CN100439118C

CN100439118C - Mother set for thermal sensitive porous printing and and method for manufacturing same

Info

Publication number: CN100439118C
Application number: CNB2005100990498A
Authority: CN
Inventors: 沼仓健一
Original assignee: Tohoku Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2005-04-04
Filing date: 2005-09-06
Publication date: 2008-12-03
Anticipated expiration: 2025-09-06
Also published as: CN1847023A

Abstract

The invention relates to a master mask used in thermal sensitive porous plate print with better transmission and high anti-static property, and a relative production, wherein it is characterized in that: said master mask has one thermo-plastic resin film and a porous support with at least one of porous resin film and porous fiber film on the thermo-plastic resin film; said porous support comprises the conductive material at least including the ion polymer whose Tg is at least 10Deg. C and the drying adhesive is 0.01-2.0g/m<SUP>2</SUP>.

Description

Mother plate for thermal sensitive porous printing and manufacture method thereof

Technical field

The present invention relates to transmission property excellence, have the manufacture method of mother plate for thermal sensitive porous printing and this mother plate for thermal sensitive porous printing of high-antistatic performance.

Background technology

, used on the thermoplastic resin membrane, with the mother plate for thermal sensitive porous printing that bonding agent is fitted separately or the mixed porous thin paper of copying natural fiber and synthetic fibers obtains as the porous support in the past.In this mother plate for thermal sensitive porous printing, be conceived to further improve transmission property, printing ink permeability and antistatic property etc., various schemes have been proposed.For example, open in the flat 3-193445 communique, proposed to use that to contain fiber number be that the thin paper of following synthetic fibers of 1 dawn or 1 dawn is as the porous support the spy.But this scheme can not solve above-mentioned problem fully.In addition, the spy opens in the clear 62-198459 communique, has proposed to form on the thermoplastic resin membrane by printing processes such as photogravure, offset printing, aniline printings the method for the radiation-curing type resin pattern that is actually close-shaped.But, in printing process, the wire spoke of resin pattern is arranged to 50 μ m or is difficult below the 50 μ m, Printing Department can not bore a hole, and therefore can produce the uneven problem of printing.

In addition, open in the flat 3-240596 communique the spy, proposed to contain the dispersion liquid of aqueous dispersion polymers and cataloid and dry and obtain mother plate for thermal sensitive porous printing, this mother matrix and low viscous ink for inking have been used in combination in thermoplastic resin membrane's surface coating.But, in this scheme, exist the perforate footpath of porous layer little, in porous printing use printing ink in the past, printing ink is difficult for passing through, and can not be printed the problem of concentration fully.

In addition, open in the clear 54-33117 communique, proposed not use the mother plate for thermal sensitive porous printing that in fact only contains the thermoplastic resin membrane of porous support the spy.By this scheme, the percent thermal shrinkage height, in thickness 3 μ m or the film below the 3 μ m, the pierceability that is produced by thermal head is also good, the press quality excellence.

But this mother plate for thermal sensitive porous printing exists a little less than the stiffness (stiffness), transmits difficulty on printing machine, for improving transmission property, then will use thick thermoplastic resin membrane, can reduce the pierceability that is caused by thermal head, and the uneven problem of printing takes place.

In addition, proposed thermoplastic resin membrane's one side coating liquid and dry and the mother plate for thermal sensitive porous printing that obtains (opening flat 8-332785 communique and the spy opens flat 10-24667 communique) with reference to the spy with porous resin film.But the porosity of the porous resin film ratio thin paper in the past of this scheme is low, and thermal insulation is low, though therefore have the perforation footpath uniformity height that is produced by thermal head, the tendency that the footpath of boring a hole diminishes.This just means that thermal sensitivity reduces the tendency that can not say so.In addition, in the above-mentioned mother plate for thermal sensitive porous printing, only use the porous resin film, be difficult to strengthen stiffness.

In addition, open flat 10-147075 communique and the spy opens in the flat 10-236011 communique, proposed on thermoplastic resin membrane's one side lamination porous resin film and porous fiber film successively and the mother plate for thermal sensitive porous printing that obtains the spy.

But, in these mother plate for thermal sensitive porous printing, existence is a purpose to suppress the humidity dependence, use the low resin of hydrophily, this resin is charged easily, and the static that mother plate for thermal sensitive porous printing produces when understanding owing to transmission is attached on the printing machine internal face, hinder and transmit smoothly and batching to printing drums, mother plate for thermal sensitive porous printing is rolled up to drum with the state of fold, in coiling process, the problem that card only stops printing machine taking place.

In addition, in the mother plate for thermal sensitive porous printing in the past, use the low subclass surfactant type antistatic additive that divides usually.Low minute subclass surfactant like this has the deterioration that produces antistatic property owing to the motion of itself, and antistatic property depends on the shortcoming of environmental changes such as humidity.

Therefore, can't provide excellent mother plate for thermal sensitive porous printing now, that is, the mother plate for thermal sensitive porous printing with sufficient stiffness can not take place because paperboard that the static in printing machine causes and the fold on drum.

Summary of the invention

Brief summary of the invention

The objective of the invention is to, provide can not take place because the transmission deterioration bad and bad to batching of printing drums, that have sufficient stiffness (コシ), antistatic property that causes of static in the printing machine is few, owing to be the water system coating material, so manufacture method of the mother plate for thermal sensitive porous printing of environmental safety excellence and this mother plate for thermal sensitive porous printing.

For solving above-mentioned problem, present inventors have carried out found that of further investigation, contain Tg at the ionic polymers more than 10 ℃ or 10 ℃ by use, and dry pickup is 0.01～2.0g/m ²Conductive material as antistatic additive, then can not take place because the transmission that causes of static in the printing machine is bad and batching on printing drums is bad, and have sufficient stiffness, and, can reduce the carrying capacity of environment when making owing to be the water system material.

The present invention is based on present inventors' above-mentioned discovery and carries out, and is as the measure that solves above-mentioned problem, as described below.That is,

＜1〉a kind of mother plate for thermal sensitive porous printing, it is characterized in that, this mother matrix have the thermoplastic resin membrane and this thermoplastic resin membrane have any one the porous support at least that contains in porous resin film and the porous fiber film on the one side at least, this porous support contain at least Tg be more than 10 ℃ or 10 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.This＜1〉mother plate for thermal sensitive porous printing put down in writing in, by the porous support that comprises the conductive material that contains ionic polymers at least is set on the thermoplastic resin membrane, the fault that the static that produces in the time of can not transmitting causes can keep transmission property.In addition, be set at 0.01～2.0g/m by adhesion amount with this conductive material ²Scope, can fully remain the antistatic property of removing the static that produces when transmitting, can also give necessary stiffness when transmitting.Have, the glass transition temperature of above-mentioned ionic polymers (Tg) is more than 10 ℃ or 10 ℃ again, therefore can prevent sticking page or leaf, thereby can normally make a plate and transmit.

＜2〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the superficial layer of porous support is the porous resin film, this porous resin film contain Tg be more than 10 ℃ or 10 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

＜3〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the porous support is to have the porous resin film and constitute on the porous fiber film, this porous resin film contain Tg be more than 10 ℃ or 10 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

＜4〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the superficial layer of porous support is the porous fiber film, this porous fiber film contain Tg be more than 10 ℃ or 10 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

＜5〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the porous support is to have the porous fiber film and constitute on the porous resin film, this porous fiber film contain Tg be more than 10 ℃ or 10 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

＜6〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, ionic polymers is the anionic property polymer.

＜7〉according to above-mentioned＜6〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the anionic property polymer contains alkali metal salt.

＜8〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, conductive material contains surfactant.This＜8 in the record mother plate for thermal sensitive porous printing in, because conductive material contains low molecule-type surfactant, therefore the wettability of conductive material and porous support improves, and can keep the epithelium continuity, can improve antistatic property thus.

＜9〉according to above-mentioned＜8〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, low molecule-type surfactant is non-ionic species surfactant.

＜10〉according to above-mentioned＜8〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the HLB value is more than 9 or 9.

＜11〉according to above-mentioned＜8〉in the mother plate for thermal sensitive porous printing of record, wherein, be 5～70 ° for the static contact angle of pet film.Since this＜11〉record mother plate for thermal sensitive porous printing in, static contact angle is 5～70 °, therefore the wettability for the matrix material of coating improves, and can keep the epithelium continuity, thereby can improve anti-static function.

＜12〉according to above-mentioned＜1〉in the mother plate for thermal sensitive porous printing of record, wherein, be 1.0 * 10 in the sheet resistance value of porous support one side of mother plate for thermal sensitive porous printing ⁵～1.0 * 10 ¹³Ω.This＜1〉record mother plate for thermal sensitive porous printing in because the sheet resistance value of porous support one side is 1.0 * 10 ⁵～1.0 * 10 ¹³Ω, the static that produces in the time of can fully removing plate-making and transmission can not take place because the fault that static causes can keep transmission property.

＜13〉according to above-mentioned＜1〉in the record mother plate for thermal sensitive porous printing, wherein, with conductive material attached on the porous support.

＜14〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the porous fiber film contains synthetic fibers.This＜14〉record mother plate for thermal sensitive porous printing in, this porous support comprises synthetic fibers, so stiffness etc. do not rely on the environment of humidity etc., can have full intensity.

＜15〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the porous fiber film contains the composite fibre of synthetic fibers and natural fiber.This＜15〉record mother plate for thermal sensitive porous printing in, therefore the porous support is the compound formation of synthetic fibers and natural fiber, can keep the stiffness equal strength, can reduce cost simultaneously.

＜16〉according to above-mentioned＜1〉the middle mother plate for thermal sensitive porous printing of putting down in writing, wherein, the bending stiffness of mother plate for thermal sensitive porous printing is 20～110mN in the MD direction.This＜16〉record mother plate for thermal sensitive porous printing in because bending stiffness is 20～110mN in the MD direction, can not produce the fault when transmitting, the faults such as fold in the time of can also preventing version.

