JPH041279A - Desensitized ink composition - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of carrying out printing of good quality on a plurality of a developer sheet while preventing diffusion and migration of desensitized ink to a portion necessary for color developing which occur in printing with the desensitized ink. CONSTITUTION:A desensitized ink composition comprises a pigment such as titanium oxide, and absorbed or adsorbed therein, a compound represented by the formula, wherein X represents hydrogen or 1 to 4C alkyl, AO represents oxyalkylene; n represents a mole number; R represents hydrogen or an organic group; B represents an acid anhydride having a double bond; and m represents a mole number of 5 or more.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to desensitizing ink compositions.

(Prior Art) Carbonless pressure-sensitive copying paper, also called carbonless paper, has been in practical use for some time.

It usually consists basically of a top paper coated with microcapsules containing a solution of an electron-donating colorless dye and a bottom paper coated with an electron-accepting color developer. The colorless dye is released and encounters the color developer on the base paper to develop color and produce a visible copy image. In addition, an inner paper (a paper-like support with microcapsules containing a colorless dye solution on one side and a color developer fully coated on the other side) is used to serve as both the top paper and the bottom paper. By inserting it between the two, you can make multiple copies. In addition, if a layer of microcapsules containing a colorless dye solution and a layer of a color developer are laminated and coated on one side of a support, a pressure-sensitive color image can be obtained even with a single sheet of paper, which can be used as self-contained paper. (Self-contained paper with a single layer coating, in which both layers are mixed together without being laminated, has also been announced).

As described above, the layer consisting of microcapsules containing a colorless dye solution and the layer consisting of a color developer, that is, the color developer layer, are the basic elements of carbonless pressure-sensitive copying paper, and many proposals have been made in the past. Ta.

Famous examples of colorless dyes include triphenylmethane-type lactone dyes represented by crystalviolent raftone and xanthine phthalide-type lactone dyes represented by 3-, diethylamino-6-methyl-7-anilinofluorane. As a color developer, activated clays represented by acid clay, activated clay, etc., novolac type polycondensation resins of substituted phenols represented by para-octylphenol or para-phenylphenol, and aldehydes such as formaldehyde, or 3 , aromatic carboxylic acid metal salts typified by zinc salt of 5-di-methylbenzylsalicylate, and the like are well-known as those on a practical level.

Desensitized ink has a color developer coated layer as described above, that is, a color developer layer (
It has been used for the purpose of disabling color development by applying it to areas where color development is unnecessary (the normal front side of bottom paper or inner paper, or the coated surface of self-contained paper).

In order to actually apply desensitizing ink to the developing surface, it is necessary to improve the accuracy of repeated work (improve registration), improve the surface quality of the lunar surface, improve the accuracy of the amount of adhesion, and diversify form designs. Various printing methods (flexo/gravure printing, letterpress printing, offset printing, silk screen printing, etc.) are often used for the purpose of improving work efficiency, etc. Therefore, it is necessary to use inks that are compatible with these printing methods. A desensitizing agent and other auxiliary materials, additives, etc. are blended and put into practical use in the form of a composition. (A composition formulated for printing in this way is called a desensitizing ink.) For this reason, in addition to the ability to prevent color development and erasing, that is, desensitizing ability, the desensitizing agent has various properties. It must be mentioned that a desensitized ink with printing suitability depending on the printing method can be prepared.

