CN1769360A - Heat-sensitive adhesive material - Google Patents

Heat-sensitive adhesive material Download PDF

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Publication number
CN1769360A
CN1769360A CN 200510128373 CN200510128373A CN1769360A CN 1769360 A CN1769360 A CN 1769360A CN 200510128373 CN200510128373 CN 200510128373 CN 200510128373 A CN200510128373 A CN 200510128373A CN 1769360 A CN1769360 A CN 1769360A
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heat
sensitive adhesive
adhesive material
thermo
mass parts
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CN100589973C (en
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后藤宽
久乡智之
森田充展
稻叶宪彦
北野亨
山口岳人
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Ricoh Co Ltd
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Ricoh Co Ltd
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Abstract

In order to provide heat-sensitive adhesive materials that represent high pressure-sensitive adhesive strength with respect to rough adherends such as cardboards or polyolefin wraps and lower decrease of adhesive strength with time, are thermally activated with lower energy and exhibit excellent blocking resistance, heat-sensitive adhesive materials are disclosed that contain a support, an underlayer, and a heat-sensitive adhesive layer, in this order, wherein the underlayer comprises a thermoplastic resin and a hollow filler, and the glass transition temperature of the thermoplastic resin is -70 DEG C or higher and below 0 DEG C.

Description

Heat-sensitive adhesive material
Background of invention
Technical field
The present invention relates to a kind of heat-sensitive adhesive material, it is non-binding property at normal temperatures that this material has, but demonstrates binding property by heating, and the thermo-sensitivity bonding coat that this binding property continues after demonstrating binding property, for adherend bounding force excellence, can carry out thermal activation by low-yield.
Description of related art
The adhesive label sheet be applied to more and more price show with label, description of commodity (barcode) with label, quality show with label, measure demonstration with label, advertising with label purposes such as (putting up product).In addition, for the recording mode of label, variety of ways such as ink-jet recording, thermal photography mode, pressure sensitive recording mode have also been developed.
As such adhesive label sheet, for example normally on the reverse side of the information recording surface of label, the structure of lamination adhesive layer and interleaving paper, because it is when fitting, only need to remove interleaving paper, the adhesive label sheet by being pressed on the clung body, just can be fitted simply, therefore be used widely.In common adhesive label sheet, use after removing interleaving paper, yet the interleaving paper of removing is difficult to substantially all be dropped by recycling.So, in recent years, just be subjected to people as the thermo-sensitivity adhesive label sheet that does not show fusible, as not need interleaving paper heat-sensitive adhesive material at normal temperatures and paying close attention to (referring to opening flat 6-25869 communique in fact) with thermal adhesive floor.
Thermal adhesive layer in such temperature-sensitive adhesive label sheet for example contains thermoplastic resin and hot melt property material, also contains bonding imparting agent as required.(referring to " then brief guide " the 12nd edition, the 131st～135 page, clear and 55 years, the polymer publication can be issued).
Yet the thermal adhesive layer in the above-mentioned thermo-sensitivity adhesive label sheet is after demonstrating binding property, and bounding force reduces in time, in addition, needs high heat energy when thermal activation.
So, for this point is improved, for example, proposed between supporter and thermal adhesive layer to be provided with and contained the thermal insulation layer of plastic hollow particle and water-soluble tackiness agent, thus the heat energy (highly sensitiveization) (referring to No. 2683733 communique of special permission and the flat 10-152660 communique of Te Kai) when being reduced in thermal activation.According to above-mentioned proposal, the reduction of heat energy has obtained better result when the thermal adhesive layer is carried out thermal activation.Yet, in this is proposed, there is not fusible water-soluble binder at normal temperatures owing to used, therefore, the bounding force of uneven surface clung body such as corrugated cardboard or polyolefine wrapping paper is not also reached practical degree.In addition, demonstrate after the binding property bounding force in time and the problem that reduces also is not resolved, present situation is to expect to have further improvement, exploitation.
In addition, from the viewpoint of water tolerance, label intensity, smoothness, even supporter, to the also growth promptly of demand of film or synthetic paper.With respect to film and synthetic paper growth of requirement, there is the situation that does not also comprise the thermal adhesive coating fluid as such supporter.As reason not to be covered like this, following points.
(1) because supporter is film, synthetic paper, the thermo-sensitivity bonding coat is difficult to infiltrate, and is easy to generate troubles such as crawling, pin hole, delay spot in the preparation.
(2) because supporter is film, synthetic paper, lower with the stationarity of active coating, when thermalization was lived, active coating came off easily.
(3) because supporter is film, synthetic paper, when thermalization was lived, supporter itself tightened into wrinkle easily.
(4) because supporter is film, synthetic paper, intensity is higher and be difficult to destroy, and therefore when peeling off the label that is fitted on the commodity, only has the thermo-sensitivity bonding coat to remain in and (sticks with paste residual) on the commodity, the appearance variation.
Concerning above-mentioned (1), suitableization of the addition by the tensio-active agent that in thermo-sensitivity bonding coat etc., adds and dispersion agent etc., it can be improved, but for above-mentioned (2), (3) and (4), have the distinctive problem of heat-sensitive adhesive material of using film, synthetic paper, present situation is it can't be improved fully at present.
In addition, as one of problem of present heat-sensitive adhesive material, what can enumerate is the bonding phenomenon.So-called bonding phenomenon though be meant and do not expect to produce bonding, still demonstrates fusible phenomenon, and it is initiated being exposed to for a long time under the situations such as temperature atmosphere higher than normal temperature.Even at the cylinder state or under any situation of the state of being piled up after being cut into many, if in case cause bonding, thermal adhesive layer and outside (with the reverse side of the thermal adhesive layer of seizing supporter on both sides by the arms) will be bonding, not only on paper feed, cause obstruction, the printing of outside is also produced bad influence.
So; as preventing the agglutinating method; disclose and in the thermal adhesive coating fluid, mixed the method (referring to the public clear 62-21835 communique of spy) with oilness paraffin, the surface of passing through mineral compound or colloidal solid protection hot melt property material; suppress the softening of hot melt property material, thus prevent the agglutinating method (referring to the spy open flat 6-57223 communique, the spy opens flat 6-100847 communique and the flat 6-100848 communique of Te Kai) etc.Yet if blended wax, not only bonding prevents that effect is insufficient, on the contrary, also can reduce binding property.If surface by mineral compound and colloidal solid protection hot melt property material; can be in the fusion of hot melt property material, diffusion spended time; generation is difficult to demonstrate problems such as the binding property, adhesive capacity reduction of thermal adhesive coating fluid, and the practicality aspect is undesirable.In addition, improve the bonding phenomenon, yet present situation is to produce side effects such as bounding force significantly reduces, need is not causing transportation under the agglutinating cold condition, preserve in practice by using dystectic softening agent.
In addition, for printer, wish that safety, power saving, device are tight, for example, opening flat 11-79152 communique, spy the spy opens flat 11-65451 communique, spy and opens flat 10-35126 communique, spy and open that flat 11-157141 communique, spy are opened flat 11-311945 communique, the spy opens in 2001-303036 communique and the Te Kai 2001-48139 communique etc., as the method for thermal activation, disclosed and used a heat activation method.
As such activation method, by using hot head, the energy consumption when having reduced thermal activation, the close mode of security and device are improved with comparing at present.Yet, the heat head is being used as under the situation of activation method, because the heat head activates when adding thermo-contact thermo-sensitivity bonding coat, on the resistive element of heat head, can adhere to a large amount of pasty state throw outs, therefore, exist because of heat energy can't be passed to the bounding force that causes in the thermo-sensitivity bonding coat efficiently and reduce and cause the fatal like this defective of a heat short lifeization.
As the improvement of such problem, proposed to open the method for on the heat head, adding release layer that flat 11-79152 communique is representative, and above-mentioned spy opens the method for inserting diaphragm between heat head and thermosensitive type bonding coat of flat 11-65451 communique with above-mentioned spy.Yet according to above-mentioned proposal, heat conductivity reduces on the contrary, can't the sufficient heat of thermotropism active coating supply, and existence can not demonstrate the problem of abundant bounding force, in addition, exists the manufacturing cost of heat head higher, the present situation that can't popularize on market.
Summary of the invention
The 1st purpose of the present invention is to provide a kind of heat-sensitive adhesive material, this material is strong to the bounding force of uneven surface clung bodies such as corrugated cardboard and polyolefine wrapping paper, bounding force is along with the reduction of time is also few, can carry out thermal activation with low-yield, and anti-cohesiveness is also good, even particularly synthetic paper or plastics film are used as under the situation of supporter, the thermo-sensitivity bonding coat can not come off yet during thermal activation, can prevent to produce shrinking into ridges of supporter, it is residual can not to produce pasty state when changing label.
The 2nd purpose of the present invention provides a kind of heat-sensitive adhesive material, and this material can improve anti-cohesiveness or improve because the pasty sludge that produces in the activation of heat head adheres to the adherent reduction that causes, demonstrates stable bond properties.
Heat-sensitive adhesive material of the present invention, in the 1st mode, by between thermo-sensitivity bonding coat and supporter, setting contains second-order transition temperature (Tg) and is the thermoplastic resin of 0 ℃ of less than more than-70 ℃ or-70 ℃ and the bottom of hollow packing, mix thermo-sensitivity bonding coat and bottom increasing the amount of tackiness agent in when heating, thereby improve bounding force with respect to uneven surface clung body such as corrugated cardboard and polyolefine wrapping paper.In addition,, produce insulation effect, not only can be arranged on thermo-sensitivity adhesion coating in the upper strata, can also improve anti-cohesiveness with low-yield thermal activation by in bottom, using the high spherical hollow particle of plastics of hollow rate.In addition, though with synthetic paper or plastics film as in the situation of supporter, the thermo-sensitivity bonding coat can not come off yet during thermal activation, can prevent to produce shrinking into ridges of supporter, can stick with paste residual generation when changing label and improve.
Heat-sensitive adhesive material of the present invention in the 2nd mode, contains heat sensitive recording layer and protective layer successively on the one side of supporter and this supporter, have the thermo-sensitivity bonding coat that contains thermoplastic resin and hot melt property material on the reverse side of this supporter.
Above-mentioned protective layer contains polyvinyl alcohol and the hydrazide compound with reactive carbonyl.In heat-sensitive adhesive material of the present invention, can improve anti-cohesiveness, improve because the paste slag that produces in hot head activation adheres to the binding property reduction that causes, demonstrate stable bond properties.
The accompanying drawing summary
Fig. 1 is the energising pattern of 1 check design in the expression printing matching test method.
The description of preferred implementation
(heat-sensitive adhesive material of the 1st mode)
Heat-sensitive adhesive material of the present invention in the 1st mode, contains bottom and thermo-sensitivity bonding coat at least successively on the one side of supporter and this supporter, can also contain other layer as required.In addition, do not have at above-mentioned supporter on another aspect of bottom and thermo-sensitivity bonding coat various recording layers and protective layer to be set.
＜supporter 〉
As above-mentioned supporter, its shape, structure, size are had no particular limits, can suitably select according to purpose, as above-mentioned shape, can enumerate for example tabular etc., as said structure, it can be single layer structure, also can be laminar structure,, can suitably select according to size of above-mentioned heat-sensitive adhesive material etc. as above-mentioned size.
Material as above-mentioned supporter has no particular limits, and can suitably select according to purpose, for example can enumerate inorganic materials or organic materials.As above-mentioned inorganic materials, for example can enumerate glass, quartz, silicon, silicon oxide, aluminum oxide, SiO 2, metal etc.As above-mentioned organic materials, for example can enumerate polyolefine such as vibrin such as derivatived celluloses such as paper such as good quality paper, art paper, art paper, synthetic paper, cellulosetri-acetate, polyethylene terephthalate (PET), polybutylene terephthalate, poly-carbonic acid paper, polystyrene, polymethylmethacrylate, polymeric amide, polyethylene, polypropylene etc.Wherein, preferred good quality paper, art paper, plastics film, synthetic paper, special preferably plastic film, synthetic paper.
As above-mentioned synthetic paper, can enumerate the synthetic paper that constitutes by synthon such as polyethylene, polypropylene, polyethylene terephthalate, polymeric amide and with above-mentioned materials be attached to the part of paper, simultaneously, the synthetic paper that forms on the two sides.As this synthetic paper, in commercially available product, can enumerate FPG, FGS, GFG, KPK etc. that prince's oiling society produces.
When supporter is film, synthetic paper, compare with the good quality paper that obtains by paper pulp etc., old paper etc., the infiltration variation of thermo-sensitivity bonding coat etc., in addition, stationarity is also extremely low.In addition, consider, use the contact activation mode of heat head noticeable gradually from the trend of the security of in recent years process of thermal activation, high speed, economy (ォ Application デ マ Application De).The hot activity of contact by the heat head has the side effect of cutting the active aspect of reverse side, particularly in thermal activation, comprehensive in order to activate label, the heat head self becomes high temperature, and coming off of thermo-sensitivity bonding coat is remarkable, yet, in the present invention, even with film, when synthetic paper is used as supporter, film and synthetic paper comes off, shrinks in the time of also can preventing thermal activation, it is residual also can not produce paste when in addition, label is changed.
In order to improve the adhesivity of coating layer, above-mentioned supporter is preferably handled (chromic acid etc.), etch processes, easy adhesion process, antistatic treatment etc. by Corona discharge Treatment, oxidizing reaction and is carried out surface modification treatment.In addition, in above-mentioned supporter, preferably add white pigments such as titanium oxide and make it become white.
Thickness as above-mentioned supporter has no particular limits, and can suitably select according to purpose, is preferably 50～2000 μ m, more preferably 100-1000 μ m.
＜bottom 〉
Above-mentioned bottom contains thermoplastic resin and the hollow packing of second-order transition temperature (Tg) for 0 ℃ of less than more than-70 ℃ or-70 ℃, can also contain other composition according to purpose.Above-mentioned second-order transition temperature is preferably-70～-2 ℃, more preferably-70～-5 ℃.
-thermoplastic resin-
As second-order transition temperature (Tg) is more than-70 ℃ or-70 ℃, the thermoplastic resin that less than is 0 ℃, have no particular limits, can suitably select according to purpose, for example, can enumerate the caoutchouc latex of graft copolymerization vinyl monomer, acrylate copolymer, alkylmethacrylate polymer, acrylate-alkylmethacrylate polymer, acrylic styrene copolymer, acrylate-methacrylic ester-styrol copolymer, vinyl-vinyl acetate copolymer etc., these materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
If use the thermoplastic resin that surpasses the high glass-transition temperature (Tg) of thermoplastic resin second-order transition temperature (Tg) in the above-mentioned bottom, can not obtain the feature of bottom fully, bounding force to uneven surface clung bodies such as corrugated cardboard and polyolefine wrapping paper weakens, and only reaches the bounding force of the thermo-sensitivity bonding coat that is arranged on the upper strata.
-hollow packing-
As above-mentioned hollow packing, there is no particular limitation, and using normally used volume average particle size is mineral filler or the organic filler of 0.5～10 μ m.As above-mentioned mineral filler, for example, can enumerate lime carbonate, silicon-dioxide, titanium oxide, aluminium hydroxide, clay, calcined clay, Magnesium Silicate q-agent, magnesiumcarbonate, hard charcoal, zinc oxide, barium sulfate, surface-treated lime carbonate, silicon-dioxide etc.
As above-mentioned organic filler, for example, can enumerate micropowders such as urea-formaldehyde resin, vinylbenzene-Sipacril 2739OF, polystyrene resin etc.
Wherein, if consider the problem of low-yield thermal activation (high sensitive thermal activation), the volume average particle size that preferably has insulation effect is 2.0～5.0 μ m, and hollow rate is the spherical hollow particle of plastics more than 70% or 70%.More preferably, the maximum particle diameter of hollow particle is 10.0 μ m or below the 10.0 μ m, and volume average particle size is that 2.0～5.0 μ m and hollow rate are the hollow particle more than 70% or 70% simultaneously.
Because the particle insulation effect that above-mentioned hollow rate is low is insufficient, therefore, comes the heat energy of self-heating head to be discharged into the outside by supporter, high sensitive thermal activation deleterious.If above-mentioned volume average particle size is greater than 5.0 μ m, when on using these particulate bottoms, the thermo-sensitivity bonding coat being set, oarse-grained part can generate the part that does not form the thermo-sensitivity bonding coat, when thermal activation, bounding force reduces easily, if less than 2.0 μ m are difficult to guarantee that hollow rate is more than 70% or 70%, the result causes highly sensitive thermal activation effect deterioration.
The spherical hollow particle of above-mentioned so-called plastics is meant with the thermoplastic resin to be shell, contains air, other gas in inside, has been the hollow particle of foamed state.
Wherein, above-mentioned so-called hollow rate is meant the external diameter of hollow minute particle and the ratio of internal diameter, by following mathematic(al) representation 1 expression.
＜mathematic(al) representation 1 〉
Hollow rate (%)=(internal diameter of hollow minute particle)/(external diameter of hollow minute particle) * 100
In addition, the viewpoint of the bounding force from the thermal activation mode of guaranteeing to use the heat head, the hollow rate of the hollow particle that uses in the preferred above-mentioned bottom is more than 70% or 70%.
Satisfy the material of the spherical hollow particle of plastics of above condition as formation, for example, any one in preferred vinyl cyanide-vinylidene chloride-methylmethacrylate copolymer and vinyl cyanide-methacrylonitrile-methacrylic acid iso-borneol (the イ ソ ボ ニ Le) ester copolymer.
In addition, be the thermoplastic resin of 0 ℃ of less than more than-70 ℃ or-70 ℃ and the mass ratio of above-mentioned hollow packing as second-order transition temperature (Tg) in the above-mentioned bottom, with respect to the above-mentioned thermoplastic resin of 1 mass parts, above-mentioned hollow packing is preferably 0.1～2 mass parts.If above-mentioned hollow packing less than 0.1 mass parts, highly sensitive thermal activation variation, cohesiveness reduces, if surpass 2 mass parts, bounding force to uneven surface clung body such as corrugated cardboard and polyolefine wrapping paper reduces, and the bounding force of the thermo-sensitivity bonding coat that is arranged in the upper strata is only arranged.
