JP2001098156A - Sizing agent composition for printing paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sizing agent composition for printing paper capable of imparting excellent paper handleability, printing characteristics and imaging characteristics to various printing papers such as a black-and-white electrophotographic copying paper for business use, a color copying paper, an ink-jet printer paper and facsimile receiving paper. SOLUTION: The sizing agent composition for printing paper is an aqueous emulsion containing (A) a water-insoluble organopolysiloxane oil containing (a) a 2-20C alkyl or aralkyl group and (b) an amino group in the molecule and (B) a sizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing composition for printing paper, and more particularly to a sizing composition for printing paper which improves printing characteristics and paper handling properties of printing paper.

[0002]

2. Description of the Related Art Conventionally, when printing is performed by an electronic copying machine using recycled paper, especially in a humid rainy season, paper handling is deteriorated and two sheets of paper are sent at the same time. In some cases, the printability was deteriorated and the printed lexical characters were blurred. Also,
When several sheets of facsimile paper are transmitted one on top of another, if the paper handling property is low, two or three sheets may be transmitted with their sheets overlapped, and the whole text may not be transmitted. One of the reasons is that the tackiness of a glue component (sizing agent) such as polyvinyl alcohol, starch glue or carboxymethyl cellulose adhered to the paper surface is improved with an increase in humidity. In order to prevent this, a method has been proposed in which a polyalkylsiloxane modified with a carboxyl group, a hydroxy group, an epoxy group, an amino group, an isocyanate group, a thioether group, a mercapto group, or the like is used as an anti-offset liquid. 58-52
589). Further, a method of applying a pigment, polyvinyl alcohol, and a silicone emulsion to a recording paper (see Japanese Patent Publication No. 3-24908) and a method of including a silicone oil in a heat-fusible ink layer (Japanese Patent Laid-Open No.
JP-A-42280) and a method of applying a coating solution obtained by dissolving an organic resin and silicone oil in an organic solvent to a thermal transfer recording sheet (see JP-A-4-1421989) are known. However, a method using a modified polyalkylsiloxane as an offset preventing liquid (Japanese Patent Publication No. 58-52)
No. 589), when copying is continued for a long time, the heat roll or the heating roll is worn out, the roll surface becomes rough, and the releasability gradually decreases. Further, in the method using silicone emulsion (see Japanese Patent Publication No. 3-24908), the emulsion is destroyed by many compounding agents, and in the method using an organic solvent (see Japanese Patent Application Laid-Open No. 4-128989), the working environment may be deteriorated. There is a drawback in that consideration must be given to the occurrence of pollution and fire. In addition, these methods cannot impart sufficient paper handling properties and printing characteristics during color copying to various types of printing paper.For example, even if several sheets of received paper in a facsimile machine are reused as they are and facsimile transferred. It was not possible to send the full text because two or three sheets were transmitted with overlapping. For these reasons, it has been desired to improve the paper handling property and the printing characteristics, and in particular, to have an excellent paper handling property such that the received paper in a facsimile machine can be reused.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve the above-mentioned disadvantages, and as a result, have reached the present invention. That is, an object of the present invention is to provide excellent printing properties, printing characteristics, and printing properties for various types of printing paper, such as office black-and-white electronic copier paper, color copier paper, inkjet printer paper, and facsimile receiving paper. An object of the present invention is to provide a printing paper sizing composition which imparts properties.

[0004]

According to the present invention, there is provided a water-insoluble organo (A) containing (a) an alkyl or aralkyl group having 2 to 20 carbon atoms in a molecule and (b) an amino group. The present invention relates to a sizing composition for printing paper, which is an aqueous emulsion containing a polysiloxane oil and a sizing agent (B).

