JPH09250096A - Printing paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain printing paper provided with printability/handleability by a forms rotary press, having high ink absorbing capacity, high ink absorbing rate, high resolution and high colorability for water-soluble ink to be used in ink jet printers, with printed water-soluble ink set in the paper layer and presenting high resistance to water, thus esp. suitable to ink jet printers. SOLUTION: This printing paper is so designed that the outer layer and/or inner layer of the pulp fiber basal paper contains a compound prepared by reaction between (a) a dibasic carboxylic acid and (b) a polyakylene polyamine in the molar ratio a/b of 1:(1.1-1.5) to form a polyamide polyamine which is, in turn, reacted with (c) an epihalohydrin in the molar ratio b/c of 1:(1.1 to 1.8).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to recording sheets. More specifically, the present invention has both recording suitability by an inkjet recording system using a water-soluble ink, printing suitability by a foam press, etc., and recording suitability by an electrophotographic system, and further, after recording by the inkjet recording system. The present invention relates to a recording paper having water resistance such that the recording of the water-soluble ink does not bleed by rain or drinking water.

[0002]

2. Description of the Related Art Today, the amount of bills, direct mails, etc., to be mailed to homes, offices, etc. is enormous. For billing statements, direct mail, etc., standard forms such as ruled lines and designs are printed on form paper,
Individual information such as an address and a bar code is printed on the form. Up to now, printing of a standard form and printing of individual information have been performed separately. That is, the customer selects by bidding a printing company that will print the ruled lines and designs of the standard form, and the selected printing company prints the form on the form paper with the offset type rotary press, aiming at the sewing machine, A certain form that has been processed such as marginal punch is created and delivered to the customer, and the customer uses the NIP such as the laser beam printer.
(Non-impact printer) is used to print individual information and mail it. The form paper used in this method is suitable for printing a fixed form by a form rotary press, and cutting it into a predetermined paper width to create a constant form. b) It is necessary to have suitability for use, etc. Therefore, quality design of foam paper is performed from the papermaking stage. The printability and workability of (a) are the requirements required to perform form printing continuously at a high speed with a roll of paper at the printing processing stage, and to perform subsequent processing such as perforations and marginal punches. There
There are no paper mess, no stain on the plate, and little wear of the blade such as the sewing machine blade. As measures against paper gusset, adjustments are made to eliminate grammage, moisture, and paper thickness unevenness by adjusting the lip opening of the inlet in the width direction and by automatic control with a BM meter. As for the externally added size part, starch, PV
The surface strength of the paper is measured by the wax pick test (JIS P
9129), the sizing agent is added internally and / or externally so that the paper does not lose water due to dampening water during printing. There is. Further, as a measure for preventing wear of the sewing machine blade and the like, the content of the filler such as calcium carbonate, talc, and clay internally added to the paper is set to 10% by weight or less. The aptitude for use in (b) is a requirement that the end user who is a customer needs when printing individual information, and is the laser beam type N.
There are no expansion and contraction of the paper at the time of IP printing, sufficient printability, no electrostatic damage, and no inclination. If the expansion and contraction of the paper is large, it will lead to a shift of the digits from the ruled lines of the form during printing. Therefore, it is necessary to set the freeness of the pulp fiber to 400 cc or more to prevent the expansion and contraction of the paper. Also,
To obtain sufficient printability, smoothness should be at least 2.
It is necessary to set the time to 0 seconds or more, and in order to prevent electrostatic damage, that is, paper jam due to static electricity, a conductive agent is mixed with starch or PVA applied to the front and back surfaces of the paper to reduce the electric resistance value. It is necessary to manage. Further, in the case of printing with NIP such as a laser beam, the heat received from the heat roll may shrink the paper and cause an oblique tilt phenomenon in which the folds after printing are not uniform. To prevent this,
The freeness is set to be high and the fiber orientation angle is at least within 0 ± 5 ° so that the paper does not warp even if the paper shrinks. In a method in which a printing company creates a standard form using a form rotary press using such paper, and then the customer prints individual information using the NIP, printing and processing of the form,
Since the process of printing individual information and mailing will be spread over between the two companies, it will take time and effort from the form creation to the shipping, leading to higher costs.

Under the circumstances, a system in which an ink jet printer is connected to an offset type rotary press has been developed. This makes it possible to continuously and consistently perform printing, printing of individual information, and necessary processing at one place, from the aspect of maintaining confidentiality of data and high-speed and inexpensive processing, such as printing and processing. It is expected that the process of recording individual information and the process of mailing can be changed to the system separated at two places. Ink jet printers used in this system are generally those in which water-soluble ink is ejected as fine droplets by various operating principles and adhered to recording paper such as paper to form dots for recording.
It can be said to be suitable for printing individual information on a form because it has features such as low noise, easy multicoloring, and high flexibility in recording patterns. In general, an inkjet printer recording sheet using a water-soluble ink is required to have good ink absorbability in the thickness direction of the recording sheet and high ink absorption speed as printability. There is. As a result, it is possible to prevent the occurrence of phenomena such as ink droplets flowing out from the recording surface after printing, and after printing, the water-soluble ink spreads laterally in the vicinity of the printing surface of the paper and oozes out, and the recorded image becomes thick and It is possible to maintain high colorability even in multicolor printing without causing deterioration, and further, the printed water-soluble ink is transferred to the metal roll provided immediately after the exit of the microwave dryer of the inkjet printer. Therefore, the transferred water-soluble ink will not be retransferred to the paper and cause paper stain. Therefore, the foam paper used in this system needs to have at least printability in a foam rotary press and printability in an inkjet printer. When the above-mentioned foam paper is used in this system, printing on the foam rotary press is performed well, but when printing with an inkjet printer, the paper will not be lost due to dampening water during printing. By the action of the sizing agent added and / or externally added, the absorption of the water-soluble ink of the ink jet printer to the paper is hindered, the phenomenon such as outflow of ink droplets occurs, and the printed water-soluble ink is It is not completely dried by the wave and is transferred to the metal roll provided immediately after the exit of the microwave dryer of the inkjet printer, and the transferred water-soluble ink is retransferred to the paper and causes paper stains. It will reduce the value of the form in which the information is printed. In addition, even if the individual information is clearly printed by this system, the starch, P, etc. applied to the front and back surfaces of the paper as a measure to prevent plate stains.
Chemicals such as VA exist in the outer layer without penetrating the inside of the paper by the sizing agent added internally and / or externally so that the paper is not lost by the dampening water during printing. Moreover, since these do not have water resistance, when the printed surface on which the water-soluble ink is printed comes into contact with water such as rain or drinking water due to the use of paper, the water-soluble ink is dissolved along with the elution of starch, PVA and the like. Also elutes and causes bleeding, making it impossible to read the printed information, or if the printed information form is a barcode, it becomes impossible to read the barcode.
There is a drawback in that the printing information may be meaningless, and it has not been sufficiently satisfactory to use the conventional foam paper in a foam printing system incorporating the above-mentioned inkjet printer.