＜17〉manufacture method of mother plate for thermal sensitive porous printing is characterized in that, this method contains following operation:

On thermoplastic resin membrane's one side at least, form the porous support that contains any one the porous support at least in porous resin film and the porous fiber film and form operation; At least the conductive material painting process that contains the conductive material coating fluid of ionic polymers in this porous support surface coating.This＜17〉record the manufacture method of mother plate for thermal sensitive porous printing in, form operation and the conductive material painting process can produce high-quality mother plate for thermal sensitive porous printing expeditiously by the porous support.

＜18〉according to＜17〉manufacture method of mother plate for thermal sensitive porous printing of record, wherein, the conductive material coating fluid is a water system, and does not have ignition point.This＜18 the record the mother plate for thermal sensitive porous printing manufacture method in, the conductive material coating fluid is a water system, so can reduce the load to environment.

＜19〉according to＜17〉manufacture method of mother plate for thermal sensitive porous printing of record, wherein, conductive material is 2～80mPas with the viscosity of coating fluid 25 ℃ the time.This＜19〉record the manufacture method of mother plate for thermal sensitive porous printing in, by conductive material is set at 2～80mPas with the viscosity of coating fluid 25 ℃ the time, can eliminate the faults such as porous support crimping when being coated with the hole.

＜20〉according to＜17〉manufacture method of mother plate for thermal sensitive porous printing of record, wherein, conductive material is 4～9 with the pH value of coating fluid.This＜20〉record mother plate for thermal sensitive porous printing manufacture method in, by conductive material is set at 4～9 with the pH value of coating fluid, can solves the problem that coating apparatus corrodes, and the deterioration of chargeding performance can be reduced to slight.

Description of drawings

Fig. 1 is the pattern sectional drawing that an example of mother plate for thermal sensitive porous printing of the present invention is shown.

Fig. 2 is the pattern sectional drawing that an example of mother plate for thermal sensitive porous printing of the present invention is shown.

Fig. 3 is the pattern sectional drawing that an example of mother plate for thermal sensitive porous printing of the present invention is shown.

Fig. 4 is the pattern sectional drawing that an example of mother plate for thermal sensitive porous printing of the present invention is shown.

The specific embodiment

(mother plate for thermal sensitive porous printing)

Mother plate for thermal sensitive porous printing of the present invention have the thermoplastic resin membrane and this thermoplastic resin membrane at least the one side on contain in porous resin film and the porous fiber film at least any one the porous support and constitute, optionally, can contain other layers formation again.

Here, above-mentioned mother plate for thermal sensitive porous printing, for example, the superficial layer of Fig. 1 and porous support 1 shown in Figure 4 is a porous resin film 2, this porous resin film 2 preferably contains the mode that Tg is the conductive material of the ionic polymers more than 10 ℃ or 10 ℃, porous support 1 shown in Figure 4 is to have porous resin film 2 and form on porous fiber film 3, this porous resin film 2 especially preferably contain ionic polymers, dry pickup is 0.01～2.0g/m ²The mode of conductive material.

In addition, above-mentioned mother plate for thermal sensitive porous printing, for example, the superficial layer of Fig. 2 and porous support 1 shown in Figure 3 is a porous fiber film 3, this porous fiber film 3 preferably contain Tg be more than 10 ℃ or 10 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²The mode of conductive material, porous support 1 shown in Figure 3 is to have porous fiber film 3 and form on porous resin film 2, this porous fiber film 3 especially preferably contains the mode of the conductive material of ionic polymers.

＜thermoplastic resin membrane 〉

As above-mentioned thermoplastic resin membrane, material, thickness, size, shape etc. all have no particular limits, can look purpose, from normally used known material mother plate for thermal sensitive porous printing, suitably select, as above-mentioned material, preferred thermoplastic resin can be enumerated, for example, mylar, polyamide, polyvinyl resin, acrylic resin, Corvic, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer etc.

As above-mentioned mylar, can enumerate, for example, the copolymer of pet resin, ethylene glycol terephthalate and ethylene isophthalate, terephthalic acid (TPA)-1, the copolymer of 6-hexylene glycol ester and terephthalic acid (TPA) cyclohexanedimethanoester ester etc., wherein, from improving on the perforation sensitivity this point, copolymer, the terephthalic acid (TPA)-1 of preferred especially ethylene glycol terephthalate and ethylene isophthalate, the copolymer of 6-hexylene glycol ester and terephthalic acid (TPA) cyclohexanedimethanoester ester.

Optionally, can in above-mentioned thermoplastic resin membrane, add lubricants such as fire retardant, heat stabilizer, antioxidant, ultra-violet absorber, antistatic additive, pigment, dyestuff, fatty acid ester, wax, defoamers such as polysiloxanes etc.Having, is purpose to give easy sliding property again, can add for example inorganic particulates such as clay, mica, titanium oxide, calcium carbonate, potter's clay, talcum, wet silicon dioxide, dry type silica; Be organic filler of constituent etc. with acrylic compounds, phenylethylene etc., and can enumerate method of coating surface activating agent etc.

As above-mentioned thermoplastic resin membrane, preferred biaxial stretch-formed resin film as this biaxial stretch-formed resin film, can be enumerated, for example, and biaxially stretched polyester resin film, biaxial stretch-formed polyvinyl resin film, biaxial stretch-formed polypropylene resin film etc.

Preferred 0.1～5.0 μ m of above-mentioned thermoplastic resin membrane's thickness is more preferably 0.1～3.0 μ m.If above-mentioned thickness less than 0.1 μ m is then thin excessively, become membrane stability to worsen, printability resistance reduces, if surpass 5.0 μ m, then pierceability reduces.

＜porous support 〉

Above-mentioned porous support contain in porous resin film and the porous fiber film at least any one, optionally can also have other the layer.

-porous resin film-

Above-mentioned porous resin film, as long as have in the inner and surperficial structure that contains a plurality of holes of film, shape for hole, average pore size, porositys etc. have no particular limits, can look purpose suitably selects, shape as above-mentioned hole, it preferably on thickness direction continuous structure, preference as, have be connected atypic bar-shaped, spherical, or dendritic (be not the unit tangle up of the weak point of class Sihe paper, neither be in the combination of simple shape of formation in the printing etc.) the three-dimensional structure of complexity, the structure of similar so-called sponge gourd, alveolate texture, honey comb structure etc.

Preferred 2～50 μ m of the average pore size of above-mentioned hole are more preferably 5～30 μ m.During above-mentioned average pore size less than 2 μ m, printing ink trafficability characteristic variation, therefore, if use low viscosity ink for obtaining sufficient printing ink throughput, image then can take place spread and sink in and blend the phenomenon that printing-ink in the printing oozes out from the rear end of the mother matrix of the sidepiece of printing drums and package.In addition, the phenomenon that the empty film rate in the porous resin film reduces increases, and hinders the perforation that is caused by thermal head easily.On the other hand, if average pore size surpasses 50 μ m, the printing ink that is produced by the porous resin film suppresses the effect step-down, and the printing ink surplus when printing between printing drums and the film is extruded, and the ink pollution back side of paper takes place and spread and sink in fault such as to ooze.Particularly the average pore size of the hole in the porous resin film is 20 μ m or 20 μ m when following, and the porous resin rete is thick more, printing-ink be difficult to more by, therefore, can control the transfer printing amount of printing ink by the thickness of this layer to printing.Because it is inhomogeneous that the uneven thickness of above-mentioned porous resin film produces printing for a moment, therefore expect the thickness homogeneous.

Preferred 2～100 μ m of the thickness of above-mentioned porous resin film, be more preferably 5～50 μ m, during above-mentioned thickness less than 5 μ m, after the perforation that causes by thermal head, the porous resin film is difficult to remain in the back side of perforated portion, can not control the transfer printing amount of printing ink, the back side that is easy to generate printed article is by ink pollution.In addition, film is thick more, and it is big more that the printing ink transfer printing amount of porous resin film suppresses effect, and during printing, printing ink can be regulated by the thickness of porous resin film to the transfer printing amount of paper.

The density of above-mentioned porous resin film is preferred 0.01～1g/cm usually ³, preferred especially 0.1～0.7g/cm ³The not enough 0.01g/cm of above-mentioned density ³The time, the film strength deficiency, in addition, film itself also damages easily.

Preferred 0.1～the 35g/m of the adhesion amount of above-mentioned porous resin film ², be more preferably 0.5～25g/m ², preferred especially 1～11g/m ²Above-mentioned adhesion amount increases, and hinders printing ink to pass through, and if the portrait degradation is not enough 0.1g/m ²The time, it is difficult that the control of printing ink transfer printing amount becomes, and surpasses 35g/m ²The time, hinder printing ink to pass through, make the image variation.

The 1st formation method as porous resin film with said structure, for example, Te Kaiping 10-24667 communique is disclosed, be used in the good solvent of the resin that forms the porous resin film and poor solvent can mix fully mutually the time, to contain resin and be coated on the thermoplastic resin membrane formation of dry back for the good solvent of this resin and the liquid of poor solvent with half precipitation state.The liquid that contains this resin, its good solvent and poor solvent is in dry run, and good solvent is evaporation earlier, and poor solvent increases relatively, separates out resin by the concentrated grade of resin, forms tridimensional network.In the 1st formation method, form the porous resin film of sponge gourd shape structure usually, select the fast solvents of evaporation rate such as ether or ketone, can boost productivity.

As the resin material that constitutes above-mentioned porous resin film, have no particular limits, can suitably select according to purpose, can enumerate, for example, vinyl-based resins such as polyvinyl acetate resin, polyvinyl butyral resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, SAN; Polyamide-based resin such as polybutene resin, nylon; Polyphenylene oxide resin, (methyl) acrylate, polycarbonate resin; Cellulose derivatives such as cellulose acetate, acetic acid butyl cellulose, acetic acid propyl cellulose etc.These can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.Wherein, for forming porous resin film, preferably use thermoplastic resin as the printing ink trafficability characteristic excellence of the object of the invention.