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The components of the present invention will be described in detail. The component (A) merely imparts releasability, lubricity, smoothness and anti-blocking properties to printing paper to improve paper handling. Rather, the component (B) is a component which imparts an effect of hydrophobizing the binder component to improve water resistance, and further, has an effect of fixing pigments to media paper for ink jet printers and sublimation type printers. .
The organopolysiloxane oil of the component (A)
It contains at least one (a) alkyl or aralkyl group having 2 to 20 carbon atoms and (b) amino group in the molecule, and is water-insoluble. In addition, water insolubility means that the same amount of water as the component (A) is placed in a beaker and stirred at room temperature.
It can be judged by separating into two layers after standing for 24 hours. The molecular structure of the organopolysiloxane may be linear, branched, or cyclic, and there is no particular limitation on the type and the like. (a) As an alkyl group or aralkyl group having 2 to 20 carbon atoms, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, phenylmethyl, phenyl An ethyl group is exemplified. (b) The amino group is preferably one in which a nitrogen atom is bonded to a silicon atom via a carbon atom. Specifically, the amino group has the formula: -Q- (NHCH ₂ CH ₂ ) _a N
Amino group represented by HR ¹ and the like. In the formula, Q is a divalent hydrocarbon group, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group;
An arylene group represented by the formula: —C ₆ H ₄ —;
An alkylene arylene group represented by (CH ₂ ) ₂ C ₆ H ₄ — is exemplified. Of these, propylene groups are the most common. R ¹ is a hydrogen atom or a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a cyclohexyl group. a is an integer of 0 to 5, and 0 or 1 is generally used. Examples of such an amino group include groups represented by the following formula.

Embedded image

As the organopolysiloxane oil of the component (A), for example, an average formula:

Embedded imageInclude linear diorganopolysiloxanes represented by
It is. In the above formula, R is substituted with 1 to 20 carbon atoms or
Unsubstituted monovalent hydrocarbon group, specifically, methyl
Group, ethyl group, propyl group, butyl group, pentyl group,
Xyl, heptyl, octyl, decyl, dodecyl
Saturated aliphatic hydrocarbon groups such as vinyl group; vinyl group, allyl
An unsaturated aliphatic hydrocarbon group such as a hexenyl group or a hexenyl group;
Saturated alicyclic hydrocarbons such as pentyl and cyclohexyl groups
Group; aromatic carbon such as phenyl, tolyl, and naphthyl
Hydrogen groups; or hydrogen atoms bound to carbon atoms of these groups
Halogen-substituted carbon in which the carbon atom is partially substituted by a halogen atom
A hydride group is illustrated. Of these, the methyl group is the most
General. This R need not be the same in the molecule.
Difference between two or more combinations
I do not support it. R^TwoRepresents an alkyl group having 2 to 20 carbon atoms.
Or an aralkyl group, and the alkyl group is ethyl.
Group, propyl group, butyl group, pentyl group, hexyl group,
Examples include heptyl, octyl, decyl, and dodecyl groups
Aralkyl groups include phenylmethyl and phenyl
An example is a ruethyl group. Among them, the composition of the present invention
Color printer paper, inkjet printer paper
Or when used for sublimation printer paper,
Affinity and compatibility with printing colors such as red, yellow, blue, and black
From the nature, R^Two Has from 6 to 15 carbon atoms
Is preferable, and more preferably in the range of 8 to 14.
No. This R^TwoIs usually introduced into the molecule by a carbon atom
Having alkyl groups or aralkyl groups of 2 to 20
Chloorganosiloxane is used as a copolymer component. This shik
Loorganosiloxanes have, for example, the formula:

Embedded image Α- to the methyl hydrogen cyclotetrasiloxane represented by
It is synthesized by an addition reaction of methylstyrene or an α-olefin represented by the formula: CH ₂ ＣＨCH (CH ₂ ) ₉ CH ₃ using a catalyst such as chloroplatinic acid. X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, and a formula: -Q
— (NHCH ₂ CH ₂ ) _a NHR ¹ is a group selected from the amino groups represented by NHR ^1.
And the same groups as described above. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the amino group include the same groups as described above. l is 0 or an integer of 1 or more, and 10 to 1000
, And more preferably in the range of 50 to 500. m is 0 or an integer of 1 or more, preferably 2 to 200, and more preferably 5 to 10
More preferably, it is in the range of 0. However, when m is 0, it is necessary that X at the terminal of the molecular chain is an alkyl group or an aralkyl group having 2 to 20 carbon atoms. n is 0 or an integer of 1 or more, preferably in the range of 2 to 30, and more preferably in the range of 2 to 20. However, when n is 0, it is necessary that X at the terminal of the molecular chain is an amino group represented by the formula: -Q- (NHCH ₂ CH ₂ ) _a NHR ¹ . R ¹ , Q and a
Is the same as above. In the above average formula, the formula:

Embedded image As compared with the siloxane unit represented by the formula:

Embedded image It is preferable that the number of siloxane units represented by the formula is larger from the viewpoint of affinity for the dye and compatibility. The viscosity at 25 ° C. of the organopolysiloxane oil of the component (A) is usually in the range of 10 to 10000 mm ² / s.
It is preferably in the range of 0 to 10000 mm ² / s.

As the organopolysiloxane oil of the component (A), an organopolysiloxane represented by the following formula is exemplified.

Embedded image

The organopolysiloxane oil of the component (A) has, for example, the formula: H ₂ N (CH ₂ ) ₃ Si (C
The aminopropyl (methyl) dialkoxysilane represented by H ₃ ) (OCH ₃ ) ₂ is hydrolyzed with excess water, and the resulting hydrolyzed condensate, octamethylcyclotetrasiloxane and tetramethyltetradodecylcyclotetrasiloxane Is manufactured by heating to 80 to 110 ° C. using a basic catalyst such as sodium hydroxide to carry out equilibrium polymerization, and when the desired viscosity is reached, neutralizing the basic catalyst with an acid. (JP-A-53-98499).
Reference).

The sizing agent of the component (B) is usually coated on the surface (one side or both sides) of electronic copying machine paper, facsimile coated paper, color printing paper or ink jet printing media paper. , Barium sulfate, diatomaceous earth, calcium carbonate, talc,
It is a binder component for fixing and holding kaolin, silica, alumina, cationic polymers and the like. Examples of the component (B) include starches such as wheat flour, starch, corn starch, rice flour, potato starch, and cellulose derivatives such as casein, carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; and polyvinyl alcohol and polyvinylmethylether. Synthetic lake charge;
Examples include water-based binders such as polyacrylates, latexes such as styrene-butadiene rubber, and urethane emulsions. Among them, the sizing agent (B-1) having an emulsifying ability is carboxymethylcellulose,
Methyl cellulose and polyvinyl alcohol, and all other components are sizing agents (B-2) having no emulsifying ability. As the component (B), cellulose derivatives such as casein, carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; polyvinyl alcohol, polyvinylmethylether, and polyacrylates are preferable, and have emulsifying ability such as carboxymethylcellulose, methylcellulose, and polyvinylalcohol. Sizing agent (B-1) is most preferred. When using the sizing agent (B-1) having such an emulsifying ability,
An aqueous emulsion can be prepared without using a surfactant. In this case, a uniform and stable emulsion can be obtained by dissolving and dispersing the polyvinyl alcohol of the component (B-1) in water and adding the component (A) to the dispersion or passing through an emulsifier. The component (B-1) and the surfactant (D) having an emulsifying ability can be used in combination. On the other hand, when a sizing agent (B-2) having no emulsifying ability is used, a surfactant (D) having an emulsifying ability is required. In this case, the organopolysiloxane oil of the component (A) may be used as a surfactant of the component (D), for example,
It is preferable to emulsify using a nonionic surfactant alone or a mixture of a nonionic surfactant and a cationic surfactant, and then blend the resultant with the sizing agent of the component (B-2). As a method of emulsifying the component (A) in advance, usually,
After kneading the components (A) and (D), a small amount of water is added, and the mixture is emulsified by an emulsifier such as a colloid mill, a homomixer, and a line mixer. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyalkylene alkyl esters, and sorbitan alkyl esters. As the cationic surfactant, a quaternary ammonium salt type activator is most typical. For example, 20 parts by weight of the component (A), 3 to 5 parts by weight of a nonionic surfactant, and 0 parts of a cationic surfactant
A suitable emulsion can be obtained by blending in a range of from 1.5 to 1.5 parts by weight and 73.5 to 77 parts by weight of water. The component (B) is usually used after being dispersed in water.