By the way, some proposals have been made so far regarding the absorbability and water resistance of the water-soluble ink of the ink jet recording paper. For example, JP-A-52-53
No. 012 discloses that the surface of a substantially unsized paper base paper to which a wet paper strength enhancer is added almost uniformly is coated with a paint for ordinary surface coating, and the inside of the paper base paper is Ink jet recording paper made of a water-based ink that has been penetrated into the ink is described. Further, in JP-A-53-49113, a surface of a wood pulp paper sheet in which a fine powdery urea-formalin resin component and a wet strength enhancer component are mixed is impregnated with a water-soluble polymer. Ink jet recording papers using water-based inks are described. Although these inkjet recording papers have good water-soluble ink absorbency, the ink density is not sufficient because the area around the dots is easily blurred and the ink penetrates deep into the paper layer. When water was applied to the surface, the print was blurred or disappeared, and the water resistance was insufficient. Further, these ink jet recording papers are not particularly considered for printability with respect to oil-based inks, and thus cannot be said to have sufficient form printability. Increasing the water resistance of ink jet recording paper using water-soluble ink has also been studied. For example, JP-A-55-53591 discloses a water-soluble dye having a salt of a sulfonic acid group and / or a carboxyl group in a molecule on a recording surface formed by spraying a water-soluble metal salt. The recording medium liquid containing the liquid is deposited in a droplet state,
It is described that the dye is formed into a salt insoluble in water to form a water-resistant recorded image, and JP-A-56-84
Japanese Patent No. 992 describes an inkjet recording medium containing a polycationic polyelectrolyte. However, even with these materials, the water resistance of the water-soluble ink is not sufficiently satisfactory, and
Foam printability with oil-based inks is not always sufficient.

[0005]

[Problems to be solved by the invention]
Equipped with printing suitability with an inkjet printer using water-soluble ink and printing suitability with a rotary press,
It is the current situation that a recording sheet for water-resistant foams, which does not allow water-soluble ink records after printing with an inkjet printer to bleed by rain or drinking water, has not yet been developed. . Under such circumstances, the development of a recording paper which has printability and workability by a foam rotary press, good printability by an inkjet printer using a water-soluble ink, and high water resistance after printing is desired. There is.

[0006]

The inventor of the present invention has made extensive studies and found that good printability by an ink jet printer using a water-soluble ink and high water resistance after printing are obtained. To achieve this, a cationic reaction product that allows the printed water-soluble ink to penetrate into the paper layer and further causes the penetrated water-soluble ink to completely fix in the paper layer is added to the base paper and And / or it has been found that it is necessary to apply it externally, which also leads to the required surface strength, internal strength,
Printing / processing suitability such as rigidity, toner fixability, fiber orientation,
It was concluded that it does not adversely affect NIP printing suitability such as dimensional stability, and based on this, the present invention was completed. That is, the present invention provides printing and workability by a foam rotary press, and further has high ink absorption capacity, high ink absorption speed, high resolution, and high chromaticity with respect to a water-soluble ink used in an inkjet printer, and is printed. As a recording paper particularly suitable for an ink jet printer in which a water-soluble ink is fixed in a paper layer and exhibits high water resistance, a reaction product of polyamide polyamine and epihalohydrin is contained in an outer layer and / or an inner layer of a pulp fiber base paper. It is characterized by what is done.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In order to incorporate a reaction product of polyamide polyamine and epihalohydrin into the outer layer of pulp fiber base paper, external addition coating or impregnation using a size press or the like can be carried out. Can be done by doing. FIG. 1 shows coating layers (2) and (2) in which a reaction product of polyamide polyamine and epihalohydrin is externally applied to both outer layers of a pulp fiber base paper (1).
A cross-sectional view of a recording sheet (3) having a sheet is shown.