In the above-mentioned porous resin film,, optionally, can also add in the scope of not damaging purpose of the present invention and effect, for example, filler, antistatic additive, antitack agent, surfactant, anticorrisive agent, defoamer etc.

Above-mentioned filler is to add for the size in the formation of regulating the porous resin film, intensity, aperture, stiffness etc.Here, so-called above-mentioned filler is the notion that contains pigment, powder and fibrous material, wherein, and preferred especially needle-like, tabular or fibrous filler.

Can enumerate as above-mentioned filler, for example, mineral substance needle-like fillers such as magnesium silicate, sepiolite, potassium titanate, wollastonite, eakleite, gypsum fiber; Artificial mineral's class needle-like fillers such as non-oxidized substance class needle-like whisker, composite oxides class whisker; Plate-like fillers such as mica, glass fibre, talcum; Natural or synthetic fibers shape filler such as carbon fiber, polyester fiber, glass fibre, vinylon fiber, nylon fiber, acrylic fiber etc.

As above-mentioned pigment, for example can use, contain the organic polymer particle of polyvinyl acetate resin, Corvic, PMA resin; Inorganic pigments such as carbon black, zinc oxide, titanium dioxide, calcium carbonate, silica.These can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.

The addition of above-mentioned filler is 5～200 mass parts with respect to above-mentioned resin 100 mass parts preferably.During addition less than 5 mass parts of above-mentioned filler, warpage takes place easily, the porous resin film strength reduces when surpassing 200 mass parts.

The 2nd formation method as above-mentioned porous resin film, be used in the good solvent of the resin that constitutes the porous resin film and the situation that poor solvent can not mix mutually, for example, Te Kaiping 11-23885 communique is disclosed, be to be coated on the thermoplastic resin membrane based on the liquid of w/o type (water-in-oil type) emulsion, and dry, the method for formation porous resin film.The porous resin film that is formed by this w/o type emulsion has alveolate texture, honey comb like tridimensional network usually.The porous resin film that forms by the 2nd formation method is, to be coated on based on the liquid of w/o type emulsion on the thermoplastic resin membrane, dry back forms, and mainly with after the water section drying, formation is by the hole of printing ink, and the resin in the solvent (also can contain additives such as filler, emulsifying agent) becomes structure.

As above-mentioned resin, have no particular limits, can suitably select according to purpose, for example, can enumerate, acrylic resin, esters resin, polyurethanes resin, acetal-based resin, olefine kind resin, vinylidene chloride resin, epoxylite, amide-type resin, styrene resin, vinyl-based resin, cellulose derivative, their modifier or their copolymer etc., wherein special optimal ethylene butyral resinoid, polyurethanes resin.

In the formation of above-mentioned w/o type emulsion, the more intense HLB of lipophile is that 2.5～6 surfactant is effectively, but is 8～20 surfactant by use HLB at aqueous phase, also can obtain stabilized uniform w/o type emulsion.The use of high molecular surfactant also is one of method that obtains more stable and uniform emulsion.In addition, adding tackifier such as polyvinyl alcohol, polyacrylic acid in water system is effective to the stabilisation of emulsion.

Be the size in the formation of regulating above-mentioned porous resin film, intensity, aperture and stiffness etc., can further add additives such as filler in the porous resin film.Wherein, preferred especially needle-like, tabular or fibrous filler.In addition, as filler can from the same material of above-mentioned the 1st formation method suitably select.

Preferred 0.3～the 30g/m of dry back adhesion amount of the porous resin film in the above-mentioned the 1st and the 2nd formation method ²If less than 0.3g/m ², then can not control the printing ink adhesion amount, printed article is stain.In the time of on an opposite side that can not will be fitted in as the porous thin paper of printing ink trafficability characteristic support with bonding agent etc. with the thermosensitive film of porous resin film, the stiffness of mother matrix itself dies down, operating difficulties, so the preferred 20g/m of dry back adhesion amount of perforated membrane itself ²Or 20g/m ²More than.On the other hand, adhesion amount surpasses 30g/m ²The time, then hinder printing ink and pass through, the image variation.

-porous fiber film-

As above-mentioned porous fiber film, have no particular limits for material, size, structure etc., can suitably select according to purpose, as above-mentioned material, can enumerate, for example, mineral fibres such as glass, sepiolite, various metals; Animal origin such as wool, silk; Natural fibers such as cotton, abaca, paper mulberry, three forks, paper pulp; Regenerated fiber such as man-made hair, artificial silk; Synthetic fibers such as polyester, polyvinyl alcohol, acrylic compounds; Semisynthetic fibres such as carbon fiber; Thin papers such as inorfil with whisker structure.Wherein, preferably contain natural fiber.

Above-mentioned porous fiber film is by the synthetic fibers that the synthetic resin that uses by polyester and acrylic compounds etc. forms, can expect to prevent degradation fault under the change in size that causes owing to intensity and moisture absorption and the intensity.Weight per unit area (level ground amount) and thickness also have preferred range, but are not limited thereto.

In addition, above-mentioned porous fiber film preferably contains the composite fibre of synthetic fibers and natural fiber.At this moment, has the advantage that cost is reduced significantly by the use natural fiber.But, because compound natural fiber worries that intensity can reduce, therefore, as the cooperation ratio in the scope that can ignore the influence that intensity reduces, preferred synthetic fibers 95～30%, natural fiber 5～70% are more preferably synthetic fibers 95～60%, natural fiber 5～40%.

For the rugosity of the fibrous material that constitutes above-mentioned porous fiber film (for example, diameter), length, shape, have no particular limits, can suitably select according to thermoplastic resin membrane's penetration hole diameter, the thickness of film etc., preferred 20 μ m of the diameter of above-mentioned fibrous material (rugosity) or below the 20 μ m are more preferably 1～10 μ m.During above-mentioned diameter less than 1 μ m, hot strength can die down, and can hinder printing ink to pass through when surpassing 20 μ m, produces the deinking image that is caused by fiber.

Preferred 0.1～the 10mm of the length of above-mentioned fibrous material is more preferably 1～6mm.During the curtailment 0.1mm of above-mentioned fibrous material, hot strength can die down, and when surpassing 10mm, is difficult to evenly disperse.

The weight per unit area of above-mentioned porous fiber film has no particular limits, and can look purpose and suitably select, preferred 1～20g/m ², be more preferably 3～10g/m ²Above-mentioned weight per unit area surpasses 20g/m ²The time, the trafficability characteristic of printing ink reduces, and the distinctiveness of image descends, not enough 1g/m ²The time, as printing ink permeability support, can not obtain full intensity.

As above-mentioned porous fiber film, can be commercially available, also can be suitably to form.In addition, the method as forming above-mentioned porous fiber film has no particular limits, and can look purpose and suitably select, and can form by the method for for example record such as special public clear 49-18728 communique, special public clear 49-8809 communique.

＜conductive material 〉

At least contain ionic polymers as above-mentioned conductive material, optionally can also contain surfactant etc.

-ionic polymers-

As above-mentioned ionic polymers, so long as glass transition temperature (Tg) is to get final product more than 10 ℃ or 10 ℃, have no particular limits, can look purpose suitably selects, but from more positively not taking place owing to the fault that the static that produces when transmitting causes, keep convective viewpoint, preferred anionic polymer.

Have no particular limits as above-mentioned anionic property polymer, but can enumerate, for example, anionic acrylic base polymer, styrene-propene acids polymer etc.As these concrete commercially available product, can enumerate, for example, NK polymer WS-500 (Xin Zhong village Industrial Co., Ltd system), NK polymer WS-52-U (Xin Zhong village Industrial Co., Ltd system) etc.

Above-mentioned anionic property polymer, preferably contain at least alkali metal salt and ammonium salt at least any one.By containing in this alkali metal salt and the ammonium salt any one at least, ion is easy to move, even at the state of over dry, also can show excellent antistatic property.

As above-mentioned alkali metal salt, have no particular limits, can look purpose and suitably select, but can enumerate, for example, lithium salts, sodium salt, sylvite, rubidium salt, cesium salt etc.

As above-mentioned ammonium salt, can enumerate, for example, the salt of making by ammonia, methyl amine, ethylamine, n-butylamine, dimethyl amine, diethylamide, dibutylamine, Trimethylamine, triethylamine, tri-n-butyl amine, dimethyl MEA, triethanolamine, dimethyl stearylamine, methyl dilauryl amine etc.

In the situation of above-mentioned alkali metal salt, the influence of ion depends on alkali-metal ionization tendency, and the size of its surface resistivity is rubidium≤potassium＜sodium＜caesium＜lithium.

In the situation of above-mentioned ammonium salt, the size of surface resistivity is, triethanolamine＜dimethyl MEA＜triethylamine=ammonia, and the number of the hydroxyalkyl in the nitrogen substituting group is many more, and surface resistivity is more little, and antistatic behaviour is high more.

Preferred 20 quality % of the content of above-mentioned ionic polymers in conductive material or more than the 20 quality %.

The glass transition temperature of above-mentioned ionic polymers (Tg) must be more than 10 ℃ or 10 ℃, and is preferred more than 40 ℃ or 40 ℃.During 10 ℃ of above-mentioned vitrification point less thaies, for example, can when being made tubular, mother plate for thermal sensitive porous printing stick together.

As the method for analyzing contained above-mentioned ionomer in the mother plate for thermal sensitive porous printing, have no particular limits, can suitably select according to purpose, for example, can be in mother plate for thermal sensitive porous printing, by measuring the sheet resistance value of conductive material coated face, judge whether to contain ionic polymers.Usually be insulator for organic matter, and ionic polymers have electric conductivity.Therefore, owing to whether contain ionic polymers, above-mentioned sheet resistance value is different, so can judge by measuring it.