Hollow packing in the above-mentioned bottom and the mixing quality of thermoplastic resin are than (hollow packing: thermoplastic resin) be preferably 1: 0.5～1: 3.0, more preferably 1: 1.5～1: 2.5.In this scope, can obtain with respect to the fusible excellent especially heat-sensitive adhesive material of minute surfaces such as SUS.
In addition, the hollow packing in the bottom and the mixing quality of thermoplastic resin are than (hollow packing: thermoplastic resin) be preferably 1: 6.0～1: 20.0, more preferably 1: 8.0～1: 16.0.In such scope, can obtain particularly heat-sensitive adhesive material to the adhesivity excellence of border face and corrugated cardboard face.
Above-mentioned bottom is had no particular limits, can form, for example, can mix suitable formation of coating method of the prime-coating liquid of mentioned component by use according to known method.
As above-mentioned coating method, for example, can enumerate blade coating method, intaglio printing coating method, intaglio printing offset printing coating method, bar type coating method, roller coating method, scraper coating method, air doctor blade coating method, point type coating method, U point type coating method, AKKU coating method, level and smooth coating method, nick version printing coating method, reverse roller method, 4 rollers or 5 roller coating methods, dip coated method, canopy coating method, slip coating method, mould coating method etc.
The glue spread of above-mentioned prime-coating liquid according to drying coated amount meter, is preferably 1～35g/m 2, 2～25g/m more preferably 2If the not enough 1g/m of the glue spread of above-mentioned prime-coating liquid 2, undertaken by heating when bonding, can't obtain sufficient adhesive effect and insulation effect and worsen, if surpass 35g/m 2, because bounding force and insulation effect reach capacity, this is not preferred economically.
＜thermo-sensitivity bonding coat 〉
Above-mentioned thermo-sensitivity bonding coat contains thermoplastic resin, bonding imparting agent and hot melt property material, also contains the congruent melting agent, and other composition as required.
-thermoplastic resin-
As above-mentioned thermoplastic resin, have no particular limits, can suitably select according to purpose, if use with above-mentioned bottom in the similar resin of thermoplastic resin that uses, because the intermiscibility between the two layers of resin is good, bounding force for uneven surface clung body such as corrugated cardboard and polyolefine wrapping paper improves, and is preferred therefore.
As above-mentioned thermoplastic resin, for example can enumerate caoutchouc latex, acrylate copolymer, alkylmethacrylate polymer, acrylate-alkylmethacrylate polymer, acrylic styrene copolymer, acrylate-methacrylic ester-styrol copolymer, vinyl-vinyl acetate copolymer of graft copolymerization vinyl monomer etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
The content of above-mentioned thermoplastic resin in above-mentioned thermo-sensitivity bonding coat is preferably 10～60 quality %, more preferably 15～50 quality %.When the containing quantity not sufficient 10 quality % and surpass 60 quality % of above-mentioned thermoplastic resin,, therefore do not expect because bounding force all produces reduction.In addition, surpass under the situation of 60 quality %, under the temperature of preserving environment usually, can produce and demonstrate the trouble (bonding) that bounding force etc. is preserved at the containing ratio of low Tg resin.
-hot melt property material-
Above-mentioned hot melt property material is solid at normal temperatures, therefore can not give resin plasticity-, yet, pass through heating and melting, make resin produce swelling or softening, demonstrate binding property, because behind heating and melting, produce crystallization lentamente, after removing thermal source, binding property can also continue for a long time.
As above-mentioned hot melt property material, for example, the benzotriazole cpd shown in the preferred following structural formula (1).
Figure A20051012837300131
Structural formula (1)
Wherein, in the said structure formula 1, R 1And R 2Each other can be identical, also can be inequality, expression hydrogen atom, alkyl and α, any one of α-Er Jiajibianji.X represents hydrogen atom or halogen atom.
As abovementioned alkyl, preferred carbonatoms is 1～8 alkyl, for example, can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl etc., and these groups can also be substituted base and further replace.
As above-mentioned substituting group, can enumerate hydroxyl, halogen atom, nitro, carboxyl, cyano group or have the specified substituent alkyl of (for example, can also be replaced), aryl, heterocyclic radical etc. by halogen atom or nitro.
Benzotriazole cpd as said structure formula (1) expression, for example can enumerate 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two (1, the 1-dimethyl benzyl) benzotriazole phenyl), 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-sec-butyl-5 '-tert-butyl-phenyl) benzotriazole etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
In addition, as above-mentioned hot melt property material, the hydroxy-benzoic acid ester cpds of preferred following structural formula (2) expression.
Structural formula (2)
Wherein, in said structure formula (2), R 3Any one of expression alkyl, alkenyl, aralkyl and aryl, these groups can also further be substituted base and replace.
As abovementioned alkyl, can enumerate carbonatoms and be 1～18 alkyl, for example, can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, straight chain shape alkyl such as positive decyl, isobutyl-, isopentyl, the 2-methyl butyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, the 2-ethyl-butyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, the 2-ethyl pentyl group, the 3-ethyl pentyl group, the 2-methylheptyl, the 3-methylheptyl, the 4-methylheptyl, the 5-methylheptyl, the 2-ethylhexyl, the 3-ethylhexyl, sec.-propyl, sec-butyl, the 1-ethyl propyl, the 1-methyl butyl, 1, the 2-dimethyl propyl, the 1-methylheptyl, the 1-ethyl-butyl, 1, the 3-dimethylbutyl, 1, the 2-dimethylbutyl, 1-ethyl-2-methyl-propyl, 1-methyl hexyl, 1-ethyl heptyl, 1-propyl group butyl, 1-sec.-propyl-2-methyl-propyl, 1-ethyl-2-methyl butyl, 1-propyl group-2-methyl-propyl, the 1-ethylhexyl, 1-propyl group amyl group, 1-sec.-propyl amyl group, 1-sec.-propyl-2-methyl butyl, 1-sec.-propyl-3-methyl butyl, the 1-Methyl Octyl, 1-propyl group hexyl, 1-isobutyl--3-methyl butyl, neo-pentyl, the tertiary butyl, uncle's hexyl, tert-pentyl, branched-chain alkyls such as uncle's octyl group; Cycloalkyl such as cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-tert-butylcyclohexyl, 4-(2-ethylhexyl) cyclohexyl, bornyl, isobornyl, adamantyl etc., these groups can also further be substituted base and replace.
As above-mentioned alkenyl, carbonatoms is that 2～8 alkenyl is fit to, for example, can enumerate vinyl, allyl group, 1-propenyl, methylpropenyl, crot(on)yl, 1-butylene base, 3-butenyl, pentenyl, 4-pentenyl, 2-hexenyl, 5-hexenyl, 2-heptenyl, 2-octenyl etc., these groups can also further be substituted base and replace.
As above-mentioned aralkyl, have no particular limits, can suitably select according to purpose, for example, can enumerate benzyl, phenylethyl, phenyl propyl etc., these groups can also further be substituted base and replace.
As above-mentioned aryl, for example, can enumerate phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, benzo phenanthryl, pyrenyl etc., these groups can also further be substituted base and replace.
As the substituting group of abovementioned alkyl, alkenyl, aralkyl and aryl, can enumerate hydroxyl, halogen atom, nitro, carboxyl, cyano group or have the specified substituent alkyl of (for example, can also be replaced), aryl, heterocyclic radical etc. by halogen atom or nitro.
Hydroxy-benzoic acid ester cpds as said structure formula (2) expression, for example, can enumerate NSC 40536, m-Salicylic acid ethyl ester, m-Salicylic acid phenyl ester, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, the inferior propyl ester of P-hydroxybenzoic acid, the positive butyl ester of P-hydroxybenzoic acid, P-hydroxybenzoic acid stearate, P-hydroxybenzoic acid cyclohexyl, benzyl p-hydroxybenzoate, P-hydroxybenzoic acid 4-benzyl chloride ester, P-hydroxybenzoic acid 4-methyl benzyl ester, P-hydroxybenzoic acid phenyl ester etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
In addition, as above-mentioned hot melt property material, for example, preferably with the compound of following structural formula (3), (4) and (5) any one expression.
Structural formula (3)
Wherein, in structural formula (3), R 4And R 5Mutually the same or inequality, expression alkyl or alkoxyl group.Y represents hydrogen atom or hydroxyl.
Figure A20051012837300162
Structural formula (4)
Wherein, in structural formula (4), R 6Any one of expression hydrogen atom, halogen atom, alkyl and alkoxyl group.Y represents hydrogen atom or hydroxyl.
Figure A20051012837300163
Structural formula (5)
Wherein, in structural formula (5), R 7Any one of expression hydrogen atom, halogen atom, alkyl and alkoxyl group.
In said structure formula (3)～(5),, can enumerate and the identical group of said structure formula (1) as abovementioned alkyl.
As above-mentioned alkoxyl group, for example, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy, bay oxygen base etc.
As the compound of said structure formula (3) expression, for example, can enumerate toluene acyloin, anisoin, an anisoin, the acyloin of deoxidation toluene, deoxidation anisoin, 4,4 '-diethylbenzene acyloin, 4,4 '-diethoxy bitter almond oil camphor etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
Compound as said structure formula (4) expression, for example, can enumerate 1-hydroxyl-2-naphthoic acid phenyl ester, 1-hydroxyl-2-naphthoic acid-to chlorobenzene ester, 1-hydroxyl-2-naphthoic acid-adjacent chlorobenzene ester, 1-hydroxyl-2-naphthoic acid-to methyl phenyl ester, 1-hydroxyl-2-naphthoic acid-o-methyl-benzene ester, 1,4-dihydroxyl-2-naphthoic acid phenyl ester, 1,4-dihydroxyl-2-naphthoic acid-to chlorobenzene ester, 1, the adjacent chlorobenzene ester of 4-dihydroxyl-2-naphthoic acid etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
As the compound of said structure formula (5) expression, for example, can enumerate phenylformic acid-3-hydroxylphenyl ester, phenylformic acid-4-hydroxylphenyl ester, phenylformic acid-2-hydroxylphenyl ester, neighbour-tolyl acid-3-hydroxylphenyl ester, right-chloro-benzoic acid-3-hydroxylphenyl ester etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
With the compound of above-mentioned structural formula (1)-(5) expression, preferred use at room temperature is a solid, fused material during heating.The fusing point of these compounds is preferably more than 70 ℃ or 70 ℃, and more preferably more than 80 ℃ or 80 ℃, higher limit is about 200 ℃.
If 70 ℃ of above-mentioned fusing point less thaies when the thermal adhesive coating fluid, can be created in the troubles (bonding) on preserving such as demonstrating bounding force under the temperature of common preservation environment.In addition, demonstrate the trouble that bounding force etc. is made in the time of also can being created on the support coating dry heat sensitive binder coating fluid.On the other hand,,, must spend lot of energy, produce the trouble on using owing to demonstrate bounding force if fusing point surpasses 200 ℃.In addition, in that electrothermal sensitive recording paper is used as supporter, demonstrate by lot of energy under the situation of bounding force, because the heat sensitive recording layer color development, existence can't be read the trouble of printed images.
In addition, the volume average particle size of the hot melt property material by said structure formula (1)～(5) expressions is set to 0.5 μ m or below the 0.5 μ m, make dynamic thermal sensitivity improve, thereby this material become the heat-activatable adhesive that just can mix with thermoplastic resin and bonding imparting agent by low-yield.In addition, by above-mentioned volume average particle size is set, thereby improve at the keeping quality (improving anti-cohesiveness) of preserving temperature under the environment usually.
Total content as the compound of said structure formula (1)～(5) of above-mentioned hot melt property material expression is preferably 25～80 quality %, 35～70 quality % more preferably, if above-mentioned hot melt property material contain quantity not sufficient 25 quality %, when mixing with the thermoplastic resin of second-order transition temperature (Tg), can be created in the trouble (bonding) in the preservations such as demonstrating bounding force under the temperature under the common preservation environment, and bounding force reduces, if surpass 80 quality %, then bounding force will reduce.
-bonding imparting agent-
Above-mentioned bonding imparting agent adds for the bounding force that improves the thermo-sensitivity bonding coat, it is had no particular limits, can from known material, suitably select according to purpose, for example, (for example can enumerate rosin derivative, rosin, polymerized rosin, staybelite), terpenoid resin (for example, terpine resin, aromatic series sex change terpine resin, terpene phenol resin, hydrogenated terpene resin), petroleum resinoid, phenolic resinoid, xylene resin etc.These bonding imparting agents can significantly improve the bounding force of thermo-sensitivity bonding coat by mixing with thermoplastic resin and hot melt property material.
The fusing point of above-mentioned bonding imparting agent (or softening temperature) is preferably more than 80 ℃ or 80 ℃, more preferably 80～200 ℃.If 80 ℃ of above-mentioned fusing point (or softening temperature) less thaies, the temperature preserving usually under the environment will produce the trouble (anti-cohesiveness reduction) of preservation.
The content of above-mentioned bonding imparting agent in above-mentioned thermo-sensitivity bonding coat is preferably 1～30 quality %, more preferably 1～20 quality %.If the above-mentioned quantity not sufficient 1 quality % that contains, bounding force significantly reduces, if surpass 30 quality %, will be created in the trouble (anti-cohesiveness reduction) in the preservation under the common preservation envrionment temperature and the reduction of the initial stage bounding force under low temperature environment.
-congruent melting agent-
The suitable use of above-mentioned congruent melting agent at room temperature is solid, and fused compound during heating, the fusing point of this compound are preferably more than 70 ℃ or 70 ℃, and more preferably more than 80 ℃ or 80 ℃, its higher limit is about 150 ℃.If 70 ℃ of above-mentioned fusing point less thaies, as the thermal adhesive coating fluid time, can be created in and to demonstrate the trouble (bonding) that bounding force etc. is preserved under the temperature of common preservation environment, coating on supporter, during dry heat sensitive binder coating fluid, can produce the trouble in the manufacturing that demonstrates bounding force.On the other hand, if fusing point surpasses 150 ℃, can't obtain the effect of congruent melting heat-transmission meltbility material.
As above-mentioned congruent melting agent, have no particular limits, can from known material, suitably select according to purpose, consider according to the effect of the above-mentioned hot melt property material of congruent meltingization with to the viewpoint of the intermiscibility excellence of thermoplastic resin, preferably with the dibenzyl oxalate compound of following structural formula (6) expression.
Figure A20051012837300181
Structural formula (6)
Wherein, in said structure formula (6), Z represents any one of hydrogen atom, halogen atom and alkyl.
In addition, as abovementioned alkyl, halogen atom, can enumerate and the identical group of said structure formula (1).
As the dibenzyl oxalate compound of said structure formula (6) expression, for example, can enumerate oxalic acid two-to methyl benzyl ester, oxalic acid two-to benzyl ethyl ester, oxalic acid two-to benzyl chloride ester, dibenzyl oxalate etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
In above-mentioned thermo-sensitivity bonding coat, except that mentioned component, in order to prevent bonding, can add organism such as inorganicss such as titanium oxide, aluminum oxide, colloid silica, kaolin, talcum, Metallic stearates, paraffin, natural wax, synthetic wax, natural fats and oils, polystyrene powder, in addition, as required, can also add other composition such as dispersion agent, defoamer, tackifier.
Above-mentioned thermo-sensitivity bonding coat is had no particular limits, can form, for example, mixed suitable formation of coating method of the prime-coating liquid of mentioned component by use according to known method.
As above-mentioned coating method, for example, can enumerate blade coating method, intaglio printing coating method, intaglio printing offset printing coating method, bar type coating method, roller coating method, scraper coating method, air doctor blade coating method, point type coating method, U point type coating method, AKKU coating method, level and smooth coating method, nick version printing coating method, reverse roller method, 4 rollers or 5 roller coating methods, dip coated method, canopy coating method, slip coating method, mould coating method etc.
In addition, the drying conditions when above-mentioned coating or printing is not carry out drying in the fused temperature range at the hot melt property material and the congruent melting agent that use.As the exsiccant method, heat extraction air-dry dry beyond, can also use drying means by the thermal source of infrared rays, microwave, high frequency waves.
The glue spread of above-mentioned thermo-sensitivity bonding coat coating fluid in drying coated amount, is preferably 5～30g/m usually 2, 5～20g/m more preferably 2If the not enough 5g/m of the glue spread of above-mentioned thermo-sensitivity bonding coat coating fluid 2, undertaken can't obtaining sufficient adhesive when bonding by heating, in addition, owing to use the low thermoplastic resin of second-order transition temperature (Tg) in bottom, anti-cohesiveness worsens; If surpass 30g/m 2, because the insulation effect variation of bottom, economy worsens, and is not preferred therefore.
The total thickness of above-mentioned bottom and above-mentioned thermo-sensitivity bonding coat is preferably 13～30 μ m.In addition, be preferably more than 30% below 70% with respect to the thickness of the thermo-sensitivity bonding coat of underlayer thickness.
If above-mentioned total thickness less than 13 μ m can be difficult to attach to nonspecular surface clung bodies such as corrugated cardboards,, between bottom and thermo-sensitivity bonding coat, can produce and peel off, and destroy in the generation layer if surpass 30 μ m.In addition, the thickness by the thermo-sensitivity bonding coat is set to more than 30% can also further reduce activation evergy below 70%.Usually, because the thickness of thermo-sensitivity bonding coat is thick more, just more activation energy must be arranged, if active coating surpasses 70%, because necessary above volume of activation is arranged, film, the synthetic paper of pretending to supporter are easy to generate thermal contraction.On the other hand, if be lower than 30%, with respect to concavo-convex clung body, do not have fixed effect, stickiness significantly reduces.