As a reaction product of a polyamide polyamine and epihalohydrin, a dibasic carboxylic acid (a) and a polyalkylene polyamine (b) are prepared (a) :( b) = 1:
Epihalohydrin (c) was added to the polyamide polyamine obtained by reacting at a molar ratio of 1.1 to 1.5, and (b) :( c) = to the polyalkylene polyamine (b).
A compound obtained by reacting at a molar ratio of 1: 1.1 to 1.8 is preferable. The reaction product of polyamide polyamine and epihalohydrin is described in JP-B-35-3547 and
It can be obtained by the known method described in JP-B-46-7607. That is, a polyamide polyamine may be first synthesized from a dibasic carboxylic acid and a polyalkylene polyamine, and then the polyamide polyamine may be dissolved in water and reacted with epihalohydrin. The reaction between the dibasic carboxylic acid and the polyalkylene polyamine is a dehydration condensation reaction, and is 140 ° C to 200 ° C, preferably 150 ° C to 1
Perform in the range of 80 ° C. The reaction molar ratio between the dibasic carboxylic acid and the polyalkylene polyamine is 1 dibasic carboxylic acid.
0.8 to 2.0 of polyalkylene polyamine per mole
A molar range is preferable, and a 1.1-1.5 mol range is particularly desirable. The reaction ratio of polyalkylene polyamine is 0.
When it is less than 8 mol, the cation equivalent of the polyhalogenated polyalkylenepolyamine reaction product becomes low, which lowers the ink absorbability, which is not preferable, and when it exceeds 2.0 mol, the amount of unreacted polyalkylenepolyamine in the polyamidepolyamine is low. Undesirably increases. The obtained polyamide polyamine is dissolved in water, pH is adjusted to 7 to 11, and epihalohydrin is reacted in the range of 30 ° C to 80 ° C. The reaction molar ratio of epihalohydrin was 0.5 with respect to the polyalkylene polyamine used for the polyamide polyamine.
The range is preferably from 2.2 to 2.2 mol, and particularly preferably from 1.1 to 1.8 mol. The reaction ratio of epihalohydrin is 0.
If it is less than 5 mol, sufficient water resistance cannot be obtained, and if it exceeds 2.2 mol, the ink absorbency is lowered, which is not preferable. The obtained reaction product is preferably acidified using hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or the like in order to impart storage stability. As the dibasic carboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid,
Aliphatic dibasic carboxylic acids such as itaconic acid and aromatic dibasic carboxylic acids such as isophthalic acid and terephthalic acid can be used. Among them, adipic acid is used because of its ink absorbency, water resistance and economical efficiency. Is preferred. Polyalkylene polyamine has two primary amino groups in the molecule,
And a polyalkylenepolyamine having at least one secondary amino group, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, minobispropylamine, and 3-azahexane-1,6-diamine. Of these, diethylenetriamine is preferable among them from the viewpoints of ink absorbency, water resistance, economy, and little yellowing of the paper. Examples of epihalohydrin include epichlorohydrin and epibromhydrin, and epichlorohydrin is preferable from the economical viewpoint.

The pulp fiber base paper used in the present invention is preferably made of 100% L-BKP pulp.
Not only virgin pulp but also used paper and N-BKP can be blended within a range that does not affect the suitability as foam paper. And, it is preferable to use a freeness of 400 to 530 cc. Freeness is 400cc
When it is less than the above range, the dimensional stability is deteriorated when used as a foam paper, which may cause a shift in the girder or a tilt. In addition, the oil absorbency of the paper becomes poor, and the settability (dryability) of the oil-based ink used in offset printing becomes poor. When the freeness exceeds 530 cc, the degree of fibrillation of pulp fibers due to beating is small and the surface strength becomes weak, which causes plate stains. Further, as the filler to be added internally, an absorbent filler of water-soluble ink is used, and calcium carbonate, talc, clay, synthetic silica or the like can be used, but the content in the pulp fiber base paper is 2 It is preferably set to 10% by weight. These fillers may be used alone or in combination. When the content exceeds 10% by weight, the blades such as perforations and marginal punches are severely worn during foam processing, which makes continuous processing impossible for a long time. In addition, the paper-making paper strength of the paper is lowered, and the dehydration property is deteriorated, which deteriorates the operability, which is not preferable. If the content of the filler is less than 2% by weight, the opacity of the paper is lowered and the absorbability of the water-soluble ink is deteriorated, which is not preferable. The addition of the internally added sizing agent is effective in controlling the liquid absorbency in a coating device such as a size press that exerts a size effect on a papermaking machine, and it is possible to use a material that has little change in sizing property immediately after papermaking. Neutral rosin sizing is preferred for neutral formulations and rosin emulsion sizing is preferred for acidic formulations. The content of the internally added sizing agent in the pulp fiber base paper is preferably 0.07 to 0.56% by weight in the case of the neutral rosin sizing agent,
It is particularly desirable that the content be 0.21 to 0.42% by weight.
Also, in the case of rosin emulsion sizing agent,
0.50% by weight is preferable, and 0.10 to 0.30% by weight is particularly desirable. Neutral rosin sizing agent
If the content of the rosin emulsion sizing agent is less than 0.05% by weight, the water-soluble ink permeates into the inside of the recording paper to lower the print density on the surface of the recording paper and cause strikethrough. Is not preferable. If the content of the neutral rosin sizing agent exceeds 0.56% by weight and that of the rosin emulsion sizing agent exceeds 0.50% by weight, the absorbability of the water-soluble ink into the paper layer becomes poor and the water resistance of the ink becomes poor. Is not preferable. Also, a known amount of a size fixer such as a sulfuric acid band, a paper strength enhancer such as cationic starch, a pitch remover such as talc, and a pH control agent such as caustic soda, which are known as other chemicals, should be internally added to the pulp stock solution. You can Note that the paper strength enhancer may be applied not only internally but also externally applied if necessary.