Regarding desensitizers, U.S. Patent No. 2777780, Japanese Patent Publication No. 4
No. 4-27255, No. 45-21448, No. 46-2
No. 2651, No. 46-29546, JP-A-47-32
No. 915, Special Publication No. 47-38201, No. 48-405
No. 0, Japanese Patent Publication No. 48-6805, Special Publication No. 49-4484
No. 49-19647, No. 49-23008, No. 49-23850, JP-A No. 49-43708, No. 4
No. 9-72009, No. 49-77709, No. 49-7
No. 7710, No. 49-15513, No. 49-8350
No. 9, German Patent Application (OLS) No. 2343800, r
Although it is detailed in FfJ2359079 and FfJ2361856, the following specific examples can be given. Quaternary ammonium salts such as dodecyltrimethylammonium chloride and octadecyl ammonium chloride; High molecular weight amines such as dodecylamine; 2.
4. Substituted oxazoline such as 4-trimethyl-2-oxazoline: Reaction product of alkylene oxide and diamine or polyamine derivative having a cyclic structure in the molecule such as xylene diamine or N-7 minopropyl piveridine; polyoxyethylene Alkylamine, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol, polypropylene glycol, polyoxypropylene alkyl amine,
Examples include polymers having glutamic acid-γ-alkyl ester residues, spiroacetal diamines, N-(aminoalkyl)-lactams, and grindyl ether adducts of amines.

(Problems to be Solved by the Invention) However, when printing with desensitizing ink on a developer sheet such as carbonless pressure-sensitive copying paper, generally the desensitizer and pigment have hydrophilic properties. Another problem is that the dampening liquid is taken into the desensitized ink area of the printing plate, and the desensitized ink gradually diffuses and migrates to areas where color development is required, resulting in a decrease in color development performance in that area or disappearance. Ta. Furthermore, if the supply of the dampening liquid is reduced, the desensitized ink will adhere to the entire area where coloring is required.

Therefore, an object of the present invention is to prevent the desensitizing ink from spreading to areas where color development is required, which occurs when printing with the desensitizing ink on the developer sheet, and to produce a large number of high-quality printed matter (the ) An object of the present invention is to provide a desensitizing ink composition that enables the following.

(Means for Solving the Problems) The above-mentioned object of the present invention is to completely absorb the compound represented by the following general 2 (11) or to reduce the amount of water containing the adsorbed pigment when printing with desensitized ink on a color developer sheet. This was achieved by printing with sensitive ink.

- Shipping (1) % formula %) (wherein, X is a hydrogen atom or an alkyl group of 01 to C4,
AO represents oxyalkylene, n is an integer representing the number of moles of oxyalkylene that is a constituent unit, R represents a hydrogen atom or an organic group, B is an acid anhydride having a double bond, and m is the number of moles of the constituent unit. An integer of 5 or more indicating ) The polymer used as the ink additive of the present invention is oxyethylene -〇H2CH20- (hereinafter abbreviated as EO)
unit and/or oxypropylene H5 -CH2-CH-0-C (hereinafter abbreviated as BO) unit and 2H5 /'! ! or oxybutylene -CH2-CH-0-1
-CH2CH2 unit, and n indicating the total number of moles of general formula (1) of EO and/or PO and/'' or BO is 3 or more and 2
The amount is in the range of 00 mol, preferably in the range of 5 to 60 mol, but may be larger.

More preferred are EO monopolymers, EO and PO copolymers, and EO and BO copolymers. At this time, the copolymer may be either a random copolymer or a block copolymer.

Further, X in the general formula (I) of the present invention is a hydrogen atom or C1-
4 represents an alkyl group, preferably a hydrogen atom or methyl.

Further, in the general formula of the present invention (R in 11 is a hydrogen atom or 01
~2o represents an alkyl group, alkenyl group, aryl group, or aralyl group. These groups may be substituted with a )-rogen group, hydroxy group, or alkoxy group.

Further, B in the general formula (I) of the present invention represents an acid anhydride having a double bond, and preferred examples thereof include maleic anhydride and itaconic anhydride, with maleic anhydride being particularly preferred. Moreover, these salts may be used.

Furthermore, m in the general formula (1) of the present invention is an integer of 5 or more indicating the number of moles of the structural unit, preferably an integer of 10 to 200, and may be larger than this.

Titanium oxide, zinc oxide, silicon dioxide, etc. can be used as the pigment that absorbs or adsorbs the polymer represented by the general formula (1) of the present invention. Titanium oxide is preferred.

As the treatment method with the polymer represented by general formula (I), either a known dry method or wet method can be used.

