JP2009119772A - Press-bonding paper for inkjet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide press-bonding paper for inkjet recording on which a printed image printed by inkjet printing can exhibit an excellent clearance and water resistance. <P>SOLUTION: This press-bonding paper 1 for inkjet recording has base paper 2, and a bonding layer 3 which is formed at least on one of surfaces of the base paper 2. The bonding layer 3 is constituted by applying a bondable composition containing a pressure-sensitive adhesive, an inorganic filler and an ink fixative on the base paper 2. The ink fixative is a cationic polymer which is obtained by making third class amines, second class amines and epihalohydrine react with one another by a mole ratio of 1:1.2 to 5:1.8 to 5.5. Also, the ink fixative contains the cationic polymer for which the viscosity of a solution having a concentration of 60 wt.% of the cationic polymer at a temperature of 25°C reaches 10 to 100 mPa s. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive paper for ink-jet recording used for so-called pressure-sensitive postcards.

In recent years, the confidentiality of personal information has become important, and the demand for crimped postcards has increased.
Such a crimped postcard generally prints necessary information on a crimped postcard paper having an adhesive surface that exhibits adhesiveness by pressurization, and the adhesive surface is crimped by applying pressure by folding the paper. It is produced by configuring in a form. The pressure-sensitive postcard paper is required to have clearness of printing, and quality that the printed image is difficult to be transferred when the adhesive surface is peeled off.

By the way, conventionally, a laser printer has been used for printing on the pressure-bonded postcard paper. However, when printing is performed using a laser printer, heating is required, and there is a problem that an unpleasant odor is generated at the time of heating, and the pressure-bonding property of the pressure-bonded postcard paper tends to be lowered.
Therefore, in recent years, ink jet printing using water-soluble ink has been adopted.

In addition to the quality naturally required for pressure-bonded paper, the pressure-sensitive paper for ink-jet recording is required to have excellent clarity and water resistance of aqueous ink printing by ink-jet printing.
Such a pressure-sensitive adhesive paper for ink-jet recording contains a pressure-sensitive adhesive, a fine particle filler, and an ink fixing agent. As the ink fixing agent, an alkylamine / epichlorohydrin polycondensate having a quaternization rate of 84% or more is used. A pressure-sensitive postcard paper for ink-jet recording, which is obtained by coating the surface of the adhesive layer composition used, has been developed (see Patent Document 1).
In addition, a pressure-sensitive adhesive paper for inkjet using an adhesive composition comprising a cold sealant, a fine mineral powder, and a polydimethylamine epichlorohydrin and / or a modified dimethylamine epichlorohydrin condensate has been developed (patent) Reference 2).

JP 2007-237550 A Japanese Patent Application Laid-Open No. 10-52985

  However, the conventional pressure-sensitive adhesive paper for ink-jet recording has not yet been satisfactory in print clarity and water resistance. In particular, when printing is performed in full color, there are problems that the printing becomes unclear and the durability against water tends to be insufficient.

  The present invention has been made in view of such conventional problems, and is intended to provide a pressure-sensitive adhesive paper for ink jet recording in which a printed image printed by ink jet printing can exhibit excellent sharpness and water resistance. To do.

In a first aspect of the present invention, there is provided a pressure-sensitive adhesive paper for ink jet recording having a base paper and an adhesive layer formed on at least one surface of the base paper.
The adhesive layer is formed by applying an adhesive composition containing a pressure sensitive adhesive, an inorganic filler, and an ink fixing agent to the base paper,
The ink fixing agent is a cationic polymer obtained by reacting tertiary amines, secondary amines, and epihalohydrins in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively. And a pressure-sensitive adhesive paper for ink-jet recording comprising the cationic polymer having a viscosity of 10 to 100 mPa · s at a temperature of 25 ° C. in a 60 wt% aqueous solution of the cationic polymer. (Claim 1).

A second invention is a pressure-sensitive adhesive paper for ink-jet recording having a base paper and an adhesive layer formed on at least one surface of the base paper.
The adhesive layer is formed by applying an adhesive composition containing a pressure sensitive adhesive, an inorganic filler, and an ink fixing agent to the base paper,
The ink fixing agent is prepared by reacting tertiary amines, secondary amines, and epihalohydrins in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively, and further to a quaternizing agent. A cationic polymer obtained by reacting the cationic polymer with a viscosity of 10 to 100 mPa · s at a temperature of 25 ° C. in a 60 wt% aqueous solution of the cationic polymer. The pressure-sensitive adhesive paper for ink jet recording.

The most notable point in the pressure-sensitive adhesive paper for ink jet recording of the first invention and the second invention is that the fixing agent contains the cationic polymer.
That is, in the first invention, the ink fixing agent comprises a tertiary amine, a secondary amine, and an epihalohydrin in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively. The cationic polymer obtained by reacting at a temperature of 25 wt. C. in a 60 wt% aqueous solution of the cationic polymer contains the cationic polymer having a viscosity of 10 to 100 mPa · s.
In the second aspect of the invention, the ink fixing agent contains a tertiary amine, a secondary amine, and an epihalohydrin in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively. A cationic polymer obtained by further reacting with a quaternizing agent, wherein the cationic polymer has a viscosity of 10 to 100 mPa · s at a temperature of 25 ° C. in a 60 wt% aqueous solution of the cationic polymer. Contains.

Therefore, in the pressure-sensitive adhesive paper for ink jet recording according to the first and second inventions, the adhesive layer containing the ink fixing agent exhibits excellent sharpness and water resistance with respect to ink for ink jet printing. Can do. In particular, it is excellent in sharpness and water resistance for full-color printing.
The ink fixing agent has almost no amine odor. Therefore, it is possible to prevent the working environment from deteriorating when the adhesive composition is applied to the base paper to form the adhesive layer.