When the reaction product of the polyamide polyamine and epihalohydrin reacted at the above molar ratio is externally applied to or impregnated with the pulp fiber base paper, the total amount of the reaction product as a solid content is 1. 0-5.0 g / m ² ,
Desirably, it is contained in both sides of the paper making so as to be 1.5 to 3.0 g / m ² and dried. When the reaction product is contained in both sides of the paper within this range, the water resistance of the water-soluble ink after printing can be obtained. The total amount of the reactants is 1.
When it is less than 0 g / m ² , the water resistance of the water-soluble ink is deteriorated, and when it comes into contact with water, it causes bleeding in printing, which is not preferable. When the total amount of the reaction product exceeds 5.0 g / m ² , the drying load in the after-dryer becomes large and the operability is deteriorated, which is not preferable. When the reaction product is externally applied to the pulp fiber base paper, it is made into an aqueous solution and, if necessary, a commonly used binder such as corn starch, oxidized starch, tapioca starch, PVA, CM.
C, mixed with other cellulose derivatives, and coated on the base paper with a size press, roll coater, or other type of coater.

The externally added sizing agent is used by mixing it with the reaction product of the above-mentioned polyamide polyamine and epihalohydrin,
Cationic surface sizing agents that do not affect the reactants are preferred. The anionic surface sizing agent is not preferable because it causes a chemical reaction with the above-mentioned reactant which is cationic and aggregates. The total amount of the cationic surface sizing agent as solid content is 0.010 to 0.082 g / m ² , preferably 0.01.
It is contained in both sides of the papermaking paper so as to be 6 to 0.057 g / m ² and dried. Total amount of solids is 0.010g
If it is less than / m ² , the water-soluble ink after inkjet printing spreads laterally in the vicinity of the paper surface and oozes out, resulting in a thick recorded image (characters and image bleeding failure), which is not preferable. If the total amount of solids exceeds 0.082 g / m ² , it is not preferable because the absorbability of the water-soluble ink into the paper layer becomes poor and the water resistance of the ink becomes poor. Needless to say, a nonionic surface sizing agent can be used as the externally added sizing agent.

Here, a recording paper containing a reaction product of a polyamide polyamine and epihalohydrin in an outer layer and / or an inner layer of a pulp fiber base paper has printability and workability by a foam rotary press and is used for an ink jet printer. It has a high ink absorption capacity, a high ink absorption rate, a high resolution, and a high color property for the water-soluble inks that are printed, and the reason why the printed water-soluble ink is fixed in the paper layer and exhibits high water resistance is Although not necessarily clear, it is considered that the reaction product has a cation group, a halohydrin group which is a reactive group, and an azetidinium group in the molecule.
That is, in printing with a foam rotary press, by incorporating the reaction product in the outer layer and / or the inner layer of the pulp fiber base paper, the inking property and setting property of the oil-based ink are improved, and good printing / workability is improved. It is supposed to be shown. Further, a water-soluble ink for ink jet comprising a direct dye or an acid dye having an anion group is applied, and the anion group of the water-soluble ink forms an ionic bond with the cation group of the reactant and is fixed on the paper. Therefore, it is considered that the water-soluble ink exhibits high ink absorption capacity, high ink absorption speed, high resolution, and high chromaticity. Then, by microwave drying after printing with an inkjet printer, the halohydrin group in the reaction product, and the azetidinium group react with the amino group having active hydrogen in the dye and the sulfone group to insolubilize the dye itself in water. It is presumed that the water-soluble ink will be completely fixed in the paper layer, and high water resistance will be imparted to rain and drinking water.

[0013]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing examples. Of course, the present invention is not limited to the examples below. In the examples,% means “% by weight” unless otherwise specified. In the following examples, three types of polyamide polyamine epihalohydrin shown as reactants I, II, and III below were used as the reaction products of polyamide polyamine and epihalohydrin. <Reactant I> Adipic acid 43 in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser.
8 g (3 mol) and 412 g (4 mol) of diethylenetriamine were added, dehydration condensation was performed at 150 to 160 ° C. for 4 hours, and 108 g (6 mol) of generated water was removed to the outside of the system.
After cooling the reaction product to 120 ° C., water was added to obtain a polyamide polyamine aqueous solution having a solid content of 25%. Next, sulfuric acid was added to the obtained polyamide polyamine aqueous solution to adjust the pH to 8.5, and then the mixture was cooled to 30 ° C. and 555 g of epichlorohydrin
(6 mol) was added over 5 hours. During this time, the temperature inside the flask was maintained at 30 to 50 ° C. After the addition of epichlorohydrin was completed, the reaction was continued by further stirring at the same temperature for 5 hours. After adjusting the pH to 5 with sulfuric acid, add water to obtain a solid content of 3
A reaction product I having 0% and a viscosity of 65 cp (25 ° C.) was obtained.

<Reactant II> Similar to the method for obtaining the reactant I except that 140 g (1 mol) of adipic acid, 123.6 g (1.2 mol) of diethylenetriamine, and 148 g (1.6 mol) of epichlorohydrin were used. The reaction product II having a solid content of 30% and a viscosity of 80 cp (25 ° C.) was obtained.

<Reaction product III> 123.2 g of adipic acid
(0.8 mol), diethylenetriamine 92.7 g
(0.9 mol), and epichlorohydrin 101.8
g (1.1 mol) and using hydrochloric acid instead of sulfuric acid.
Reactant III was obtained with 0% and a viscosity of 96 cp (25 ° C).

