JPS63283982A - Desensitizing ink - Google Patents

Abstract

PURPOSE:To suppress or prevent color development of a dye precursor, by using as a main constituent a derivative obtained by the reaction of a polyether amine derivative with a compound having at least one oxirane group. CONSTITUTION:A substance obtained by a reaction of a polyether amine deriva tive of formula I or II, wherein each of R1 and R3 is hydrogen, a lower alkyl or phenyl, R2 is a lower alkyl, and each of n, x, y and z is an integer of 1-100, with a compound having at least one oxirane group is incorporated. The com pound having at least one oxirane group in the molecule thereof may be an alkylene oxide such as ethylene oxide and propylene oxide. The reaction of the polyether amine derivative with the oxirane group-containing compound can be easily effected, and is achieved by addition polymerization in the absence of catalysts or in the presence of a basic catalyst. The reaction product is obtained as a light-colored or light yellow liquid, which is low in affinity for water, is high in affinity for a vehicle resin, and is therefore convenient for use.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a desensitizing ink having excellent desensitizing effects for use in pressure-sensitive copying paper. More specifically, the present invention relates to a desensitizing ink for suppressing or preventing the color development of the dye precursor in pressure-sensitive copying paper, which is composed of a combination of a colorless or light-colored dye precursor and a developer that develops the color.

In general, pressure-sensitive copying paper consists of a sheet having a microcapsule layer containing a solution of an electron-donating basic dye called a dye precursor (hereinafter referred to as an "rCB sheet") and an electrophilic color developer coating layer. (hereinafter referred to as "rCF sheet"). In addition, we have applied microcapsules containing a color developer on the surface and a dye precursor on the back (hereinafter referred to as rCFB sheet).
If it is used between the CB sheet and the CF receipt, it is possible to make multiple copies.

In the pressure-sensitive copying paper used in this manner, a desensitizing ink is applied to the CF sheet using a printing machine or the like in areas where copying is not necessary to suppress or prevent color development of the dye precursor.

[Conventional technology]

Known examples of flJJI include quaternary ammonium salts (Japanese Patent Publication No. 3921/1989), tertiary amines having two polyethylene oxide groups (Japanese Patent Publication No. 295/1986),
46), initial condensate of urea resin (Special Publication No. 46-356)
No. 97), polyoxyethylene monoalkyl ester (Japanese Patent Publication No. 47-38201), ethylene oxide addition compound of polyalkylene polyamine (Japanese Patent Publication No. 49-230)
08), propylene oxide addition compounds of alkylene diamines (Japanese Patent Publication No. 49-23850), polypropylene glycol with an average molecular weight of 400 to 5000 (Japanese Patent Publication No. 55-1919), glycidyl ester or glycidyl ether addition compounds of polyamines (Japanese Patent Publication No. 51-1986) -2
2416), diaza-bicycloalkenes or their salts (Japanese Patent Publication No. 54-26926), spiroacecool diamines (Japanese Patent Publication No. 55-16188), active hydrogen polyamines and alkylene oxides, do addition compounds (Japanese Patent Publication No. 53
-23724) Others are known.

These desensitizers are prepared and used in printing inks, ie, desensitizing inks, suitable for printing methods such as letterpress printing, intaglio printing, planographic printing, and stencil printing.

[Problem that the invention seeks to solve]

In recent years, research on color developers has progressed, and CF and CFB sheets using polyvalent metal salts of salicylic acid derivatives and/or polyvalent metal salts of salicylic acid co-condensed resins as color developers have improved coloring ability and stability of colored images. It has been improved and some parts have been put into practical use.

For example, Special Publication No. 51-25174, No. 52-1327
No., JP-A-54-40898, JP-A-61-1004
No. 93, Japanese Patent Application No. 18027/1986, Japanese Patent Application No. 1802/1983
Representative examples include polyvalent metal salts of salicylic acid having various substituents, as proposed in No. 9673, etc., and polyvalent metal salts of salicylic acid condensates.

Since these CF receipts and CFB sheets that use salicylic acid-based polyvalent metal salts as a color developer have a large color-developing ability, it is difficult to use desensitized inks that were previously used with phenolic resin-based color developers. The desensitizing effect on the dye precursor is insufficient, and a sufficient effect cannot be obtained unless the amount of ink applied is increased.

However, increasing the amount of ink will slow down the drying speed and cause problems during printing, such as smearing due to insufficient drying and ink bleeding to unprinted areas.

In addition, adducts of alkylamines and ethylene oxide or propylene oxide that have been proposed in some cases have excellent desensitizing effects, but they generally have a high affinity for water, which poses a problem especially when used as offset printing inks. I had left it behind.