Heat-sensitive adhesive material of the present invention is by said structure, the bounding force of uneven surface clung body such as each clung body, particularly corrugated cardboard and polyolefine wrapping paper strengthened, and be low-yield thermal activation and the also good material of anti-cohesiveness.
Secondly, heat-sensitive adhesive material of the present invention preferably contains recording layer and protective layer successively on the face of the thermo-sensitivity bonding coat that does not have supporter, also contain other layer as required.
As above-mentioned recording layer, have no particular limits, can suitably select according to purpose, for example, recording layer is preferably any one of heat sensitive recording layer, heat fusing transfer printing recording ink receiving layer, electrophoto-graphic toner image receiving layer, photographic silver halide usefulness recording layer and ink for inking receiving layer.Wherein, setting contains the thermal photography of the heat sensitive recording layer of adularescent dyestuff and developer and uses heat-sensitive adhesive material as above-mentioned recording layer, or the thermal photography that heat fusing transfer printing recording ink receiving layer is set uses heat-sensitive adhesive material as above-mentioned recording layer, to each clung body, particularly the bounding force of uneven surface clung body such as corrugated cardboard and polyolefine wrapping paper strengthens, low-yield thermal activation and anti-cohesiveness are also good, are exceedingly useful.
The heat-sensitive adhesive material that＜thermal photography is used 〉
Heat sensitive recording layer in the heat-sensitive adhesive material that above-mentioned thermal photography is used contains chromogenic reagent, developer and binder resin, also contains other composition as required.
As above-mentioned white dyestuff, have no particular limits, can from known material, suitably select according to purpose, for example, can enumerate disclosed triphenylmethane dye, Material of Fluoran dyestuff, phenothiazines dyestuff, auramine class dyestuff, spiro-pyrans class dyestuff, indolinyl phthalein ketone (indolinophthalide) class dyestuff etc.
As above-mentioned white dyestuff, for example, can enumerate 3,3-two (to dimethylaminophenyl) phthalein ketone, 3,3-two (to dimethylaminophenyl)-6-dimethylamino phthalein ketone (another name crystal violet lactone), 3,3-two (to dimethylaminophenyl)-6-diethylamino phthalein ketone, 3,3-two (to dimethylaminophenyl)-6-Chlorthalidone, 3,3-two (to the dibutylamino phenyl) phthalein ketone, 3-cyclohexyl amino-6-chlorine fluorane, 3-dimethylamino-5,7-dimethyl fluorane, 3-diethylamino-7-chlorine fluorane, 3-diethylamino-7-methyl fluoran, 3-diethylamino-7,8-benzo fluorane, 3-diethylamino-6-methyl-7-chlorine fluorane, 3-(N-p-methylphenyl-N-ethylamino)-6-methyl-7-anilino fluorane, 3-pyrrolidyl-6-methyl-7-anilino fluorane, 2-(N-(3 '-trifluoromethyl) amino)-6-diethylamino fluorane, 2-(3,6-two (diethylamino)-9-(Ortho-Chloro aniline) xanthyl phenylformic acid lactan), 3-diethylamino-6-methyl-7-(a trichloromethyl anilino) fluorane, 3-diethylamino-7-(p-Chlorobenzoic acid amide base) fluorane, 3-dibutylamino-7-(p-Chlorobenzoic acid amide base) fluorane, 3-N-methyl-N-amyl group amino-6-methyl-7-anilino fluorane, 3-N-methyl-N-cyclohexyl amino-6-methyl-7-anilino fluorane, 3-diethylamino-6-methyl-7-anilino fluorane, 3-(N, the N-diethylamino)-5-methyl-7-(N, the N-dibenzyl amino) fluorane, benzoyl white methylene blue, the full pyrrole promise spirane (ベ Application ソ イ Application De リ ノ one ピ リ ロ ス ピ ラ Application) of 6 '-chloro-8 '-methoxyl group-benzindole, the full pyrrole promise spirane of 6 '-bromo-3 '-methoxyl group-benzindole, 3-(2 '-hydroxyl-4 '-dimethylaminophenyl)-3-(2 '-methoxyl group-5 '-chloro-phenyl-) phthalein ketone, 3-(2 '-hydroxyl-4 '-diethylamino phenyl)-3-(2 '-methoxyl group-5 '-nitrophenyl) phthalein ketone, 3-(2 '-hydroxyl-4 '-diethylamino phenyl)-3-(2 '-methoxyl group-5 '-aminomethyl phenyl) phthalein ketone, 3-diethylamino-6-methyl-7-(2 ', 4 '-dimethyl benzene amido) fluorane, 3-(2 '-methoxyl group-4 '-dimethylaminophenyl)-3-(2 '-hydroxyl-4 '-chloro-5 '-aminomethyl phenyl) phthalein ketone, 3-morpholino-7-(N-propyl group-trifluoromethylbenzene amido) fluorane, 3-pyrrolidyl-7-trifluoromethylbenzene amido fluorane, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylbenzene amido) fluorane, 3-pyrrolidyl-7-(two rubigan) methylamino fluorane, 3-diethylamino-5-chloro-7-(α-phenylethyl amino) fluorane, 3-(the N-ethyl-to toluino)-7-(α-phenylethyl amino) fluorane, 3-diethylamino-7-(neighbour-methoxycarbonyl phenyl amino) fluorane, 3-diethylamino-5-methyl-7-(α-phenylethyl amino) fluorane, 3-diethylamino-7-pyrrolidyl fluorane, 2-chloro-3-(N-methyl toluino)-7-(to the n-butyl aniline base) fluorane, 3-(N-benzyl-N-cyclohexyl amino)-5,6-benzo-7-Alpha-Naphthyl amino-4 ' 0-bromine fluorane, trimethylbenzene matrix between 3-diethylamino-6-methyl-7-(メ シ チ ジ ノ)-4 ', 5 '-benzo fluorane, 3-diethylamino-6-methyl-7-(2 ', 4 '-dimethyl benzene amido) fluorane, 3-(to dimethylaminophenyl)-3-(1,1-two (to dimethylaminophenyl) ethene-2-yl) phthalein ketone, 3-(to dimethylaminophenyl)-3-{1,1-two (to dimethylaminophenyl) ethene-2-yl }-6-dimethylamino phthalein ketone, 3-(to dimethylaminophenyl)-3-(1-is to dimethylaminophenyl-1-phenyl ethene-2-yl) phthalein ketone, 3-is (to dimethylaminophenyl-3-(1-is to dimethylaminophenyl-1-rubigan ethene-2-yl)-6-dimethylamino phthalein ketone, 3-(4 '-dimethylamino-2 '-methoxyl group)-3-(1 "-to dimethylaminophenyl-1 "-rubigan-1 "; 3 "-divinyl-4 "-yl) benzo phthalein ketone; 3-(4 '-dimethylamino-2 '-benzyloxy)-3-(1 "-to dimethylaminophenyl-1 "-phenyl-1 ", 3 " divinyl-4 "-yl) benzo phthalein ketone, 3-dimethylamino-6-dimethylamino-fluorenes-9-spiral shell-3 '-(6 '-dimethylamino) phthalein ketone, 3,3-two { 2-(to dimethylaminophenyl)-2-(p-methoxyphenyl) vinyl }-4,5,6,7-four Chlorthalidones, 3-two { 1,1-two (4-pyrrolidyl phenyl) ethene-2-yl }-5,6-two chloro-4,7-dibromo phthalein ketone, two (to the dimethylamino styryl)-1-naphthalene sulfonyl methane, 3-(N-methyl-N-propyl group amino)-6-methyl-7-anilino fluorane, 3-diethylamino-6-methyl-7-anilino fluorane, 3,6-two (dimethylamino) fluorane spiral shell (9,3 ')-6 '-dimethylamino phthalein ketone, 3-diethylamino-6-chloro-7-anilino fluorane, 3-N-ethyl-N-(2-ethoxycarbonyl propyl) amino-6-methyl-7-anilino fluorane, 3-N-ethyl-N-tetrahydrofurfuryl amino-6-methyl-7-anilino fluorane, 3-diethylamino-6-methyl-7-mesidino-4 ', 5 '-benzo fluorane, 3-N-methyl-N-isopropyl butyl-6-methyl-7-anilino fluorane, 3-N-ethyl-N-isopentyl-6-methyl-7-anilino fluorane etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
As above-mentioned developer, have no particular limits, can from known electrophilic compound, suitably select according to purpose, for example can enumerate phenol compound, phenylmercaptan compound, thiourea derivative, organic acid or its metal-salt etc.As this developer, for example can enumerate 4,4 '-isopropylidene biphenol, 3,4 '-isopropylidene biphenol, 4,4 '-isopropylidene two (neighbour-methylphenol), 4,4 '-Ya sec-butyl biphenol, 4,4 '-isopropylidene two (neighbour-tert.-butyl phenol), 4,4 '-cyclohexylene phenol, 4,4 '-isopropylidene two (2-chlorophenol), 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 2,2 '-methylene radical two (4-ethyl-6-tert.-butyl phenol), 4,4 '-butylidene two (the 6-tertiary butyl-2-methyl) phenol, 1,1,3-three (2-methyl-4-hydroxyl-5-tert.-butyl phenol) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 4,4 '-sulfo-two (the 6-tertiary butyl-2-methyl) phenol, 4,4 '-biphenol sulfone, 4,2 '-biphenol sulfone, 4-isopropoxy-4 '-hydroxy diphenyl sulfone, 4-benzyloxy-4 '-hydroxy diphenyl sulfone, 4,4 '-biphenol sulfoxide, p-Hydroxybenzoic acid isopropyl ester, benzyl p-hydroxybenzoate, Protocatechuic Acid benzyl ester, the gallic acid stearate, Progallin LA, Stabilizer GA 8,1,7-two (4-hydroxybenzene sulfenyl)-3,5-oxa-butane, 1,5-two (4-hydroxybenzene sulfenyl)-3-oxygen heptane, 1,3-two (4-hydroxybenzene sulfenyl)-propane, 2,2 '-methylene radical two (4-ethyl-6-tert.-butyl phenol), 1,3-two (4-hydroxybenzene sulfenyl)-2-hydroxy propane, N, N '-thiambutosine, N, N '-two (-chloro-phenyl-) thiocarbamide, salicyl aniline, 5-chloro-salicyl aniline, salicyl-neighbour-chloroaniline, 2-hydroxyl-3-naphthoic acid, the quinizine title complex of sulfocyanic acid zinc, the zinc salt of 2-acetoxy-3-naphthoic acid, 2-hydroxyl-1-naphthoic acid, 1-hydroxyl-2-naphthoic acid, the zinc of hydroxynaphthoic acid, aluminium, the metal-salt of calcium etc., two (4-hydroxy phenyl) ritalin, two (4-hydroxy phenyl) Benzyl Acetate, 4-{ β-(right-the methoxyl group phenoxy group) oxyethyl group } Whitfield's ointment, 1,3-two (4-hydroxyl cumyl) benzene, 1,4-two (4-hydroxyl cumyl) benzene, 2,4 '-biphenol sulfone, 3,3 '-diallyl-4,4 '-biphenol sulfone, α, the quinizine title complex of α-two (4-hydroxy phenyl)-Alpha-Methyl toluene sulfenyl cyanic acid zinc, tetrabromo-bisphenol, tetrabromo-bisphenol s, 4,4 '-sulfo-two (2-methylphenol), 3,4-hydroxyl-4 '-methyl-biphenol sulfone, 4,4 '-sulfo-two (2-chlorophenol) etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
The addition of above-mentioned developer in above-mentioned heat sensitive recording layer has no particular limits, and can suitably select according to purpose.With respect to the above-mentioned chromogenic reagent of 1 mass parts, be preferably 1～20 mass parts, more preferably 2～10 mass parts.
As above-mentioned binder resin, have no particular limits, can from known material, suitably select according to purpose, for example, can enumerate polyvinyl alcohol, the starch or derivatives thereof, the methoxyl group Mierocrystalline cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, methylcellulose gum, derivatived celluloses such as ethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, the acrylamide-acrylicacid ester copolymer, acrylamide-acrylicacid ester-methacrylic acid ter-polymer, the styrene-maleic anhydride copolymer alkali salt, iso-butylene-copolymer-maleic anhydride alkali salt, polyacrylamide, sodium alginate, gelatin, water-soluble polymers such as casein, in addition, can also enumerate polyvinyl acetate, urethane, polyacrylic acid, polyacrylic ester, polymethacrylate, poly-n-butyl methacrylate, vinyl chloride vinyl acetate copolymer, latex and styrene-butadiene copolymers such as vinyl-vinyl acetate copolymer, latex classes such as styrene butadiene-acrylic copolymer etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
In above-mentioned heat sensitive recording layer, can use various thermomeltable materials as filler.As this thermomeltable material; for example; can enumerate stearic acid; fatty acids such as behenic acid; stearylamide; fatty acid acyl amines such as palmitic amide; Zinic stearas; aluminum stearate; calcium stearate; zinc palmitate; fatty acid metal salts such as behenic acid zinc; right-Benzyldiphenyl; terphenyl; triphenyl methane; right-the benzyloxy peruscabin; β-benzyloxy naphthalene; β-naphthoic acid phenyl ester; 1-hydroxyl-2-naphthoic acid phenyl ester; 1-hydroxyl-2-naphthoic acid methyl esters; diphenyl carbonate; the terephthalic acid dibenzyl ester; dimethyl terephthalate (DMT); 1; the 4-dimethoxy-naphthalene; 1; 4-diethoxy naphthalene; 1; 4-benzyloxy naphthalene; 1; 2-two (phenoxy group) ethane; 1; 2-two (3-methylphenoxy) ethane; 1; 2-two (4-methylphenoxy) ethane; 1; 4-two (phenoxy group) butane; 1; 4-two (phenoxy group) 2-butane; 1; 2-two (4-anisole sulfenyl) ethane; phenyl phenacyl ketone; 1; 4-two (thiophenyl) butane; 1; 4-two (thiophenyl) 2-butane; 1; 2-two (4-anisole sulfenyl) ethane; 1; 3-two (2-vinyloxy group oxyethyl group) benzene; 1; 4-two (2-vinyloxy group oxyethyl group) benzene; right-(2-vinyloxy group oxyethyl group) biphenyl; to aryloxy biphenyl; to alkynes phenoxy group biphenyl; the dibenzoic acid methylmethane; 1; 3-dibenzoic acid base propane; the benzyl disulfide thing; 1; 1-phenylbenzene ethanol; 1; 1-phenylbenzene propyl alcohol; right-(benzyloxy) benzyl ethyl alcohol; 1; 3-two phenoxy groups-2-propyl alcohol; N-octadecyl formamyl-right-methoxycarbonyl benzene; N-octadecyl carbamyl benzene; dibenzyl oxalate; 1,5-two (right-p-methoxy-phenyl oxygen base)-3-oxa-pentane etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
In above-mentioned heat sensitive recording layer, as required, can also be used in combination various auxiliary added ingredientss, for example tensio-active agent, lubricant etc.As this lubricant, for example, can enumerate higher fatty acid or its metal-salt, higher fatty acid amides, high-grade aliphatic ester, animality wax, vegetalitas wax, mineral wax, petroleum-type wax etc.,
Above-mentioned heat sensitive recording layer is had no particular limits, can form by common known method, for example, can form as follows, white dyestuff, developer are passed through dispersion machines such as ball mill, masher, sand mill with tackiness agent, other composition respectively, grinding dispersion is after disperse particle diameter to be 1～3 μ m, as required, with itself and filler, thermally melting material (sensitizing agent) dispersion liquid etc., mix by certain prescription, preparation heat sensitive recording layer coating fluid is coated with on support, thereby forms heat sensitive recording layer.
The thickness of above-mentioned heat sensitive recording layer is different according to the composition of above-mentioned heat sensitive recording layer and the purposes of heat-sensitive adhesive material etc., cannot treat different things as the same, and is preferably 1～50 μ m.3～20 μ m more preferably.
The heat-sensitive adhesive material that＜hot tranfer is employed 〉
Employ ink-receiver layer at the hot tranfer that above-mentioned hot tranfer is employed in the heat-sensitive adhesive material, contain filler, binder resin, anti-hydrated agent, can also contain other composition as required.
As above-mentioned filler, have no particular limits, can suitably select according to purpose, for example, can enumerate micropowders such as lime carbonate, silicon-dioxide, titanium oxide, aluminium hydroxide, clay, calcined clay, Magnesium Silicate q-agent, magnesiumcarbonate, hard charcoal, zinc oxide, barium sulfate, surface-treated lime carbonate and silicon-dioxide, urea-formaldehyde resin, vinylbenzene-Sipacril 2739OF, polystyrene resin etc.
As above-mentioned binder resin, have no particular limits, can from known water soluble resin, suitably select according to purpose, for example, can enumerate derivatived celluloses such as polyvinyl alcohol, starch or derivatives thereof, methoxyl group Mierocrystalline cellulose, Natvosol, carboxymethyl cellulose, methylcellulose gum, ethyl cellulose; Water-soluble polymers such as sodium polyacrylate, Polyvinylpyrolidone (PVP), acrylamide-acrylicacid ester copolymer, acrylamide-acrylicacid ester-methacrylic acid ter-polymer, styrene-maleic anhydride copolymer alkali salt, iso-butylene-copolymer-maleic anhydride alkali salt, polyacrylamide, sodium alginate, gelatin, casein etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.
Above-mentioned filler in the above-mentioned ink-receiver layer is relevant with cohesiveness with the ratio of water soluble resin, above-mentioned filler to the content mass ratio (solids component) of water soluble resin be preferably 1: 0.1～0.2.
As above-mentioned anti-hydrated agent, have no particular limits, can suitably select according to purpose, for example, can enumerate formaldehyde, oxalic dialdehyde, chromium alum, melamine, melamine-formaldehyde resin, polyamide resin, polymeric amide-epichlorohydrin resins etc.