The water used in the present invention is a component that dilutes the above components (A) and (B) and uniformly disperses them.
It is an essential component for thinly coating the composition of the present invention on the printing paper surface.

The composition of the present invention is an aqueous emulsion containing the above-mentioned components (A) and (B) as essential components. Depending on the purpose and use of the printing paper, a filler or a trifunctional compound for increasing the strength of the printing paper may be used. Amino silane may be added. Examples of the filler include titanium dioxide, barium sulfate, diatomaceous earth, calcium carbonate, talc, kaolin, silica, alumina, and a cationic polymer. Examples of the trifunctional aminosilane include an alkoxysilane represented by the following formula. Formula: (C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ Formula: (CH ₃ O) ₃ SiC ₃ H ₆ NHC ₂ H ₄ NH ₂

The mixing ratio of each component in the composition of the present invention depends on the type and amount of various additives and is not particularly limited, but the organopolysiloxane oil of the component (A) is 3 to 40% by weight, the component (B) is It is preferable that the sizing agent be in the range of 3 to 10% by weight and the remaining 94 to 50% by weight be water. A stock solution of the composition of the present invention is prepared at such a mixing ratio, and at the time of use, 10 to 100 times the amount of water and, if necessary, a sizing agent of the component (B) are appropriately added and mixed. preferable.

The method of applying the composition of the present invention to printing paper includes a method of impregnating a printing paper with a water diluent of the composition of the present invention, a method of coating a water diluting solution of the composition of the present invention on printing paper, and papermaking. Prior to the step, a method of adding the composition of the present invention or a method of spraying a water dilution of the composition of the present invention onto printing paper may be mentioned. Above all, coating is most suitable, and by using an air doctor coater, a blade coater, a transfer roll coater, a bar coater, a reverse roll coater or the like, the composition of the present invention can be coated in a very small amount and uniformly. Depending on the purpose and application of the printing paper, it may be a two-stage coating or a multi-stage coating of more than one-stage coating. Also,
The printing paper to which the composition of the present invention is applied includes not only paper made of virgin pulp and recycled paper, but also synthetic paper such as polypropylene and polystyrene.

Since the printing paper treated with the composition of the present invention as described above is excellent in smoothness, lubricity, water resistance, anti-blocking properties, etc., it can be used continuously at high speed under high humidity in the rainy season. This has the advantage that the paper is not superimposed and printed even when copying is performed, and the paper handling property is very good.
Therefore, the thermal paper for facsimile using the composition of the present invention can be used for facsimile transfer by reusing the receiving paper as it is. In addition, even in full-color copying, the printing characteristics and the printing characteristics are further improved, and there is an advantage that a clear color copy can be obtained with good dye transfer. Such a sizing composition of the present invention can be used not only for printing paper for black and white or color electronic copiers, office information recording paper such as thermal paper for facsimile, but also for media paper for inkjet printers and media for sublimation type printers. Also suitable for paper.

[0015]

Next, the present invention will be described in detail with reference to examples. In the examples, parts and% mean parts by weight and% by weight, and the viscosity is a value measured at 25 ° C. still,
Diorganopolysiloxane represented by the following formula used in the Examples, when left to stir with an equal amount of water at room temperature,
After 24 hours, the mixture was separated into two layers.

