JP2019101113A - Surface treatment agent for resin film for printing - Google Patents

Abstract

To provide a surface treatment agent for a resin film for printing that has a good adhesive strength to an image through fixing and can form an excellent image, and a method for using the same.SOLUTION: A surface treatment agent for a resin film for printing has a polar group that includes at least any one of nitrogen atoms and oxygen atoms, and a polypropylene chain, and includes a polymer X that is solid at 25°C. A resin film for printing has a printing surface of a resin film covered with the surface treatment agent. A method for printing an image on a resin film by using a liquid developer containing toner particles containing a binder resin and a colorant and an insulating liquid, is a method for printing an image using a resin film having a printing surface covered with the surface treatment agent.SELECTED DRAWING: None

Description

  The present invention is suitably used for printing on resin films using liquid developers, dry toners, inkjet inks, etc. in image formation by, for example, electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a surface treatment agent for a resin film and a method of using the surface treatment agent.

  When printing an image on a resin film such as a polypropylene film, in order to improve the fixability of the image, a resin film coated with a surface treatment agent is used, and various surface treatment agents are studied.

  In Patent Document 1, a coating liquid containing an ethylene / (meth) acrylic acid copolymer and an isocyanate crosslinking agent obtained by blocking tetramethyl xylylene diisocyanate is applied to at least one surface of a substrate and dried to obtain an image There is disclosed an image-receiving sheet for electrostatically charged liquid development in which a layer is formed.

  Patent Document 2 discloses a liquid developer including a resin base, an oil absorption layer containing inorganic fine particles formed on the resin base, and a conductive layer formed on the oil absorption layer. Recording medium is disclosed.

  Patent Document 3 discloses an OHP paper for a liquid-dry copying machine, characterized in that a white, devitrified porous surface layer made of a saturated copolyester resin is provided on a substrate made of a transparent polyester film. ing.

  U.S. Pat. No. 5,959,015 is an electrostatically printed thermoplastic film comprising a polyolefin substrate, the polyolefin substrate having a coating on at least one side thereof for receiving toner derived from a liquid toner composition. And a thermoplastic film having a toner composition electrostatically applied to the substrate, and the coating comprising a copolymer derived from a carboxylic acid containing vinyl unsaturation.

  U.S. Pat. No. 5,959,095 comprises the steps of providing a substrate having a surface coated with a coating comprising silica, and printing the surface coated with an ink comprising a pigmented polymer and a carrier liquid. It is disclosed.

Japanese Patent Application Laid-Open No. 2007-27204 JP, 2012-163761, A JP-A-2-47667 JP-A-9-329909 Japanese Patent Publication No. 2003-510639

  However, even the surface treatment agents described in Patent Documents 1 to 5 can not be said to have sufficient fixing strength. Furthermore, when the surface treatment agent is a water-soluble polymer, when an oil-soluble layer such as a liquid developer or an oil-soluble inkjet ink is overlaid on the surface treatment agent layer, the compatibility between the layers is low. There is also a problem of deterioration.

  The present invention relates to a surface treatment agent for a resin film for printing which has good adhesive strength by fixing to an image and can form an excellent image, and a method of using the same.

  In the present invention, polymer X having a polar group containing at least one of nitrogen atom and oxygen atom and a polypropylene chain and solid at 25 ° C. (hereinafter, also simply referred to as “polymer X”) is a resin film for printing It has been found that it has excellent adhesion strength to an image by fixing as an anchor and is used as a wettability improver for a resin film for printing to form an excellent image, and is completed.

The present invention
[1] A surface treatment agent for a resin film for printing, comprising a polymer X having a polar group containing at least one of a nitrogen atom and an oxygen atom and a polypropylene chain and being solid at 25 ° C.
[2] A method of using the polymer X according to the above [1] as a surface treatment agent for a resin film for printing,
[3] A resin film for printing, wherein the printing surface of the resin film is coated with the surface treatment agent according to the above [1],
[4] A method of printing an image on a resin film using a toner developer containing a binder resin and a colorant and a liquid developer containing an insulating liquid, which is printed with the surface treatment agent according to the above [1] Method of printing an image using a surface-coated resin film
[5] A printing comprising a liquid developer containing a toner particle containing a binder resin and a colorant and an insulating liquid, and a resin film having a printing surface coated with the surface treatment agent according to the above [1]. The present invention relates to a kit, and a printed material in which a layer of the surface treatment agent according to the above [1] and a layer of an image are laminated in this order on a resin film.