(Example 1) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and a neutral rosin sizing agent as an internal sizing agent () in a stock solution of L-BKP 100% and a freeness of 470 cc. NT
-83, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed and stirred so that the content of the filler in the base paper was 3.5% and the neutral rosin sizing agent was 0.28%, and papermaking was performed with a twin wire paper machine. Reactant I and starch (corn starch, manufactured by Shikishima Starch Co., Ltd.), surface sizing agent (SS
-362 (manufactured by Japan PMC Co., Ltd.) is mixed with water and agitated to prepare a coating solution which is externally applied by a coating device, and the total solid content of the externally added chemicals as shown in Example 1 of Table 1 is 3 .17 g /
m ² , of which reactant I is 2.20 g / m ² and surface sizing agent is 0.03 g / m ²
A recording sheet having a thickness of 100 μm and a g / m ² was obtained.

A sheet of recording paper with B made by Canon
Using J-220JS, printing was performed with SHQ (super high quality) with a large amount of ink and a high image density, and the printability by the inkjet method was evaluated for the following 1) to 5). 1) "Ink absorbency" was evaluated by whether or not solid printing was performed and that part was already dry after 5 seconds of printing. ◯: The ink is absorbed in the paper and the printed surface does not shine. X: Ink remains on the paper surface and the printed surface is shiny. 2) "Bleeding of letters and images" was evaluated by printing letters and numbers and visually observing whether the outlines of the letters and numbers were clear. ◯: Good x: Poor 3) “Strike-through” was evaluated by observing whether or not the ink was bleeding out on the back side of the solid print portion. ◯: No strike-through X: There is strike-through 4) “Ink density” was evaluated by measuring the density of the solid print portion with an ink densitometer (X-Rite 404 color reflection densitometer, manufactured by Nippon Lithographic Equipment). ◯: Ink density 1.20 or more ×: Ink density 1.20
Less than 5) "Ink water resistance" is printed with solid letters, alphabets, and numbers, and after printing, it is left in a hot air dryer at 105 ° C for 3 minutes. Thereafter, the printed sheet was immersed in water at 25 ° C. for 30 seconds, and the degree of ink bleeding after immersion was visually evaluated. ○: No bleeding ×: There is bleeding 6) The form printability was evaluated by “wax pick”. The wax pick is measured according to the method of using wax of JIS P 8129, and the wax strength is 1
It was evaluated by whether or not it was 1 A or more. ◯: 11 A or more and X: less than 11 A 7) PPC suitability was evaluated by “toner fixing property”.
The test was carried out using a FT-3350 copying machine manufactured by Ricoh Co., Ltd.
After the mending tape was attached to the paper copied under the condition of ° C; 53% RH, the tape was peeled off, and the state of the toner on the adhesive surface of the tape was visually observed. ◯: Toner is not collected. X: Toner is taken. 8) The Steckigt sizing degree was measured in accordance with JIS P 8122.

(Example 2) 100% L-BKP and 470 cc freeness pulp stock solution were mixed with talc (D) as a filler.
N Talc, manufactured by Fuji Talc Industry Co., Ltd., rosin emulsion sizing agent as internal sizing agent (AL104, Japan PMC)
(Made by the same company) was mixed and stirred so that the content of the filler in the base paper was 5.0% and the rosin emulsion sizing agent was 0.15%. A coating solution prepared by mixing and stirring a sizing agent (SS-362, manufactured by Nippon PMC Co., Ltd.) in water was externally applied in the same manner as in Example 1. Table 1 shows the basis weight of the obtained recording paper, the paper thickness, and the total solid content of externally added chemicals. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 1.

Example 3 L-BKP 100% freeness 470 cc pulp stock solution was mixed with synthetic alumina sodium silicate (Tixolex 17, KOFRAN C) as a filler.
HEMICAL), a neutral rosin sizing agent (NT-83, Arakawa Chemical Industry Co., Ltd.) as an internally added sizing agent, the filler content in the base paper is 4.3%, and the neutral rosin sizing agent is 0.3%.
The reaction product I was added to the base paper obtained by mixing and stirring to 0%.
II and polyacrylamide (Surftop 100H, manufactured by Japan PMC), and a surface sizing agent (SS-362,
A coating solution prepared by mixing and stirring (manufactured by Japan PMC) in water was externally applied in the same manner as in Example 1. Table 1 shows the basis weight of the obtained recording paper, the paper thickness, and the total solid content of externally added chemicals.
The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 1.

(Example 4) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and AKD sizing agent (AS-) as an internal sizing agent in a pulp stock solution of L-BKP 100% and a freeness of 470 cc. Two
61, manufactured by Japan PMC Co., Ltd., the content of the filler in the base paper is 3.
The reaction product I and starch (corn starch, corn starch,
Shikishima Starch Co., Ltd., surface sizing agent (SS-36)
The coating liquid prepared by mixing and stirring (2, manufactured by Japan PMC Co., Ltd.) in water was externally applied in the same manner as in Example 1. Table 1 shows the basis weight of the obtained recording paper, the paper thickness, and the total solid content of externally added chemicals. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 1.

Example 5 L-BKP 100% freeness 470 cc pulp stock solution, light calcium carbonate (Tamapearl TP-121-6S, Okutama Kogyo Co., Ltd.) as a filler, neutral rosin sizing agent as an internal sizing agent ( NT
-83, manufactured by Arakawa Chemical Industry Co., Ltd., and polyacrylamide (Harmide EX-35) for internal addition as an internal addition paper strength enhancer.
N, manufactured by Harima Kasei Co., Ltd.) so that the content of the filler in the base paper is 4.2%, the neutral rosin sizing agent is 0.32%, and the internal paper strength enhancer is 0.23%. -On the base paper obtained by stirring, the reaction product I and the surface sizing agent (SS-362, Japan P
(Manufactured by MC Co., Ltd.) was mixed with water and stirred to prepare a coating solution, which was externally applied in the same manner as in Example 1. Table 1 shows the basis weight of the obtained recording paper, the paper thickness, and the total solid content of externally added chemicals. Also,
The obtained recording paper was evaluated according to the same evaluation method as in Example 1. The results are as shown in Table 1.