  As described above, according to the first and second aspects of the invention, it is possible to provide a pressure-sensitive adhesive paper for ink jet recording in which a printed image when printed by ink jet printing can exhibit excellent sharpness and water resistance. .

The pressure-sensitive adhesive paper for ink-jet recording of the present invention has the above base paper and the above adhesive layer formed on the surface of the base paper.
As the base paper, various papers applicable to inkjet printing can be employed.
The pulp materials for the base paper include kraft pulp, bleached or unbleached pulp of chemical pulp such as sulfite pulp, bleached or unbleached pulp of high yield pulp such as groundwood pulp, mechanical pulp and thermomechanical pulp, and newspaper Examples include pulp such as waste paper, magazine waste paper, cardboard waste paper, and deinked waste paper.

  Fillers, dyes, rosin sizing agents for acidic papermaking, sizing agents for alkyl ketene dimer neutral papermaking, rosin sizing agents for neutral papermaking, dry paper strength enhancers such as polyacrylamide, polyamide epichloro Additives such as a wet paper strength enhancer such as hydrin, a yield improver, a freeness improver, and an antifoaming agent can be used as necessary.

The adhesive layer is formed by applying an adhesive composition containing a pressure sensitive adhesive, an inorganic filler, and an ink fixing agent to the base paper.
Examples of the coating machine for applying the adhesive composition (coating solution) to the base paper include a size press, a film press, a gate roll coater, a blade coater, a calendar, a bar coater, a knife coater, and an air knife coater. Can be mentioned. Moreover, it can also coat on the base paper surface with a spray coater.

The adhesive composition can contain a binder, an auxiliary agent and the like in addition to the pressure-sensitive adhesive, the inorganic filler, and the ink fixing agent.
Specifically, the adhesive composition may include, if necessary, starches such as oxidized starch, phosphate esterified starch, cationized starch, and amphoteric starch, celluloses such as carboxymethylcellulose, polyvinyl alcohols, and polyacrylamides. Water-soluble polymers such as, synthetic polymer latex and the like can be added.
After the application of the adhesive composition, the adhesive layer can be formed, for example, by drying. Specifically, the product is air-dried or conditioned in an atmosphere of a predetermined temperature and humidity, and commercialized.

  The adhesive composition preferably has a property in which the pressure-sensitive adhesive, the inorganic filler, the ink fixing agent, and the auxiliary agent are dissolved and / or dispersed in a solvent such as water. . In this case, coating on the base paper is facilitated. As the solvent at this time, as shown in the examples to be described later, it is possible to use a solvent of an ink fixing agent that is generally produced in a solution state such as an aqueous solution at the time of production, and a solvent such as water is added if necessary. Can be added.

Moreover, it is preferable that the said adhesive layer contains the solid content of the said adhesive composition with a basic weight of 3-15 g / m < ² > (Claim 10).
When the basis weight is less than 3 g / m ² , the above-mentioned pressure-sensitive adhesive paper for ink-jet recording may not be able to exhibit sufficient adhesiveness but may not be able to sufficiently exhibit water resistance and print sharpness. . On the other hand, when it exceeds 15 g / m ² , the adhesive strength becomes too high, and there is a possibility that peeling after adhesion may be difficult. The solid content of the adhesive composition is a residual component when the adhesive composition is dried on the base paper and the solvent is evaporated.

The adhesive layer may contain 50 to 200 parts by mass of the inorganic filler and 5 to 70 parts by mass of the cationic polymer of the ink fixing agent with respect to 100 parts by mass of the pressure-sensitive adhesive. Item 9). When the inorganic filler is less than 50 parts by mass, the anti-blocking property is lowered, or the adhesive strength when the ink-jet recording pressure-bonded paper is bonded between the adhesive layers becomes too strong, and peeling becomes difficult. There is a risk. On the other hand, when the amount exceeds 200 parts by mass, the adhesive strength is lowered, and there is a possibility that peeling is likely to occur.
Further, when the amount of the cationic polymer of the ink fixing agent is less than 5 parts by mass, there is a possibility that the pressure-sensitive adhesive paper for ink jet recording cannot exhibit sufficient water resistance and print sharpness. On the other hand, when it exceeds 70 mass parts, there exists a possibility that adhesive strength may fall and it may become easy to peel.
In the blending ratio of the adhesive layer, the amount of the pressure-sensitive adhesive is the amount of the adhesive component, that is, the component (component other than the solvent and the volatile component) remaining after drying. It is the amount of the cationic polymer, that is, the amount of components (components other than the solvent and volatile components) remaining after drying.

The pressure-sensitive adhesive is an adhesive that does not exhibit adhesiveness at normal temperature and normal pressure, but exhibits adhesiveness when pressurized. As such a pressure-sensitive adhesive, for example, the same adhesive as disclosed in JP-A-2005-105258 and JP-A-2006-28706, or a commercially available one can be employed.
As said inorganic filler, the fine particle filler etc. which are disclosed by Unexamined-Japanese-Patent No. 2005-105258, Unexamined-Japanese-Patent No. 2006-28706, etc. are employable, for example.
In addition to the pressure-sensitive adhesive, the inorganic filler, and the ink fixing agent, the adhesive composition includes, for example, binders disclosed in JP-A-2005-105258 and JP-A-2006-28706. Resins and the like can be contained. That is, in the inkjet recording pressure-sensitive paper of the present invention, the configurations other than the ink fixing agent are the inkjet recording pressure-bonding disclosed before the filing of this application, such as JP-A-2005-105258 and JP-A-2006-28706. The configuration can be similar to that of paper.