  The surface treatment agent for a resin film for printing according to the present invention has an excellent adhesive strength upon fixing to an image, and therefore has an effect that an excellent image can be formed.

  The surface treatment agent for a resin film for printing of the present invention is a polymer having a polar group containing at least one of a nitrogen atom and an oxygen atom, and a polypropylene chain, and containing a solid polymer X at 25 ° C.

In the present invention, the reason why the polymer X exhibits good adhesive strength to a fixed image is not clear, but is considered as follows.
Since the surface of the resin film is hardly uneven, ink does not penetrate as in paper, and physical adhesion can not be expected. Further, among the resin films, polypropylene films do not have functional groups capable of participating in adhesion on the film surface, and chemical adhesion can not be expected either. Therefore, it is known that in the case of film printing, it is necessary to treat the film in advance using corona treatment or a surface treatment agent.
On the other hand, the polymer X in the present invention has a polar group containing at least one of a nitrogen atom and an oxygen atom in the molecule and a polypropylene chain. In general, it is known that materials having close SP values are easy to adhere to each other, so that the polypropylene group possessed by the polymer X is considered to be effective for adhesion to a nonpolar polypropylene film. Furthermore, since the polymer X also has a polar group, it is presumed to be effective for adhesion to a polar substance.
Furthermore, since the polymer X in the present invention is solid at room temperature (25 ° C.), the surface treatment layer formed by the polymer X is also solid at room temperature and has such a strength that breakage does not occur in the surface treatment layer. It is inferred that interfacial adhesion is sufficiently expressed by having the In the present invention, being solid at 25 ° C. is synonymous with indicating that the softening point or the melting point is 30 ° C. or more.
Moreover, while the use of a water-soluble polymer is conventionally used as a surface treatment agent for resin films, the surface treatment agent of the present application is oil-soluble because it has a polypropylene chain which is a hydrophobic group in the molecule. Since the polymer compound is a polymer compound, deterioration of the image can be suppressed even in printing using an oil-soluble developer such as a liquid developer or an inkjet ink.
Therefore, by forming an image on a resin film to which the surface treatment agent of the present invention has been applied in advance, an image which is hard to peel off and hard to deteriorate can be obtained.

  In the polymer X, examples of the polar group containing a nitrogen atom include amino, imino, cyano, azo, diazo and azi groups. As a polar group containing an oxygen atom, a hydroxyl group, a carboxy group, a carbonyl group, an ether group (-O-), an ester group (-COO-) etc. are mentioned. As a polar group containing a nitrogen atom and an oxygen atom, an isocyanate group, a urea group (-NHCONH-), etc. are mentioned. Among these polar groups, at least one selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, and an ester group is preferable from the viewpoint of the fixability between the film and the toner layer. And at least one selected from the group consisting of and ester groups is more preferred.

  Specific examples of the polymer X include polyester resins having a polypropylene chain introduced (polymer X1) and polyalkyleneimines having a polypropylene chain introduced (polymer X2).

  In the polymer X1 (polyester resin introduced with a polypropylene chain), the polyester resin is preferably a polycondensate of an alcohol component containing a dihydric or higher alcohol and a carboxylic acid component containing a dihydric or higher carboxylic acid compound.

  Examples of the divalent alcohol include aliphatic diols, preferably aliphatic diols having 2 to 20 carbon atoms, and more preferably aliphatic diols having 2 to 15 carbon atoms, and Formula (I):

(Wherein, RO and OR are oxyalkylene groups, R is ethylene and / or propylene groups, x and y indicate the average addition mole number of alkylene oxide, and each is a positive number, and x and y are The sum value is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 6 or less, further preferably 4 or less)
The alkylene oxide adduct of bisphenol A represented by these, bisphenol A, hydrogenated bisphenol A etc. are mentioned. Specific examples of the aliphatic diol having 2 to 20 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and the like. Be

  The alcohol component is preferably an alkylene oxide adduct of bisphenol A represented by the formula (I) from the viewpoint of grindability, and the content thereof is preferably 70 mol% or more, more preferably 80 mol in the alcohol component. % Or more, more preferably 90 mol% or more, further preferably 95 mol% or more, further preferably 100 mol%.