[0022]

[Table 1]

(Comparative Example 1) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and a neutral rosin sizing agent as an internal sizing agent (in a pulp stock solution of L-BKP 100% and a freeness of 470 cc) NT
-83, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed and stirred so that the content of the filler in the base paper was 6.0% and the neutral rosin sizing agent was 0.60%, and papermaking was performed with a twin wire paper machine. Starch (corn starch, manufactured by Shikishima Starch Co., Ltd.) and surface sizing agent (SS-362, Japan P) were added between the pre-dryer process and the after-dryer process on the base paper squeezed by the pressing process.
(Manufactured by MC Co., Ltd.) is mixed and stirred in water to prepare a coating solution which is externally applied by a coating device, and the total solid content of the externally added chemicals as shown in Comparative Example 1 in Table 2 is 2.50 g / m 2. ² , of which surface sizing agent was applied to 0.03 g / m ² base paper
A recording paper having a paper thickness of 1.8 μg / m ² and a thickness of 99 μm was obtained. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 2.

(Comparative Example 2) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and a neutral rosin sizing agent (as an internal sizing agent) in a stock solution of L-BKP 100% and a freeness of 470 cc. NT
-83, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed and stirred so that the content of the filler in the base paper was 4.5% and the neutral rosin sizing agent was 0.28%, and papermaking was performed with a twin wire paper machine. Polyethyleneimine (Polymin SN, manufactured by BASF Japan Ltd.) and surface sizing agent (SS-362, manufactured by Japan PMC Ltd.) were added to water between the pre-dryer process and the after-dryer process on the base paper squeezed in the pressing process. The coating liquid prepared by mixing and stirring was externally applied by a coating device, and the total solid content of external chemicals as shown in Comparative Example 2 in Table 2 was 2.8.
0 g / m ² , of which surface sizing agent is 0.10 g / m ²
82.1 g / m ^{2 of} tsubo applied to base paper, paper thickness 100μ
m recording sheets were obtained. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 2.

COMPARATIVE EXAMPLE 3 L-BKP 100% pulp stock solution with a freeness of 470 cc was mixed with talc (D) as a filler.
N Talc, manufactured by Fuji Talc Industry Co., Ltd., rosin emulsion sizing agent as internal sizing agent (AL104, Japan PMC)
(Made by the same company) was mixed and stirred so that the content of the filler in the base paper was 5.0% and the rosin emulsion sizing agent was 0.20%, and PVA and the surface sizing agent (Polymaron 1
343S, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed with water and agitated to prepare a coating solution, which was externally applied in the same manner as in Example 1 and Table 2
2. The total amount of solids of external additives as shown in Comparative Example 3 of 3.
10 g / m ² , of which surface sizing agent is 0.005 g / m ²
83.0 g / m ² applied to m ² base paper, paper thickness 10
A recording paper of 1 μm was obtained. The recording paper obtained is from Example 1.
It evaluated based on the same evaluation method as. The results are as shown in Table 2.

(Comparative Example 4) Talc (D) was added as a filler to a pulp stock solution having L-BKP 100% and a freeness of 470 cc.
N Talc, manufactured by Fuji Talc Industry Co., Ltd., rosin emulsion sizing agent as internal sizing agent (AL104, Japan PMC)
(Manufactured by the same company) was mixed and stirred so that the content of the filler in the base paper was 4.6% and the rosin emulsion sizing agent was 0.01%, and papermaking was performed with a twin wire paper machine. The PVA and the surface sizing agent (Polymaron 134) were added between the pre-dryer process and the after-dryer process on the base paper squeezed by the pressing process.
3S, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed with water and stirred to prepare a coating liquid, which was externally applied by a coating device, and Comparative Example 4 in Table 2 was obtained.
3.00 g / m in total amount of solids of external chemicals as shown in
^2, these surface sizing agent basis weight 82.6 g / m ² was applied to 0.04 g / m ² group paper, to obtain a recording sheet of paper thickness 101Myuemu. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 2.

(Comparative Example 5) A synthetic alumina soda silicate (Tixorex 17, KOFRAN C) was added as a filler to a pulp stock solution having L-BKP of 100% and a freeness of 470 cc.
HEMICAL), a neutral rosin sizing agent (NT-83, manufactured by Arakawa Chemical Industry Co., Ltd.) as an internal sizing agent, the content of the filler in the base paper is 4.0%, and the neutral rosin sizing agent is 0.0.
It mixed and stirred so that it might be 5%, and was made into paper with a twin wire paper machine. Polyethyleneimine (Polymin SN, manufactured by BASF Japan Ltd.) and surface sizing agent (SS-362, manufactured by Japan PMC Ltd.) were added to water between the pre-dryer process and the after-dryer process on the base paper squeezed in the pressing process. A coating liquid prepared by mixing and stirring was externally applied by a coating device, and the total solid content of external chemicals as shown in Comparative Example 5 in Table 2 was 2.98 g / m ² , of which surface sizing agent Is 0.005 g / m ^{2 and} is 82.2 g / m ² applied to base paper.
A recording sheet with m ² and a paper thickness of 101 μm was obtained. The obtained recording paper was evaluated based on the same evaluation method as in Example 1.
The results are as shown in Table 2.

