving layer.

5. hot transfer printing receiver sheet as claimed in claim 1, wherein said sheet supporter are the sheet supporters that mainly comprises cellulose slurry.

6. hot transfer printing receiver sheet as claimed in claim 1 wherein provides to comprise the back of the body superficial layer of fluoropolymer resin and organic and/or fine inorganic particles at least on that side that image receiving layer wherein is not provided of described sheet supporter.

7. hot transfer printing receiver sheet as claimed in claim 1, wherein said hot transfer printing receiver sheet is 30MPa or littler based on the elastic compression modulus of JIS K 7220.

8. it is the hollow particle that 130 ℃ or higher polymeric material form partition wall as described hollow particle by glass transition temperature that hot transfer printing receiver sheet as claimed in claim 1, wherein said intermediate layer comprise.

9. hot transfer printing receiver sheet as claimed in claim 8 is that the polymeric material that 130 ℃ or higher polymeric material form the described hollow particle of partition wall is obtained by the component that mainly comprises the itrile group monomer by glass transition temperature wherein.

10. hot transfer printing receiver sheet as claimed in claim 9, wherein said itrile group monomer are to be selected from least a in acrylonitrile, methacrylonitrile, α-Lv Daibingxijing, α-ethoxy propylene nitrile and the anti-maleic nitrile.

11. an image forming method that adopts hot transfer printing receiver sheet as claimed in claim 1, its be included in by the thermal dye transfer printer print during in and/or apply the step of 1.0MPa or bigger pressure treatment afterwards to described hot transfer printing receiver sheet surface.

12. a manufacturing comprises the method for the hot transfer printing receiver sheet of the sheet supporter with order forms on its at least one surface the intermediate layer of containing hollow particle and image receiving layer, this method comprise the following steps: on by at least one surface coating at described sheet supporter comprise average particulate diameter for 0.2～35 μ m and volume hollow rate for the intermediate layer coating solution of 30～97% hollow particle and make its dry described intermediate layer is provided after and/or after on described intermediate layer, providing described image receiving layer, carry out described sheet material by having the smoothing processing step of the cramping parts of forming by warm-up mill and pressure roller that become pair roller, thereby make in beginning to exert pressure the lip-deep printing smoothness of described hot transfer printing receiver sheet by adopting microstructure analysis to record after 10 milliseconds under the exerting pressure of 0.1MPa, be that the Rp value is 1.5 μ m or littler, described intermediate layer comprises two kinds of different hollow particle A of average particulate diameter and B, and the average particulate diameter L of hollow particle separately _AAnd L _BSatisfy following all relational expressions (1)～(3):

L _A＝2～35μm (1)

L _B＝0.2～9μm (2)

0.05≤L _B/L _A≤0.4 (3)。

13. the method for the hot transfer printing receiver sheet of manufacturing as claimed in claim 12, it also is included in the caliper recovery treatment step that described sheet surface is contacted after the described smoothing processing step with warm-up mill and heat described hot transfer printing receiver sheet subsequently.

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