  The divalent carboxylic acid compound is a dicarboxylic acid having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, an anhydride thereof, or an alkyl group carbon number And derivatives such as alkyl esters of 1 or more and 3 or less. Specifically, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, an alkyl group having 1 to 20 carbon atoms or Aliphatic dicarboxylic acids such as succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms can be mentioned.

  The carboxylic acid component is preferably terephthalic acid and / or fumaric acid from the viewpoint of improving the low temperature fixability of the toner and improving the dispersion stability of the toner particles to improve the storage stability, and terephthalic acid is more preferable. preferable. The content of terephthalic acid or fumaric acid or the total of both is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% in the carboxylic acid component. The above content is more preferably 95 mol% or more, and further preferably 100 mol%.

  From the viewpoint of adjusting the softening point of the polyester, the alcohol component is a trivalent or higher alcohol, and the carboxylic acid component is a trivalent or higher carboxylic acid compound, provided that the effect of the present invention is not impaired. The content of the raw material monomer having a valence of 3 or more is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1% of the total amount of the alcohol component and the carboxylic acid component. It is less than mol%.

  The alcohol component may appropriately contain a monohydric alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound.

  The equivalent ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less. is there.

  The polyester resin is prepared, for example, by polycondensation of an alcohol component and a carboxylic acid component in an inert gas atmosphere and, if necessary, in the presence of an esterification catalyst, a polymerization inhibitor or the like at a temperature of 180 ° C. to 250 ° C. Can be manufactured.

  Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bis triethanolaminate. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, based on 100 parts by mass of the total of the alcohol component and the carboxylic acid component. Preferably, it is 0.7 parts by mass or less.

  Also, a cocatalyst may be used to shorten the reaction time. Examples of promoters include gallic acid and the like. The amount of co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 100 parts by mass of the total of the alcohol component and the carboxylic acid component. Is 0.3 parts by mass or less. The mass ratio of the cocatalyst to the esterification catalyst (cocatalyst / esterification catalyst) is preferably 0.01 or more and 0.5 or less.

  In the present invention, the polyester resin may be a polyester resin which has been modified to such an extent that the properties thereof are not substantially impaired. As the modified polyester resin, for example, grafting or blocking with phenol, urethane, epoxy or the like according to the method described in JP-A-11-1336668, JP-A-10-239903, JP-A-8-20636, etc. Among the modified polyester resins, a urethane-modified polyester resin in which the polyester resin is urethane-stretched with a polyisocyanate compound is preferable.

  It is preferable to introduce a polypropylene chain after polycondensation of the alcohol component and the carboxylic acid component. The polypropylene chain can be introduced by reacting a polyester resin with polypropylene or the like having a reactive functional group. Examples of the polypropylene having a reactive functional group include terminal maleic anhydride modified polypropylene and copolymers of terminal maleic anhydride modified propylene and other olefins. Among these, from the viewpoint of further improving the fixability to a film, terminal maleic anhydride polypropylene is preferable, and one terminal maleic anhydride modified polypropylene is more preferable. By introducing a maleic anhydride moiety into the polypropylene polymer, the polyester resin and the maleic anhydride modified polypropylene can be linked via an ester bond.

  The polypropylene chain introduced into the polyester resin is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and preferably 30 parts by mass or less, more preferably 22 parts by mass with respect to 100 parts by mass of the polyester resin. It is below.

  In the polymer X1, the number average molecular weight of the polypropylene chain is preferably 300 or more, more preferably 500 or more, still more preferably 700 or more, still more preferably 1,000 or more, from the viewpoint of further improving the fixability to the film. Preferably, it is 50,000 or less, more preferably 30,000 or less, still more preferably 15,000 or less, still more preferably 10,000 or less, still more preferably 8,000 or less.

  In the polymer X2 (polyalkyleneimine introduced with a polypropylene chain), as the polyalkyleneimine, polyethyleneimine, polypropyleneimine, tetraethylenepentamine and the like can be mentioned.

  In the polymer X2, the number average molecular weight of the polyalkyleneimine is preferably 100 or more, more preferably 500 or more, and still more preferably 1,000 or more, from the viewpoint of the adsorptivity to the resin having an acid value. From the viewpoint of the dispersibility and the interaction between the film and the toner, it is preferably 15,000 or less, more preferably 10,000 or less, and still more preferably 5,000 or less.

  The proportion of the polyalkyleneimine in the polymer X2 is preferably 70% by number or more, more preferably 80% by number or more, still more preferably 90% by number in terms of the number of heteroatoms from the viewpoint of dispersion stability and adhesion to a film. The number percentage or more, more preferably 95 number percent or more, further preferably 100 number percent.