The amount of the polymer of the present invention absorbed or adsorbed into the pigment is preferably 2 to 5% by weight of the pigment, but it may be more than this.

The amount of the pigment used in the present invention is preferably 150 to 300 t (15 to 30% by weight) per 1 liter of desensitizing ink.
) and may be greater than this.

The compound represented by the symbol (■) above is manufactured and sold by a surfactant manufacturer. Moreover, it can also be synthesized by a known method.

To produce an actual desensitizing ink using the pigment of the present invention, a desensitizer, (B) a vehicle, and (C) the pigment are basically required. (In addition, it is usual to add solvents, deterioration inhibitors, optical brighteners, waxes, other additives such as paraffin wax, or other types of desensitizers, etc. to improve the practical quality.) (8) Desensitizers are produced by bringing an electron-donating or proton-accepting colorless organic compound, known as a color former, into contact with an electron-accepting or proton-releasing solid acid, known as a color developer. It has the function of reducing or eliminating the reaction that causes color development.

Regarding desensitizers, U.S. Patent No. 2777780, Japanese Patent Publication No. 4
No. 4-27255, No. 45-21448, No. 46-2
No. 2651, No. 46-29546, JP-A-47-32
No. 915, Special Publication No. 47-38201, No. 48-405
0, Japanese Patent Publication No. 486805, Japanese Patent Publication No. 49-4484, Japanese Patent Publication No. 49-19647, Japanese Patent Publication No. 49-23008, Japanese Patent Publication No. 49-23008.
No. 9-23850, JP-A No. 49-43708, JP-A-49-49
-72009, 49-77709, 49-77
No. 710, No. 49-15513, No. 49-83509
No., German Patent Application (OLS) No. 2343800, No. 2
No. 359079, No. 2361856, Special Publication No. 1986-5
6877, Japanese Patent Laid-Open No. 59-209191, etc., the following specific examples can be given. Quaternary ammonium salts such as dodecyltrimethylammonium chloride and octadecyl ammonium chloride; High molecular weight amines such as dodecylamine; 2゜4.4-
) substituted oxazolines such as Rimeter-2-oxazoline;
Reaction products of diamines or polyamine derivatives having a cyclic structure in the molecule, such as xylene diamine and N-aminopropylpiperidine, and alkylene oxide: polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol Examples include polypropylene glycol, polyoxypropylene alkylamine, polymers having glutamic acid-γ-alkyl ester residues, spiroacetal diamines, N-(aminoalkyl)-lactams, and glycidyl ether adducts of amines.

(B) Vehicle is a liquid component that disperses pigments, gives fluidity to ink, and fixes pigments, etc. to the printing surface.It usually consists of a solvent and/or resin, and is usually made of vegetable oil, mineral oil, crushed linseed oil, or alkyd. Resin, maleic acid resin, rosin-modified phenol resin, vinyl resin, etc. are used. Further, by selecting and using a general UV-curable vehicle, a UV-curable desensitized ink can be produced. UV-curable vehicles include compounds with unsaturated bonds, typically polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, and trimethylolpropane, and acrylic acid or methacrylic acid. esters, terminal epoxy acrylates and methacrylates of various glycidyl ethers, their monomers, dimers, trimers, and oligomers (prepolymers) are mainly used, and to provide film-forming ability, unsaturated alkyd resins, non-drying oils, Oil-modified alkyd resins, arylsulfonamide/formalin resins, epoxy resins, urea/formalin resins, diaryl phthalate resins, etc. may be added. As additives, photoinitiators, chain transfer agents, stabilizers, fluidity improvers, waxes, etc. can be added.

In this way, by applying an ultraviolet curable ink vehicle, it is possible to create an ultraviolet curable desensitized ink, which can be used to accelerate ink drying, speed up printing, prevent ink not drying, etc., especially in letterpress and offset printing. It will be possible to come up with an idea.