  The ink fixing agent contains the cationic polymer, and the cationic polymer includes, as described above, a tertiary amine (a), a secondary amine (b), and an epihalohydrin (c). Is a cationic polymer obtained by the reaction.

  Examples of the tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, dimethylbenzylamine, methyldibenzylamine, diethylbenzylamine, ethyldibenzylamine, di-n-propyl. Benzylamine, n-propyldibenzylamine, di-n-butylbenzylamine, n-butyldibenzylamine, tribenzylamine and the like can be employed. These tertiary amines can be used individually by 1 type, or can also be used in combination of 2 or more type. Of these, trimethylamine is particularly preferred.

  Examples of the secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dibenzylamine, methylethylamine, and methyl. -N-propylamine, methyl-n-butylamine, methylbenzylamine and the like can be employed. These secondary amines can be used individually by 1 type, or can also be used in combination of 2 or more type. Of these, dimethylamine is preferred.

Preferably, the tertiary amine is trimethylamine, and the secondary amine is dimethylamine.
Since these amines can be obtained industrially at low cost, in this case, the manufacturing cost of the above-mentioned pressure-sensitive adhesive paper for ink jet recording can be reduced.

  As the epihalohydrins, for example, epichlorohydrin, epibromohydrin, methyl epichlorohydrin, methyl epibromohydrin and the like can be employed. These epihalohydrins can be used individually by 1 type, or 2 or more types can also be mixed and used for them. Among these epihalohydrins, epichlorohydrin is particularly preferable from the viewpoint of commercial availability and reactivity.

The molar ratio of the tertiary amines (a), the secondary amines (b), and the epihalohydrins (c) is a: b: c = 1.0: 1.2 to 5.0: It is 1.8-5.5, Preferably it is a: b: c = 1.0: 1.5-5.0: 2.0-5.5. More preferably, it is 1.0: 1.5-2.5: 2.0-3.0. Within this range, the ink fixing agent exhibits desired water resistance and print sharpness, and the above-mentioned pressure-sensitive adhesive paper for ink jet recording excellent in water resistance and print sharpness can be easily obtained. Good product manufacturing becomes difficult.
In particular, in the present invention, as shown in Table 1, the molar ratio of (a), (b) and (c) is preferably an integer multiple. Actually, even if it is not a strict integer multiple, a good product can be easily obtained as long as it is within 20%, preferably within 10%. It is most common to use the number of moles of epihalohydrins (c) obtained by adding 1 to the number of moles of secondary amines (b).

In addition, the content of 1,3-dihalo-2-propanol that can be generated as a by-product during the reaction of the tertiary amines, the secondary amines, and the epihalohydrins is 300% by weight with respect to the cationic polymer. It is preferable to employ the above-described ink fixing agent of not more than ppm.
When the content of 1,3-dihalo-2-propanol exceeds 300 ppm by weight, the fixing agent may be toxic.

The ink fixing agent preferably contains the cationic polymer in which the ratio of quaternized amino groups measured by colloid titration is 90 mol% or more based on the total amino groups. ). More preferably, it is 95 mol% or more.
When the ratio of the quaternized amino group is less than 90 mol%, the ink fixing agent cannot exhibit the desired water resistance and print sharpness, and the water resistance of the pressure-sensitive adhesive paper for ink jet recording can be reduced. There is a possibility that the sharpness of printing may be deteriorated. Further, the amine odor remains in the polymer of the ink fixing agent, and the working environment may be deteriorated. In order to increase the quaternization rate, epihalohydrin may be used slightly more. However, if the amount is too large, the amount of 1,3-dihalo-2-propanol produced as a by-product increases, which causes a problem. In some cases, as in the second invention, after the reaction of the tertiary amines, secondary amines, and epihalohydrins, it can be further reacted with a quaternizing agent. Examples of the quaternizing agent include 3-chloro-2-hydroxypropyltrimethylammonium chloride (Yokkaichi Synthesis Co., Ltd .: CTA-65), glycidyltrimethylammonium chloride (Yokkaichi Synthesis Co., Ltd .: GTA-80), methyl chloride, Ethyl chloride, 3-bromo-2-hydroxypropyltrimethylammonium bromide, etc. can be used.

  The cationic polymer has a viscosity of 10 to 100 mPa · s at 25 ° C. in a 60% by weight aqueous polymer solution. Preferably it is 20-60 mPa * s. When the viscosity is outside the range of 10 to 100 mPa · s, the molecular weight of the cationic polymer is too small or too large, and the ink fixing agent may not be able to exhibit desired water resistance and print sharpness. The viscosity is measured at a polymer concentration of 60% by weight. For example, when this is converted to a concentration of 30% by weight, it corresponds to about 5 to 9 mPa · s.

The ink fixing agent preferably has a pH adjusted to 3 to 7 at a temperature of 25 ° C. (Claim 5).
When the pH exceeds 7, the amine odor of the ink fixing agent may become strong. On the other hand, when it is less than 3, the stability of the ink fixing agent is deteriorated, and for example, when it is stored for a long period of time, its characteristics may be easily deteriorated. Further, there is almost no need to set the pH to 3 or less during the production of the ink fixing agent, and there is a risk that the amount of neutralizing agent (acid) used will be increased. More preferably, the pH is 4-6.