The ratio of the above-mentioned water soluble resin of above-mentioned anti-hydrated agent is also relevant with cohesiveness, and its content mass ratio (solids component) is that with respect to 1 part of water soluble resin, anti-hydrated agent is preferably 0.3～0.5 part.Such ink-receiver layer is by containing filler and water soluble resin, and ratio in accordance with regulations contains water soluble resin and water-proofing agent and forms, in addition, calendering is handled by rolling press in the ink-receiver layer surface, its smoothness is reached more than 500 seconds or 500 seconds, except that the effect that adopts above-mentioned filler, also further improve printing quality.
-protective layer-
Above-mentioned protective layer contains poly-ethanol and the hydrazide compound with reactive carbonyl, also contains other composition as required.
Owing to contain the polyvinyl alcohol that has reactive carbonyl like this and as the protective layer of the hydrazide compound of linking agent, thermotolerance, water tolerance are high, and therefore the influence that be difficult to be under pressure, temperature, humidity produces, can improve anti-cohesiveness greatly.
Above-mentioned polyvinyl alcohol with reactive carbonyl can carry out the polymkeric substance that obtains known method preparations such as saponification by the vinyl monomer and the vinyl fatty ester copolymerization that will have reactive carbonyl.Have the vinyl monomer of reactive carbonyl as this, can enumerate the group with ester residue, group, but preferably have the vinyl monomer of diacetone base with acetonyl, concrete, preferred diacetone-acryloamide(DAA) and methyl diacetone-acryloamide(DAA).As above-mentioned vinyl fatty ester, can enumerate vinyl formate, vinyl-acetic ester, propionate etc., wherein, preferred especially vinyl-acetic ester.
Above-mentioned polyvinyl alcohol (PVA) with reactive carbonyl, also can be can copolymerization other vinyl monomer copolymerization obtain.As these can copolymerization vinyl monomer, for example, can enumerate acrylate, divinyl, ethene, propylene, vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, methylene-succinic acid etc.
The content of the reactive carbonyl among the above-mentioned PVA with reactive carbonyl is preferably 0.5～20mol% of whole polymkeric substance, if the water tolerance of considering, more preferably 2～10mol%.If above-mentioned content is less than 2mol%, actual water tolerance is insufficient, even surpass 10mol%, also water tolerance can't be increased to more than it, owing to only be at high price, be uneconomic therefore.In addition, the above-mentioned polymerization degree with PVA of reactive carbonyl is preferably 300～3000, and more preferably 500～2200.In addition, above-mentioned saponification deg with PVA of reactive carbonyl is preferably more than 80% or 80%.
Above-mentioned hydrazide compound, get final product and have no particular limits so long as have the compound of hydrazide group, can suitably select according to purpose, for example, can enumerate symmetrical diamino arteries and veins, oxalic acid two hydrazides, the formic acid hydrazides, acetic acid hydrazides, propanedioic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, the nonane diacid hydrazides, sebacic dihydrazide, the bay acid dihydrazide, the Malaysia acid dihydrazide, the fumaric acid hydrazides, methylene-succinic acid two hydrazides, phenylformic acid two hydrazides, pentanedioic acid two hydrazides, the diglycollic acid hydrazides, the winestone acid dihydrazide, the apple acid dihydrazide, the m-phthalic acid hydrazides, terephthaldehyde's acid dihydrazide, 2,7-naphthoic acid two hydrazides, polyacrylic acid hydrazides etc.These materials can use a kind separately, also can will be used in combination more than 2 kinds or 2 kinds.In these hydrazide compounds, from the aspect of water tolerance and security, preferred adipic dihydrazide.
The content of above-mentioned hydrazide compound with respect to the above-mentioned polyvinyl alcohol with reactive carbonyl of 100 mass parts, is preferably 5～40 mass parts, more preferably 15～25 mass parts.
In above-mentioned protective layer, preferably contain filler.This filler can be an alkaline matter, as its example, can enumerate aluminium hydroxide, lime carbonate, talcum, alkaline silicate class etc., matching (residue adhesion) from the heat head, preferred aluminium hydroxide and lime carbonate, if consider by suitable water-soluble control pH, preferred especially aluminium hydroxide.As the filler that contains in the above-mentioned heat sensitive recording layer, can use known material, as its example, can enumerate mineral dye such as lime carbonate zinc oxide, aluminum oxide, titanium dioxide, silicon-dioxide, aluminium hydroxide, barium sulfate, sliding soil, kaolin, alumina, clay or known pigment dyestuff etc., but be not limited to these.In addition, if the water tolerance of considering (water-fast separability), preferably silicon-dioxide, kaolin, the alumina of acid pigment (in the aqueous solution show tart pigment), from the viewpoint of color development concentration, preferred especially silicon-dioxide.
Above-mentioned protective layer is had no particular limits, can form by common known method, for example, can be by preparing protective layer coating solution according to a conventional method, this coating fluid of coating on above-mentioned recording layer, thereby formation protective layer.
Thickness to above-mentioned protective layer has no particular limits, and can suitably select according to purpose, but be preferably 1.0～7.0 μ m.
Between above-mentioned supporter and above-mentioned heat sensitive recording layer, middle layer etc. can also be set as required.Composition as constituting these layers can use above-mentioned filler, tackiness agent, thermally melting material, tensio-active agent etc.
In addition, heat-sensitive adhesive material of the present invention can also be preprinted brush layer opposing face (recording layer surface) setting of thermo-sensitivity bonding coat according to purpose, can also be provided as the label print of direction finding measure on surface or thermo-sensitivity bonding coat.Two kinds of printings can be enumerated common printing processes such as UV printing, EB printing, multi-functional printing.As printing-ink, for example, from the viewpoint of rapid-drying properties, on electrothermal sensitive recording paper, UV hardening printing ink can be used as most preferred printing ink and uses.As above-mentioned UV hardening printing ink (UV printing ink), for example can enumerate T﹠amp; The UV printing ink of the UV RNC that K TOKA produces, UV NVR, UVSOYA, UV SOYA-RNC; The UV printing ink of the FD FL of Toyo Ink Manufacturing Co., Ltd. etc.
Used the cutting back before or after heat-sensitive adhesive material of the present invention can be adapted at the thermal activation (heating) of its thermo-sensitivity bonding coat, wherein, in this heat-sensitive adhesive material, can also be pre-formed otch.Above-mentioned heat-sensitive adhesive material is adapted at using in the various uses such as label, mark, sees it is favourable from this point.
Shape as heat-sensitive adhesive material of the present invention has no particular limits, preferably can enumerate be label-like, laminar, label is laminar, roller shape etc.
Wherein, from the viewpoint of accessibility, site of storage, operability, reel on core cylindraceous, it is preferred being rolled into long chi shape that the roller shape takes care of.
(heat-sensitive adhesive material of the 2nd mode)
Heat-sensitive adhesive material of the present invention; in the 2nd mode; on the one side of supporter and this supporter, contain thermo-sensitivity recording layer and protective layer successively; on the reverse side of this supporter, contain thermo-sensitivity bonding coat, can also contain other layer as required with thermoplastic resin and hot melt property material.
Above-mentioned heat sensitive recording layer is made of heat sensitive recording layer and protective layer usually, and when reeling with the roller shape, the bonding aspect of the protection aspect of heat sensitive recording layer and thermo-sensitivity is fitted, and owing to pressure, temperature, humidity, the factor of time, the fusion of temperature-sensitive bonding coat produces bonding.In order to improve a resistance to chemical reagents and a matching, protective layer is made of mineral filler usually.
As the resin that uses in this protective layer, polyvinyl alcohol that has a reactive carbonyl by use and the hydrazide compound as linking agent can improve anti-cohesiveness.As the resin that uses up to now; can be starch based, hydroxylated cellulose, methylcellulose gum, carboxymethyl cellulose, gelatin, casein, Sudan Gum-arabic, (part) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol etc. fully; these resin thermotolerances, wet fastness are insufficient; and with state that the thermo-sensitivity bonding coat overlaps under; if exert pressure, the load of temperature, humidity; protective layer becomes than the remollescent state; in addition, with the temperature-sensitive bonding coat generation bonding that approaches to apply molten state.In contrast, polyvinyl alcohol by having reactive carbonyl and effect as the hydrazide compound of linking agent, the resin thermotolerance of protective layer, wet fastness are high, are difficult to be subjected to the influence of applied pressure, temperature, humidity.In addition, if use resin of the present invention, the thermo-sensitivity bonding coat is difficult to form molten state, because the synergy of these materials can improve anti-cohesiveness greatly.
In addition, made distribution in recent years by the printed matter of the two-layer heat-sensitive adhesive material that constitutes of heat sensitive recording layer of the present invention and temperature-sensitive bonding coat.When brushing heat sensitive recording layer by hot heading; if the resin of the protective layer of thermal photography side uses the thermotolerance beyond the present invention, the resin material of wet fastness difference; then be absorbed in the state softer than protective layer, its frictional force with the heat head improves, and causes the transmission obstacle easily.The thermo-sensitivity bonding coat of reverse side contacts with the dull and stereotyped roller that rotation drives, and with dull and stereotyped roller frictional heat, occurs bonding.This phenomenon is remarkable under hot and humid environment.Therefore, the bad effects such as (ジ ヤ system リ) and transmission interruption that compress of label occur sometimes.By in protective layer, using resin of the present invention, also controlled during printing because that protective layer does not produce is softening with the frictional force of heat head, thus can transmit smoothly.
-protective layer-
Above-mentioned protective layer contains polyvinyl alcohol and the hydrazide compound with reactive carbonyl, also contains filler and other composition as required.
As above-mentioned polyvinyl alcohol and above-mentioned hydrazide compound, can use and the identical material of above-mentioned the 1st mode heat-sensitive adhesive material protective layer with reactive carbonyl.By in the thermo-sensitivity bonding coat, containing such thermotolerance, polyvinyl alcohol that wet fastness is high with reactive carbonyl, can improve thermotolerance, the wet fastness of thermo-sensitivity bonding coat, can realize higher anti-cohesiveness.In addition, owing to improved thermotolerance, the wet fastness of temperature-sensitive bonding coat self, it is bonding that the heat of friction that drives generation owing to dull and stereotyped roller rotation when also being difficult to show owing to the heat sensitive recording layer printing certainly causes, when carrying out the thermal activation of thermo-sensitivity bonding coat by the heat head, also can improve movability with respect to head, prevent the correct adhesion of slag, bonding reduction is suppressed.
The filler that uses in above-mentioned protective layer can be the material of alkalescence; as its example; can enumerate aluminium hydroxide, lime carbonate, talcum, alkaline silicate class etc.; because the etching (residue adhesion) of heat head etc.; preferred aluminium hydroxide and lime carbonate; if consider by suitable water-soluble control pH, more preferably aluminium hydroxide.
-thermo-sensitivity bonding coat-
Above-mentioned thermo-sensitivity bonding coat contains thermoplastic resin and hot melt property material, contains polyvinyl alcohol, hydrazide compound and other composition as required with reactive carbonyl.
As the kind of above-mentioned thermoplastic resin, can enumerate (methyl) acrylate copolymer, vinylbenzene-isobutylene copolymers, copolymer in cinnamic acrylic ester, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, vinylbenzene-vinyl acetate copolymer, vinyl-acetic ester-acrylate copolymer, vinylbenzene-vinyl chloride copolymer, ethylene-acrylate copolymer, vinyl-acetic ester-ethylene-vinyl chloride copolymer, vinyl-acetic ester-ethylene-acrylate copolymer, vinyl-acetic ester-ethylene-styrene copolymer, polyhutadiene, resins such as urethane.Wherein, from the viewpoint of binding property, weathering resistance, preferably use with the various multipolymers of acrylate as monomer component.These materials can use separately, or are used in combination multiple.
As polyvinyl alcohol in the above-mentioned thermo-sensitivity bonding coat and above-mentioned hydrazide compound, can use the identical material of protective layer with the heat-sensitive adhesive material of above-mentioned the 1st mode with reactive carbonyl.
Above-mentioned polyvinyl alcohol with reactive carbonyl is preferably used as the dispersion agent of the hot melt property material in the thermo-sensitivity bonding coat.Therefore, adhesion characteristic be can improve more, higher anti-cohesiveness, printing matching realized.
By in above-mentioned thermo-sensitivity bonding coat, using hydrazide compound as linking agent, it is found that thermotolerance, the wet fastness that can further improve above-mentioned thermo-sensitivity bonding coat, realize higher anti-cohesiveness, printing matching.
Polyvinyl alcohol in the above-mentioned thermo-sensitivity bonding coat with reactive carbonyl contain ratio, be preferably 3～10 quality % of above-mentioned thermoplastic resin, more preferably 5～8 quality %.When surpassing 10 quality %, anti-cohesiveness and printing matching are improved, yet opposite is that adhesion characteristic demonstrates the tendency of reduction.When being lower than the addition of 3 quality %, adhesion characteristic is not had bad influence, yet, the anti-cohesiveness when particularly hot and humid, the printing matching abundant inadequately.
As above-mentioned hot melt property material, can enumerate dicyclohexyl phthalate (65 ℃ of fusing points), diphenyl phthalate (73 ℃ of fusing points), N-cyclohexyl-para toluene sulfonamide (86 ℃ of fusing points), phenylformic acid sucrose (98 ℃ of fusing points), ethylene glycol dibenzoate (70 ℃ of fusing points), three phenylformic acid trimethylolethanes (73 ℃ of fusing points), 4 acid pentaerythritol ester (95 ℃ of fusing points), eight acetate sucrose (89 ℃ of fusing points), pyrocatechol dibenzoate (86 ℃ of fusing points) etc., in addition, can also enumerate triethylene glycol two (3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester) (77 ℃ of fusing points), 1, (3-(3 for 6-hexylene glycol two, the 5-di-tert-butyl-hydroxy phenyl) hindered phenol compounds such as (103 ℃ of fusing points) propionic ester), 2-(5 '-(1 "; 1 "; 3 "; 3 "-tetramethyl butyl)-2 '-and hydroxy phenyl) benzotriazole (103 ℃ of fusing points), 2-(3 ', 5 '-two-(2 "; 2 "-dimethyl propyl)-2 '-and hydroxy phenyl) benzotriazole (80 ℃ of fusing points), 2-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole (138 ℃ of fusing points), 2-(3,5-di-t-butyl-2-hydroxy phenyl)-5-chlorobenzotriazole (155 ℃ of fusing points), 2-(5-methyl-2-hydroxy phenyl) benzotriazole (130 ℃ of fusing points), 2-(3,5-two tert-pentyls-2-hydroxy phenyl) benzotriazole triazole class compounds such as (80 ℃ of fusing points) etc.In these compounds, from heating the fusible longer duration in back, the viewpoint of adhesion stability is in time set out, preferred hindered phenol compound and the triazole class compounds of using, in order further to keep the fusible time length of the amorphization after the active coating fusion, these compounds can also be used in combination.These hot melt property materials and compound use as aqueous dispersions by wet type such as ball mill, sand mill, coating wobbler, ダ イ ノ ミ Le, vertical ball mill, frequency conversion mixing tank or Dry-crusher micronize, can also use by the known method micro encapsulation.The particle diameter of hot melt property material is preferably 10 μ m or below the 10 μ m, more preferably 5 μ m or below the 5 μ m, proceeding from the reality is 0.7～2 μ m.
As the object lesson of the bonding imparting agent that in above-mentioned thermo-sensitivity bonding coat, uses, can use terpine resin, aliphatic category petroleum resin, fragrant same clan petroleum resin, coumarone indeneresin, styrene resin, resol, terpene phenolic resin, Gum Rosin etc.
In above-mentioned thermo-sensitivity is bonding, can also be in the scope that does not hinder the object of the invention, add filler etc., for example, can use carbonate, oxide compound, oxyhydroxide, vitriol of aluminium, zinc, calcium, magnesium, barium, titanium etc. etc., and native silicon dioxide, zeolite, kaolin, calcined kaolin etc. contain mineral-type pigment, starch, styrene resin, polyolefin resin, melamine resin, acrylic resin, paraffin, natural wax, synthetic wax of viscosity class etc.
In above-mentioned thermo-sensitivity bonding coat, except that thermoplastic resin and hot melt property material, can also use the overcooling promotor that under low temperature environment, demonstrates high adhesion that promotes the overcooling of hot melt property material.As this overcooling promotor; can be naphthalene derivativeses such as 2-benzyloxy naphthalene; the methyl terphenyl; acetyl biphenyl; to Benzyldiphenyl; biphenyl derivatives such as 4-allyloxy biphenyl; 1; 2-two (3-methylphenoxy) ethane; 2; 2 '-two (4-methoxyl group phenoxy group) diethyl ether; polyether compounds such as two (4-p-methoxy-phenyl) ether; diphenyl carbonate; dibenzyl oxalate; oxalic acid two (p-chlorobenzyl) ester; carbonic acid such as oxalic acid two (to methyl-benzyl) ester or oxalate diester derivative etc.; wherein, dibenzyl oxalate derivative and biphenyl derivatives have the effect that promotes the overcooling of hot melt property material.
In above-mentioned thermo-sensitivity bonding coat, as required, can use macromolecular compound of hollow particle acrylic polymers with heat insulating ability and vinylidene chloride base polymer etc. etc.In addition, can also utilize main use proper sphere particulate polymethylmethacrylate etc.
In above-mentioned thermo-sensitivity bonding coat, except that mentioned component, as required, can also add various additives such as stiffening agent, sanitas, dyestuff, UV light absorber, antioxidant, pH regulator agent, defoamer.
-heat sensitive recording layer, supporter-
As above-mentioned heat sensitive recording layer and supporter, can use with above-mentioned the 1st mode in the heat sensitive recording layer material identical with supporter.
-middle layer-
Between above-mentioned thermo-sensitivity bonding coat and supporter, the preferred middle layer of containing acryloid cement of using.