  The polypropylene chain can be introduced by reacting a polyalkyleneimine with polypropylene or the like having a reactive functional group. Examples of the polypropylene having a reactive functional group include terminal maleic anhydride modified polypropylene and copolymers of terminal maleic anhydride modified propylene and other olefins. Among these, in view of safety and reactivity, terminal-maleic anhydride polypropylene is preferable, and one-terminal maleic anhydride-modified polypropylene is more preferable.

  In the polymer X2, the number average molecular weight of the polypropylene chain is preferably 300 or more, more preferably 500 or more, still more preferably 700 or more, still more preferably 1,000 or more, from the viewpoint of further improving the fixability to the film. Preferably, it is 50,000 or less, more preferably 30,000 or less, still more preferably 15,000 or less, still more preferably 10,000 or less, still more preferably 8,000 or less.

  The softening point or melting point of the polymer X is preferably 30 ° C. or more, more preferably 45 ° C. or more, still more preferably 60 ° C. or more, still more preferably 80 ° C. or more, from the viewpoint of preventing breakage in the surface treatment layer Is 100 ° C. or higher.

  The content of the polymer X in the surface treatment agent of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, further preferably 100% by mass. %. The surface treatment agent may appropriately contain additives such as an antioxidant and a viscosity modifier as long as the effects of the present invention are not impaired.

  As a method of using the surface treatment agent of the resin film for printing of the present invention containing the polymer X and an embodiment using the surface treatment agent, the following embodiment is further provided.

(A) A resin film for printing, wherein the printing surface of a resin film is coated with the surface treatment agent of the present invention, (B) A toner containing a binder resin and a colorant, and a liquid developer containing an insulating liquid A method of printing an image on a resin film using a resin film having a printing surface covered with the surface treatment agent of the present invention, an image printing method (C) Binder resin and coloring Kit for printing (D) containing a toner developer containing a toner agent and a liquid developer containing an insulating liquid, and a resin film coated on the printing surface with the surface treatment agent of the present invention Printed matter in which the treatment agent layer and the image layer are laminated in this order

  The liquid developer used together with the surface treatment agent of the present invention is not particularly limited as long as it contains a binder resin and toner particles containing a colorant and an insulating liquid, but the binder resin has an acidic group. It is preferable to contain a resin. The resin having an acidic group has good dispersion stability because the dispersant can be adsorbed by the interaction with the basic dispersant for liquid developer.

  Moreover, as a resin film, polyolefin films, such as a polypropylene film, etc. are mentioned.

  The surface treatment agent of the present invention may be applied to a resin film by, for example, dissolving the polymer X in a solvent such as chloroform, a hydrocarbon organic solvent and the like and applying the solution to a resin film and then removing the solvent by drying. it can.

  The layer of the surface treatment agent applied to the resin film is not particularly limited as long as the surface treatment agent substantially covers the entire printing surface of the resin film, but preferably 0.05 μm or more, more preferably 0.2 μm or more, Preferably it is 3 micrometers or less, More preferably, it is 1 micrometer or less.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. Physical properties of the resin and the like were measured by the following methods.

[Softening point of surface treatment agent (polymer X) and binder resin]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger, diameter 1 mm, length 1 mm Push out of the nozzle. The plunger drop amount of the flow tester is plotted against the temperature, and the temperature at which half of the sample flowed out is taken as the softening point.

[Melting point of surface treatment agent (polymer X), binder resin, and dispersant]
Using a differential scanning calorimeter "Q20" (manufactured by TA instruments), measure 0.03 to 0.04 g of a sample in an aluminum pan, and cool it from room temperature to 0 ° C. at a temperature decrease rate of 10 ° C./min. Next, the sample is heated from 0 ° C. to 200 ° C. at a heating rate of 10 ° C./min, and cooled from that temperature to −10 ° C. at a temperature lowering rate of 50 ° C./min. Finally, the sample is heated to 200 ° C. at a heating rate of 10 ° C./min to measure an endothermic peak. Let the endothermic peak top be the melting point.

[Glass transition temperature of surface treatment agent (polymer X) and binder resin]
Using a differential scanning calorimeter “DSC 210” (manufactured by Seiko Instruments Inc.), measure 0.01 to 0.02 g of a sample in an aluminum pan, raise the temperature to 200 ° C., and drop 0 ° at a temperature decrease rate of 10 ° C./min from that temperature. Cool down to ° C. Next, the sample is heated at a temperature rising rate of 10 ° C./min to measure an endothermic peak. The temperature at the intersection of the extension of the baseline below the highest endothermic peak temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak is taken as the glass transition temperature.