Embedded image

[0016]

Embodiment 1 Average formula:

Embedded image Viscosity 1 containing amino group and long chain alkyl group represented by
30 parts of a water-insoluble diorganopolysiloxane of 050 mm ² / s are uniformly dissolved and dispersed in advance in 3 parts of polyvinyl alcohol [manufactured by Nippon Gohsei; trade name: 1: 1 mixture of gosenol GL14 and GL05] and 67 parts of water. After mixing with the prepared aqueous solution and mixing for 30 minutes, the mixture was passed through a colloid mill-type emulsifier to prepare an aqueous emulsion. A treatment liquid A (diorganopolysiloxane 0.3%, polyvinyl alcohol 0.03%, water 99.67%) diluted 100 times by adding water to this aqueous emulsion was added to A4 using a simple spray gun. A plate-size recycled paper (manufactured by Fuji Xerox Office Supply Co .; Bright Recycled Paper) was evenly sprayed with an amount of 5.0 g of processing solution A per 1 m ² and dried (the amount of diorganopolysiloxane attached was 0.0
A 15 g / m ^2, the adhesion amount of the polyvinyl alcohol was 0.0015 g / m ^2. ). Using the recycled paper processed in this way, a full-color electronic copier [Fuji Xerox Co., Ltd .; A-color 628 type machine] was used to make color copies of black-and-white characters and color photographs. I was able to copy clearly.

[0017]

Comparative Example 1 Copying was performed in the same manner as in Example 1 using recycled paper that had not been treated with an aqueous emulsion. As a result, black and white characters were slightly blurred, and the sharpness of the photograph was also high. Was slightly inferior to the copy obtained in 1.

[0018]

Comparative Example 2 In Example 1, instead of the diorganopolysiloxane containing an amino group and a long-chain alkyl group,
Average formula:

Embedded image An aqueous emulsion was prepared in the same manner as in Example 1 except that the amino group-containing diorganopolysiloxane represented by The obtained recycled paper was used in Example 1.
Copying was carried out in the same manner as described above, however, color faintness slightly occurred and a clear color copy could not be obtained. From this, it was found that the amino group-containing diorganopolysiloxane had low affinity and compatibility with full color dyes such as red, yellow, and blue dyes, and was poorly familiar.

[0019]

Comparative Example 3 In Example 1, instead of the diorganopolysiloxane containing an amino group and a long-chain alkyl group,
formula:

Embedded image An aqueous emulsion was prepared in the same manner as in Example 1 except that the dimethylpolysiloxane represented by The obtained recycled paper was copied in the same manner as in Example 1. However, the color fell slightly, and a clear color copy could not be obtained. From this, it was found that the dimethylpolysiloxane had low affinity and compatibility with full color dyes such as red, yellow, and blue dyes, and was poorly familiar.

[0020]

Example 2 A facsimile thermosensitive recording paper [manufactured by KOKUYO Co., Ltd .; FAX-T210B-] obtained by spreading the treatment liquid A prepared in Example 1 to about 3 m using a simple type spray gun and spreading it.
30 (high sensitivity, A4 size width, continuous winding)], was uniformly sprayed so that the coating amount of the processing liquid A was 5 g per 1 m ² , and then dried. After that, it was rewound, set on a facsimile machine, and received three A4-size sheets. The prints were clear without blurring. further,
The three received sheets were piled up and set on a facsimile machine [manufactured by NEC; Sparc 23TA machine] and transferred to another department. Despite the rainy season and high humidity of 87%, all three were transmitted one by one, and the entire text could be transmitted smoothly. From this, it was found that the printing paper treated with the composition of the present invention had improved smoothness and lubricity, reduced tackiness, and had excellent paper handling properties.