In addition, as above-mentioned analytical method, have the viewpoint of electric conductivity from ionic polymers, the elementary analysis of conductive material coated face also is effective.That is, with the mother plate for thermal sensitive porous printing that is not coated with conductive material be coated with the mother plate for thermal sensitive porous printing of conductive material, carry out the elementary analysis with one side, poor with its detection limit promptly can be judged and whether contain ionic polymers.As above-mentioned elementary analysis, in addition, the elementary analysis of carrying out the elementary analysis of ionic polymers and only removing the conductive material of ionic polymers can detect the element that only contains effectively in ionic polymers.

Above-mentioned ionic polymers also can further carry out crosslinked for improving resistance to water.

For realizing that above-mentioned crosslinked employed crosslinking agent has no particular limits, can suitably select according to purpose, but from the viewpoint of reaction speed, crosslink density, intermiscibility, water-soluble melamine resin is the most preferred.

As above-mentioned water-soluble melamine resin, can suitably enumerate, for example, N-methylolation melamine, methoxy melamine, a part of alkyl-modified butylation melamine of quilt etc., in these, from water miscible viewpoint, preferred especially N-methylolation melamine.

Preferred 5～60 quality % of the content of above-mentioned crosslinking agent in the cross-linking type ionic polymers, more preferred 5～20 quality %.

In addition, it is crosslinked also can to use normally used acid catalyst to carry out simultaneously in above-mentioned crosslinking agent.

As above-mentioned acid catalyst, have no particular limits, can suitably select according to purpose, but can enumerate, for example ammonium dihydrogen phosphate (ADP), ammonium chloride, p-methyl benzenesulfonic acid etc.

Preferred 1～3 quality % of the content of above-mentioned acid catalyst in the cross-linking type ionic polymers.

In addition, also can use polymerization initiator.

As above-mentioned polymerization initiator, have no particular limits, can suitably select according to purpose, but can enumerate, for example, azo compounds such as peroxide such as the persulfate of potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate etc., hydrogen peroxide, benzoperoxide, lauroyl peroxide, azodiisobutyronitrile, AMBN etc.

By the number-average molecular weight of crosslinked ionic polymers such as above-mentioned crosslinking agent preferred millions of or millions of more than.

As the polymerization with ionic polymers such as above-mentioned crosslinking agent, have no particular limits, can from known method, suitably select according to purpose, can enumerate, for example, polymerisation in solution, emulsion polymerisation, suspension polymerisation, polymerisation in bulk etc., wherein, from reactive, stable viewpoint, preferred solution polymerization, emulsion polymerisation.

-surfactant-

As above-mentioned surfactant, have no particular limits, can suitably select according to purpose, but the surfactant of the low molecule-type below preferred molecular weight 2000 or 2000, can enumerate, for example, nonionic surface active agent, anionic surfactant, amphoteric surfactant etc.Wherein, preferably the surface tension that contains the aqueous solution of ionic polymers can be adjusted to the value of expectation, promotion is moistening to the forming synthetic resin thing, for example, when being used in polyester film, preferably surface tension is adjusted to 40dyn/cm or below the 40dyn/cm.

In addition, above-mentioned surfactant represents that preferably hydrophily, oil loving index (HLB value) more than 9 or 9, are more preferably more than 10 or 10, more than the most preferred 13 or 13.During above-mentioned HLB value less than 9, add low molecule-type activating agent after, conductive material can gelation.

Preferred concrete example as the surfactant that satisfies above-mentioned HLB preferred value, can enumerate, for example, polyoxyalkylene alkyl, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, fatty acid glyceride, fatty acid metal soap, alkylsulfonate, betaine type amphoteric surfactant etc.

Have again,, improve convective viewpoint from reducing sheet resistance value in aftermentioned porous support one side, in above-mentioned nonionic surface active agent, anionic surfactant, amphoteric surfactant etc., preferred nonionic surface active agent.

In addition, in above-mentioned ionic polymers, only otherwise damage purpose of the present invention, can suitably select to use, for example, ultra-violet absorber, pigment, organic filler, inorganic filler, lubricant, anti-blocking agent etc.Have again, also can suitably select to use for example cationic macromolecule, nonionic family macromolecule etc.

Mother plate for thermal sensitive porous printing of the present invention passes through to add above-mentioned surfactant, under the environment of 23 ℃-50%RH (relative humidity, together following), and preferred 5～70 ° for the static contact angle of pet film.During 5 ° of above-mentioned static contact angle less thaies, too promote moisteningly, the surfactant surplus surpasses 70 °, then can not fully promote moistening.

Be contained in the method for porous support as above-mentioned conductive material, have no particular limits, can suitably select according to purpose, but preferably be attached on this porous support.

Content (adhesion amount) in the film that contains this conductive material that adheres to (for example porous fiber film, porous resin film) must be 0.01～2.0g/m ², be more preferably 0.05～0.5g/m ²The above-mentioned quantity not sufficient 0.01g/m that contains ²The time, can not remove the static that produces when transmitting fully, further, owing to can not obtain sufficient stiffness, cause transmitting bad, surpass 2.0g/m ²The time, then damage the trafficability characteristic of printing ink, cause image not distinct.

As the method for measuring above-mentioned dry pickup, have no particular limits, can suitably select according to purpose, but can enumerate, for example, measure the preceding gross weight of conductive material coating earlier, measure the gross weight after conductive material is coated with again, divided by total spreading area, try to achieve moistening adhesion amount (g/m by the difference of gross weight before the gross weight after will being coated with and the coating ²) after, this moistening adhesion amount multiply by the coating fluid solid constituent, calculates the method (following brief note is " liquid decrement method ") of dry pickup thus.

As above-mentioned other layers, have no particular limits, can suitably select according to purpose, for example can enumerate, the hot melt adhesion prevents layer, adhesive linkage etc.

Above-mentioned hot melt adhesion prevents that layer from being that sticking the setting melted in generation when boring a hole for the one side that contacts with thermal head that prevents the thermoplastic resin membrane in above-mentioned mother plate for thermal sensitive porous printing.

Above-mentioned hot melt adhesion prevents a layer thin layer of preferably being arranged to comprise silicone oil, silicon resinoid, fluorine-type resin, surfactant, antistatic additive, heat-resistant agent, antioxidant, organic filler, inorganic particulate, pigment, dispersing aid, anticorrisive agent, defoamer etc.

Above-mentioned hot melt adhesion prevents preferred 0.005～0.4 μ m of thickness of layer, is more preferably 0.01～0.4 μ m.

Adhesion prevents the formation method of layer as above-mentioned hot melt, and there is no particular limitation, but preferably with roller coating, intaglio plate coating, oppositely coating, rod coating such as are coated with and are diluted in the solution that water, solvent etc. obtain, and drying.

Above-mentioned adhesive linkage is optionally, for bonding thermoplastic resin film and porous support are provided with.

As being used in bonding bonding agent, have no particular limits, can enumerate vinyl acetate resin, acrylic resin, polyurethane resin, polyester resin, ultraviolet electron ray curing type bonding agent etc.

The sheet resistance value of porous support one side in the above-mentioned mother plate for thermal sensitive porous printing (with the contact surface side of cylinder) preferably is 1.0 * 10 under the environment of 23 ℃-50%RH ⁵～1.0 * 10 ¹³Ω is more preferably 1.0 * 10 ⁵～1.0 * 10 ¹⁰Ω.Above-mentioned sheet resistance value surpasses 1.0 * 10 ¹³During Ω, under the environment of special low temperature and low humidity, can become electrify when in printing machine, transmitting former thus cause transmitting bad, less than 1.0 * 10 ⁵During Ω, though increase antistatic dosage etc. also can make sheet resistance value drop to this value maybe this below value, therefore for almost not influence of the transmission on printing machine.

Bending stiffness in mother plate for thermal sensitive porous printing (MD direction) is main expression transmission property and the parameter that is reducing the version fold, for example, can use L﹠amp; W STIFFNESS TESTER (ABLorentzen society system, 16-D) is set at angle of bend=30 °, and bending length=10mm measures.

If above-mentioned bending stiffness is low, cause and transmit badly have again easily, produce when causing on the drum after mother matrix is wound on plate-making easily the version fold.If the bending stiffness that has to a certain degree just aforesaid fault can not take place, transmit normally and the coiling on drum.Have the preferred 20～110mN of scope of the bending stiffness of above characteristic, be more preferably 30～70mN.

(manufacture method of mother plate for thermal sensitive porous printing)

The manufacture method of mother plate for thermal sensitive porous printing of the present invention contains the porous support and forms operation and porous fiber film formation operation, also contains conductive material painting process and other operations optionally.

-porous support formation operation-

It is to form the operation of any one porous support at least that contains in porous resin film and the porous fiber film on thermoplastic resin membrane's one side at least that above-mentioned porous support forms operation.

As the formation method of above-mentioned porous resin film, be on above-mentioned thermoplastic resin membrane, coating contains the porous resin film coating fluid of resin at least, and dry back forms the operation of porous resin film.

Above-mentioned porous resin film coating fluid preferably contains resin at least, optionally also contain other compositions, and is preferably water-in-oil type.

As the formation method of above-mentioned porous resin film, can enumerate, as mentioned above, above-mentioned the 1st formation method (opening flat 10-24667 communique) or the 2nd formation method (opening flat 11-23885 communique) etc. with reference to the spy with reference to the spy.

Formation method as above-mentioned porous fiber film, have no particular limits, can suitably select according to purpose, as mentioned above, can be short fiber to be carried out wet type copy the paper of manufacturing paper with pulp that paper obtains, also can be nonwoven and fabric, can also be grid yarn etc., waits the paper of preferably manufacturing paper with pulp from productivity ratio, cost aspect.

-conductive material painting process-

Above-mentioned conductive material painting process is the operation that contains the conductive material coating fluid of ionic polymers in the surface coating of above-mentioned porous support at least.

Above-mentioned conductive material coating fluid is a water system, and does not preferably have ignition point.

In recent years, because the situation of environmental protection is surging, therefore expect that mother plate for thermal sensitive porous printing also will reduce the load to environment.In the present invention, be air conservation, be coated with, can reduce carrying capacity of environment by using the water system composite.