[Acid value of binder resin]
It measures by the method of JIS K 0070: 1992. However, only the measurement solvent is changed to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)) from a mixed solvent of ethanol and ether specified in JIS K 0070: 1992.

[Number average molecular weight (Mn) of polyalkyleneimine and polypropylene chain]
The molecular weight distribution is measured by gel permeation chromatography (GPC) method shown below to determine the number average molecular weight.
(1) Preparation of sample solution The sample is dissolved at a concentration of 0.2 g / 100 mL in a solution of Na ₂ SO ₄ dissolved in 1% aqueous acetic acid solution at 0.15 mol / L. Next, this solution is filtered using a fluorine resin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.2 μm to remove insoluble components, and this is used as a sample solution.
(2) Molecular weight measurement A solution of Na ₂ SO ₄ dissolved in a 1% aqueous acetic acid solution at a flow rate of 1 mL per minute was used at 40 ° C. as an eluent using 0.15 mol / L as an eluent using the following measuring device and analysis column. Stabilize the column in a thermostat. Then, 100 μL of the sample solution is injected to perform measurement. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of standard pullulan (P-5 (Mw 5.9 × 10 ³ ), P-50 (Mw 4.73 × 10 ⁴ ), P-200 (Mw 2.12 × 10 5) manufactured by Showa Denko KK). ⁵ ) Use P-800 (Mw 7.08 × 10 ⁵ )) as standard samples. The parentheses indicate the molecular weight.
Measuring device: HLC-8320GPC (made by Tosoh Corporation)
Analysis column: α + α-M + α-M (manufactured by Tosoh Corporation)

[Volume median particle size of toner particles before mixing with insulating liquid]
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter Co., Ltd.)
Aperture diameter: 100 μm
Analysis software: Coulter multisizer Accucomp version 1.19 (manufactured by Beckman Coulter Co., Ltd.)
Electrolyte: Isoton II (manufactured by Beckman Coulter Co., Ltd.)
Dispersion solution: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (glyphin): 13.6) dissolved in electrolyte to adjust to 5% by mass Dispersion conditions: 10 mg of measurement sample in 5 mL of the dispersion Is added, and dispersed for 1 minute with an ultrasonic dispersion machine (machine name: US-1, manufactured by SND Co., Ltd., output: 80 W). Thereafter, 25 mL of the electrolytic solution is added, and the mixture is dispersed for 1 minute with an ultrasonic dispersion machine to prepare a sample dispersion.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolyte so that the particle size of 30,000 particles can be measured in 20 seconds, 30,000 particles are measured, and the volume is determined from the particle size distribution. Determine the median particle size (D ₅₀ ).

[Number-average molecular weight (Mn) of dispersant]
The molecular weight distribution is measured by gel permeation chromatography (GPC) according to the following method to determine the number average molecular weight.
(1) Preparation of Sample Solution A dispersant (distillation of insulating liquid from the dispersant solution) was dissolved in tetrahydrofuran so that the concentration was 0.5 g / 100 mL. Next, this solution was filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components, and used as a sample solution.
(2) Molecular weight distribution measurement Using the following measuring device and analysis column, flow tetrahydrofuran as an eluent at a flow rate of 1 mL per minute, and stabilize the column in a 40 ° C. thermostat. Then, 100 μL of the sample solution is injected to perform measurement. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodispersed polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), manufactured by Tosoh Corporation), A-5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), Those prepared using F-20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), and F-128 (1.09 × 10 ⁶ ) as standard samples are used. The parentheses indicate the molecular weight.
Measuring device: HLC-8220GPC (made by Tosoh Corporation)
Analysis column: TSKgel GMH _XL + TSKgel G3000H _XL (manufactured by Tosoh Corporation)

[Conductivity of Insulating Liquid]
Put 25 g of the insulating liquid into a 40 mL glass sample tube “screw No. 7” (manufactured by Maruem Co., Ltd.), and use the non-aqueous conductivity meter “DT-700” (manufactured by Dispersion Technology) to make the electrode It is immersed in an insulating liquid, and measurement is performed 20 times at 25 ° C. to calculate an average value to measure conductivity. The smaller the value, the higher the resistance.