An acid can be used to adjust the pH after the reaction between tertiary amines, secondary amines, and epihalohydrins. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and boric acid, and organic acids such as formic acid, acetic acid, lactic acid, citric acid, maleic acid, oxalic acid, and benzoic acid. be able to. Hydrochloric acid is preferable. These acids can also be used in combination of two or more. In the above acid, when phosphoric acids are used, the polymer aqueous solution after the reaction with tertiary amines, secondary amines, and epihalohydrins can exhibit an anticorrosive action when stored in an iron container or tank. it can. Therefore, the ink fixing agent is preferably adjusted to the pH range with an acid containing at least phosphoric acids.
In some cases, phosphoric acids can be additionally added after the desired pH adjustment with hydrochloric acid is completed. Examples of usable phosphoric acids include hypophosphorous acid, acidic phosphate, and polyphosphoric acid in addition to the above.

  Therefore, phosphoric acids can be added for pH adjustment, and other acids can be used for pH adjustment, and phosphoric acids can be added additionally. If phosphoric acids are finally added to the ink fixing agent, the phosphoric acids can serve as an anticorrosive as described above. Therefore, the ink fixing agent preferably contains phosphoric acids as an anticorrosive agent.

The ink fixing agent preferably contains 100 ppm by weight or more of the phosphoric acid in terms of an equimolar number of phosphoric acid with respect to the weight of the cationic polymer.
If it is less than 100 ppm by weight, there is a possibility that a sufficient anticorrosive effect cannot be exhibited. Regarding the phosphoric acid conversion amount, for example, when 230 wt ppm of NH ₄ H ₂ PO ₄ (formula 115) is used as phosphoric acid, this is converted to an equimolar number of H ₃ PO ₄ (formula 98). This corresponds to 196 ppm.

Next, the method for synthesizing the cationic polymer will be described in more detail.
The method for synthesizing the cationic polymer is particularly preferably a method in which a mixture of tertiary amines and secondary amines is used as a bed solution, and epihalohydrins are gradually added thereto. Conversely, there is a method in which epihalohydrins are used as a bedding solution and a mixture of tertiary amines and secondary amines is added thereto. In some cases, tertiary amines and secondary amines may be added separately in a plurality of times, not as a mixture, and epihalohydrins may be divided and used. A tertiary amine and a secondary amine are usually used in an aqueous solution of about 30 to 60% by weight, and epihalohydrins are used by themselves without dilution. Therefore, the reaction medium is usually an aqueous solvent and can be carried out without using a special solvent, but an organic solvent such as alcohol, ester, ether or the like may be appropriately mixed and used as necessary.

  There are no particular limitations on the reaction temperature and reaction time, but in short, it is only necessary that the unreacted raw material is almost consumed. Consumption of the reaction raw material can be detected by viscosity increase, pH change, inorganic halogen recovery, gas chromatography analysis, and the like. The reaction temperature is usually selected from the range of 50 to 120 ° C, preferably 60 to 90 ° C. It is also preferable to perform the ripening reaction by dropping while cooling to 50 ° C. or less and raising the temperature to 60 ° C. or more after completion of the dropping. The higher temperature is preferable for increasing the reaction rate, but when the reaction temperature exceeds the above range, coloring of the reactant becomes a problem. The reaction time is usually 1 to 24 hours, preferably 2 to 20 hours. In particular, it is preferable to select a time when almost no unreacted epihalohydrins (b) are present. It is preferable that almost no unreacted tertiary amines (a) and secondary amines (b) remain. If it remains, the odor of the resulting water resistance improver becomes worse. Since the reaction proceeds satisfactorily even without a catalyst, it is usually carried out in the absence of a catalyst, but an alkali (NaOH or KOH) may be added as necessary.

  The pressure-sensitive adhesive paper for inkjet recording can be produced by applying the adhesive composition containing the pressure-sensitive adhesive, the inorganic filler, and the ink fixing agent to the base paper.

Hereinafter, although an example and a comparative example are given and an embodiment of the present invention is described, the present invention is not limited to the following example. % Means% by weight unless otherwise specified.
First, measurement of physical properties of the ink fixing agent used in this example will be described.

1. Solution Viscosity of Cationic Polymer An aqueous solution having a cationic polymer concentration of 60% by weight was measured at 25 ° C. using a B-type viscometer and expressed in mPa · s unit. When the synthesized polymer concentration exceeds 60% by weight, the concentration is adjusted by diluting with pure water. When the concentration is less than 60% by weight (for example, sample e1 described later), the concentration is adjusted to 60% by dehydration.

2. Measurement method of quaternization rate The following colloid titration method was followed.
(1) Adjust the sample to pH 4 (adjusted with 0.5% sulfuric acid) and pH 10 (adjusted with 1.0% caustic soda).
(2) Add 3-4 drops of toluidine blue indicator.
(3) Titrate with 1/400 N polyvinyl potassium sulfate solution (PVS solution). (4) The end point is a point where the color changes from blue to magenta.
(5) Perform a blank test at the same time.
(6) Colloidal equivalent (meq / g) = (A−B) × f × 0.0025 / S
A: 1/400 P.D. required for this test. V. S. Amount of K solution (ml)
B: 1/400 P.D. required for the blank test. V. S. Amount of K solution (ml)
f: 1 / 400P. V. S. Factor of K solution S: Sampling amount (g)
The measurement result of pH 4 shows the amount of total amine, and when pH 10 it shows the amount of quaternary amine. (7) Quaternization ratio = colloid equivalent at pH 10 / colloid equivalent at pH 4 × 100

3. Measurement method of DCH (1,3-dichloro-2-propanol) Gas chromatography analysis: A known amount of an internal standard substance is added and extracted with a solvent, followed by measurement with a capillary GC and calculation by the internal standard method.