[0028]

[Table 2]

COMPARATIVE EXAMPLE 6 L-BKP 100% freeness 470 cc pulp stock solution was mixed with synthetic alumina soda silicate (Tixorex 17, KOFRAN C) as a filler.
HEMICAL), a neutral rosin sizing agent (NT-83, manufactured by Arakawa Chemical Industry Co., Ltd.) as an internally added sizing agent, the filler content in the base paper is 5.0%, and the neutral rosin sizing agent is 0.3%.
The mixture was mixed and stirred so as to be 2%, and was made into paper by a twin wire paper machine. Between the pre-dryer process and the after-dryer process, polyacrylamide (Surftop 100H, made by Japan PMC) and AKD sizing agent (AS-261, as a surface sizing agent) were added to the base paper squeezed in the pressing step.
The coating liquid prepared by mixing and stirring (manufactured by Japan PMC Co., Ltd.) in water is externally applied by a coating device, and the total solid content of external chemicals as shown in Comparative Example 6 in Table 3 is 2.38 g / m ² , of which 0.09 g of AKD sizing agent as a surface sizing agent
/ M ² base paper 83.2 g / m ² applied to base paper, paper thickness 1
A recording paper of 00 μm was obtained. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 3.

(Comparative Example 7) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and ADK sizing agent (AS-) as an internal sizing agent in a pulp stock solution of L-BKP 100% and a freeness of 470 cc. Two
61, manufactured by Japan PCM Co., Ltd., and the content of the filler in the base paper is 4.
8% and ADK gin sizing agent were mixed and stirred so as to be 0.10%, and papermaking was performed by a twin wire paper machine. Starch (corn starch, Shikishima Starch Co., Ltd.) and surface sizing agent (SS-362, Japan P) were added between the pre-dryer process and the after-dryer process on the base paper squeezed by the pressing process.
(Manufactured by MC Co., Ltd.) is mixed and stirred in water to prepare a coating liquid which is externally applied by a coating device, and the total amount of solids of external chemicals as shown in Comparative Example 7 in Table 3 is 2.95 g / m 2. ² , of which surface sizing agent was applied to 0.03 g / m ² base paper
A recording paper having a paper thickness of 1.8 μg / m ² and a thickness of 99 μm was obtained. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 3.

(Comparative Example 8) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and a neutral rosin sizing agent as an internal sizing agent () in a stock solution of L-BKP 100% and a freeness of 470 cc. NT
-83, manufactured by Arakawa Chemical Industry Co., Ltd., and polyacrylamide (Harmide EX-35) for internal addition as an internal addition paper strength enhancer.
N, manufactured by Harima Kasei Co., Ltd., so that the content of the filler in the base paper is 4.8%, the neutral rosin sizing agent is 0.32%, and the internal paper strength enhancer is 0.23%. -Mixed and made with a twin wire paper machine. Starch (corn starch, Shikishima Starch Co., Ltd.) and surface sizing agent (SS-362, Japan PMC Co., Ltd.) were mixed and stirred in water between the pre-dryer process and the after-dryer process on the base paper squeezed in the pressing process. The adjusted coating solution was externally applied by a coating apparatus, and the total solid content of external chemicals as shown in Comparative Example 8 in Table 3 was 2.26 g / m ² , of which the surface sizing agent was 0.2.
US applied to 04G / m ² groups paper grammage 82.3 g / m ^2,
A recording paper having a paper thickness of 101 μm was obtained. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 3.

(Comparative Example 9) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and a neutral rosin sizing agent as an internal sizing agent (100% L-BKP, 470 cc freeness pulp stock solution) NT
-83, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed and stirred so that the content of the filler in the base paper was 4.1% and the neutral rosin sizing agent was 0.25%, and papermaking was performed with a twin wire paper machine. Nonionic polyamide (Sumiraze resin 5001, Sumitomo Chemical Co., Ltd.), starch (corn starch, Shikishima Starch), and surface sizing agent between the pre-dryer process and the after-dryer process on the base paper squeezed in the pressing process. (SS-362, manufactured by Nippon PMC Co., Ltd.) is mixed and stirred in water to prepare a coating liquid which is externally applied by a coating device, and the total amount of solid content of externally added chemicals as shown in Comparative Example 9 in Table 3. At 3.0
0 g / m ² , of which nonionic polyamide is 1.78
g / m ^2, US surface sizing agent is applied to 0.04 g / m ² groups paper grammage 82.5 g / m ^2, to obtain a recording sheet of paper thickness 101Myuemu. The obtained recording paper was evaluated based on the same evaluation method as in Example 1. The results are as shown in Table 3.

(Comparative Example 10) Light calcium carbonate (Tamapearl TP-121-6S, manufactured by Okutama Kogyo Co., Ltd.) as a filler, and a neutral rosin sizing agent (as an internal sizing agent) in a pulp stock solution having L-BKP of 100% and a freeness of 470 cc. N
(T-83, manufactured by Arakawa Chemical Industry Co., Ltd.) was mixed and stirred so that the content of the filler in the base paper was 3.4% and the neutral rosin sizing agent was 0.28%, and was made into paper by a twin wire paper machine. . Cationic polyacrylamide (Polystron 311, Arakawa Chemical Co., Ltd.), starch (corn starch, Shikishima Starch Co., Ltd.) and surface sizing agent between the pre-dryer process and the after-dryer process on the base paper squeezed in the pressing process. (SS-362, manufactured by Japan PMC Co., Ltd.) is mixed and stirred in water to prepare a coating liquid, which is externally applied by a coating device, and the total solid content of external chemicals as shown in Comparative Example 10 in Table 3. 3.12 g / m ² , of which cationic polyacrylamide 1.85 g / m ² and surface sizing agent 0.03 g / m ² .
82.4 g / m ^{2 of} tsubo applied to m ² base paper, paper thickness 10
A recording paper of 1 μm was obtained. The recording paper obtained is from Example 1.
It evaluated based on the same evaluation method as. The results are as shown in Table 3.