Above-mentioned conductive material is 2～80mPas 25 ℃ the time preferably with the viscosity of coating fluid, is more preferably 5～40mPas.During above-mentioned viscosity is not enough 2mPas, can not fully be coated with necessary adhesion amount, the applied liquid of porous support stretches when surpassing 80mPas, and coating can not continue to carry out.

The above-mentioned conductive material pH preferred 4～9 of coating fluid.

The known stoste that contains the composite of above-mentioned conductive material is strong acid.But, when considering coating apparatus, use the equipment of having implemented antirust processing, even strong acid is also no problem, but when not being antirust equipment, preferably be adjusted into neutrality.If consider this one side of corrosion of above equipment, the pH value of coating fluid preferred 4～9, preferred especially 6～7.

As above-mentioned other operations, have no particular limits, can suitably select according to purpose, can enumerate, for example, antiblocking layers forms operation etc.

As above-mentioned porous fiber film and the film adhered method that contains the porous resin film, have no particular limits, can suitably select according to purpose, but preference as, applying porous resin film coating fluid on thermoplastic resin membrane's one side, at least after the dry and epitheliumization of the superficial layer of this porous resin film, fit with the porous fiber film that has been coated with bonding agent.If lamination porous fiber film before above-mentioned porous resin film forms then can hinder the formation of porous resin film, the porous resin film that can not obtain expecting.In addition, because bonding agent might stop up the hole of porous resin film, therefore preferably be coated on the method on the porous fiber film.

As (lamination) above-mentioned porous fiber film and the employed bonding agent when having the film of above-mentioned porous resin film of fitting, from printing ink trafficability characteristic aspect, the material of the high viscosity state in the preferred hole that can not stop up the porous resin film, the viscosity of above-mentioned bonding agent before solidify fully preferred 100mPas or more than the 100mPas in the time of 25 ℃ is more preferably 300mPas or more than the 300mPas.

At this moment, if use solvent type adhesive as above-mentioned bonding agent, owing to can invade the porous resin film, plugging hole, therefore, when lamination porous resin film and porous fiber film, preferably there is not the method for solvent at least, from this point, can suitably use no-solvent type bonding agent, water-based emulsion type bonding agent.

Coating process as above-mentioned bonding agent, have no particular limits, can look purpose and suitably select, can enumerate, for example, (1) will be coated on the coating fluid of organic solvent dilutings such as ethyl acetate on the porous fiber film, after the drying, with the method for porous resin film applying, (2) method of solvent-free direct coating etc., wherein, from the environment aspect with do not produce the viewpoint of residual solvent, the method for preferred solvent-free direct coating.

Coating process as above-mentioned bonding agent, have no particular limits, can look purpose and suitably select, can enumerate, for example, scraper plate rubbing method, inverse roller coating cloth method, wheel commentaries on classics gravure rubbing method, scraper rubbing method, spraying process, offset rotary gravure rubbing method, roller are licked rubbing method, excellent Tu Fa etc.

As above-mentioned bonding agent, for the adhesive strength that obtains stipulating and satisfy above-mentioned condition, special optimization polyurethane class bonding agent.As this polyurethanes bonding agent, the preferred no-solvent type polyurethane adhesive of the adhesive strength that just can obtain expecting with low adhesion amount.When use emulsion type polyurethane bonding agent is coated with, the flexible of porous fiber film takes place, the no-solvent type polyurethane adhesive is preferably used in deterioration aspects such as warpage.

Have no particular limits as above-mentioned no-solvent type polyurethane adhesive, can look purpose suitably selects, can enumerate single liquid moisture-curable urethane prepolymer that (1) reaction by polyol component and isocyanate prepolymer composition obtains, the biliquid curing type bonding agent that (2) can be divided into polyol component and isocyanate prepolymer composition.

As above-mentioned polyol component, so long as two ends have hydroxyl, and be that liquid is just passable, have no particular limits, can suitably select according to purpose, can enumerate, for example, two ends have PPG, PEPA of hydroxyl etc.

As above-mentioned isocyanate prepolymer composition, can enumerate, for example, hexamethylene diisocyanate (HMDI), 2,4 diisocyanate based-1-hexahydrotoluenes, 2,6-is diisocyanate based-the 1-hexahydrotoluene, diisocyanate based cyclobutane, tetramethylene diisocyanate, the neighbour, and paraxylene vulcabond (XDI), dicyclohexyl methyl hydride diisocyanate, the dimethyl dicyclohexyl methyl hydride diisocyanate, hexahydro m xylene diisocyanate (HXDI), LDI Arrcostab aliphatic or ester ring type vulcabond such as (moieties of this Arrcostab preferably have 1～6 charcoal atom); Toluene support-2,4-vulcabond (TDI), toluene support-2,6-vulcabond, diphenyl methane-4,4 '-vulcabond (MDI), 3-MDPM-4,4 '-vulcabond, and to phenylene vulcabond, chloro phenylene-2,4-vulcabond, naphthalene-1,5-vulcabond, diphenyl-4,4 '-vulcabond, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond, 1,3,5-triisopropylbenzene-2, aromatic diisocyanates such as 4-vulcabond, diphenyl ether vulcabond etc.These can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.

When being coated with the no-solvent type polyurethane adhesive on above-mentioned porous fiber film, if viscosity is too high, can cause fibre shedding, the generation coating is bad, and therefore preferably with the cylinder heating, viscosity decline is coated with again.The viscosity of above-mentioned no-solvent type polyurethane adhesive preferably is 3000cp or below the 3000cp in the time of 25 ℃.More preferred 300～1500cp.When above-mentioned viscosity surpasses 3000cp,, may damage the printing ink trafficability characteristic, cause that easily fibrage comes off with porous resin film applying back occlusion of openings portion.

When using above-mentioned no-solvent type bonding agent, be purpose, preferably be cured with the reaction of the mother plate for thermal sensitive porous printing that promotes to be wound as the cylinder shape.The temperature of this curing is preferred below 50 ℃ or 50 ℃, and is preferred especially below 40 ℃ or 40 ℃.When above-mentioned solidification temperature surpasses 50 ℃, the thermoplastic resin membrane can be taken place shrink, produce the problem of mother matrix warpage.In addition,, have no particular limits, can suitably select according to purpose as long as can obtain the purpose bonding force above-mentioned hardening time.

The adhesion amount of above-mentioned bonding agent, different with mother plate for thermal sensitive porous printing (laminate of thermoplastic resin membrane and porous fiber film) in the past, do not need to consider to hinder the influence of perforation, as long as the adhesive strength that can obtain expecting, and get final product in the scope in the hole of not stopping up porous resin film and porous fiber film, have no particular limits, can suitably select, preferred 0.05～5.0g/m according to purpose ², be more preferably 0.1～3.0g/m ²

The mother plate for thermal sensitive porous printing of the manufacture method manufacturing by mother plate for thermal sensitive porous printing of the present invention is, can not damage the pierceability that produces by thermal head, do not lose good portrait quality and stain few feature, and mother matrix can not occur in the printing machine because the card that static causes ends and the fold on drum, can solve the high-quality product of problem in the past.

Below, embodiments of the invention are described, but the present invention is not subjected to any qualification of these embodiment.

[experiment 1]

(embodiment 1)

The making of-mother plate for thermal sensitive porous printing-

Make the laminated body of thermoplastic resin membrane and porous resin film at first, as follows.

Dissolve and even disperse the porous resin film coating fluid of following composition, while stirring to wherein slowly adding water 25.0 mass parts that contain hydroxyethylcellulose (HEC) 1 quality %, the emulsion coating fluid of modulation gonorrhoea.

The prescription of＜porous resin film coating fluid 〉

Acetal resin (Sekisui Chemical Co., Ltd's system, KS-1) 2.5 mass parts

Talcum 0.8 mass parts

Surfactant (daylight ケミカ Le Co., Ltd. system, SO15U) 0.1 mass parts

Surfactant (Shin-Etsu Chemial Co., Ltd's system, KF6012) 0.1 mass parts

Surfactant (ジヨ Application ソ Application society system, J711) 0.2 mass parts

Ethyl acetate 43.0 mass parts

Then, the emulsion coating fluid through port mould coating method (ダイコ one テイ Application グ) that obtains is coated on Biaxially oriented polyester film (thickness 2.0 μ m, 100 ℃ * 3 minutes percent thermal shrinkage is vertical/horizontal=11%/12%) on, and carry out drying, and to make dried adhesion amount be 3.0g/m ², the laminated body of making thermoplastic resin membrane and porous resin film.

The thickness of the porous resin film that obtains is 16 μ m, and the average perforate of the porous resin film of measuring by following method directly is 18.6 μ m.

The mensuration in the average perforate footpath of-porous resin film-

The average hole of above-mentioned porous resin film is opened the mensuration in footpath and is taken 10 photos by any 10 places to the porous resin film under electron microscope (multiplying power is 100 times), after with scanner image information being imported computer, application image is resolved software (Off リ one ウエア: Scion Image) carry out binaryzation, convert by circle from perforate part area and measure the perforate footpath.1000 perforate footpaths of arbitrary extracting from a photo, the mean value of obtaining 10 photos is as average perforate footpath.

The making of＜porous fiber film 〉

At first, not drawn polyester fiber (テイジ Application Co., Ltd. system of mixing 0.2 dawn of fiber number, the long 3mm of fiber, テピ Le ス TK08PN) polyester binder fiber (the sheath composition: low-melting point PET of 40 quality % and 1.5 dawn of fiber number, the long 5mm of fiber, 110 ℃ of heat fusing temperature, core composition: PET/ ユニチカ Co., Ltd. system, メ Le テイ 4080) 60 quality % make the porous fiber film by cylinder mould machine.

The weight per unit area of the porous fiber film that obtains is 7.5g/m ², thickness is 28 μ m.

Then, be antistatic and enhancing porous support, on the porous fiber film that obtains, be coated with the conductive material A coating fluid (solid constituent=10.0 quality %) of following composition and make in [0049] section the dry pickup that the liquid decrement method of explanation measures (below, note by abridging be " dry pickup ") be 0.3g/m ²And it is dry.In addition, the coating fluid of this conductive material A is water system and does not have ignition point.