4). Odor measurement method A beaker is weighed so that the cationic polymer in the aqueous cationic polymer solution is constant (0.5 g), and the beaker is covered with aluminum foil. Next, it heats for 2.5 minutes with a 120 degreeC jet oven, Then, a gas detection pipe | tube (made by Gastex company: for ammonia) is stabbed into an aluminum foil part, and a density | concentration (ppm) is measured.

Example 1
First, an ink fixing agent is prepared as follows.
That is, first, 200.0 g of a dimethylamine aqueous solution with a concentration of 50 wt% (dimethylamine amount: 2.218 mol) and a concentration of 30% in a glass autoclave with a capacity of 1000 ml equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube. 291.0 g of trimethylamine aqueous solution (amount of trimethylamine: 1.477 mol) was charged, 274.0 g (2.961 mol) of epichlorohydrin was introduced over 2 hours while cooling to 40 ° C. after nitrogen substitution, and at the same temperature. Hold for 1 hour. Next, the temperature was raised to 80 ° C., and further aging was performed for 3 hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5 with 77.0 g of hydrochloric acid having a concentration of 35 wt% and 0.82 g of phosphoric acid having a concentration of 75 wt% (730 wt ppm with respect to the cationic polymer obtained after the reaction). Was adjusted to 0.0, and 840.0 g of an ink fixing agent containing a cationic polymer having a concentration of 58% by weight and a quaternization rate of 91% was obtained. This is designated as sample e1. The yield in this example was 99.7%.
The ink fixing agent of this example contains a cationic polymer having a viscosity of 21 mPa · s when the concentration is 60% by weight aqueous solution (cationic polymer aqueous solution). Moreover, the content of 1,3-dichloro-2-propanol (DCH) was less than 100 ppm by weight. The pH of the reaction product before pH adjustment was 12. For sample e1, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 2 below.

Next, examples and comparative examples in which an ink fixing agent is prepared with a different composition from that in Example 1 will be described.
(Example 2)
First, in an autoclave similar to that in Example 1, 200.0 g of a 50 wt% dimethylamine aqueous solution (dimethylamine amount: 2.218 mol) and 218.5 g of a 30 wt% trimethylamine aqueous solution (trimethylamine amount: 1.109). Mol) 257.0 g (2.777 mol) of epichlorohydrin was introduced over 2 hours while charging and cooling to 40 ° C. after nitrogen substitution, and maintained at the same temperature for 1 hour, and further heated to 80 ° C. 3 Aged for hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5.0 with 54.5 g of 35 wt% hydrochloric acid and 0.92 g of 75 wt% phosphoric acid, and the cationic polymer concentration was 60 wt%. The ink fixing agent was obtained by diluting with pure water. This is designated as sample e2. The viscosity of the cationic polymer in sample e2 was 36 mPa · s. For sample e2, the formulation (preparation composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 2 below.

(Example 3)
First, in an autoclave similar to that in Example 1, 200.0 g of a 50 wt% dimethylamine aqueous solution (dimethylamine amount: 2.218 mol) and 174.8 g of a 30 wt% trimethylamine aqueous solution (trimethylamine amount: 0.887). Mole) 246.0 g (2.659 mol) of epichlorohydrin was introduced over 2 hours while charging and cooling to 40 ° C. after nitrogen substitution, maintained at the same temperature for 1 hour, and further heated to 80 ° C. 3 Aged for hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5.0 with 46.2 g of hydrochloric acid with a concentration of 35 wt% and 0.87 g of phosphoric acid with a concentration of 75 wt%, and the cationic polymer concentration was 60 wt%. The ink fixing agent was obtained by diluting with pure water. This is designated as sample e3. The viscosity of the cationic polymer in sample e3 was 40 mPa · s. The pH of the reaction product before pH adjustment was 10.5. For sample e3, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 2 below.

Example 4
First, in an autoclave similar to that in Example 1, 200.0 g of a 50 wt% dimethylamine aqueous solution (dimethylamine amount: 2.218 mol) and 145.7 g of a 30 wt% trimethylamine aqueous solution (trimethylamine amount: 0.739). Mole) 239.0 g (2.583 mol) of epichlorohydrin was introduced over 2 hours while charging and cooling to 40 ° C. after nitrogen substitution, maintained at the same temperature for 1 hour, and further heated to 80 ° C. 3 Aged for hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5.0 with 38.5 g of hydrochloric acid having a concentration of 35 wt% and 0.82 g of phosphoric acid having a concentration of 75 wt%, and the cationic polymer concentration was further 60 wt%. The ink fixing agent was obtained by diluting with pure water. This is designated as sample e4. The viscosity of the cationic polymer in sample e4 was 48 mPa · s. For sample e4, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 2 below.

(Example 5)
First, in an autoclave similar to that in Example 1, 200.0 g of a 50 wt% dimethylamine aqueous solution (extra dimethylamine: 2.218 mol) and 145.7 g of a 30 wt% trimethylamine aqueous solution (amount of trimethylamine: 0.739) Mole) 239.0 g (2.583 mol) of epichlorohydrin was introduced over 2 hours while charging and cooling to 40 ° C. after nitrogen substitution, maintained at the same temperature for 1 hour, and further heated to 80 ° C. 3 Aged for hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 4.0 with 38.5 g of hydrochloric acid with a concentration of 35 wt% and 1.6 g of phosphoric acid with a concentration of 75 wt%, and the cationic polymer concentration was 60 wt%. The ink fixing agent was obtained by diluting with pure water. This is designated as sample e5. The viscosity of the cationic polymer in sample e5 was 48 mPa · s. For sample e5, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 2 below.