[Means to solve the problem]

The present inventors conducted various studies to solve such problems, and found that general formula (1) or (II) (wherein R1, Ra
represents a hydrogen atom, a lower alkyl group, or a phenyl group, R1 represents a lower alkyl group, and n, x, and ySz each represent an integer value of 1 to 10'O. The present invention has been completed based on the discovery that the above-mentioned problems can be solved by using as a main component a derivative obtained by reacting a compound containing at least one oxirane group with a compound containing at least one oxirane group.

General formula (1) or (■) used in the present invention
The polyetheramine derivatives represented by are known, and specific examples thereof include the following, and those having various molecular weights are available.

On the other hand, as compounds containing at least one oxirane group in the molecule, alkylene oxides such as ethylene oxide and propylene oxide, Epicote 8
Examples include arylene glycidyl ethers such as No. 28, alkyl glycidyl ethers, and the like.

It is easy to react the polyether amine derivative represented by the general formula (1) or (II) with a compound containing an oxirane group, and it can be obtained by addition polymerization without a catalyst or in the presence of a basic catalyst. be able to.

The substance used in the present invention is generally obtained as a light-colored or pale yellow liquid substance, has a low affinity for water, and has a high affinity with the vehicle resin used for preparing the desensitizing ink, which is advantageous. be.

The desensitizing ink of the present invention has a desensitizing subcomponent of 10 to 60% of the undesirable components of the desensitizing ink. , amount%, preferably 15~
It contains 50% by weight.

Components other than the desensitized side of the barrel for obtaining the desensitized ink of the present invention (1) Vehicle resin: rosin-modified phenol resin, rosin-modified maleic acid resin, rosin varnish f JLIM
Fat? Ink resins such as leic acid resin, styrene maleic acid resin, terpenized phenolic resin, polyamide resin, and alkyd resin are generally used, and account for 10 to 511%, preferably 15 to 30% by weight of the desensitized ink (in nonvolatile matter). Contains.

(11) Titanium dioxide, zinc oxide, barium sulfate, magnesium hydroxide, talc, and calcium carbonate are used as additives to improve printability, whiteness, and hiding power.
-50% by weight, preferably 15-40% by weight.

In addition, glycol solvents such as ethylene glycol, diethylene glycol, polyethylene glycol, and polypropylene glycol, linseed oil, tung oil,
Drying oils such as soybean oil, semi-drying oils such as cottonseed oil, rapeseed oil, and rice bran oil, paraffins, metallic soaps, ultraviolet absorbers,
Antioxidants, lubricants, fluorescent brighteners, etc. can be used in combination.

Furthermore, when preparing ink for flexographic or gravure printing, a continuous solvent such as lower alcohols, esters, ketones, etc. is added, and the viscosity and volatilization rate are adjusted according to tJiMI.

In order to obtain the desensitizing ink of the present invention, various known methods can be used, and if necessary, known desensitizing agents may be used in combination.

[Action and effect]

The desensitizing ink containing as an active ingredient a substance obtained by reacting the polyetheramine derivative of the present invention with a compound containing one or more oxirane groups can be used not only for letterpress and dry offset printing, but also for flexo and gravure printing. It is possible to provide the ink with physical properties that can be printed on many types of printing machines such as offset printing and the like.

The desensitizing effect of the ink of the present invention is thought to be due to the fact that the amine component of the desensitizer neutralizes the color development site (M point) of the acidic color developer, thereby inactivating the color developer.

The desensitizing ink of the present invention has an excellent desensitizing effect on clay-based (e.g. acid clay, activated clay, acpulgite) W1 colorants, phenol formaldehyde polymer color developers, etc., but especially on salicylic acid derivatives. For polyvalent metal salts or polyvalent metal salts of salicylic acid cocondensation resins, in addition to the excellent desensitization effect, the desensitized printed area undergoes very little change (coloration) over time.

Furthermore, the desensitized ink of the present invention is generally widely used as a pressure-sensitive dye (dye precursor). Various fluoranes,
When applied to the developer surface, it exhibits an excellent desensitizing effect (color development prevention effect) for triallylmethane phthalide, pyridyl phthalide, acyl leucophenothiazine, and rhodamine anilinolactam compounds.

The desensitizer used in the desensitizing ink of the present invention generally has extremely low solubility in water, so it has excellent printability not only for desensitizing printing by gravure, flexo, and letterpress printing methods, but also for wet offset printing. Since it has a sufficient desensitizing effect with a small amount, it can support high-speed printing.

CF receipts and CFB sheets coated with the desensitizing ink of the present invention have a good printed surface without yellowing or odor over time.

The desensitizing ink of the present invention can exhibit a sufficient desensitizing effect by printing on the developer coated surface (CF surface) in an amount of Ig/ai or more, preferably 2 to 10 g/c.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples.