[0034]

[Table 3]

FIG. 2 shows the relationship between the internally added sizing agent and the reaction product I. The internal sizing agent is NT as a neutral rosin sizing agent.
-83 (manufactured by Arakawa Chemical Industry Co., Ltd.), AL104 (manufactured by Japan PMC Co., Ltd.) as a rosin emulsion sizing agent, and externally applied reaction product I, starch (corn starch, Shikishima starch Co., Ltd.), surface sizing agent (SS). -362, Japan PMC
Co., Ltd.) was used. The base paper is L-BKP100
%, Freeness 470 cc pulp stock solution with light calcium carbonate (Tamapearl TP-121-6S,
(Okutama Kogyo Co., Ltd.) is mixed and stirred so that the content in the base paper is 3.5%, the amount of the internally added sizing agent is changed, papermaking is performed by a twin wire paper machine, and water is obtained by pressing in a press process. I used the one. The external addition coating was performed in the same manner as in Example 1 except that the solid content of the reaction product I was changed. The ink absorptivity, ink water resistance, ink density, and strikethrough of the obtained recording paper were evaluated based on the same evaluation methods as in Example 1. The dry load was evaluated as follows. ○: Can be operated under normal conditions without causing operational trouble. ×: Operation is not possible under normal conditions, and vapor pressure must be increased and papermaking speed must be reduced. Alternatively, troubles such as stains on the dryer may occur. As shown in FIG. 2, a shaded area is preferable, and a shaded area is optimum.

FIG. 3 shows the relationship between the surface sizing agent and the reactant I. As external coating, Reactant I, starch (corn starch, Shikishima Starch Co., Ltd.), surface sizing agent (SS-36)
2, manufactured by Japan PMC Co., Ltd.) was used. The base paper is L
-100% BKP and 470 cc freeness pulp stock solution with light calcium carbonate (Tamapearl TP-
121-6S, manufactured by Okutama Kogyo Co., Ltd.), a neutral rosin sizing agent as an internally added sizing agent (NT-83, manufactured by Arakawa Chemical Industry Co., Ltd.)
Was mixed and stirred so that the content of the filler in the base paper was 3.5% and the neutral rosin sizing agent was 0.28%, papermaking was carried out with a twin wire paper machine, and water was obtained in the press step to obtain water. I used one. A recording solution was obtained by externally applying the surface sizing agent and the coating liquid with different amounts of the reactant I added to the base paper. The ink absorbency, ink water resistance, characters, and image bleeding of the obtained recording paper were evaluated based on the same evaluation methods as in Example 1. A shaded area is preferable as shown in FIG. 3, and a shaded area is optimum.

[0037]

Since the present invention is configured as described above in detail, it has the following effects. The recording paper of the present invention, in printing by an inkjet printer using a water-soluble ink, has high ink absorption capacity, high ink absorption speed, high resolution, printability with high colorability, and printing / workability by a foam press, The water-soluble ink record after printing with an inkjet printer is water-resistant so that it does not bleed by rain, drinking water, etc. Even if it is used, it is not necessary to handle it carefully so as not to get it wet with rain or drinking water, and it becomes easy to store it for a long period of time. Further, the recording paper of the present invention can be used as a single paper such as a rotary printing paper, a PPC paper, an ink jet recording paper since it has the characteristics as described above.

[Brief description of drawings]

FIG. 1 is a sectional view of a recording sheet of the present invention.

FIG. 2 is a diagram showing a relationship between an internally added sizing agent and a reaction product of a polyamide polyamine and epihalohydrin.

FIG. 3 is a diagram showing a relationship between a surface sizing agent and a reaction product of a polyamide polyamine and epihalohydrin.

[Explanation of symbols]

 1 Base paper 2 Coating layer 3 Recording paper

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seitaro Ando 4-15-5 Hamadayama, Suginami-ku, Tokyo (72) Inventor Ryo Wakatsuki 1-3-3 Imai 16-1, Chuo-ku, Chiba, Chiba Prefecture -102

Claims (6)

[Claims] 1. A recording paper comprising a pulp fiber base paper containing an outer layer and / or an inner layer containing a reaction product of polyamide polyamine and epihalohydrin. 2. A recording paper for ink jet printing, characterized in that the outer layer and / or inner layer of the pulp fiber base paper contains a reaction product of polyamide polyamine and epihalohydrin. 3. A reaction product of a polyamide polyamine and epihalohydrin comprises a dibasic carboxylic acid (a) and a polyalkylene polyamine (b) (a) :( b) = 1: 1.
Epihalohydrin (c) is added to the polyamide polyamine obtained by reacting at a molar ratio of 1 to 1.5, and (b) :( c) = 1: to the polyalkylene polyamine (b).
The recording paper according to claim 1 or 2, which is a compound obtained by reacting at a molar ratio of 1.1 to 1.8. 4. The recording paper according to claim 3, wherein the dibasic carboxylic acid is adipic acid, the polyalkylenepolyamine is diethylenetriamine, and the epihalohydrin is epichlorohydrin. 5. A base paper, wherein an absorbent filler of a water-soluble ink and a sizing agent are internally added, and a paper strengthening agent is internally and / or externally applied. Three
Or the recording sheet described in 4. 6. A sizing agent is externally applied and coated on at least one side of a base paper.
Or the recording sheet described in 5.