(Example 6)
First, in an autoclave similar to that in Example 1, 200.0 g of a 50 wt% dimethylamine aqueous solution (dimethylamine amount: 2.218 mol) and 291.0 g of a 30 wt% trimethylamine aqueous solution (trimethylamine amount: 1.477). Mol) 274.0 g (2.961 mol) of epichlorohydrin was introduced over 2 hours while charging and cooling to 40 ° C. after nitrogen substitution, maintaining at the same temperature for 1 hour, and further raising the temperature to 80 ° C. 3 Aged for hours. Next, after cooling to room temperature (25 ° C.), the pH is adjusted to 5.0 with 77.0 g of hydrochloric acid having a concentration of 35 wt%, and further diluted with pure water so that the concentration of the cationic polymer becomes 60 wt%. An ink fixing agent was obtained. This is designated as sample e6. The viscosity of the cationic polymer in sample e6 was 20 mPa · s. From the comparison between this example and Example 1, it is understood that the pH of 5.0 can be adjusted only by 77.0 g of hydrochloric acid having a concentration of 35 wt% without using 0.82 g of phosphoric acid having a concentration of 75 wt%. For sample e6, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 3 below.

(Example 7)
First, an aqueous cationic polymer solution (ink fixing agent in Example 1) having a cationic polymer concentration of 58% and a quaternization ratio of 91% was prepared in exactly the same manner as in Example 1. Thereafter, 6.4 g (0.022 mol) of 3-chloro-2-hydroxypropyltrimethylammonium chloride and 4.7 g (0.022 mol) of glycidyltrimethylammonium chloride as a quaternizing agent were added to the obtained cationic polymer aqueous solution. And stirred at 60 ° C. for 2 hours. In this way, an ink fixing agent was obtained. This is designated as sample e7. The pH of the sample e7 was 4.8, and the quaternization rate of the cationic polymer reached 99%. Moreover, the solution viscosity rose to 23 mPa · s. For sample e7, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 3 below.

(Comparative Example 1)
First, 200.0 g of dimethylamine aqueous solution with a concentration of 50 wt% (dimethylamine amount: 2.218 mol) and trimethylamine with a concentration of 30 wt% were added to a 1000 ml glass autoclave equipped with a stirrer, thermometer, and nitrogen gas introduction tube. Charged 655.6 g (amount of trimethylamine: 3.327 mol), introduced 307.8 g (3.326 mol) of epichlorohydrin over 2 hours while cooling to 40 ° C. after nitrogen substitution, and kept at the same temperature for 1 hour The mixture was further heated to 80 ° C. and aged for 3 hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5.0 with hydrochloric acid to obtain an ink fixing agent having a cationic polymer concentration of 60 wt%. This is designated as sample c1. The viscosity of the cationic polymer in sample c1 was 15 mPa · s. For sample c1, the formulation (preparation composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 3 below.

(Comparative Example 2)
First, after replacing with nitrogen in a glass autoclave having a capacity of 1000 ml with a stirrer, a thermometer, and a nitrogen gas inlet tube, 200.0 g (dimethylamine amount: 2.218 mol) of a dimethylamine aqueous solution having a concentration of 50 wt% was charged. While cooling to 0 ° C., 46.2 g (0.443 mol) of hydrochloric acid having a concentration of 35 wt% was introduced. Subsequently, 164.2 g (1.775 mol) of epichlorohydrin was introduced at the same temperature over 2 hours and aged at 80 ° C. for 2 hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5.0 with hydrochloric acid, and further diluted with pure water so that the cationic polymer concentration was 60 wt%, to obtain an ink fixing agent. This is designated as sample c2. The viscosity of the cationic polymer in sample c2 was 50 mPa · s. For sample c2, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 3 below.

(Comparative Example 3)
First, after replacing with nitrogen in a glass autoclave having a capacity of 1000 ml with a stirrer, a thermometer, and a nitrogen gas inlet tube, 200.0 g (dimethylamine amount: 2.218 mol) of a dimethylamine aqueous solution having a concentration of 50 wt% was charged. While cooling to ° C., epichlorohydrin was introduced over 20 hours in 205.0 g (2.215 mol) and aged at 80 ° C. for 2 hours. Next, after cooling to room temperature (25 ° C.), the pH was adjusted to 5.0 with hydrochloric acid, and further diluted with pure water so that the cationic polymer concentration was 60 wt% to obtain an ink fixing agent. This is designated as sample c3. The viscosity of the cationic polymer in sample c3 was 1100 mPa · s. For sample c3, the formulation (prepared composition), pH, polymer concentration (at 60% concentration), quaternization rate, viscosity (mPa · s), odor, and DCH content at the time of preparation are shown in Table 3 below.

(Application examples)
In this example, a pressure-sensitive adhesive paper for ink-jet recording was prepared using the ink fixing agents (sample e1 to sample e7 and sample c1 to sample c3) obtained in Examples 1 to 7 and Comparative Examples 1 to 3, respectively, and the evaluation was made. Is an example of
As shown in FIGS. 1 to 4, the pressure-sensitive adhesive paper 1 for ink-jet recording of this example has a base paper 2 and an adhesive layer 3 formed on at least one surface thereof. The adhesive layer 3 is formed by coating the base paper 2 with an adhesive composition containing at least a pressure-sensitive adhesive, an inorganic filler, and an ink fixing agent. In this example, as the ink fixing agent, each sample obtained in Examples 1 to 7 and Comparative Examples 1 to 3 is used. In this example, the adhesive composition includes a composition containing a binder and an auxiliary agent (dispersant, antifoaming agent, wetting agent) in addition to the pressure-sensitive adhesive, the inorganic filler, and the ink fixing agent. Use.