The thermoplastic resin that uses in above-mentioned middle layer can be enumerated resins such as (methyl) acrylate copolymer, vinylbenzene-isobutylene copolymers, copolymer in cinnamic acrylic ester, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, vinyl-acetic ester-acrylate copolymer, copolymer in cinnamic acrylic ester, vinyl-acetic ester-ethylene-acrylate copolymer.
In addition, as required, in the middle layer, can be fit to use hollow packing, wax class of inorganic or organic filler, air bag state etc.
Clung body as heat-sensitive adhesive material of the present invention attaches has no particular limits, and can suitably select its size, shape, structure, material etc. according to purpose, as above-mentioned materials, and polyolefine such as the listed polyethylene of Shi Heing, polypropylene for example; Resin boards such as vinylformic acid, polyethylene terephthalate (PET), polystyrene, nylon; Metal sheet such as SUS, aluminium; Paper product such as envelope, corrugated cardboard; The packing stationery of packaging groups such as polyolefine, polyvinyl chloride, polyethylene non-woven fabrics (envelope etc.) etc.
Wherein, from strong to the bounding force of uneven surface clung bodies such as corrugated cardboard and polyolefine wrapping paper, the viewpoint that can firmly attach is seen, is favourable.
Process of thermal activation as the above-mentioned thermo-sensitivity bonding coat in the heat-sensitive adhesive material of the present invention has no particular limits, and can suitably select according to purpose, for example, can enumerate hot blast activatory method, hot-rolling activatory method, a heat activatory method etc.
Wherein, a preferred heat activatory method, the activation method of following heat-sensitive adhesive material of the present invention is particularly preferred.At this moment, by using existing thermal photography printing device the two sides of above-mentioned heat-sensitive adhesive material is heated, thereby can carry out the thermal activation of the record and the above-mentioned thermo-sensitivity bonding coat of above-mentioned heat sensitive recording layer, these methods are favourable in this.
[embodiment]
Below, the present invention is described in detail by embodiment, however the present invention is not limited to following embodiment.
(preparation example 1-1)
The preparation of-prime-coating liquid (A-1 liquid)-
(Japanese silicon-dioxide Industrial Co., Ltd produces dispersed with stirring by noncrystal silicon-dioxide, ニ Star プ ジ ェ Le AZ-200, solid component concentration 97 quality %, volume average particle size 2.5 μ m, oil number 320ml/100g) 4.6 mass parts, 2-EHA-methyl methacrylate-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd produces) 24.4 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ ィ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 70.9 mass parts formation, preparation prime-coating liquid [A-1 liquid].
(preparation example 1-2)
The preparation of-prime-coating liquid (A-2 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastics (1) (vinyl cyanide-vinylidene chloride-methylmethacrylate copolymer, solid component concentration 41 quality %, volume average particle size 3.6 μ m, hollow rate 90%) 14.6 mass parts, 2-EHA-methyl methacrylate-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd produces) 21.7 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 63.6 mass parts formation, preparation prime-coating liquid [A-2 liquid].
(preparation example 1-3)
The preparation of-prime-coating liquid (A-3 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastics (2) (vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer, solid component concentration 33 quality %, volume average particle size 3.0 μ m, hollow rate 91%) 18.2 mass parts, the multipolymer of n-butyl acrylate-methyl methacrylate (second-order transition temperature (Tg)=-62 ℃, solid component concentration 50 quality %, JSR society produces) 24.0 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 57.7 mass parts formation, preparation prime-coating liquid [A-3 liquid].
(preparation example 1-4)
The preparation of-prime-coating liquid (A-4 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (3) (vinyl cyanide-vinylidene chloride-methylmethacrylate copolymer, solid component concentration 41 quality %, volume average particle size 3.2 μ m, hollow rate 70%) 22.0 mass parts, 2-EHA-methyl methacrylate-cinnamic multipolymer (second-order transition temperature (Tg)=-5 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd produces) 16.2 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 61.7 mass parts formation, preparation prime-coating liquid [A-4 liquid].
(preparation example 1-5)
The preparation of-prime-coating liquid (A-5 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (4) (vinyl cyanide-vinylidene chloride-methylmethacrylate copolymer, solid component concentration 40 quality %, volume average particle size 1.5 μ m, hollow rate 50%) 30.0 mass parts, 2-EHA-methyl methacrylate-cinnamic multipolymer (second-order transition temperature (Tg)=-30 ℃, solid component concentration 50.0 quality %, Showa Highpolymer Co., Ltd produces) 12.0 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 57.9 mass parts formation, preparation prime-coating liquid [A-5 liquid].
(preparation example 1-6)
The preparation of-prime-coating liquid (A-6 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (2) (vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer, solid component concentration 33 quality %, volume average particle size 3.0 μ m, hollow rate 91%) 6.1 mass parts, ethane-acetic acid ethyenyl ester-acrylic acid multipolymer (second-order transition temperature (Tg)=-20 ℃, solid component concentration 53 quality %, firmly changing ケ system テ Star Network ス society produces) 30.2 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 63.6 mass parts formation, preparation prime-coating liquid [A-6 liquid].
(preparation example 1-7)
The preparation of-prime-coating liquid (A-7 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (5) (vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer, solid component concentration 33 quality %, volume average particle size 6.0 μ m, hollow rate 91%) 27.3 mass parts, 2-EHA-methyl methacrylate-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd produces) 16.3 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 56.3 mass parts formation, preparation prime-coating liquid [A-7 liquid].
(preparation example 1-8)
The preparation of-prime-coating liquid (A-8 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (2) (vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer, solid component concentration 33 quality %, volume average particle size 3.0 μ m, hollow rate 91%) 18.2 mass parts, the multipolymer of n-butyl acrylate-methyl acrylate-methyl methacrylate (second-order transition temperature (Tg)=0 ℃, solid component concentration 55 quality %, JSR society produces) 21.8 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ ィ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 59.9 mass parts formation, preparation prime-coating liquid [A-8 liquid].
(preparation example 1-9)
The preparation of-prime-coating liquid (A-9 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (2) (vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer, solid component concentration 33 quality %, volume average particle size 3.0 μ m, hollow rate 91%) 44.6 mass parts, the multipolymer of n-butyl acrylate-methyl methacrylate (second-order transition temperature (Tg)=-62 ℃, solid component concentration 50 quality %, JSR society produces) 6.5 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ ィ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 48.8 mass parts formation, preparation prime-coating liquid [A-9 liquid].
(preparation example 1-10)
The preparation of-prime-coating liquid (A-10 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (2) (vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer, solid component concentration 33 quality %, volume average particle size 3.0 μ m, hollow rate 91%) 3 mass parts, the multipolymer of n-butyl acrylate-methyl methacrylate (second-order transition temperature (Tg)=-62 ℃, solid component concentration 50 quality %, JSR society produces) 34.0 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ ィ ス ジ ヤ パ Application society) mixture of 0.1 mass parts and water 62.9 mass parts formation, preparation prime-coating liquid [A-10 liquid].
(preparation example 1-11)
The preparation of-prime-coating liquid (A-11 liquid)-
Dispersed with stirring is by 2-EHA-methyl methacrylate-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd's product) mixture of 90.3 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ ィ ス ジ ヤ パ Application society) 0.1 mass parts and water 9.6 mass parts formation, preparation prime-coating liquid [A-11 liquid].
(preparation example 1-12)
The preparation of-prime-coating liquid (A-12 liquid)-
Dispersed with stirring is by the spherical hollow particle of plastic-like (1) (vinyl cyanide-vinylidene chloride-methylmethacrylate copolymer, solid component concentration 41 quality %, volume average particle size 3.6 μ m, hollow rate 90%) mixture that constitutes of 23.4 mass parts, styrene-butadiene copolymer latex (second-order transition temperature (Tg)=+ 4 ℃) 10 mass parts, tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ イ ス ジ ヤ パ Application society) 0.1 mass parts and water 66.5 mass parts, preparation prime-coating liquid [A-12 liquid].
(preparation example 2-1)
The preparation of-hot melt property material dispersion liquid [B-1 liquid]-
Use sand mill, dispersion is by 40.0 mass parts 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole (fusing point (mp)=138 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-1 liquid].
(preparation example 2-2)
The preparation of-hot melt property material dispersion liquid [B-2 liquid]-
Use sand mill, dispersion is by 40.0 mass parts 2-(2 '-hydroxyls-3 ', 5 '-di-t-butyl)-5-chlorobenzotriazole (fusing point (mp)=152 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-2 liquid].
(preparation example 2-3)
The preparation of-hot melt property material dispersion liquid [B-3 liquid]-
Use sand mill, dispersion is by 40.0 mass parts 2-(2 '-hydroxyls-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole (fusing point (mp)=80 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-3 liquid].
(preparation example 2-4)
The preparation of-hot melt property material dispersion liquid [B-4 liquid]-
Use sand mill, dispersion is by 40.0 mass parts benzyl p-hydroxybenzoates (fusing point (mp)=113～115 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-4 liquid].
(preparation example 2-5)
The preparation of-hot melt property material dispersion liquid [B-5 liquid]-
Use sand mill, dispersion is by 40.0 mass parts P-hydroxybenzoic acid n-propyls (fusing point (mp)=99～100 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-5 liquid].
(preparation example 2-6)
The preparation of-hot melt property material dispersion liquid [B-6 liquid]-
Use sand mill, dispersion is by 40.0 mass parts anisoins (fusing point (mp)=99～100 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-6 liquid].
(preparation example 2-7)
The preparation of-hot melt property material dispersion liquid [B-7 liquid]-
Use sand mill, dispersion is by 40.0 mass parts 1-dihydroxyl-2-naphthoic acid phenyl ester (fusing point (mp)=94～96 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off ィ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-7 liquid].
(preparation example 2-8)
The preparation of-hot melt property material dispersion liquid [B-8 liquid]-
Use sand mill, dispersion is by 40.0 mass parts phenylformic acid-3-hydroxylphenyl ester (fusing point (mp)=135 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.0 μ m, thus preparation hot melt property material dispersion liquid [B-8 liquid].
(preparation example 3-1)
The preparation of-congruent melting agent dispersion liquid [C-1 liquid]-
Use sand mill, dispersion is by two pairs of methyl benzyls of 40.0 mass parts oxalic acid ester (fusing point (mp)=101 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off イ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.2 μ m, thus preparation congruent melting agent dispersion liquid [C-1 liquid].
(preparation example 3-2)
The preparation of-congruent melting agent dispersion liquid [C-2 liquid]-
Use sand mill, dispersion is by two pairs of methyl benzyls of 40.0 mass parts oxalic acid ester (fusing point (mp)=80 ℃), 6.7 mass parts polyvinyl alcohol (the 30 quality % aqueous solution), 0.2 mass parts tensio-active agent (オ Le Off ィ Application PD-001, Nishin Chemical Industry Co. Lt produces) and the mixture of 53.1 mass parts water formation, make that median size is 1.2 μ m, thus preparation congruent melting agent dispersion liquid [C-2 liquid].
(preparation example 4-1)
The preparation of-thermal adhesive coating fluid [D-1 liquid]-
Uniform mixing is by the multipolymer of 10 mass parts n-butyl acrylate-methyl acrylates (second-order transition temperature (Tg)=-62 ℃, solid component concentration 50 quality %, JSR society product), 6 mass parts polymerized rosin latex (145 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 37.5 mass parts hot melt property material dispersion liquids [B-1 liquid], 7 mass parts congruent melting agent dispersion liquids [C-1 liquid], thereby preparation thermal adhesive coating fluid [D-1 liquid].
(preparation example 4-2)
The preparation of-thermal adhesive coating fluid [D-2 liquid]-
Uniform mixing is by 9 mass parts 2-EHA-methyl methacrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 37.5 mass parts hot melt property material dispersion liquids [B-2 liquid], 7 mass parts congruent melting agent dispersion liquids [C-2 liquid], thereby preparation thermal adhesive coating fluid [D-2 liquid].
(preparation example 4-3)
The preparation of-thermal adhesive coating fluid [D-3 liquid]-
Uniform mixing is by the multipolymer of 10 mass parts n-butyl acrylate-methyl acrylates (second-order transition temperature (Tg)=-62 ℃, solid component concentration 50 quality %, JSR society product), 6 mass parts polymerized rosin latex (145 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 19 mass parts hot melt property material dispersion liquids [B-1 liquid], 19 mass parts hot melt property material dispersion liquids [B-2 liquid], 7 mass parts congruent melting agent dispersion liquids [C-1 liquid], thereby preparation thermal adhesive coating fluid [D-3 liquid].
(preparation example 4-4)
The preparation of-thermal adhesive coating fluid [D-4 liquid]-
Uniform mixing is by 10 mass parts 2-EHA-n-butyl acrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-30 ℃, solid component concentration 50.0 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 19 mass parts hot melt property material dispersion liquids [B-2 liquid], 19 mass parts hot melt property material dispersion liquids [B-3 liquid], 7 mass parts congruent melting agent dispersion liquids [C-1 liquid], thereby preparation thermal adhesive coating fluid [D-4 liquid].
(preparation example 4-5)
The preparation of-thermal adhesive coating fluid [D-5 liquid]-
Uniform mixing is by 9 mass parts 2-EHA-methyl methacrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-5 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts polymerized rosin latex (145 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 37.5 mass parts hot melt property material dispersion liquids [B-4 liquid], thereby preparation thermal adhesive coating fluid [D-5 liquid].
(preparation example 4-6)
The preparation of-thermal adhesive coating fluid [D-6 liquid]-
Uniform mixing is by 9.4 mass parts ethane-acetic acid ethyenyl esters-acrylic acid multipolymer (second-order transition temperature (Tg)=-20 ℃, solid component concentration 53 quality %, firmly changing ケ system テ Star Network Co., Ltd. produces), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 37.5 mass parts hot melt property material dispersion liquids [B-5 liquid], thereby preparation thermal adhesive coating fluid [D-6 liquid].
(preparation example 4-7)
The preparation of-thermal adhesive coating fluid [D-7 liquid]-
Uniform mixing is by 10 mass parts 2-EHA-n-butyl acrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-30 ℃, solid component concentration 50.0 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts polymerized rosin latex (145 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 19 mass parts hot melt property material dispersion liquids [B-4 liquid], 19 mass parts hot melt property material dispersion liquids [B-5 liquid], thereby preparation thermal adhesive coating fluid [D-7 liquid].
(preparation example 4-8)
The preparation of-thermal adhesive coating fluid [D-8 liquid]-
Uniform mixing is by the multipolymer of 10 mass parts n-butyl acrylate-methyl acrylates (second-order transition temperature (Tg)=-62 ℃, solid component concentration 50 quality %, JSR society product), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), 37.5 mass parts hot melt property material dispersion liquids [B-6 liquid] and the mixture that constitutes, thereby preparation thermal adhesive coating fluid [D-8 liquid].
(preparation example 4-9)
The preparation of-thermal adhesive coating fluid [D-9 liquid]-
Uniform mixing is by 9 mass parts 2-EHA-methyl methacrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 37.5 mass parts hot melt property material dispersion liquids [B-7 liquid], thereby preparation thermal adhesive coating fluid [D-9 liquid].
(preparation example 4-10)
The preparation of-thermal adhesive coating fluid [D-10 liquid]-
Uniform mixing is by 9 mass parts 2-EHA-methyl methacrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-65 ℃, solid component concentration 55.4 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 37.5 mass parts hot melt property material dispersion liquids [B-8 liquid], thereby preparation thermal adhesive coating fluid [D-10 liquid].
(preparation example 4-11)
The preparation of-thermal adhesive coating fluid [D-11 liquid]-
Uniform mixing is by 10 mass parts 2-EHA-n-butyl acrylates-cinnamic multipolymer (second-order transition temperature (Tg)=-30 ℃, solid component concentration 50.0 quality %, Showa Highpolymer Co., Ltd's product), 6 mass parts terpenes phenol latex (150 ℃ of softening temperatures, nonvolatile component 50%), the mixture that constitutes of 19 mass parts hot melt property material dispersion liquids [B-7 liquid], 19 mass parts hot melt property material dispersion liquids [B-8 liquid], 7 mass parts congruent melting agent dispersion liquids [C-1 liquid], thereby preparation thermal adhesive coating fluid [D-11 liquid].
(embodiment 1)
The preparation of-heat-sensitive adhesive material-
In the paper weight as support is 80g/m 2Art paper (OK ア De ニ ス ラ Off, Oji Paper society produce) in do not have on the one side of coat, barrier coating coating fluid [A-1] makes that dry adhesive capacity is 15g/m 2, drying forms bottom.Coating thermo-sensitivity bonding coat coating fluid [D-1] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms the thermo-sensitivity bonding coat.Prepare heat-sensitive adhesive material by above method.
(embodiment 2)
The preparation of-heat-sensitive adhesive material-
The formation of the ink-receiver layer of＜heat fusing transfer printing recording paper 〉
In the paper weight as support is 80g/m 2Good quality paper on, to use volume average particle size as pigment composition be the aluminum hydroxide particles of 0.4～0.5 μ m and styrene-maleic anhydride copolymer basic salt resin as binder resin, preparation filler/binder resin ratio of components is 1/0.2 coating fluid.Use steel wire bar evenly to be coated with this coating fluid so that the ink image receiving layer to be set, thus preparation heat fusing transfer printing printing ink blank film.
Then, on the support dignity that does not have ink-receiver layer of the heat fusing transfer printing recording paper of gained, barrier coating coating fluid [A-2] makes that dry adhesive capacity is 5g/m 2, drying forms bottom.Coating thermo-sensitivity bonding coat coating fluid [D-2] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms the thermo-sensitivity bonding coat.Prepare heat-sensitive adhesive material by above method.