(Q pigments are mainly added to adjust the viscosity of the desensitized ink and to give opacity, mattness, easeability, etc. to the desensitized printed area, and include titanium dioxide, zinc oxide, calcium carbonate, etc.) Inorganic pigments such as , magnesium carbonate, and silicon dioxide, and organic pigments (plastic pigments) such as urea resin, melamine resin, and styrene resin are used.

Of course, the desensitizing ink of the present invention can be used in flexible printing, gravure printing,
Any type of printing ink formulation can be used, such as letterpress printing, offset printing, silk screen printing, etc. but,
The greatest effect is that it can provide a desensitizing ink that is most suitable for the offset printing method, which is the most widely used printing method at present, but for which a fully satisfactory desensitizing ink has not yet been developed. This is true not only for ordinary penetrant-drying inks but also for ultraviolet curing inks.

(E) Examples The present invention will be explained below using typical examples, but the present invention is not limited in any way.

Example 1 A desensitizing ink was prepared using the following formulation.

A desensitized ink was prepared using titanium oxide that was absorbed or adsorbed by a dry method and printed in the same manner.

First, a binder resin and a wax were dissolved in a desensitizer, and then a white pigment was added thereto and an ink was formed using a three-line printing roll.

Using this desensitizing ink, a commercially available carbonless pressure-sensitive copying paper medium (N-4
Offset printing was carried out on the developing surface of the color developing layer containing para-phenylphenol formalin resin.

The printing plate used was Fuji Photo Film's 28th edition SO-■1.
The test was performed by printing for 10 minutes at a speed of 100 m/y.

A 11% aqueous solution of H liquid NO4 manufactured by Tokyo Ink was used as a humidifying liquid. On the other hand, titanium oxide, which is the white pigment of the desensitizing ink, is represented by the following coating Comparative Example 1 of Compound of General Formula (I) Polypropylene Glycol (Molecular Weight 2000) Comparative Example 2
Polyethylene glycol (molecular weight 2000) Comparative Example 3 When printing with oleic acid blank ink, the desensitizing ink spread to the areas where color development was required on the developing surface, and a desensitizing effect was observed in those areas. In the case of the inks using pigments 1, 2, and 3.4 of the present invention, no spread of the desensitized ink was observed. With the pigments of Comparative Examples 1.2.3, almost no effect was observed.

Example 2 A desensitizing ink was prepared using the following formulation.

An ultraviolet curable desensitized ink was prepared using the following formulation.

Add rosin-modified maleic acid resin to desensitizer and heat at 150℃ for 1
Dissolved by heating for an hour. To this, titanium dioxide 35 of Example 1
of the mixture was added and kneaded in a three-roller mill to prepare a desensitizing ink.

Example 1 was repeated with the same good results, except that offset printing was performed on the developing side of a commercially available carbonless pressure-sensitive copying paper medium (N-40 super color developing layer uses salicylic acid derivative zinc salt). Obtained.

Example 3 Components other than the pigment were mixed and dissolved, and then the pigment of Example 1 was added to prepare an ink using a three-roll mill.

Example 2 was repeated except that this ink was used, and similar good results were obtained without any effect on ultraviolet curing.

Example 4 Example 2 was repeated except that the printing plate of Example 2 was used as a commercially available silver salt type direct printing plate (Mitsubishi Silver Master) and a dampening liquid exclusively for Mitsubishi Silver Master was used as the dampening liquid. Good results were obtained. Obtained.

(Effects of the Invention) Printing using the desensitized ink of the present invention has the advantage of preventing diffusion and migration to areas where color development is required, and allowing high-quality printing to be performed on a large number of color developer sheets. You can get the same effect.

Claims (1)

[Scope of Claims] A desensitizing ink composition comprising a pigment that has absorbed or adsorbed a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a hydrogen atom or an alkyl group of C_1 to C_4, AO represents oxyalkylene, and n represents the number of moles of the oxyalkylene constituent unit. R is a hydrogen atom or an organic group, B is an acid anhydride with a double bond, m
is an integer of 5 or more indicating the number of moles of the structural unit. )