  The pressure-sensitive adhesive paper 1 for ink-jet recording in this example is used as a so-called pressure-bonded postcard. After printing is performed on the adhesive layer 3 by ink jet printing, as shown in FIGS. 3 and 4, the pressure-sensitive adhesive paper 1 for ink jet recording is folded, the adhesive layers 3 are overlapped with each other, and pressed to bond the bonding surfaces. be able to.

Hereinafter, the manufacturing method of the pressure-sensitive adhesive paper for inkjet recording of this example will be described.
First, a methyl methacrylate grafted natural rubber adhesive ("Flutite FB672IJ" manufactured by Mitsui & Co. Solvent Coating Co., Ltd.) was prepared as a pressure sensitive adhesive, and silica (manufactured by Tosoh Silica Co., Ltd.) as an inorganic filler. Nipgel AY-603 ") was prepared, and partially saponified polyvinyl alcohol (" NK-05R "manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was prepared as a binder. In addition, as an auxiliary agent, a dispersant (“Emulgen A-60” manufactured by Kao Corporation), an antifoaming agent (“SN deformer 480 manufactured by San Nopco Co., Ltd.), a wetting agent (Daiichi Kogyo Seiyaku Co., Ltd.) "Neocol SW-C")) made by the manufacturer was prepared.

  Next, with respect to 100 parts by mass of the adhesive component of the pressure-sensitive adhesive, 80 parts by mass of the inorganic filler and 40 parts by mass of the ink fixing agent (each sample e1 to e7 or each sample c1 to c3) in terms of the cationic polymer amount, 25 parts by mass of the binder, 1 part by mass of the dispersant, 2 parts by mass of the antifoaming agent, and 2 parts by mass of the wetting agent were mixed to obtain 10 types of adhesive compositions. The blending amount of the dispersant, antifoaming agent, and wetting agent is the same as that of the pressure-sensitive adhesive and the ink fixing agent, that is, the amount of solid components, that is, the remaining components after drying (other than the solvent and volatile components that evaporate during drying). Component). These ten types of adhesive compositions are the same except that the types of ink fixing agents used are different.

Next, each adhesive composition was applied to a postcard paper, and the coated surface was dried. Application was performed so that the solid content in each adhesive composition was 9 g / m ^{2 in} basis weight. In this way, as shown in FIGS. 1 and 2, the adhesive layer 3 is formed on the surface of the base paper 2 (postcard paper), and ten types of pressure-sensitive adhesive papers 1 (samples E1 to E7 and samples C1 to C1) are formed. Sample C3) was prepared. Note that the pressure-sensitive recording papers for ink jet recording of Samples E1 to E7 and Samples C1 to C3 were prepared using the ink fixing agents of Samples e1 to e7 and Samples c1 to c3, respectively. Table 4 shows the composition and the like of each pressure-sensitive adhesive paper for ink jet recording.

Next, evaluation of print sharpness and water resistance was performed on the pressure-sensitive recording papers (Sample E1 to Sample E7 and Sample C1 to Sample C3) produced in this example.
(Print sharpness evaluation test)
Ink made by Kodak Versamarks, ie, black (black # 2003), magenta (magenta # 2002), cyan (cyan # 2001), and yellow (yellow # 2014) inks, respectively, are sample E1 to sample E7. Samples C1 to C3 were solidly printed by inkjet printing, and after drying, the density was measured using a Macbeth densitometer (RD-920). As the ink jet printer, “PIXUS 560I” manufactured by Canon Inc. was used. The five levels shown below with the printing density of the pressure-bonded paper (sample C2) prepared using an ink fixing agent containing a copolymer of dimethylamine and epichlorohydrin as the cationic polymer as a reference (relative value 100) Evaluation was performed. The results are shown in Table 5 below.

The evaluation criteria for print sharpness are as follows.
A: considerably higher than dimethylamine / epichlorohydrin (relative value over 105).
○: higher than dimethylamine / epichlorohydrin (relative values 101 to 105).
Δ: Same as dimethylamine / epichlorohydrin (relative value 100).
X: Lower than dimethylamine epichlorohydrin (relative value 95 to 99).
XX: considerably lower than dimethylamine / epichlorohydrin (relative value less than 95)

(Water resistance evaluation test)
Similar to the print clarity evaluation test, each ink was solid printed by inkjet printing on the pressure-sensitive papers of Samples E1 to E7 and Samples C1 to C3. After drying for 1 hour, each sample after printing is immersed in 25 ° C. ion exchange water for 1 minute, and the presence or absence of printing blur and the state thereof are observed with the naked eye. Went. The results are shown in Table 5 below.

The evaluation criteria for water resistance are as follows.
A: Printing blur does not occur.
○: Slight bleeding occurs.
Δ: There is a printing blur, but there is no problem in use.
X: There is a printing blur and there is a problem in use.
XX: Printing bleeding is severely unusable.

In this example, the transfer of the printed image after pressure bonding was examined for each of the pressure-sensitive recording papers (samples E1 to E7 and samples C1 to C3).
(Transcription evaluation test)
First, pattern printing (characters and solids) was performed by an ink jet printer on a half region on one side of the adhesive layer surface of each ink jet recording pressure-sensitive adhesive paper. Printing was performed in an indoor room at 20 ° C. and 65% RH using an inkjet printer (PIXUS 560I manufactured by Canon Inc.) filled with ink of each color. Subsequently, it was left to stand for 30 minutes to dry. Next, each pressure-bonded paper 1 after printing was folded so that the adhesive layers 3 overlap each other (see FIGS. 3 and 4). At this time, the half area on which printing was performed and the other area on which printing was not performed were uniformly overlapped. Subsequently, the joint surface was pressure-bonded with a dry sealer. Thereafter, the joint surface was peeled by hand, and the presence or absence and degree of ink transfer to a region where printing was not performed were visually determined. The results are shown in Table 5 below.