[Boiling point of insulating liquid]
Using a differential scanning calorimeter “DSC 210” (manufactured by Seiko Instruments Inc.), measure 6.0 to 8.0 mg of the sample in an aluminum pan, raise the temperature to 350 ° C. at a heating rate of 10 ° C./min, and show the endothermic peak taking measurement. The endothermic peak on the highest temperature side is taken as the boiling point.

[Viscosity of Insulating Liquid and Liquid Developer at 25 ° C.]
Put 6 to 7 mL of the measurement solution in a 10 mL screw tube, and use the rotational vibration viscometer "Biscomate VM-10A-L" (Seconik Co., Ltd., detection terminal: made of titanium, φ 8 mm), using the tip of the detection terminal Fix the screw tube at a position where the liquid level is 15 mm above the part, and measure the viscosity at 25 ° C.

Examples 1 and 2
The starting monomers, esterification catalyst and esterification cocatalyst shown in Table 1 are placed in a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser equipped with a dewatering tube, and a nitrogen inlet tube. Polycondensation was performed at 235 ° C. in a mantle heater in a nitrogen atmosphere, and after confirming that the raw material monomers were uniformly melted, the pressure was reduced to 60 torr and dehydration condensation was performed for 1 hour to obtain a polyester resin [PES]. Then, it is cooled to normal pressure 160 ° C., and one end maleic anhydride modified polypropylene [Ma-PP] (X-10065, made by Baker Hughes, Mn: 1000) is added, and further kept at 220 ° C. for 1 hour addition After polymerization, a polycondensation reaction was performed for 2 hours under the conditions of 220 ° C. and 60 torr, and a polymer having physical properties shown in Table 1 was extracted.

Example 3
In a four-neck separable flask, 9 parts by mass of polyethyleneimine 1200 [PEI 1200] (manufactured by Junsei Chemical Co., Ltd., Mn: 3400), maleic anhydride modified polypropylene [Ma-PP] (X-10065, manufactured by Baker Hughes, 59.9 parts by mass of Mn: 1000) and 68.9 parts by mass of xylene were added, and the temperature was raised to 140 ° C. over 1.5 hours while stirring in a nitrogen stream, and the reaction water was distilled off using a Dean-Stark tube. Thereafter, the temperature was raised to 160 ° C. over 2 hours, and the pressure was further reduced to 100 Torr to completely distill off the xylene. After cooling to 100 ° C. and taking it out of the flask, it was solidified on a vat. The sufficiently solidified reaction product at room temperature (25 ° C.) was ground using a lab mixer to recover the polymer. The melting point of the obtained polymer was 90.degree.

Comparative Example 1
150 parts by mass of 1-bromodocosan [C22] (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of polyethyleneimine 1200 [PEI1200] (manufactured by Junsei Chemical Co., Ltd.), dehydrated acetonitrile (into a four-neck separable flask equipped with a cooling pipe) 40 parts by mass of Kojun Pharmaceutical Co., Ltd. and 87 parts by mass of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the temperature was raised to 80 ° C. in a nitrogen stream to carry out a reaction for 24 hours. After completion of the reaction, potassium carbonate residue was removed by a centrifugal separator "3-30KS" (manufactured by Sigma), and the supernatant was distilled off under reduced pressure to obtain a polymer. The melting point of the obtained polymer was 63.degree.

Comparative example 2
In a four-neck separable flask, 11 parts by mass of polyethyleneimine 600 [PEI 600] (manufactured by Junsei Chemical Co., Ltd., molecular weight: 600), maleic anhydride-modified branched polypropylene [branched Ma-PP] (X-10087, Baker Hughes 61.6 parts by mass and 72.6 parts by mass of xylene were added, and the temperature was raised to 140 ° C. over 1.5 hours while stirring in a nitrogen stream, and the reaction water was distilled off using a Dean-Stark tube. Thereafter, the temperature was raised to 160 ° C. over 2 hours, and the pressure was further reduced to 100 Torr to completely distill off the xylene. It cooled to 80 degreeC and took out the polymer from the flask.

Comparative example 3
80 parts by mass of 1-bromododecane [C12] (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of polyethyleneimine 1200 [PEI 1200] (manufactured by Junsei Chemical Co., Ltd.), dehydrated acetonitrile 40 parts by mass of Wako Pure Chemical Industries, Ltd. and 87 parts by mass of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the temperature was raised to 80 ° C. in a nitrogen stream to carry out a reaction for 24 hours. After completion of the reaction, potassium carbonate residue was removed by a centrifugal separator "3-30KS" (manufactured by Sigma), and the supernatant was distilled off under reduced pressure to obtain a polymer.