[0021]

COMPARATIVE EXAMPLE 4 Three sheets of facsimile thermosensitive recording paper not treated with an aqueous emulsion were overlaid and transmitted several times using a facsimile machine in the same manner as in Example 2. , Even if the first sheet is transmitted smoothly, the second and third sheets are transmitted with overlapping,
The full text could not be sent.

[0022]

Embodiment 3 Average formula:

Embedded image A viscosity containing an amino group and an aralkyl group represented by the formula 11
To 20 parts of a 10 mm ² / s water-insoluble diorganopolysiloxane, 5 parts of a polyoxyethylene (6 mol) lauryl ether surfactant was added and kneaded for 20 minutes. Next, an emulsion was prepared by adding and kneading three parts of 75 parts of water over 60 minutes. This emulsion is added to an aqueous solution of methylcellulose (methylcellulose 10).
And 90 parts of water, and 100 parts of an aqueous solution (uniformly dissolved and dispersed over 2 hours) was added to prepare an aqueous emulsion. Using a simple spray gun, a treatment liquid B diluted by adding 20 times more water to this aqueous emulsion was used.
The coating amount of the processing liquid B per m ² is applied to the printing surface of the facsimile thermosensitive recording paper [manufactured by KOKUYO; FAX-T210B-30 (high sensitivity, A4 size width, continuous winding)] extended to about 3 m. After spraying uniformly to 5 g, the mixture was dried (the amount of diorganopolysiloxane attached was 0.5 g).
025 g / m ² , and the adhered amount of methylcellulose was 0.1%.
It was 0125 g / m ² . ). After that, it was rewound, set on a facsimile machine, and received three A4-size sheets. The prints were clear without blurring. Further, the received three sheets are overlapped and a facsimile machine [manufactured by NEC;
Sparek 23TA machine] and transferred to another department. Despite the rainy season and high humidity of 87%, all three were transmitted one by one, and the entire text could be transmitted smoothly. From this, it was found that the printing paper treated with the composition of the present invention had improved smoothness and lubricity, reduced tackiness, and had excellent paper handling properties.

[0023]

The sizing composition for printing paper of the present invention is an aqueous emulsion containing the water-insoluble organopolysiloxane oil of the above component (A) and the sizing agent of the component (B). It has the feature of improving the paper handling, printing and printing properties of various printing papers such as paper for electronic copying machines, thermosensitive recording paper such as facsimile machines, and media paper for ink jet printers and sublimation printers. Such a composition of the present invention has the advantages that the receiving paper in a facsimile machine can be reused and that the printing characteristics particularly during color copying are good.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tadashi Takimoto 2-2 Chikusa Beach, Ichihara-shi, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. 2 Toray Dow Corning Silicone Co., Ltd. Research and Development Division F-term (reference) 4J002 AB01X AB02X AB03X AB04X BE02X BE04X BG04X CH023 CP08W EH046 EN136 FD010 FD20X FD313 FD316 GK04 HA07

Claims (3)

[Claims] (1) (A) (a) having 2 to 20 carbon atoms in a molecule;
A water-insoluble organopolysiloxane oil containing an alkyl group or an aralkyl group of (b) and an amino group, and an aqueous emulsion containing (B) a sizing agent. Composition. 2. The aqueous emulsion contains (A)
water-insoluble organopolysiloxane oil containing (a) an alkyl or aralkyl group having 2 to 20 carbon atoms and (b) an amino group, (B-1) a sizing agent having an emulsifying ability, and (C) The printing paper sizing composition according to claim 1, comprising water. 3. The method of claim 1, wherein the aqueous emulsion comprises (A)
(A) a water-insoluble organopolysiloxane oil containing an alkyl group or aralkyl group having 2 to 20 carbon atoms and (b) an amino group, (B-2) a sizing agent having no emulsifying ability, (C 2. The sizing composition for printing paper according to claim 1, wherein the composition comprises water and (D) a surfactant having an emulsifying ability.