The evaluation criteria for transcription are as follows.
○: Ink transfer is not observed at all.
Δ: Ink transfer is slightly observed, but there is no practical problem.
X: The ink is transferred and is not practical.

  As is known from Table 5, Sample E1 to Sample E7 were practically satisfactory levels for both the print sharpness and water resistance. On the other hand, the sample C1 and the sample C3 have a problem in use in terms of water resistance against the black ink. In addition, Sample C2 showed clearly low characteristics as compared with Samples E1 to E7, although the print clarity and water resistance were at levels that were not problematic in practice. As for the transfer of printing, all of Samples E1 to E7 and Samples C1 to C3 showed excellent results.

It is considered that the reason why the difference between the sample E1 to the sample E7 and the sample C1 to the sample C3 in the sharpness and water resistance of the printing is as described above is in the ink fixing agent.
That is, Samples E1 to E7 are obtained by reacting tertiary amines, secondary amines, and epihalohydrins in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively. An ink fixing agent containing the cationic polymer having a viscosity of 10 to 100 mPa · s at a temperature of 25 ° C. in a 60 wt% aqueous solution of the cationic polymer was used. On the other hand, in sample C1 to sample C3, an ink fixing agent containing a cationic polymer deviating from the above range was used.
Therefore, it can be seen that by using an ink fixing agent containing a cationic polymer that satisfies the above conditions, a pressure-sensitive adhesive paper for ink jet recording excellent in print sharpness and water resistance can be constituted.

The perspective view which shows the whole press-bonding paper for inkjet recording concerning an Example (application Example). Sectional drawing of the crimping | compression-bonding paper for inkjet recording concerning an Example (application Example). Explanatory drawing which shows a mode that the pressure-sensitive adhesive paper for inkjet recording concerning an Example (application Example) is bent by making the adhesive layer side into an inner side. Explanatory drawing which shows the state which folded the pressure-sensitive adhesive paper for inkjet recording concerning an Example (application Example).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Crimp paper for inkjet recording 2 Base paper 3 Adhesive layer

Claims (10)

In the pressure-sensitive adhesive paper for ink-jet recording having a base paper and an adhesive layer formed on at least one surface of the base paper,
The adhesive layer is formed by applying an adhesive composition containing a pressure sensitive adhesive, an inorganic filler, and an ink fixing agent to the base paper,
The ink fixing agent is a cationic polymer obtained by reacting tertiary amines, secondary amines, and epihalohydrins in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively. A pressure-sensitive adhesive paper for ink-jet recording comprising the cationic polymer having a viscosity of 10 to 100 mPa · s at a temperature of 25 ° C. in a 60 wt% aqueous solution of the cationic polymer. In the pressure-sensitive adhesive paper for ink-jet recording having a base paper and an adhesive layer formed on at least one surface of the base paper,
The adhesive layer is formed by applying an adhesive composition containing a pressure sensitive adhesive, an inorganic filler, and an ink fixing agent to the base paper,
The ink fixing agent is prepared by reacting tertiary amines, secondary amines, and epihalohydrins in a molar ratio of 1: 1.2 to 5: 1.8 to 5.5, respectively, and further to a quaternizing agent. A cationic polymer obtained by reacting the cationic polymer with a viscosity of 10 to 100 mPa · s at a temperature of 25 ° C. in a 60 wt% aqueous solution of the cationic polymer. Pressure-sensitive adhesive paper for inkjet recording.   3. The cationic polymer according to claim 1, wherein a content of 1,3-dihalo-2-propanol which can be generated as a by-product upon reaction of the tertiary amine, the secondary amine and the epihalohydrin is the cationic polymer. A pressure-sensitive adhesive paper for ink-jet recording, which employs 300 ppm by weight or less of the above ink fixing agent.   4. The cationic polymer according to claim 1, wherein the ratio of the quaternized amino groups measured by colloid titration is 90 mol% or more based on all amino groups. 5. A pressure-sensitive adhesive paper for ink-jet recording.   The pressure-sensitive adhesive paper for ink jet recording according to any one of claims 1 to 4, wherein the ink fixing agent has a pH adjusted to 3 to 7 at a temperature of 25 ° C.   6. The pressure-sensitive adhesive paper for ink-jet recording according to claim 5, wherein the ink fixing agent is adjusted to the pH range with an acid containing at least phosphoric acids.   The pressure-sensitive adhesive paper for ink jet recording according to any one of claims 1 to 6, wherein the ink fixing agent contains phosphoric acids as an anticorrosive agent.   The pressure-sensitive adhesive paper for ink jet recording according to any one of claims 1 to 7, wherein the tertiary amine is trimethylamine, and the secondary amine is dimethylamine.   The adhesive layer according to any one of claims 1 to 8, wherein the adhesive layer includes 50 to 200 parts by mass of the inorganic filler and 100% by mass of the cationic polymer of the ink fixing agent with respect to 100 parts by mass of the pressure-sensitive adhesive. A pressure-sensitive adhesive paper for ink-jet recording, containing 5 to 70 parts by mass. According to any one of claims 1 to 9, the adhesive layer, an ink jet recording crimping paper, wherein the basis weight 3 to 15 g / m ² containing solids of the adhesive composition.

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