Production Example of Binder Resin A 10 liter four-necked flask equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, as shown in Table 2 for the alcohol component, carboxylic acid component, esterification catalyst and polymerization inhibitor. The temperature was raised to 230 ° C., and the reaction was carried out for 12 hours, and then the pressure was further reduced to 8.3 kPa and the reaction was carried out for 1 hour to obtain a polyester resin (binder resin A).

Production Example 1 of Dispersant [Dispersant D1]
In a four-neck separable flask, 9 parts by mass of polyethyleneimine 1200 (manufactured by Junsei Chemical Co., Ltd.), 59.9 parts by mass of polypropylene succinic anhydride (Ma-PP) (manufactured by Baker Hughes), and 68.9 parts by mass of xylene The temperature was raised to 140 ° C. over 1.5 hours while stirring in a nitrogen stream, and the reaction water was distilled off using a Dean-Stark tube. Thereafter, the temperature was raised to 160 ° C. over 2 hours, and the pressure was further reduced to 100 Torr to completely distill off the xylene. After cooling to 100 ° C. and taking it out of the flask, it was solidified on a vat. The reaction material solidified sufficiently at room temperature was crushed and collected by a laboratory mixer.

Production Example 2 of Dispersant [Dispersant D2]
50 g of methyl ethyl ketone as a reaction solvent was placed in a 1 L four-necked flask equipped with a cooling pipe, a nitrogen introducing pipe, a stirrer and a thermocouple, and the inside of the reaction vessel was replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a mixture of the raw material monomers shown in Table 4, a polymerization initiator, and 50 g of methyl ethyl ketone was dropped over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the reaction was further allowed to proceed at 80 ° C for 3 hours. The solvent was distilled off at 80 ° C. to obtain a copolymer having physical properties shown in Table 4.

Production example of liquid developer [Liquid developer LT-1, LT-2]
Binder resin A and coloring agent “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., Phthalocyanine Blue 15: 3) in the amounts shown in Table 5 were previously used in a 20 L Henschel mixer at a rotational speed of 1500 r / After stirring and mixing for 3 minutes at min (circumferential velocity 21.6 m / sec), the mixture was melt-kneaded under the following conditions.

(Melting and kneading conditions)
A continuous double-open-roll type kneader "Kinedex" (manufactured by Nippon Coke Industry Co., Ltd., roll outer diameter: 14 cm, effective roll length: 55 cm) was used. The operating conditions of the continuous two open roll type kneader are: high rotation side roll (front roll) circumferential speed 75 r / min (32.4 m / min), low rotation side roll (back roll) circumferential speed 35 r / min (15.0 m) / min), a roll gap of 0.1 mm at the end of the kneaded material supply port side. The temperature of the heating medium and the temperature of the cooling medium in the roll are 130 ° C for the raw material input side of the high rotation side roll and 100 ° C for the kneaded material discharge side, 10 ° C for the raw material input side of the low rotation side roll and 10 ° C for the kneaded material discharge side. there were. The feed rate of the raw material mixture to the kneader was 10 kg / h, and the average residence time in the kneader was about 3 minutes.

The kneaded material obtained above was rolled and cooled with a cooling roll, and then roughly crushed to about 1 mm using a hammer mill. The obtained coarsely pulverized product was finely pulverized and classified by a pneumatic jet mill "IDS" (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain toner particles having a volume median particle size (D ₅₀ ) of about 8 μm.

  The dispersant and the insulating liquid shown in Table 5 were weighed into a container, and the dispersant was completely dissolved in the insulating liquid by hot water bathing and ultrasonic irradiation. Subsequently, zirconia beads and toner particles having a particle diameter of 0.8 mm shown in Table 5 were sequentially added, and pulverized using a paint shaker (manufactured by Asada Iron Works Co., Ltd.). After the particle size of the toner particles reached 2.8 μm, the beads were filtered using a Kiriyama funnel. The filtrate was diluted with an insulating liquid to a toner concentration of 25% by mass to obtain a liquid developer.