(embodiment 3)
The preparation of-heat-sensitive adhesive material-
The formation of＜heat sensitive recording layer 〉
The preparation of-non-foaminess thermal insulation layer formation coating fluid [E liquid]-
Dispersed with stirring by the small hollow particle dispersion of 30 mass parts (based on the copolymer resins of vinylidene chloride-vinyl cyanide, solid component concentration is 32 quality %, median size is 3.6 μ m, degree of hollowness 92%), the mixture that constitutes of 10 mass parts styrene-butadiene copolymer latexes (second-order transition temperature (Tg)=+ 4 ℃), 0.1 mass parts tensio-active agent (ダ プ ロ W-77, ェ レ メ Application テ ィ ス ジ ヤ パ Application society) and 60 mass parts water, form coating fluid [E liquid] thereby prepare non-foaminess thermal insulation layer.
The preparation of-chromogenic reagent dispersion liquid [F liquid]-
The mixture that dispersed with stirring is made of 20 mass parts 3-di-n-butyl amino-6-methyl-7-anilino fluoranes, 10 mass parts polyvinyl alcohol (the 10 quality % aqueous solution) and 70 mass parts water, thereby preparation chromogenic reagent dispersion liquid [F liquid].
The preparation of-developer dispersion [G liquid]-
Use sand mill to disperse by the lime carbonate of 10 mass parts 4-isopropoxy-4 '-hydroxy diphenyl sulfones, 25 mass parts polyvinyl alcohol (the 10 quality % aqueous solution), 15 mass parts and the mixture of 50 mass parts water formation, making median size respectively is about 1.5 μ m, thus preparation developer dispersion [G liquid].
Then, by above-mentioned chromogenic reagent dispersion liquid [F liquid]: above-mentioned developer dispersion [G liquid]=1: 8 (mass ratio) mixes stirring with it, thereby prepares heat sensitive recording layer coating fluid [H liquid].In average paper weight is 80g/m 2Single face enamelled paper surface on, be coated with above-mentioned non-foaminess thermal insulation layer and form coating fluid [E liquid], make that dry thick quality is 4g/m 2, drying is to be provided with non-foaminess thermal insulation layer.On non-foaminess thermal insulation layer, be 5g/m by quality after the drying 2Be coated with above-mentioned chromogenic reagent dispersion liquid [F liquid], drying is to be provided with heat sensitive recording layer.Afterwards, carry out supercalendering and handle, make that Wang Yan formula smoothness is 2000 seconds, thereby preparation has the electrothermal sensitive recording paper of heat sensitive recording layer.
Then, on the support dignity that does not have ink-receiver layer of the heat fusing transfer printing recording paper of gained, barrier coating coating fluid [A-3] makes that dry adhesive capacity is 4g/m 2, drying forms bottom.Coating thermo-sensitivity bonding coat coating fluid [D-3] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms the thermo-sensitivity bonding coat.Prepare heat-sensitive adhesive material by above method.
(embodiment 4)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 3, barrier coating coating fluid [A-4] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-3] makes that dry adhesive capacity is 15g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 3, preparation heat-sensitive adhesive material.
(embodiment 5)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 3, barrier coating coating fluid [A-5] makes that dry adhesive capacity is 5g/m 2, drying forms bottom.Coating thermo-sensitivity bonding coat coating fluid [D-4] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 3, preparation heat-sensitive adhesive material.
(embodiment 6)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-6] makes that dry adhesive capacity is 5g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-5] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 7)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-6] makes that dry adhesive capacity is 5g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-6] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 8)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-6] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-3] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 9)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-7] makes that dry adhesive capacity is 5g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-3] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 10)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-9] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-7] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 11)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-9] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-8] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 12)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-10] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-3] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 13)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-3] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-9] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 14)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-10] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-10] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 15)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-3] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-11] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(embodiment 16)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 3, the protective layer coating solution of the following composition of coating on heat sensitive recording layer makes that dry adhesion quality is 3g/m 2, roll processing, make that the smoothness of exsiccant protection aspect is beyond 5000 seconds, according to the method identical with embodiment 3, the preparation heat-sensitive adhesive material.
The preparation of＜protective layer coating solution 〉
Mixing has the PVA of two acetonyls by 40 mass parts aluminium hydroxide dispersion liquids (solids component 50 quality %), 6 mass parts Zinic stearas dispersion liquids (solids component 30 quality %), 1 part of dioctyl succinate aqueous solution (solids component 5 quality %), 200 mass parts, and (dipropyl one monomers unit content is 4 quality %; the polymerization degree is 1600, saponification deg is 98%; chemical industry society of SHIN-ETSU HANTOTAI product) mixture of the 10 quality % aqueous solution, 40 mass parts adipic dihydrazide (linking agent) aqueous solution (solids component 10 quality %), 43 mass parts formation, thereby preparation protective layer coating solution.
(comparative example 1)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, do not have at supporter on the face of coat, coating thermo-sensitivity bonding coat coating fluid [D-1] makes that dry adhesive capacity is 10g/m 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(comparative example 2)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-8] makes that dry adhesive capacity is 10g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-1] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(comparative example 3)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-11] makes that dry adhesive capacity is 15g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-1] makes that dry adhesive capacity is 10g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
(comparative example 4)
The preparation of-heat-sensitive adhesive material-
Except in embodiment 1, barrier coating coating fluid [A-12] makes that dry adhesive capacity is 4g/m 2, drying forms bottom, and coating thermo-sensitivity bonding coat coating fluid [D-3] makes that dry adhesive capacity is 15g/m on bottom 2, drying forms beyond the thermo-sensitivity bonding coat, according to the method identical with embodiment 1, preparation heat-sensitive adhesive material.
Table 1
Supporter (paper weight) Recording layer (paper weight) Bonding bottom The thermal adhesive layer
Coating fluid Adhesive capacity Coating fluid Adhesive capacity
Embodiment 1 Single face enamelled paper (80g/m 2) Do not have A-1 15g/m 2 D-1 10g/m 2
Embodiment 2 Single face enamelled paper (80g/m 2) Fusion transfer printing layer (45g/m 2) A-2 5g/m 2 D-2 10g/m 2
Embodiment 3 Single face enamelled paper (80g/m 2) Heat sensitive recording layer (9g/m 2) A-3 4g/m 2 D-3 10g/m 2
Embodiment 4 Single face enamelled paper (80g/m 2) Heat sensitive recording layer (9g/m 2) A-4 10g/m 2 D-3 15g/m 2
Embodiment 5 Single face enamelled paper (80g/m 2) Heat sensitive recording layer (9g/m 2) A-5 5g/m 2 D-4 10g/m 2
Embodiment 6 Single face enamelled paper (80g/m 2) Do not have A-6 5g/m 2 D-5 10g/m 2
Embodiment 7 Single face enamelled paper (80g/m 2) Do not have A-6 5g/m 2 D-6 10g/m 2
Embodiment 8 Single face enamelled paper (80g/m 2) Do not have A-6 10g/m 2 D-3 10g/m 2
Embodiment 9 Single face enamelled paper (80g/m 2) Do not have A-7 5g/m 2 D-3 10g/m 2
Embodiment 10 Single face enamelled paper (80g/m 2) Do not have A-9 10g/m 2 D-7 10g/m 2
Embodiment 11 Single face enamelled paper (80g/m 2) Do not have A-9 10g/m 2 D-8 10g/m 2
Embodiment 12 Single face enamelled paper (80g/m 2) Do not have A-10 10g/m 2 D-3 10g/m 2
Embodiment 13 Single face enamelled paper (80g/m 2) Do not have A-3 10g/m 2 D-9 10g/m 2
Embodiment 14 Single face enamelled paper (80g/m 2) Do not have A-10 10g/m 2 D-10 10g/m 2
Embodiment 15 Single face enamelled paper (80g/m 2) Do not have A-3 10g/m 2 D-11 10g/m 2
Embodiment 16 Single face enamelled paper (80g/m 2) Heat sensitive recording layer A-3 4g/m 2 D-3 10g/m 2
Comparative example 1 Single face enamelled paper (80g/m 2) Do not have Do not have Do not have D-1 10g/m 2
Comparative example 2 Single face enamelled paper (80g/m 2) Do not have A-8 10g/m 2 D-1 10g/m 2
Comparative example 3 Single face enamelled paper (80g/m 2) Do not have A-11 15g/m 2 D-1 10g/m 2
Comparative example 4 Single face enamelled paper (80g/m 2) Do not have A-12 4g/m 2 D-3 15g/m 2
Then, to embodiment 1～16 and the comparative example 1～4 that obtains, as follows, estimate bounding force, bounding force in time and cohesiveness at once.The result is shown in table 3, table 4 and the table 5.
＜the mensuration of bounding force at once 〉
Each heat-sensitive adhesive material is cut into the rectangle of 25mm * 150mm, (big storehouse Electric Co., Ltd produces to use the temperature-sensitive printing device, TH-PMD), at top part: each energy is 0.35mJ/ point, 0.45mJ/ point, 0.5mJ/ point, print speed: 4ms/ is capable, plate is pressed: under the capable condition of 6kgf/, heat-sensitive adhesive material is carried out thermal activation.Then, on clung body (polyolefine wrapping paper and corrugated cardboard), attaching in the longitudinal direction by the rubber rollers that is forced into 2kg, after 1 hour, is 180 degree in peel angle, and peeling rate is to peel off under the condition of 300mm/min.
(MODEL DPS-5, IMADA produces) measures bounding force at this moment by measuring cell, with 0.1 second interval reading of data, represents with mean value.In addition, unit is gf/25mm.This test is implemented down at the environment of normal temperature environment (23 ℃, 65%).
＜in time the mensuration of bounding force 〉
Each heat-sensitive adhesive material is cut into the rectangle of 25mm * 150mm, (big storehouse Electric Co., Ltd produces to use the temperature-sensitive printing device, TH-PMD), in the probe condition: each energy is the 0.5mJ/ point, print speed: 4ms/ is capable, plate is pressed: under the capable condition of 6kgf/, heat-sensitive adhesive material is carried out thermal activation.Then, on clung body (polyolefine wrapping paper and corrugated cardboard), attaching in the longitudinal direction by the rubber rollers that is forced into 2kg, after 1 week, is that 180 degree, peeling rate are to peel off under the condition of 300mm/min in peel angle.
(MODEL DPS-5, IMADA produces) measures bounding force at this moment by measuring cell, with 0.1 second interval reading of data, represents with mean value.In addition, unit is gf/25mm.This test is implemented down at the environment of normal temperature environment (23 ℃, 65%).
[judgement criteria of PO wrapping paper bounding force]
◎: 1500gf/25mm or more than the 1500gf/25mm
Zero: 1000gf/25mm or more than the 1000gf/25mm, not enough 1500gf/25mm
△: 700gf/25mm or more than the 700gf/25mm, not enough 1000gf/25mm
*: not enough 700gf/25mm
[judgement criteria of corrugated cardboard bounding force]
◎: 700gf/25mm or more than the 700gf/25mm
Zero: 500gf/25mm or more than the 500gf/25mm, not enough 700gf/25mm
△: 300gf/25mm or more than the 300gf/25mm, not enough 500gf/25mm
*: not enough 300gf/25mm
＜cohesiveness evaluation 〉
The one side of thermo-sensitivity bonding coat in each heat-sensitive adhesive material is contacted with its reverse side, at 200gf/cm 2Pressure, 50 ℃ of exsiccant conditions under, placed 24 hours.Then, peel off the sample after at room temperature placing,, the cohesiveness of this moment is estimated based on grade and the judgement criteria shown in the following table 2.
Table 2
Grade Bounding force Peel off sound The point-like transfer printing Peel off
10 Deadweight
9 Have some There is not sound
8 Have Have some
7 Have
6 Some
5 30～50％
4 50%～all
3 Some
2 30～50％
1 50%～all
◎: grade 10
Zero: grade 8～9
△: class 6～7
*: below the class 5 or 5
Table 3
Adhesion characteristic (gf/25mm)
The PO wrapping paper
1. 0.30mJ/ point (at once) Estimate 2. 0.40mJ/ point (at once) Estimate 3. 0.50mJ/ point (at once) Estimate 4. through after a while (after 1 week) Estimate
Embodiment 1 960 △ 1280 ○ 1440 ○ 1535 ◎
Embodiment 2 1420 ○ 1580 ◎ 1570 ◎ 1490 ○
Embodiment 3 1650 ◎ 1630 ◎ 1640 ◎ 1670 ◎
Embodiment 4 1220 ○ 1580 ◎ 1570 ◎ 1465 ○
Embodiment 5 1030 ○ 1350 ◎ 1600 ◎ 1390 ○
Embodiment 6 1290 ○ 1650 ◎ 1680 ◎ 1760 ◎
Embodiment 7 1370 ○ 1650 ◎ 1680 ◎ 1725 ◎
Embodiment 8 1400 ○ 1750 ◎ 1760 ◎ 1830 ◎
Embodiment 9 930 △ 960 △ 945 △ 1070 △
Embodiment 10 760 △ 770 △ 745 △ 845 △
Embodiment 11 800 △ 825 △ 810 △ 890 △
Embodiment 12 1050 ○ 1560 ◎ 1610 ◎ 1885 ◎
Embodiment 13 1610 ◎ 1575 ◎ 1590 ◎ 1680 ◎
Embodiment 14 890 △ 1380 ○ 1615 ◎ 1925 ◎
Embodiment 15 1585 ◎ 1605 ◎ 1590 ◎ 1655 ◎
Embodiment 16 1590 ◎ 1700 ◎ 1680 ◎ 1680 ◎
Comparative example 1 500 × 640 × 720 △ 715 △
Comparative example 2 600 × 710 △ 725 △ 700 △
Comparative example 3 850 △ 1210 ○ 1450 ○ 1620 ◎
Comparative example 4 650 × 720 △ 715 △ 745 △
Table 4
Adhesion characteristic (gf/25mm)
Corrugated cardboard
1. 0.30mJ/ point (at once) Estimate 2. 0.40mJ/ point (at once) Estimate 3. 0.50mJ/ point (at once) Estimate 4. through after a while (after 1 week) Estimate
Embodiment 1 400 △ 520 ○ 610 ○ 680 ○
Embodiment 2 620 ○ 630 ○ 610 ○ 450 △
Embodiment 3 710 ◎ 690 ○ 700 ◎ 640 ○
Embodiment 4 570 ○ 710 ◎ 690 ○ 415 △
Embodiment 5 500 ○ 615 ○ 720 ◎ 400 △
Embodiment 6 650 ○ 730 ◎ 735 ◎ 810 ◎
Embodiment 7 615 ○ 660 ○ 650 ○ 690 ○
Embodiment 8 630 ○ 680 ○ 685 ○ 745 ◎
Embodiment 9 430 △ 415 △ 420 △ 395 △
Embodiment 10 380 △ 395 △ 370 △ 350 △
Embodiment 11 415 △ 405 △ 420 △ 395 △
Embodiment 12 525 ○ 730 ◎ 715 ◎ 855 ◎
Embodiment 13 680 ○ 665 ○ 670 ○ 705 ◎
Embodiment 14 435 △ 650 ○ 730 ◎ 790 ◎
Embodiment 15 640 ○ 655 ○ 645 ○ 640 ○
Embodiment 16 750 ◎ 740 ◎ 740 ◎ 670 ○
Comparative example 1 200 × 250 × 280 × 90 ×
Comparative example 2 230 × 285 × 290 × 95 ×
Comparative example 3 350 △ 480 △ 580 ○ 610 ○
Comparative example 4 200 × 290 × 295 × 150 ×
Table 5
Cohesiveness (grade) Estimate
Embodiment 1 9 ○
Embodiment 2 10 ◎
Embodiment 3 10 ◎
Embodiment 4 10 ◎
Embodiment 5 10 ◎
Embodiment 6 9 ○
Embodiment 7 10 ◎
Embodiment 8 9 ○
Embodiment 9 10 ◎
Embodiment 10 10 ◎
Embodiment 11 10 ◎
Embodiment 12 8 ○
Embodiment 13 10 ◎
Embodiment 14 9 ○
Embodiment 15 10 ◎
Embodiment 16 10 ◎
Comparative example 1 10 ◎
Comparative example 2 10 ◎
Comparative example 3 2 ×
Comparative example 4 10 ◎
Result by table 3～table 5 can confirm, the second-order transition temperature that does not have thermoplastic resin in the comparative example 1, bottom of bottom is that the second-order transition temperature of thermoplastic resin in 0 ℃ comparative example 2 and the bottom is+4 ℃ comparative example 4, any adhesion characteristic, particularly adhesion characteristic in time all worsens.In addition, can confirm that the comparative example 3 that bottom does not contain filler worsens on anti-cohesiveness.
In contrast, embodiment 1～16 adhesion characteristic excellence, bounding force does not in time reduce yet, and anti-cohesiveness is also good.Can judge embodiment 16 because protective layer contains polyvinyl alcohol and the hydrazide compound with reactive carbonyl, anti-cohesiveness is improved.
(embodiment 17)
-dispersion liquid A preparation-
Uniform mixing 100 mass parts 2-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole, 50 mass parts, 10% polyvinyl alcohol lysate, 200 mass parts water, use ball mill that it is pulverized, make that median size is 1.0 μ m, thus preparation dispersion liquid A.
-dispersion liquid B preparation-
Uniform mixing 100 mass parts oxalic acid two (to methyl-benzyl) esters, 50 mass parts, 10% polyvinyl alcohol lysate, 200 mass parts water use ball mill that it is pulverized, and make that median size is 1.0 μ m, thus preparation dispersion liquid B.
The preparation of-thermo-sensitivity bonding coat coating fluid C-
(clear and polymer society produces by 100 mass parts thermoplastic resin latex AP5570, solids component 55 quality %, second-order transition temperature-65 ℃), (waste river chemistry society produces the bonding imparting agent latex of 70 mass parts E100, solids component 50%, 145 ℃ of softening temperatures), the ratio of 540 mass parts dispersion liquid A, 150 mass parts dispersion liquid B, 130 mass parts water, fully mix, thus preparation thermo-sensitivity bonding coat coating fluid C.