The composition of-conductive material A coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 100 mass parts

This conductive material A coating fluid is 6.1 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

With toluene is solvent, changes gravure rubbing method coating polyurethanes bonding agent by wheel, and the laminated body and the above-mentioned porous fiber film of above-mentioned thermoplastic resin membrane and porous resin film carried out lamination, obtains laminated body 30 ℃ of following dryings.

Then, in the one side thermoplastic resin membrane and the opposition side porous resin film, by steel wire bar (ワイヤ one バ one) coating method coating water-soluble silicon oil (FZ2101, Japanese ユニチカ Co., Ltd. system) the 1 quality % aqueous solution, and dry.By above operation, make mother plate for thermal sensitive porous printing shown in Figure 3.In addition, the mother plate for thermal sensitive porous printing that obtains confirms to contain ionic polymers by the following method.

" ionic high molecular confirmation method "

At the mother plate for thermal sensitive porous printing that has been coated with conductive material A coating fluid be not coated with on the mother plate for thermal sensitive porous printing of conductive material A coating fluid, by fluorescent x-ray analyzer (3270, リガ Le society system), the detected level of the many permeability tunica fibrosa main component elements surface, in ionic polymers.In addition, the main component element in the above-mentioned ionic polymers that detects in advance is sulphur (S), sodium (Na), bromine (Br).

Its result, with respect on the mother plate for thermal sensitive porous printing that is not coated with conductive material A coating fluid, S is 1000cps, and Na is 100cps, and Br is 80cps, on the mother plate for thermal sensitive porous printing that has been coated with conductive material A coating fluid, S is 5000cps, and Na is 800cps, and Br is 900cps, determine significantly, S, Na, Br reading (cps) separately all has increase.

In addition, in the following embodiments, as mentioned above, by observe out S, Na on the mother plate for thermal sensitive porous printing that has been coated with the conductive material coating fluid, Br reading is separately compared with the mother plate for thermal sensitive porous printing that is not coated with the conductive material coating fluid that increase is all arranged, and can confirm to contain ionic polymers.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, do not confirm the faults such as coiling that generation is caused by static.

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on the porous fiber film surface of Ce Dinging is 4.5 * 10 with the sheet resistance meter ⁸Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 45mN in the MD direction.

(comparative example 1)

The making of-mother plate for thermal sensitive porous printing-

The conductive material B coating fluid (solid constituent=9 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.29g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of comparative example 1.

The composition of-conductive material B coating fluid-

Polyurethane polymer 7 mass parts

Cationic surfactant (エレガ Application 264A; Japan grease society system) 2 mass parts

Water 91 mass parts

This conductive material B coating fluid is 5.6 at 25 ℃ pH, and the Tg of polyurethane polymer is 210 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, generation causes transmitting bad by the coiling that static causes.

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 2.5 * 10 with the sheet resistance meter ¹³Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 46mN in the MD direction.

(comparative example 2)

The making of-mother plate for thermal sensitive porous printing-

Remove that to remove the coating fluid that the cationic surfactant obtains in the conductive material B coating fluid of coating from comparative example 1 and make dry pickup be 0.09g/m ², be 4.1 at 25 ℃ pH, carry out again beyond the drying, same with comparative example 1, the mother plate for thermal sensitive porous printing of making comparative example 2.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value of mensuration porous fiber film is 4.0 * 10 with the sheet resistance meter ¹³Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 18mN in the MD direction.

(embodiment 2)

The making of-mother plate for thermal sensitive porous printing-

Remove the porous fiber film be not provided with among the embodiment 1, at the conductive material C coating fluid (solid constituent=4.3 quality %) of the following composition of porous resin film surface coating, and to make dry pickup be 0.15g/m ², and beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 2 shown in Figure 1.In addition, this conductive material C coating fluid is a water system, and does not have ignition point.

The composition of-conductive material C coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 43 mass parts

Water 57 mass parts

This conductive material C coating fluid is 6.5 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous resin film surface is 7.5 * 10 with the sheet resistance meter ⁹Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 30mN in the MD direction.

(comparative example 3)

The making of-mother plate for thermal sensitive porous printing-

The conductive material D coating fluid (solid constituent=4 quality %) that removes the following composition of coating to be replacing the conductive material C coating fluid in embodiment 2, and to make dry pickup be 0.15g/m ², and carry out beyond the drying, similarly to Example 2, make the mother plate for thermal sensitive porous printing of comparative example 3.

The composition of-conductive material D coating-

Polyurethane polymer 4 mass parts

Cationic surfactant (エレガ Application 264A; Japan grease society system) 1 mass parts

Water 95 mass parts

This conductive material D coating fluid is 6.0 at 25 ℃ pH, and the Tg of polyurethane polymer is 210 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous resin film surface is 7 * 10 with the sheet resistance meter ¹³Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 32mN in the MD direction.

(embodiment 3)

The making of-mother plate for thermal sensitive porous printing-

In embodiment 1, laminated thermoplastic resin membrane and porous fiber film, applying porous resin film coating fluid and the dry porous resin film that forms on this porous fiber film.At the conductive material E coating fluid (solid constituent=2.9 quality %) of the following composition of porous resin film surface coating, and to make dry pickup be 0.1g/m ², and it is dry, make the mother plate for thermal sensitive porous printing of embodiment 3 shown in Figure 4.In addition, this conductive material E coating fluid is a water system, and does not have ignition point.

The composition of-conductive material E coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 29 mass parts

Water 71 mass parts

This conductive material E coating fluid is 6.8 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous resin film surface is 8.1 * 10 with the sheet resistance meter ¹⁰Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 40mN in the MD direction.

(comparative example 4)

The making of-mother plate for thermal sensitive porous printing-

The conductive material F coating fluid (solid constituent=3.75 quality %) that removes the following composition of coating to be replacing the conductive material E coating fluid in embodiment 3, and to make dry pickup be 0.11g/m ², and carry out beyond the drying, similarly to Example 3, make the mother plate for thermal sensitive porous printing of comparative example 4.

The composition of-conductive material F coating-

Polyurethane polymer 3 mass parts

Cationic surfactant (エレガ Application 264A; Japan grease society system) 0.75 mass parts

Water 96.25 mass parts

This conductive material F coating fluid is 6.3 at 25 ℃ pH, and the Tg of polyurethane polymer is 210 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains after preserving for 1 week under 50 ℃ the environment, under the environment of 23 ℃-65%RH, was placed 24 hours.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, generation causes transmitting bad by the coiling that static causes.

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous resin film surface is 9.0 * 10 with the sheet resistance meter ¹³Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 41mN in the MD direction.

(embodiment 4)

The making of-mother plate for thermal sensitive porous printing-

Porous resin film among the embodiment 1 is not set, laminated thermoplastic resin membrane and porous fiber film, at the conductive material G coating fluid (solid constituent=3.2 quality %) of the following composition of this porous fiber film surface coating, and to make dry pickup be 0.1g/m ², and it is dry, make the mother plate for thermal sensitive porous printing of embodiment 4 shown in Figure 2.In addition, this conductive material G coating fluid is a water system, and does not have ignition point.

The composition of-conductive material G coating fluid-

Styrene-acrylonitrile copolymer acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 32 mass parts

Water 68 mass parts

This conductive material G coating fluid is 6.5 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 8.0 * 10 with the sheet resistance meter ¹⁰Ω.

(comparative example 5)

The making of-mother plate for thermal sensitive porous printing-

The conductive material H coating fluid (solid constituent=3.75 quality %) that removes the following composition of coating to be replacing the conductive material G coating fluid in embodiment 4, and to make dry pickup be 0.11g/m ², and carry out beyond the drying, similarly to Example 4, make the mother plate for thermal sensitive porous printing of comparative example 5.

The composition of-conductive material H coating-

Polyurethane polymer 3 mass parts

Water 96.25 mass parts

This conductive material H coating fluid is 6.3 at 25 ℃ pH, and the Tg of polyurethane polymer is 210 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 9.0 * 10 with the sheet resistance meter ¹³Ω.

(embodiment 5)

The making of-mother plate for thermal sensitive porous printing-

The conductive material I coating fluid (solid constituent=8 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.25g/m ², and carry out beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 5.In addition, this conductive material I coating fluid is a water system, and does not have ignition point.

The composition of-conductive material I coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 80 mass parts

Water 20 mass parts

This conductive material I coating fluid is 5.9 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate 1 〉

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 9.0 * 10 with the sheet resistance meter ⁸Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 43mN in the MD direction.

＜estimate 2 〉

In the anionic property polymer that in embodiment 5, uses, use up face scraping article (ス system one スバ one) and go up coated with anionic polymer and dry at PET film (thickness is 16 μ m).When carrying out its sample surfaces elementary analysis (x-ray fluorescence analysis), detect a large amount of Na.Hence one can see that, and the anionic property polymer contains alkali metal salt.

＜estimate 3 〉

In embodiment 5 employed conductive material I coating fluids, add the surfactant that has various HLB values on a small quantity, observe its liquid condition.Its result in HLB value=8.5 o'clock, adds the back gelation, can not use as coating fluid.In HLB value=9.5 o'clock, after the interpolation, do not cause gelation, as not influence of coating fluid.Even in HLB value=13.3 o'clock, after the interpolation, do not cause gelation yet.In addition, the results are shown in table 1.

Table 1

The HLB value	The gelation of liquid
The HLB value	The gelation of liquid	8.5	Have
9.5	Do not have	8.5	Have
9.5	Do not have	13.3	Do not have

＜estimate 4 〉

In embodiment 5, use in the conductive material I coating fluid, adding is as polyoxyalkylene alkane alkyl ether (the ア Network チノ one Le B-7W of nonionic class surfactant, the system HLB of society of Matsumoto Yushi-Seiyaku Co., Ltd. value=12.1) 25 quality %, the static contact angle of measuring pet film by liquid notes method is about 5 °.In addition, when adding above-mentioned polyoxyalkylene alkyl 0.04 quality %, above-mentioned static contact angle is about 65 °.Have, when not adding polyoxyalkylene alkyl, above-mentioned static contact angle is about 80 ° again.As a comparison, the static contact angle of pure water is about 115 °.In addition, the results are shown in table 2.