The polymer obtained in Examples and Comparative Examples was used as a surface treatment agent, and applied to a polypropylene (PP) film by the following method.
Untreated side of polypropylene (PP) film (biaxially stretched polypropylene film FOR # 25 manufactured by Futamura Chemical Co., Ltd.) using a bar coater (tabletop coating machine TC-1 manufactured by Mitsui Electric Seiki Co., Ltd.) After applying a solution (solution concentration: 2.0 mass%) in which each polymer obtained in Examples and Comparative Examples is dissolved in isoparaffin (Isopar L, manufactured by ExxonMobil, viscosity 1 mPa · s at 25 ° C.) Dried for 3 minutes at ° C. However, when it was difficult to dissolve in isoparaffin at normal temperature, a solution heated to a temperature higher than the melting point or dissolved in chloroform was used. The thickness of the surface treatment agent layer after drying was 0.3 μm.

  The wettability test and the fixing test were conducted by the following method using the PP film coated with the surface treatment agent.

[Wettability test]
On the surface treating agent layer, different Dainpen ^{(EnerDyne TM pens Variety, Enercon Industries} Corporation) surface energy value minus the line 2cm in. After the lapse of 10 seconds, the drawn line did not bounce or shrink, and the maximum value of the dyne pen holding the line was taken as the surface tension of the surface treatment agent layer. The surface tension of the surface treatment agent layer was set to less than 30 mN / m if the lines drawn were not retained for all the dyne pens. The results are shown in Table 6-1.

[Fixing test]
The liquid developer LT-1 was coated on the surface treatment agent layer using a bar coater such that the film thickness after drying was 3.5 μm, and dried at 120 ° C. for 3 minutes.
Immediately after drying, a mending tape “Scotch Mending Tape 810” (manufactured by 3M Japan Co., Ltd., width 18 mm) was attached to the coating, and a weight of 190 g was reciprocated 5 times from the top of the tape. Subsequently, the stuck tape was vigorously peeled off, and finally the image density before and after tape peeling was measured using a colorimetric system (Spectroeye manufactured by X-rite), and the fixing rate was calculated from the following equation.
Further, the fixing test was conducted similarly in the case where the PP film was not coated with the surface treatment agent. The results are shown in Table 6-1.

  Furthermore, in the case of using the liquid developer LT-2 instead of the liquid developer LT-1 in the above-mentioned fixing test, and using the liquid developer LT-2 instead of the liquid developer LT-1, the surface treatment agent The fixing test was carried out in the same manner as in the case where the concentration of the solution was changed to 6.0% by mass and the surface treatment agent layer having a thickness of 0.9 μm was applied. The results are shown in Tables 6-2 and 6-3, respectively.

From the above results, the surface treatment agents of Examples 1 to 3 have the action as a wettability improver for improving the wettability of the resin film, and are good for the liquid developer layer assuming a fixed image. It can be seen that it has adhesive strength.
On the other hand, the surface treatment agents of Comparative Examples 1 and 3 can not adhere a fixed image, and have no effect of improving the wettability of a resin film. On the other hand, although the surface treatment agent of Comparative Example 2 can be used as a wettability improver for a resin film, it does not have adhesiveness to a fixed image.

  The surface treatment agent for a resin film for printing according to the present invention is printing on a resin film using a liquid developer, a dry toner, an inkjet ink or the like in image formation by electrophotography, electrostatic recording, electrostatic printing or the like. Are preferably used.

Claims (7)

  A surface treatment agent for a resin film for printing, comprising a polymer X having a polar group containing at least one of a nitrogen atom and an oxygen atom and a polypropylene chain and being solid at 25 ° C.   The surface treatment agent according to claim 1, wherein the polar group is at least one selected from the group consisting of an amino group, a hydroxyl group, a carboxy group, and an ester group.   The method to use polymer X of Claim 1 or 2 as a surface treatment agent of the resin film for printing.   The resin film for printing by which the printing surface of the resin film was coat | covered with the surface treating agent of Claim 1 or 2.   A method of printing an image on a resin film using a liquid developer containing a toner particle containing a binder resin and a colorant and an insulating liquid, wherein the surface treatment agent according to claim 1 or 2 has a printing surface Method of printing an image using a coated resin film.   A printing kit comprising: a toner developer containing a binder resin and a colorant; a liquid developer containing an insulating liquid; and a resin film coated on the printing surface with the surface treatment agent according to claim 1 or 2 .   A printed material in which a layer of the surface treatment agent according to claim 1 and a layer of an image are laminated in this order on a resin film.