The preparation of-prime-coating liquid D-
By 100 mass parts hollow particle latex ロ-ペ イ Network HP-91 (ロ-ム ﹠amp; Ha-ス society produces, hollow rate 50%, solids component 27.5 quality %), (clear and polymer society produces 220 mass parts macromolecule resin latex AD83, principal constituent ethylidene vinyl-acetic ester, solids component 56 quality %, second-order transition temperature-2 ℃), the ratio of 440 mass parts water, fully mix, thus preparation prime-coating liquid D.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 22.2 quality %.
The preparation of-heat-sensitive adhesive material E-
At the hot head dummy 120LCS-0 of the リ of Co., Ltd. コ-product (supporter: on the opposite face of heat sensitive recording layer prince's oiling product ユ Port synthetic paper film), use steel wire bar barrier coating coating fluid D, make that dried thickness is 20.0 μ m, after the drying, coating thermo-sensitivity bonding coat coating fluid C, make that dried thickness is 15.0 μ m, drying, thus the preparation total thickness is the heat-sensitive adhesive material E of 35.0 μ m.
(embodiment 18)
Except in embodiment 17, (clear and polymer society produces the macromolecule resin AD83 that will use in bottom, principal constituent ethylidene vinyl-acetic ester, solids component 56 quality %, second-order transition temperature-2 ℃) is changed to FREX751 (Sumitomo Chemical society produces, solids component 50 quality %, second-order transition temperature-15 ℃) in addition, according to the method identical with embodiment 17, the heat-sensitive adhesive material of preparation embodiment 18.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 22.2 quality %.
(embodiment 19)
Except in embodiment 18, underlayer thickness is 9.0 μ m, and the thickness of thermo-sensitivity bonding coat is 6.0 μ m, and total thickness is beyond the 15.0 μ m, according to the method identical with embodiment 18, and the heat-sensitive adhesive material of preparation embodiment 19.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 22.2 quality %.
(embodiment 20)
Except in embodiment 18, underlayer thickness is 13.0 μ m, and the thickness of thermo-sensitivity bonding coat is 7.0 μ m, and total thickness is beyond the 20.0 μ m, according to the method identical with embodiment 18, and the heat-sensitive adhesive material of preparation embodiment 20.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 22.2 quality %.
(embodiment 21)
Except in embodiment 18, underlayer thickness is 21.0 μ m, and the thickness of thermo-sensitivity bonding coat is 7.0 μ m, and total thickness is beyond the 28.0 μ m, according to the method identical with embodiment 18, and the heat-sensitive adhesive material of preparation embodiment 21.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 22.2 quality %.
(embodiment 22)
Except in embodiment 21, with the hollow particle latex ロ-ペ ィ Network HP-91 (ロ-ム ﹠amp of bottom; Ha-ス society produces, hollow rate 50%, solids component 27.5 quality %) be changed to R300 (this grease of pine society produces hollow rate 90%, solids component 33 quality %) in addition, according to the method identical, the heat-sensitive adhesive material of preparation preparation embodiment 22 with embodiment 21.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 22.2 quality %.
(embodiment 23)
The preparation of-prime-coating liquid F-
(this grease of pine society produces according to 100 mass parts R300, hollow rate 90%, solids component 33 quality %), (Sumitomo Chemical society produces 230 mass parts macromolecule resin latex FREX751, principal constituent ethylidene vinyl-acetic ester, solids component 50 quality %, second-order transition temperature-15 ℃), the ratio of 410 mass parts water, fully mix preparation prime-coating liquid F.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 28.6 quality %.
Except in embodiment 22, prime-coating liquid is replaced with beyond the prime-coating liquid F, according to method similarly to Example 22, the heat-sensitive adhesive material of preparation embodiment 23.
(embodiment 24)
The preparation of-prime-coating liquid G-
(this grease of pine society produces according to 100 mass parts R300, hollow rate 90%, solids component 33 quality %), (Sumitomo Chemical society produces 130 mass parts macromolecule resin latex FREX751, principal constituent ethylidene vinyl-acetic ester, solids component 50 quality %, second-order transition temperature-15 ℃), the ratio of 260 mass parts water, fully mix preparation prime-coating liquid G.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 50.0 quality %.
Except in embodiment 22, prime-coating liquid is replaced with beyond the prime-coating liquid G, according to method similarly to Example 22, the heat-sensitive adhesive material of preparation embodiment 24.
(embodiment 25)
The preparation of-prime-coating liquid H-
(this grease of pine society produces according to 100 mass parts R300, hollow rate 90%, solids component 33 quality %), (Sumitomo Chemical society produces 60 mass parts macromolecule resin latex FREX751, principal constituent ethylidene vinyl-acetic ester, solids component 50 quality %, second-order transition temperature-15 ℃), the ratio of 155 mass parts water, fully mix preparation prime-coating liquid H.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 110.0 quality %.
Except in embodiment 22, prime-coating liquid is replaced with beyond the prime-coating liquid H, according to method similarly to Example 22, the heat-sensitive adhesive material of preparation embodiment 25.
(embodiment 26)
The preparation of-prime-coating liquid F-
(this grease of pine society produces according to 100 mass parts hollow particle R300, hollow rate 90%, solids component 33 quality %), (clear and polymer society produces 120 mass parts macromolecule resin latex AP5570, solids component 55 quality %, second-order transition temperature-65 ℃), the ratio of 270 mass parts water, fully mix preparation prime-coating liquid I.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 50.0 quality %.
Except in embodiment 24, prime-coating liquid is replaced with beyond the prime-coating liquid I, according to method similarly to Example 24, the heat-sensitive adhesive material of preparation embodiment 26.
(embodiment 27)
The preparation of-prime-coating liquid J-
(this grease of pine society produces according to 100 mass parts hollow particle R300, hollow rate 90%, solids component 33 quality %), (clear and polymer society produces 120 mass parts macromolecule resin latex AP5570, solids component 55 quality %, second-order transition temperature-65 ℃), the ratio of 160 mass parts vinylformic acid-silicone resin latex US224 (the synthetic society in East Asia produces solids component 40 quality %, 10 ℃ of second-order transition temperatures), 440 mass parts water, fully mix preparation prime-coating liquid J.This moment, the ratio with respect to the macromolecule resin of bottom hollow particle was 50.0 quality %.
Except in embodiment 26, prime-coating liquid is replaced with beyond the prime-coating liquid J, according to method similarly to Example 26, the heat-sensitive adhesive material of preparation embodiment 27.
(comparative example 5)
The preparation of-prime-coating liquid K-
According to 100 mass parts hollow particle latex ロ-ペ イ Network HP-91 (ロ-ム ﹠amp; Ha-ス society produces, hollow rate 50%, solids component 27.5 quality %), (the Network ラ レ of Co., Ltd. produces 410 mass parts polyvinyl alcohol water solutions, solids component 30 quality %, second-order transition temperature is more than 100 ℃ or 100 ℃), the ratio of 240 mass parts water, fully mix preparation prime-coating liquid K.
Except in embodiment 17, prime-coating liquid is replaced with beyond the prime-coating liquid K, according to the method identical, the heat-sensitive adhesive material of preparation comparative example 5 with embodiment 17.
(comparative example 6)
Except in embodiment 17, with the hollow particle latex ロ-ペ イ Network HP-91 (ロ-ム ﹠amp of prime-coating liquid; Ha-ス society produces, hollow rate 50%, solids component 27.5 quality %) (Mitsui Chemicals society produces to be changed to ア Le マ テ Star Network ス SPMM-47BF, hollow rate 0%, solids component 47.5 quality %) in addition, according to the method identical with embodiment 17, the heat-sensitive adhesive material of preparation comparative example 6.
(comparative example 7)
Except in embodiment 17, be not provided with beyond the bottom, according to the method identical, obtain the heat-sensitive adhesive material of comparative example 7 with embodiment 17.
To each heat-sensitive adhesive material that obtains, as follows each characteristic is estimated.The results are shown in table 6, table 7 and table 8.
＜thermal activation condition 〉
Heat-sensitive adhesive material is prepared as the wide 4cm that is, length is the size of 10cm, (TEC society produces at the heat head, TH-0976SP) be that 8 points/mm, resistance are under 500 Ω, the full some energising, at activation energy is 0.30mJ/ point, 0.45mJ/ point, 0.60mJ/ point, print speed 100mm/ second, and plate is pressed under the capable condition of 6kgf/ and activated.All tests are here implemented under the temperature environment condition is 22 ℃, the environment of 65%RH.
The observation of the heat-shrinkable of＜thermo-sensitivity adhesive label 〉
By visual observation since the shrinkability that causes because of heat of the thermo-sensitivity adhesive label of above-mentioned thermal activation by following grading index it is estimated.
[grading index]
Zero: do not find the thermal contraction of label fully
△: only find the thermal contraction of label once in a while
*: the thermal contraction of label is remarkable
＜bounding force is measured 〉
By being forced into the rubber rollers of 2kg, the activated face of activatory heat-sensitive adhesive material label is attached on the clung body along its length, after 2 minutes, be 180 ° in peel angle, peeling rate is to peel off under the condition of 300mm/min.The mean drag value that shows bounding force this moment by numerical value.In addition, unit is gf/40mm.Here, all test is implemented under the temperature environment condition is 22 ℃, the environment of 65%RH.
[metewand of PO wrapping paper bounding force]
◎: 1500gf/40mm or more than the 1500gf/40mm
Zero: 1000gf/40mm or more than the 1000gf/40mm, not enough 1500gf/40mm
△: 700gf/40mm or more than the 700gf/40mm, not enough 1000gf/40mm
*: not enough 700gf/40mm
[judgement criteria of corrugated cardboard bounding force]
◎: 700gf/40mm or more than the 700gf/40mm
Zero: 500gf/40mm or more than the 500gf/40mm, not enough 700gf/40mm
△: 300gf/40mm or more than the 300gf/40mm, not enough 500gf/40mm
*: not enough 300gf/40mm
＜stick with paste residual 〉
Measure by above-mentioned bounding force, during attachment labels that visual observation is peeled off, the paste that sticks on the corrugated cardboard is residual, estimates by following grading index.
Zero: do not find to stick with paste residual vestige fully
△: only find to stick with paste residual vestige once in a while
*: it is remarkable to stick with paste residual vestige
Table 6
Adhesion characteristic (gf/40mm)
The PO wrapping paper
0.30mJ/ the point Estimate 0.45mJ/ the point Estimate 0.60mJ/ the point Estimate
Embodiment 17 660 × 980 △ 1160 ○
Embodiment 18 920 △ 1050 ○ 1100 ○
Embodiment 19 1050 ○ 1100 ○ 1390 ○
Embodiment 20 1100 ○ 1220 ○ 1380 ○
Embodiment 21 1490 ○ 1880 ◎ 2330 ◎
Embodiment 22 1980 ◎ 2360 ◎ 2450 ◎
Embodiment 23 2030 ◎ 2440 ◎ 2270 ◎
Embodiment 24 1770 ◎ 2010 ◎ 2400 ◎
Embodiment 25 1680 ◎ 1940 ◎ 2220 ◎
Embodiment 26 2380 ◎ 2650 ◎ 2600 ◎
Embodiment 27 2240 ◎ 2410 ◎ 2440 ◎
Comparative example 5 110 × 260 × 290 ×
Comparative example 6 320 × 510 × 880 △
Comparative example 7 50 × 220 × 340 ×
Table 7
Adhesion characteristic (gf/40mm)
Corrugated cardboard
0.30mJ/ the point Estimate 0.45mJ/ the point Estimate 0.60mJ/ the point Estimate
Embodiment 17 160 × 400 △ 520 ○
Embodiment 18 250 × 520 ○ 600 ○
Embodiment 19 430 △ 600 ○ 730 ◎
Embodiment 20 580 ○ 770 ◎ 990 ◎
Embodiment 21 740 ◎ 1240 ◎ 1640 ◎
Embodiment 22 1320 ◎ 1790 ◎ 1820 ◎
Embodiment 23 1350 ◎ 1840 ◎ 1690 ◎
Embodiment 24 1100 ◎ 1330 ◎ 1730 ◎
Embodiment 25 940 ◎ 1240 ◎ 1700 ◎
Embodiment 26 1720 ◎ 1810 ◎ 1750 ◎
Embodiment 27 1690 ◎ 1730 ◎ 1700 ◎
Comparative example 5 10 × 45 × 140 ×
Comparative example 6 120 × 155 × 460 △
Comparative example 7 6 × 22 × 75 ×
Table 8
Activation energy 0.30mJ/ point Activation energy 0.45mJ/ point Activation energy 0.60mJ/ point
Film shrinks Stick with paste residual Film shrinks Stick with paste residual Film shrinks Stick with paste residual
Embodiment 17 ○ △ △ ○ × ○
Embodiment 18 ○ △ △ ○ × ○
Embodiment 19 ○ ○ △ ○ × ○
Embodiment 20 ○ ○ △ ○ × ○
Embodiment 21 ○ ○ △ ○ × ○
Embodiment 22 ○ ○ ○ ○ × ○
Embodiment 23 ○ ○ ○ ○ △ ○
Embodiment 24 ○ ○ ○ ○ ○ ○
Embodiment 25 ○ ○ ○ ○ ○ ○
Embodiment 26 ○ ○ ○ ○ ○ ○
Embodiment 27 ○ ○ ○ ○ ○ ○
Comparative example 5 ○ × △ × × △
Comparative example 6 × △ × △ × ○
Comparative example 7 × × × × × ×
Found that of table 6, table 7 and table 8 arranged, it is 100 ℃ that there is the second-order transition temperature of the thermoplastic resin in the bottom in comparative example 5, too high, it is 0% (not having hollow) that there is the hollow packing hollow rate in the bottom in comparative example 6, comparative example 7 is not owing to be provided with bottom, compare with embodiment, any binding property all worsens.
The evaluation that the 0.30mJ/ of embodiment 17 in the table 6 is ordered, evaluation that the 0.30mJ/ of the embodiment in the table 7 17 is ordered, the evaluation that the 0.30mJ/ of the embodiment in the table 7 18 is ordered are all bad, this is because the heat energy that adds of heat head does not reach optimizing, is that 0.45mJ/ point and the 0.60mJ/ result of ordering is as can be known clear and definite to this heat energy that adds from the heat head.
In addition, film that the 0.60mJ/ of the embodiment 17～22 in the table 8 is ordered shrinks that to estimate variation be because the heat energy that adds of heat head does not reach optimizing, is that 0.45mJ/ point and the 0.60mJ/ result of ordering is as can be known clear and definite to this heat energy that adds from the heat head.
Therefore, the heat-sensitive adhesive material of embodiment 17～27 depends on the condition of heating means (activation method), and evaluation result is how many changes.Yet, can confirm, the heat-sensitive adhesive material of embodiment 17～27, if adopting the heat energy 0.45mJ/ point that adds of the heating condition instant heating head of approximate optimization estimates, compare with comparative example 5～7, even when adopting synthetic paper as supporter, film does not take place yet to be shunk, stick with paste residual, coarse clung body such as corrugated cardboard and polyolefine wrapping paper are all had good binding property.
(embodiment 2-1)
(1) preparation of dye dispersion liquid
Dispersion makes that by the aqueous solution of 10 quality % of 20 mass parts 3-dibutylamino-6-methyl-N-7-anilino fluorane, 20 mass parts polyvinyl alcohol (PVA), the composition that 60 mass parts water constitute median size is 0.5 μ m.
(2) preparation of developer
Use ball mill to disperse to make that by the aqueous solution of 10 quality % of 20 mass parts 4-isopropoxy-4 '-hydroxy diphenyl sulfones, oxalic acid two (right-methyl-benzyl) ester, 10 mass parts lime carbonate, 30 mass parts polyvinyl alcohol (PVA), the composition that 30 mass parts water constitute median size is 0.5 μ m.
(3) preparation of heat sensitive recording layer coating fluid
Mixing is by PVA (the solids component 10 quality % of 20 mass parts A liquid, 60 mass parts B liquid, 30 mass parts carboxyl sex change, KL-318, the Network ラ レ of Co., Ltd. produces), the mixture that 1 mass parts sulfo-dioctyl succinate (solids component 5 quality %) constitutes, preparation heat sensitive recording layer coating fluid.
(4) preparation of protective layer coating solution
Mixing is by 40 mass parts aluminium hydroxide dispersion liquids (solids component 50 quality %); 6 mass parts Zinic stearas dispersion liquids (solids component 30 quality %); 1 quality sulfo-part dioctyl succinate (solids component 5 quality %); 200 mass parts have the PVA of two acetonyls, and (dipropyl one monomers unit content is 4 quality %; the polymerization degree is 1600; saponification deg is 98%; Shin-Etsu Chemial Co., Ltd's product) aqueous solution of 10 quality %; 10 mass parts hexanodioic acid hydrazides (linking agent) aqueous solution (solids component 10 quality %); the composition that 43 mass parts water constitute, the preparation protective layer coating solution.
(5) coating of heat sensitive recording layer and protective layer
(paper weight is 60g/m at supporter 2Good quality paper) go up coating temperature-sensitive recording layer coating liquid, make that the dry adhesion weight of dyestuff is 0.6g/m 2, drying forms heat sensitive recording layer.Then, be coated with protective layer coating solution thereon, make that dry adhesion weight is 3g/m 2, carry out press polish after the drying and handle, make that the smoothness of protection aspect is 5000 seconds.
(6) preparation of hot melt property material dispersion liquid
Use ball mill uniform mixing 100 mass parts 2-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole, the lysate of 50 mass parts methylcellulose gum 10%, 200 mass parts water, disperse, make that median size is 1.0 μ m.
(7) preparation of temperature-sensitive slurry
(clear and polymer society produces by 100 mass parts thermoplastic resin latex AP5570, solids component 55 quality %, second-order transition temperature-65 ℃), the bonding imparting agent latex of 70 mass parts E100 (terpenol principal constituent, the chemical society in waste river produces, solids component 50%, 145 ℃ of softening temperatures), the ratio of 540 mass parts hot melt property material dispersion liquids, 130 mass parts water fully mixes preparation temperature-sensitive slurry.