CB receipts and CF receipts used in Examples and Comparative Examples were prepared as follows.

2B>-22λ1 100 parts of a 10% aqueous solution of ethylene maleic anhydride and 240 parts of water were mixed, and the pH was adjusted to 4 with a 1Ox NaOH aqueous solution.
．． 0, and 3-diethylamino-6-methyl-
After emulsifying 200 parts of alkylnaphthalene in which 5% by weight of 7-aniline fluoran was dissolved in a homomixer, 60 parts of a methylated methylolmelamine aqueous solution (Mitsui Toatsu Chemical r Neelamine T-530J) with a solid content of 50% was added and stirred. The mixture was maintained at 55° C. for 3 hours to obtain a microcapsule liquid with an average particle size of 5.0 μm.

To 100 parts of this microcapsule liquid, 20 parts of wheat starch granules, 20 parts of 20% oxidized starch, and 116 parts of water were added and stirred.
A CB receipt was obtained by applying the solid content to 5 g/rrl of paper on a paper with a solid content of 5 g/rrl.

The zinc salt of 3.5-di-α-methylbenzylsalicylic acid in CF Receipt A was wet-pulverized using a sand grinding mill in the presence of a small amount of polymeric anionic surfactant, and the solid content was 40%. An aqueous suspension of % by weight was prepared.

Using the aqueous suspension, a water-based paint having the following composition (solid content: 3
A CF-sheet (A) was prepared by coating and drying so that the dry coating amount of 40 g/rd high-quality paper was 5.5 g/g.

Composition of water-based paint Solid weight part Soft calcium carbonate 100 Color developer 20 Adhesive side Oxidized starch 8 Synthetic latex 8 Salicylic acid-α, α1 dimethoxy p instead of 3,5-di-α-methylbenzylsalicylic acid in CF Kushi-B - CF receipt B) was prepared in the same manner using the zinc salt of xylene-mesitylene cocondensation resin.

Polyoxypropylene diamine and Epicor shown in Example-1)
828 (liquid epoxy resin synthesized from bisphenol A and eclohydrin) at a 3:1 molar ratio, 50 parts of a rosin-modified phenolic resin was added to 50 parts of a pale yellow liquid, and the resin was dissolved by heating to form a festival. 40 parts of titanium dioxide was added to this face and uniformly kneaded using a three-roll mill to obtain a desensitized ink.

The resulting desensitized ink was applied to pressure-sensitive copy paper CF receipt ^) and CP receipt B) using a letterpress printing machine in an application amount of 3.
g/rrf.

When the obtained desensitized printing paper and CB receipt were combined and printed using an electric typewriter (IBM-65 model), the desensitized printing area did not develop any color at all on both CF combs (A) and (B) and was sufficiently reduced. A sensory effect was observed.

4. of polyoxypropylene triamine and Epicote 828 shown in Example-2. Add 20 parts of maleic acid resin to 50 parts of the condensation reaction product (pale yellow liquid) with a molar ratio of 2t, heat and melt to create a face, then add 20 parts of titanium oxide and 10 parts of calcium carbonate and mix with a mixer. After stirring, the mixture was kneaded in a three-roll mill to obtain a desensitized ink.

When the obtained desensitized ink was printed on CF receipt A) and CF comb (B) using a wet offset printing machine at a coating amount of 3.5 g/nf, both printed areas and non-image areas were printed. The printed line was clearly separated and the print quality was good.

A typewriter (IBM-65
When color was developed using a mold), no color was developed in the desensitized printed area, and a sufficient desensitizing effect was observed.

Example 3 A desensitizing ink was prepared in the same manner as in Example 1 using a pale yellow liquid composition obtained by reacting propylene oxide in an amount of 6 times the molar amount under alkaline conditions as a desensitizing component.

It was confirmed that the desensitized printed area printed by the letterpress printing method had a sufficient desensitizing effect when combined with the CB receipt.

Comparative Example Polypropylene glycol (molecular weight 300
A desensitizing ink was prepared in the same manner as in Example 1 except that 0) was used, and letterpress printing (coating amount: 3 g/rrf) was performed on CF receipt ^) and CF receipt B).

When coloring was performed using a typewriter using a combination of CB receipts in the same manner as in Example 1, a pale black colored image was generated even in the fIis printing area, and a sufficient desensitization effect could not be obtained.

Claims (1)

[Claims] 1) General formula (I) or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1, R_3 is a hydrogen atom, a lower alkyl group,
Alternatively, it represents a phenyl group, R_2 represents a lower alkyl group, and n, x, y, and z each represent an integer value of 1 to 100. 1. A desensitizing ink characterized by containing a substance obtained by reacting a polyetheramine derivative represented by the following formula with a compound containing at least one oxirane group.