Table 2

Activating agent addition (quality %)	Contact angle (°)
Activating agent addition (quality %)	Contact angle (°)	25	5
0.04	65	25	5
0.04	65	0	80

(comparative example 6)

The making of-mother plate for thermal sensitive porous printing-

The conductive material J coating fluid (solid constituent=7.7 quality %) that removes the following composition of coating to be replacing the conductive material I coating fluid in embodiment 5, and to make dry pickup be 0.25g/m ², and carry out beyond the drying, similarly to Example 5, make the mother plate for thermal sensitive porous printing of comparative example 6.

The composition of-conductive material J coating fluid-

Polyurethane polymer 6 mass parts

Cationic surfactant (エレガ Application 264A; Japan grease society system) 1.7 mass parts

Water 92.3 mass parts

This conductive material J coating fluid is 6.2 at 25 ℃ pH, and the Tg of polyurethane polymer is 210 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application テ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 9.0 * 10 with the sheet resistance meter ¹³Ω.

(embodiment 6)

The making of-mother plate for thermal sensitive porous printing-

The conductive material K coating fluid (solid constituent=8.05 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.25g/m ², and carry out beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 6.In addition, this conductive material K coating fluid is a water system, and does not have ignition point.

The composition of-conductive material K coating fluid-

Polyoxyalkylene alkyl (ア Network チノ one Le B-7W, the system HLB of society of Matsumoto Yushi-Seiyaku Co., Ltd. value=about 12.1) 0.05 mass parts

Water 19.95 mass parts

This conductive material K coating fluid is 6.3 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, do not confirm the fault that generation is caused by static.

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 9.5 * 10 with the sheet resistance meter ⁷Ω.

(embodiment 7)

The making of-mother plate for thermal sensitive porous printing-

The conductive material L coating fluid (solid constituent=6.5 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.3g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 7.In addition, this conductive material L coating fluid is a water system, and does not have ignition point.

The composition of-conductive material L coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 65 mass parts

Polyoxyalkylene alkyl (ア Network チノ one Le B-7W, the system HLB of society of Matsumoto Yushi-Seiyaku Co., Ltd. value=about 12.1) 0.01 mass parts

Water 34.99 mass parts

This conductive material L coating fluid is 6.6 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 7.0 * 10 with the sheet resistance meter ⁷Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 50mN in the MD direction.

(comparative example 7)

The making of-mother plate for thermal sensitive porous printing-

In embodiment 7, removing the above-mentioned conductive material L coating fluid of coating and making dry pickup is 0.005g/m ², 25 ℃ pH is 6.9, and beyond the drying, similarly to Example 7, makes the mother plate for thermal sensitive porous printing of comparative example 7.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, confirm generation, cause transmitting bad by the faults such as coiling that static causes.

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 8.0 * 10 with the sheet resistance meter ¹³Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 15mN in the MD direction.

(embodiment 8)

The making of-mother plate for thermal sensitive porous printing-

The conductive material α coating fluid (solid constituent=10 amount %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.3g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 8.In addition, this conductive material α coating fluid is a water system, and does not have ignition point.

The composition of-conductive material α coating fluid-

Acrylic compounds cationic polymer (IN-197, high terebinth Pharmaceutical Co., Ltd system) 40 mass parts

Water 60 mass parts

This conductive material α coating fluid is 5.9 at 25 ℃ pH, and the Tg of anionic property polymer is 59 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, do not confirm the faults such as coiling that cause by static.

In addition, the mother plate for thermal sensitive porous printing that obtains is carried out damping in 12 hours under the environment of 23 ℃-50%RH, (アジレ Application トテ Network ノロジ one society's system, 4339B) sheet resistance value on mensuration porous fiber film surface is 5.3 * 10 with the sheet resistance meter ¹⁰Ω.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 47mN in the MD direction.

In addition, be convenient, the result's of embodiment 1～8 and comparative example 1～7 summary is shown in table 3.

[table 3]

	Material is formed	Low molecule-type surfactant	Dry pickup (g/m ²)	Preserve the fault that all backs are caused by static down at 50 ℃	Sheet resistance value (Ω)	Bending stiffness (mN)
	Material is formed	Low molecule-type surfactant	Dry pickup (g/m ²)		Sheet resistance value (Ω)	Bending stiffness (mN)	Embodiment 1	Conductive material A	Do not have	0.3	Do not have	4.5×10 ⁸	45
Comparative example 1	Conductive material B	Do not have	0.29	Have	2.5×10 ¹³	46	Embodiment 1	Conductive material A	Do not have	0.3	Do not have	4.5×10 ⁸	45
Comparative example 1	Conductive material B	Do not have	0.29	Have	2.5×10 ¹³	46	Comparative example 2	-	Do not have	0.09	Have	4.0×10 ¹³	18
Embodiment 2	Conductive material C	Do not have	0.15	Do not have	7.5×10 ⁹	30	Comparative example 2	-	Do not have	0.09	Have	4.0×10 ¹³	18
Embodiment 2	Conductive material C	Do not have	0.15	Do not have	7.5×10 ⁹	30	Comparative example 3	Conductive material D	Do not have	0.15	Have	7.0×10 ¹³	32
Embodiment 3	Conductive material E	Do not have	0.1	Do not have	8.0×10 ¹⁰	40	Comparative example 3	Conductive material D	Do not have	0.15	Have	7.0×10 ¹³	32
Embodiment 3	Conductive material E	Do not have	0.1	Do not have	8.0×10 ¹⁰	40	Comparative example 4	Conductive material F	Do not have	0.11	Have	9.0×10 ¹³	41
Embodiment 4	Conductive material G	Do not have	0.1	Do not have	8.0×10 ¹⁰	40	Comparative example 4	Conductive material F	Do not have	0.11	Have	9.0×10 ¹³	41
Embodiment 4	Conductive material G	Do not have	0.1	Do not have	8.0×10 ¹⁰	40	Comparative example 5	Conductive material H	Do not have	0.11	Have	9.0×10 ¹³	41
Embodiment 5	Conductive material I	Do not have	0.25	Do not have	9.0×10 ⁸	43	Comparative example 5	Conductive material H	Do not have	0.11	Have	9.0×10 ¹³	41
Embodiment 5	Conductive material I	Do not have	0.25	Do not have	9.0×10 ⁸	43	Comparative example 6	Conductive material J	Do not have	0.25	Have	9.0×10 ¹³	42
Embodiment 6	Conductive material K	Have	0.25	Do not have	9.5×10 ⁷	41	Comparative example 6	Conductive material J	Do not have	0.25	Have	9.0×10 ¹³	42
Embodiment 6	Conductive material K	Have	0.25	Do not have	9.5×10 ⁷	41	Embodiment 7	Conductive material L	Have	0.3	Do not have	7.0×10 ⁷	50
Comparative example 7	-	Have	0.005	Have	8.0×10 ¹³	15	Embodiment 7	Conductive material L	Have	0.3	Do not have	7.0×10 ⁷	50
Comparative example 7	-	Have	0.005	Have	8.0×10 ¹³	15	Embodiment 8	Conductive material α	Do not have	0.3	Do not have	5.3×10 ¹⁰	47

[experiment 2]

(embodiment 9)

The making of-mother plate for thermal sensitive porous printing-

The conductive material M coating fluid (solid constituent=8.5 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.25g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 9.In addition, this conductive material M coating fluid is a water system, and does not have ignition point.

The composition of-conductive material M coating fluid-

Styrene-propene acid copolymer (anionic property polymer) 80 mass parts

Polyoxyalkylene alkyl (ア Network チノ one Le B-7W, the system HLB of society of Matsumoto Yushi-Seiyaku Co., Ltd. value=about 12.1) 0.5 mass parts

Water 19.5 mass parts

This conductive material M coating fluid is 6.8 at 25 ℃ pH, and the Tg of anionic property polymer is 55 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains is after preserving for 1 week under 50 ℃ the environment, use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, do not confirm the fault that generation is caused by static.

In addition, use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) when this mother plate for thermal sensitive porous printing is implemented to use the printing of complete (ベ ) image, can access good image.In addition, the results are shown in table 4.

＜estimate 2 〉

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, do not confirm and produce sticking page or leaf, can normally transmit and make a plate.In addition, the results are shown in table 5.

(comparative example 8)

The making of-mother plate for thermal sensitive porous printing-

The conductive material N coating fluid (solid constituent=10 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 2.5g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of comparative example 8.

The composition of-conductive material N coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 500 mass parts

Polyoxyalkylene alkyl (ア Network チノ one Le B-7W, the system HLB of society of Matsumoto Yushi-Seiyaku Co., Ltd. value=about 12.1) 3.13 mass parts

This conductive material N coating fluid is 6.6 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

But when this mother plate for thermal sensitive porous printing was implemented to use the printing of complete (ベ ) image, fecund was given birth to the deinking part, can not obtain good image to use printing machine (サテリオ 400, the リコ of Co., Ltd. one system).In addition, the results are shown in table 4.

(comparative example 9)

The making of-mother plate for thermal sensitive porous printing-

The conductive material O coating fluid (solid constituent=1.61 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.005g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of comparative example 9.

The composition of-conductive material O coating fluid-

Styrene-propene acid copolymer (WS-52-U, Xin Zhong village chemical industry Co., Ltd. system, anionic property polymer) 1.6 mass parts

Water 98.39 mass parts

This conductive material O coating fluid is 6.2 at 25 ℃ pH, and the Tg of anionic property polymer is 68 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains is after preserving for 1 week under 50 ℃ the environment, use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, the coiling that generation causes owing to static, generation transmits bad.

But, use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) when this mother plate for thermal sensitive porous printing is implemented to use the printing of complete (ベ ) image, to obtain good image.In addition, the results are shown in table 4.