(8) coating of temperature-sensitive slurry
Opposite at the heat sensitive recording layer of above-mentioned (5) is coated with, and makes that dry adhesive capacity is 15g/m 2, drying prepares heat-sensitive adhesive material of the present invention.
(embodiment 2-2)
Except in embodiment 2-1 (7) heat sensitive adhesive liquid, according to the dry ratio with respect to thermoplastic resin latex AP5570 is 12%, (dipropyl one monomers unit content is 4 quality % to add the PVA with two acetonyls, the polymerization degree is 1600, saponification deg is 98%, Shin-Etsu Chemial Co., Ltd's product) beyond the aqueous solution of 10 quality %, with the same preparation of embodiment 2-1 heat-sensitive adhesive material of the present invention.
(embodiment 2-3)
Except in embodiment 2-1 (7) heat sensitive adhesive liquid, according to the dry ratio with respect to thermoplastic resin latex AP5570 is 1 quality %, (dipropyl one monomers unit content is 4 quality % to add the PVA with two acetonyls, the polymerization degree is 1600, saponification deg is 98%, Shin-Etsu Chemial Co., Ltd's product) beyond the aqueous solution of 1 quality %, with the same preparation of embodiment 2-1 heat-sensitive adhesive material of the present invention.
(embodiment 2-4)
Except the methylcellulose gum 10 quality % lysates that in embodiment 2-1 (6) hot melt property dispersion liquid, use, according to the dry ratio with respect to thermoplastic resin latex AP5570 is 2%, use has the PVA of two acetonyls, and (dipropyl one monomers unit content is 4 quality %, the polymerization degree is 1600, saponification deg is 98%, Shin-Etsu Chemial Co., Ltd's product) beyond the aqueous solution of 10 quality % replaces, with the same preparation of embodiment 2-1 heat-sensitive adhesive material of the present invention.
(embodiment 2-5)
Except in the heat sensitive adhesive liquid of embodiment 2-4, according to the dry ratio with respect to thermoplastic resin latex AP5570 is 10%, (dipropyl one monomers unit content is 4 quality % to add the PVA with two acetonyls, the polymerization degree is 1600, saponification deg is 98%, Shin-Etsu Chemial Co., Ltd's product) beyond 10% the aqueous solution, with the same preparation of embodiment 2-4 heat-sensitive adhesive material of the present invention.
(embodiment 2-6)
Except in the heat sensitive adhesive liquid of embodiment 2-4, (dipropyl one monomers unit content is 4 quality % to PVA with two acetonyls, the polymerization degree is 1600, saponification deg is 98%, Shin-Etsu Chemial Co., Ltd's product) 10% aqueous solution, with dry ratio is 10% to use beyond hexanodioic acid hydrazides (linking agent) the 10 quality % aqueous solution, with the same preparation of embodiment 2-4 heat-sensitive adhesive material of the present invention.
(embodiment 2-7)
Except in the heat sensitive adhesive liquid of embodiment 2-6, according to the dry ratio with respect to thermoplastic resin latex AP5570 is 6.5%, (dipropyl one monomers unit content is 4 quality % to add the PVA with two acetonyls, the polymerization degree is 1600, saponification deg is 98%, Shin-Etsu Chemial Co., Ltd's product) beyond 10% the aqueous solution, with the same preparation of embodiment 2-6 heat-sensitive adhesive material of the present invention.
(embodiment 2-8)
Except coating between the thermo-sensitivity bonding coat of embodiment 2-7 and supporter makes that as the thermoplastic resin latex AP5570 in middle layer dry adhesive capacity is 15g/m 2, be coated with, beyond the drying, with the same preparation of embodiment 2-7 heat-sensitive adhesive material of the present invention.
(comparative example 2-1)
Following except using (9) protective layer coating solution replaces (4) protective layer coating solution of embodiment 2-1, prepares the heat-sensitive adhesive material of comparative example equally with embodiment 2-1.
(9) preparation of protective layer coating solution
Mixing is by 40 mass parts aluminium hydroxide dispersion liquids (solids component 50 quality %), 6 mass parts Zinic stearas dispersion liquids (solids component 30%), the 1 mass parts sulfo-dioctyl succinate aqueous solution (solids component 5%), carboxy-modified PVA (the solids component 10 quality % of 200 mass parts; KL-318; the Network ラ レ of Co., Ltd. produces), 12.5% lysate of 50 mass parts polyamide epichlorohydrin, the composition that 43 mass parts water constitute, thereby the preparation protective layer coating solution.
(comparative example 2-2)
Except that using the thermo-sensitivity bonding coat in embodiment 2-2, use to replace the thermo-sensitivity bonding coat of comparative example 2-1, prepare the heat-sensitive adhesive material of comparative example 2-2 equally with comparative example 2-1.
(comparative example 2-3)
Except that using the thermo-sensitivity bonding coat in embodiment 2-3, use to replace the thermo-sensitivity bonding coat of comparative example 2-1, prepare the heat-sensitive adhesive material of comparative example 2-3 equally with comparative example 2-1.
(comparative example 2-4)
Except that using the thermo-sensitivity bonding coat in embodiment 2-8, use to replace the thermo-sensitivity bonding coat of comparative example 2-1, prepare the heat-sensitive adhesive material of comparative example 2-4 equally with comparative example 2-1.
Then, based on following method each heat-sensitive adhesive material that obtains in embodiment and the comparative example is estimated.The result is shown in the table 9.
Table 9:
" note: in the table, embodiment～-8 are changed to embodiment 2-1～2-8, comparative example 1～4 is changed to comparative example 2-1～2-4 "
Bounding force Cohesiveness Matching
The SUS plate Corrugated cardboard 60℃ 40℃， 90％ The scratch of flat board and temperature-sensitive adhesive face
Measure after 2 minutes Measure after 7 days Measure after 2 minutes Measure after 7 days 22℃， 65％ 40℃， 90％
Embodiment 1 2650 2500 1530 1630 8 6 △ △
Embodiment 2 1560 1440 1090 1110 9 6 ◎ △
Embodiment 3 2180 2320 1300 1260 7 6 ○ △
Embodiment 4 2580 2720 1570 1490 7 6 ○ △
Embodiment 5 1950 1880 1210 1180 9 6 ◎ ○
Embodiment 6 2640 2600 1450 1320 10 8 ◎ ○
Embodiment 7 2540 2800 1300 1250 10 10 ◎ ◎
Embodiment 8 2600 3210 2410 2640 9 9 ◎ ◎
Comparative example 1 2670 2520 1510 1580 3 3 △ ×
Comparative example 2 1570 1430 1110 1140 4 3 ○ ×
Comparative example 3 2020 2140 1270 1250 3 3 △ ×
Comparative example 4 2570 2990 2370 2720 2 1 × ×
＜activation method 〉
The heat-sensitive adhesive material for preparing in embodiment and the comparative example is cut into the size of wide 4cm, long 10cm, and (TEC society produces, and TH-0976SP) is 8 points/mm, and resistance is 500 Ω, and full some energising is 26.0mJ/mm at activation energy down at the heat head 2, print speed 100mm/ second, diameter is that the dull and stereotyped pressure of the silicon class of 1cm is under the capable condition of 6kgf/, and the bonding aspect of thermo-sensitivity contact with the heat head, enforcement activates under 22 ℃, the environment of 65%RH.
＜bounding force is measured 〉
Rubber rollers by being pressurised into 2kg is attached to the activated face of activatory heat-sensitive adhesive material label in the aforesaid method on the clung body along its length, after 2 minutes and after 7 days, be that 180 °, peeling rate are to peel off under the condition of 300mm/min in peel angle.The Resistance Value that shows bounding force this moment by numerical value.In addition, unit is gf/40mm.
＜cementation test method 〉
The protection aspect of the heat sensitive recording layer of the heat-sensitive adhesive material for preparing in embodiment and the comparative example is contacted with the bonding aspect of thermo-sensitivity, at 2kg/cm 2Pressure under, keeping after 24 hours under 60 ℃, 30%RH and 40 ℃, 90% condition, peel test specimen at room temperature is according to the following grade evaluation cohesiveness of this moment.
Grade 10: do not peel off with having sound
Grade 9: certain sound is arranged when peeling off, but do not peel off with having resistance
Grade 8: certain sound is arranged when peeling off, certain resistance is arranged
Grade 7: produce when peeling off and peel off sound and peel resistance, have peel resistance but the transfer printing of discovery layer
Class 6: find small point-like transfer printing when peeling off
Class 5: bonding aspect of thermo-sensitivity or thermal photography aspect produce 30～50% transfer printing thing when peeling off
Class 4: bonding aspect of thermo-sensitivity or thermal photography aspect produce the transfer printing thing more than 50% or 50% when peeling off
Grade 3: label produces part destruction when peeling off
Grade 2: label produces 30～50% destruction when peeling off
Grade 1: label produces the destruction more than 50% or 50% when peeling off
＜printing matching test method 〉
The heat-sensitive adhesive material for preparing in embodiment and the comparative example is cut into the size of wide 4cm, long 10cm, the heat head (TEC society produces, TH-0976SP) be 8 points/mm, resistance be 500 Ω, 1 grid energising down, be 15.0mJ/mm at activation energy 2, print speed 100mm/ second, diameter be that the dull and stereotyped pressure of silicon of 1cm is under the capable condition of 6kgf/, and the bonding aspect of thermo-sensitivity contact with the heat head, at 22 ℃, the environment of 65%RH and 40 ℃, 90%RH enforcement down prints.Contact the scratch situation of observing the bonding aspect of thermo-sensitivity that contacts with dull and stereotyped roller this moment, the situation that is clamminess that abrades the temperature-sensitive adhesive face that causes by visual, hand, judge according to following grade.Show 1 grid powered-on mode among Fig. 1.Evaluation based on this pattern is as follows.
[metewand]
◎: both do not had scuff mark, sensation is not clamminess yet
Zero: find certain scuff mark, but the sensation that is not clamminess
△: can confirm that scuff mark is clearly, also feel certain being clamminess
*: can know the affirmation scuff mark, feel and be clamminess fully
Heat-sensitive adhesive material of the present invention is because strong to the bounding force of the uneven surface clung body of corrugated cardboard etc. and polyolefine wrapping paper, bounding force reduces few in time, can be by low-yield activation, and anti-cohesiveness is also good, even particularly under situation about using as the synthetic paper of supporter or plastics film, there be not coming off of thermo-sensitivity bonding coat during thermal activation yet, can prevent shrinking into ridges of supporter, the paste that can improve when changing label is residual, for example is suitable for industry use, commercial use and family and uses.

Claims (28)

1. a heat-sensitive adhesive material is characterized in that, this material has bottom and thermo-sensitivity bonding coat at least successively on a face of supporter and this supporter,
Above-mentioned bottom contains thermoplastic resin and the hollow packing of second-order transition temperature (Tg) for 0 ℃ of less than more than-70 ℃ or-70 ℃.
2. heat-sensitive adhesive material as claimed in claim 1, wherein, the thermo-sensitivity bonding coat contains thermoplastic resin, bonding imparting agent and hot melt property material.
3. heat-sensitive adhesive material as claimed in claim 1, wherein, the thermoplastic resin in bottom is at least a kind that is selected from acrylate copolymer, alkylmethacrylate polymer, acrylate-alkylmethacrylate polymer, acrylic styrene copolymer, acrylate-methacrylic ester-styrol copolymer and the vinyl-vinyl acetate copolymer.
4. heat-sensitive adhesive material as claimed in claim 1, wherein, the hollow packing in bottom is that volume average particle size is the spherical hollow particle of 2.0～5.0 μ m, and the hollow rate of this spherical hollow particle is more than 70% or 70%.
5. heat-sensitive adhesive material as claimed in claim 4, wherein, the material of spherical hollow particle is plastics, and these plastics are at least a kind that is selected from vinyl cyanide-vinylidene chloride-methylmethacrylate copolymer and the vinyl cyanide-methacrylonitrile-isobornyl methacrylate multipolymer.
6. heat-sensitive adhesive material as claimed in claim 1, wherein, the thermoplastic resin in the bottom and the mass ratio of hollow packing are that with respect to the above-mentioned thermoplastic resin of 1 mass parts, above-mentioned hollow packing is 0.1～2 mass parts.
7. heat-sensitive adhesive material as claimed in claim 1, wherein, the hollow packing in the bottom and the mixing quality of thermoplastic resin are than (hollow packing: thermoplastic resin) be 1: 0.5～1: 3.0.
8. heat-sensitive adhesive material as claimed in claim 1, wherein, the hollow packing in the bottom and the mixing quality of thermoplastic resin are than (hollow packing: thermoplastic resin) be 1: 6.0～1: 20.0.
9. heat-sensitive adhesive material as claimed in claim 2, wherein, the thermoplastic resin in the thermo-sensitivity bonding coat is at least a kind that is selected from acrylate copolymer, alkylmethacrylate polymer, acrylate-alkylmethacrylate polymer, acrylic styrene copolymer, acrylate-methacrylic ester-styrol copolymer, the vinyl-vinyl acetate copolymer.
10. heat-sensitive adhesive material as claimed in claim 2, wherein, the hot melt property material in the thermo-sensitivity bonding coat is the benzotriazole cpd of following structural formula (1) expression,
Figure A2005101283730003C1
Structural formula (1)
Wherein, in the said structure formula (1), R 1And R 2Mutually the same or inequality, expression hydrogen atom, alkyl and α, any one of α-Er Jiajibianji, X are represented hydrogen atom or halogen atom.
11. heat-sensitive adhesive material as claimed in claim 2, wherein, the hot melt property material in the thermo-sensitivity bonding coat is the hydroxy-benzoic acid ester cpds of following structural formula (2) expression,
Figure A2005101283730003C2
Structural formula (2)
Wherein, in the said structure formula (2), R 3Any one of expression alkyl, alkenyl, aralkyl and aryl, these groups can also further be substituted base and replace.
12. heat-sensitive adhesive material as claimed in claim 2, wherein, the hot melt property material in the thermo-sensitivity bonding coat is the compound of any expression of following structural formula (3), (4) and (5),
Figure A2005101283730003C3
Structural formula (3)
Wherein, in the said structure formula (3), R 4And R 5Mutually the same or inequality, expression alkyl or alkoxyl group, Y represents hydrogen atom or hydroxyl,
Structural formula (4)
Wherein, in the said structure formula (4), R 6Any one of expression hydrogen atom, halogen atom, alkyl and alkoxyl group, Y represents hydrogen atom or hydroxyl.
Figure A2005101283730004C1
Structural formula (5)
Wherein, in structural formula (5), R 7Any one of expression hydrogen atom, halogen atom, alkyl and alkoxyl group.
13. heat-sensitive adhesive material as claimed in claim 2, wherein, the thermo-sensitivity bonding coat also contains congruent melting agent, and this congruent melting agent is the dibenzyl oxalate compound of following structural formula (6) expression,
Structural formula (6)
Wherein, in said structure formula (6), Z represents any one in hydrogen atom, halogen atom and the alkyl.
14. heat-sensitive adhesive material as claimed in claim 1, wherein, the total thickness of bottom and thermo-sensitivity bonding coat is 13～30 μ m.
15. heat-sensitive adhesive material as claimed in claim 1 wherein, does not have at supporter to contain recording layer and protective layer successively on the face of thermo-sensitivity bonding coat.
16. heat-sensitive adhesive material as claimed in claim 15, wherein, recording layer is any one of heat sensitive recording layer, heat fusing transfer printing recording ink receiving layer, electrophoto-graphic toner image receiving layer, photographic silver halide usefulness recording layer and ink for inking receiving layer.
17. heat-sensitive adhesive material as claimed in claim 16, wherein, heat sensitive recording layer contains adularescent dyestuff and developer.
18. heat-sensitive adhesive material as claimed in claim 15, wherein, protective layer contains polyvinyl alcohol and the hydrazide compound with reactive carbonyl.
19. heat-sensitive adhesive material as claimed in claim 15 wherein, has the ink image that forms by UV hardening printing ink.
20. heat-sensitive adhesive material as claimed in claim 15 wherein, has the preprinted of visual information on the record aspect, apply the coupling printing of (sensing) function that has direction finding on the bonding aspect of thermo-sensitivity.
21. heat-sensitive adhesive material as claimed in claim 1, wherein, supporter is any one of synthetic paper and plastics film.
22. heat-sensitive adhesive material as claimed in claim 1, wherein, this material be label-like, laminar, label is laminar and any one of roller shape.
23. heat-sensitive adhesive material, it is characterized in that, this material has heat sensitive recording layer successively on a face of supporter and this supporter and protective layer has the thermo-sensitivity bonding coat, has the thermo-sensitivity bonding coat at the reverse side of this supporter, and this layer contains thermoplastic resin and hot melt property material; Above-mentioned protective layer contains polyvinyl alcohol and hydrazide compound with reactive carbonyl.
24. heat-sensitive adhesive material as claimed in claim 23, wherein, the thermo-sensitivity bonding coat contains the polyvinyl alcohol with reactive carbonyl.
25. heat-sensitive adhesive material as claimed in claim 23 wherein, has the dispersion agent of the polyvinyl alcohol of reactive carbonyl as the hot melt property material in the thermo-sensitivity bonding coat.
26. heat-sensitive adhesive material as claimed in claim 24, wherein, the thermo-sensitivity bonding coat contains hydrazide compound.
27. heat-sensitive adhesive material as claimed in claim 24, wherein, the polyvinyl alcohol in the thermo-sensitivity bonding coat with reactive carbonyl contain 3～10 quality % that ratio is a thermoplastic resin.
28. heat-sensitive adhesive material as claimed in claim 23 wherein, has the middle layer of containing acryloid cement between thermo-sensitivity bonding coat and supporter.
CN200510128373A 2004-09-13 2005-09-13 Heat-sensitive adhesive material Expired - Fee Related CN100589973C (en)

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