Table 4

	Material is formed	Preserve the fault that 1 all backs are caused by static down at 50 ℃	Image quality
	Material is formed		Image quality	Embodiment 9	Conductive material M	Do not have	Well
Comparative example 8	Conductive material N	Do not have	Deinking is obvious	Embodiment 9	Conductive material M	Do not have	Well
Comparative example 8	Conductive material N	Do not have	Deinking is obvious	Comparative example 9	Conductive material O	Have	Well

(comparative example 10)

The making of-mother plate for thermal sensitive porous printing-

The conductive material P coating fluid (solid constituent=8.5 quality %) that removes the following composition of coating to be replacing the conductive material A coating fluid in embodiment 1, and to make dry pickup be 0.25g/m ², carry out again beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of comparative example 10.

The composition of-conductive material P coating fluid-

Styrene-propene acid copolymer (anionic property polymer) 80 mass parts

Water 19.5 mass parts

The Tg of the anionic property polymer of this conductive material P coating fluid is 3 ℃.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one makes) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print, because sticking page or leaf, it is bad that transmission takes place, and affirmation can not normally be made a plate.In addition, the results are shown in table 5.

Table 5

	Material is formed	Dry pickup (g/m ²)	Tg(℃)	Sticking page or leaf	Transmission property	Plate-making property
	Material is formed	Dry pickup (g/m ²)	Tg(℃)	Sticking page or leaf	Transmission property	Plate-making property	Embodiment 9	Conductive material M	0.25	55	Do not have	Well	Normally
Comparative example 10	Conductive material P	0.25	3	Have	Bad	Unusually	Embodiment 9	Conductive material M	0.25	55	Do not have	Well	Normally

(embodiment 10)

The making of-mother plate for thermal sensitive porous printing-

Except that with the porous fiber film among the embodiment 1 according to the following change, make the mother plate for thermal sensitive porous printing of embodiment 10 similarly to Example 1.

The making of-porous fiber film-

At first, not drawn polyester fiber (テイジ Application Co., Ltd. system of mixing 0.2 dawn of fiber number, the long 3mm of fiber, テピ Le ス TK08PN) polyester binder fiber (the sheath composition: low-melting point PET of 50 quality % and 1.5 dawn of fiber number, the long 5mm of fiber, 110 ℃ of heat fusing temperature, core composition: PET/ ユニチカ Co., Ltd. system, メ Le テイ 4080) 50 quality % make the porous fiber film by cylinder mould machine.

The weight per unit area of the porous fiber film that obtains is 7.5g/m ², thickness is 30 μ m.

＜estimate

In addition, use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) when this mother plate for thermal sensitive porous printing is implemented to use the printing of complete (ベ ) image, can obtain good image.

(embodiment 11)

The making of-mother plate for thermal sensitive porous printing-

Except that with the porous fiber film among the embodiment 1 according to the following change, make the mother plate for thermal sensitive porous printing of embodiment 11 similarly to Example 1.

The making of-porous fiber film-

At first, not drawn polyester fiber (テイジ Application Co., Ltd. system of mixing 0.2 dawn of fiber number, the long 3mm of fiber, テピ Le ス TK08PN) polyester binder fiber (the sheath composition: low-melting point PET of 35 quality % and 1.5 dawn of fiber number, the long 5mm of fiber, 110 ℃ of heat fusing temperature, core composition: PET/ ユニチカ Co., Ltd. system, メ Le テイ 4080) 15 quality % mix abaca 50 quality % again, make the porous fiber film by cylinder mould machine.The weight per unit area of the porous fiber film that obtains is 8.5g/m ², thickness is 33 μ m.

＜estimate

(embodiment 12)

The making of-mother plate for thermal sensitive porous printing-

Removing the conductive material A coating fluid among the coating embodiment 1 and making dry pickup is 0.15g/m ², and beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of embodiment 12.

＜estimate

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 38mN in the MD direction.In addition, the results are shown in table 6.

(comparative example 11)

The making of-mother plate for thermal sensitive porous printing-

Removing the conductive material A coating fluid among the coating embodiment 1 and making dry pickup is 2.5g/m ², and beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of comparative example 11.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print,, cause that transmission is bad because stiffness is strong excessively.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 120mN in the MD direction.In addition, the results are shown in table 6.

(comparative example 12)

The making of-mother plate for thermal sensitive porous printing-

Removing the conductive material A coating fluid among the coating embodiment 1 and making dry pickup is 0.005g/m ², and beyond the drying, similarly to Example 1, make the mother plate for thermal sensitive porous printing of comparative example 12.

＜estimate

The mother plate for thermal sensitive porous printing that obtains under the environment of 23 ℃-65%RH, was placed 24 hours after preserving for 1 week under 50 ℃ the environment.Use printing machine (サテリオ 400, the リコ of Co., Ltd. one system) that this mother plate for thermal sensitive porous printing is carried out continuous 50 times and make a plate repeatedly and print and since stiffness excessively a little less than, cause transmit bad.

In addition, the mother plate for thermal sensitive porous printing that obtains is used L﹠amp; (AB Lorentzen society system 16-D), is set at angle of bend=30 °, bending length=10mm to W STIFFNESS TESTER, measures bending strength, is 18mN in the MD direction.In addition, the results are shown in table 6.

Table 6

	Dry pickup (g/m ²)	Bending stiffness (mN)	Transmission property
	Dry pickup (g/m ²)	Bending stiffness (mN)	Transmission property	Embodiment 12	0.15	38	Well
Comparative example 11	2.5	120	Bad	Embodiment 12	0.15	38	Well
Comparative example 11	2.5	120	Bad	Comparative example 12	0.005	18	Bad

[experiment 3]

When the conductive material A coating fluid of embodiment 1 liquid viscosity 25 ℃ the time is made 30mPas, when being coated with, the porous support special problem can not take place.

When the liquid viscosity of above-mentioned conductive material A coating fluid 25 ℃ the time made 85mPas, the applied liquid of porous support stretched, and coating can not continue to carry out.

When the liquid viscosity of above-mentioned conductive material 25 ℃ the time made 1.3mPas, liquid viscosity was low excessively, can not satisfy the coating of necessary adhesion amount.

In addition, the results are shown in table 7.

Table 7

Liquid viscosity (mPas)	Coating to the porous support
Liquid viscosity (mPas)	Coating to the porous support	85	Support is wound on the cylinder
30	Normally	85	Support is wound on the cylinder
30	Normally	1.3	Can not be coated with the adhesion amount of expectation

The present invention is that mother plate for thermal sensitive porous printing can not take place because the transmission that the static in the printing machine causes is bad and bad to the package of printing drums, has sufficient stiffness, the antistatic property deterioration is few, owing to be the water system coating material, therefore have excellent environmental safety, be applicable to porous printing.

Claims

1. mother plate for thermal sensitive porous printing, it is characterized in that, this mother matrix has the thermoplastic resin membrane and contain any one porous support at least in porous resin film and the porous fiber film on this thermoplastic resin membrane's one side at least, this porous support contain at least Tg be more than 55 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

2. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, the superficial layer of porous support is the porous resin film, this porous resin film contain Tg be more than 55 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

3. according to the mother plate for thermal sensitive porous printing of putting down in writing in the claim 1, wherein, the porous support is to have the porous resin film and constitute on the porous fiber film, this porous resin film contain Tg be more than 55 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

4. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, the superficial layer of porous support is the porous fiber film, this porous fiber film contain Tg be more than 55 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

5. according to the mother plate for thermal sensitive porous printing of putting down in writing in the claim 1, wherein, the porous support is to have the porous fiber film and constitute on the porous resin film, this porous fiber film contain Tg be more than 55 ℃ ionic polymers, dry pickup is 0.01～2.0g/m ²Conductive material.

6. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, ionic polymers is the anionic property polymer.

7. according to the mother plate for thermal sensitive porous printing of record in the claim 6, wherein, the anionic property polymer contains alkali metal salt.

8. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, conductive material contains surfactant.

9. according to the mother plate for thermal sensitive porous printing of record in the claim 8, wherein, surfactant is non-ionic species surfactant.

10. according to the mother plate for thermal sensitive porous printing of record in the claim 8, wherein, the HLB value of surfactant is more than 9 or 9.

11., wherein, be 1.0 * 10 in the sheet resistance value of porous support one side of mother plate for thermal sensitive porous printing according to the mother plate for thermal sensitive porous printing of record in the claim 1 ⁵～1.0 * 10 ¹³Ω.

12. according in the claim 1 record mother plate for thermal sensitive porous printing, wherein, with conductive material attached on the porous support.

13. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, the porous fiber film contains synthetic fibers.

14. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, the porous fiber film contains the composite fibre of synthetic fibers and natural fiber.

15. according to the mother plate for thermal sensitive porous printing of record in the claim 1, wherein, the bending stiffness of mother plate for thermal sensitive porous printing is 20～110mN on direction of transfer.

16. the manufacture method of mother plate for thermal sensitive porous printing is characterized in that, this method contains following operation:

On thermoplastic resin membrane's one side at least, form the porous support that contains any one the porous support at least in porous resin film and the porous fiber film and form operation; At least contain the conductive material painting process that Tg is the conductive material coating fluid of the ionic polymers more than 55 ℃ in this porous support surface coating.

17. according to the manufacture method of the mother plate for thermal sensitive porous printing of claim 16 record, wherein, conductive material is 5～70 ° with the static contact angle between coating fluid and the PETG.

18. according to the manufacture method of the mother plate for thermal sensitive porous printing of claim 16 record, wherein, the conductive material coating fluid is a water system, and does not have ignition point.

19. according to the manufacture method of the mother plate for thermal sensitive porous printing of claim 16 record, wherein, conductive material is 2～80mPas with the viscosity of coating fluid 25 ℃ the time.

20. according to the manufacture method of the mother plate for thermal sensitive porous printing of claim 16 record, wherein, conductive material is 4～9 with the pH value of coating fluid.