JPH01120384A - Desensitizing ink - Google Patents

Abstract

PURPOSE:To minimize water solubility and obtain an adequate desensitization effect even with a small swell of desensitizing ink showing outstanding printing properties not only in desensitization printing of photogravure, flexography and relief printing system but also in wet type offset printing by adding an aminoester acetate derivative with a specific part structure to ink. CONSTITUTION:Desensitization ink contains an aminoester acetate derivative with a part structure-CH2CH2N(CH2COOR)2. Consequently, desensitization ink for the inhibition or blocking of color development of coloring matter precursor used for pressure-sensitive copying paper is obtained. R is an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, each with 1-18 carbon atoms.

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 color developer that develops the color. .

Generally, pressure-sensitive copying paper consists of a sheet (hereinafter referred to as "rCB sheet") that has a microcapsule layer containing a solution of an electron-donating basic dye called a dye precursor, and an electron-accepting color developer. Sheet with a coating layer (hereinafter referred to as rCF
(referred to as "sheet"). In addition, if you use a sheet coated with a color developer on the surface and microcapsules containing a dye precursor on the back side (hereinafter referred to as rCFB sheet J) by sandwiching it between CB receipts and CF receipts, you can make multiple copies. It is possible.

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

[Conventional technology]

Known desensitizers include quaternary ammonia salts (Japanese Patent Publication No. 33-3921), tertiary amines having two polyethyleneoxy groups (Japanese Patent Publication No. 46-29546),
First M-condensed metal product of urea resin (Special Publication No. 35697, 1977),
Polyethyleneoxymonoalkyl ether
-38201), ethylene oxyto addition compound of polyalkylene polyamine (Japanese Patent Publication No. 49-23008),
Propylene oxide addition compound of alkylene diamine (
Special Publication No. 49-23850), average molecular weight 400-50
00 polypropylene glycol (Special Publication No. 55-191
No. 9), glycidyl ester or glycidyl ether addition compound of polyamine (Japanese Patent Publication No. 51-22416)
, diazabicycloalkenes or their salts (Special Publication 1984)
-26926), spiroacetal diamine (Japanese Patent Publication No. 55-16188), active hydrogen polyamine and alkylene oxide addition compound (Japanese Patent Publication No. 53-23724)
etc. 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. 51-25274, No. 52-1327
No., JP-A-54-40898, JP-A No. 61-100493
Typical examples thereof include polyvalent metal salts of salicylic acid having various substituents, as proposed in Japanese Patent Application No. 18027/1982, and Japanese Patent Application No. 1962/1967, and polyvalent metal salts of salicylic acid condensates.

These CF receipts and CFB sheets that use salicylic acid-based polyvalent metal salts as a color developer have a high color development ability, so
Previously, when desensitizing inks used for phenolic resin color developers were used, the desensitizing effect on dye precursors was insufficient, and a sufficient effect could not be obtained unless the amount of ink was increased. do not have.

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

Furthermore, although some adducts of alkylamines and ethylene oxide or propylene oxide that have been proposed have excellent desensitizing effects, they generally have a high affinity for water, and this remains a problem, especially when used as offset printing inks. was.

[Means to solve the problem]

The present inventors conducted various studies to solve such problems, and the partial structure (1) -CHzCHJ(ClbCOOR)z (1)
(R represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group having 1 to 18 carbon atoms). The present invention was completed by discovering that the problem can be solved.

The aminoacetic acid ester derivative having the partial structure (0) used in the present invention has the partial structure (n) -CHtCHJH
Ethylene amines having the general formula (III)
represents an alkyl group, cycloalkyl group, aralkyl group, or aryl group. ) It can be easily synthesized from halogenated acetate esters represented by Specific examples of ethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexazine.

On the other hand, halogenated acetate esters include butyl acetate chloride, hexyl acetate chloride, benzyl acetate chloride, decyl acetate chloride, stearyl acetate chloride, ethyl acetate bromide, propyl acetate bromide, cyclohexyl acetate bromide, and acetic acid bromide. Naphthyl, nonyl acetate bromide, dodecyl acetate bromide, stearyl acetate bromide, ethyl acetate iodide, butyl acetate iodide, pentyl iodoacetate, phenyl acetate iodide, lauryl iodoacetate, etc. It may be used in
If necessary, one or more types can be used, but of course the invention is not limited to these.

The substance used as a desensitizer in the present invention is generally obtained as a light-colored or light yellow oily substance, but it has a high affinity with the vehicle resin used for preparing the desensitizing ink.
It also has moderate hydrophilicity and lipophilicity suitable for various printing methods.

The desensitizing ink of the present invention contains a compound as a desensitizer component in an amount of 10 to 60% by weight, preferably 30 to 50% by weight, based on the nonvolatile components of the desensitizing ink.

Components other than the desensitizer for obtaining the desensitizing ink of the present invention include (1) vehicle resins such as rosin-modified phenol resin, rosin-modified maleic acid resin, rosin ester resin, maleic acid resin, styrene-maleic acid resin, and terpenized Ink resins such as phenolic resins, polyamide resins, and alkyd resins are generally used, and account for 10 to 50% by weight, preferably 15 to 30% by weight of the desensitized ink (in the non-repeat portion).
Contains.

(2) Titanium dioxide, zinc oxide, barium sulfate, magnesium oxide, talc, silica, and calcium carbonate are used as pigments to improve printability, whiteness, and shading power.
It is contained in an amount of 0 to 50% by weight, preferably 15 to 30% by weight.

In addition, as necessary, glycol solvents, drying oils such as linseed oil, tung oil, and soybean oil, semi-drying oils such as cottonseed oil, rapeseed oil, and rice bran oil, paraffins, metallic soaps, ultraviolet absorbers, antioxidants, A lubricant, optical brightener, etc. can be used in combination.

Furthermore, when preparing ink for flexography or gravure printing, volatile solvents such as lower alcohols, esters, and ketones are added to adjust the viscosity and volatilization rate.

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 desensitized ink containing the aminoacetic acid ester derivative of the present invention as an active ingredient can have ink physical properties that allow printing not only on letterpress and dry offset printing, but also on various printing machines such as flexo, gravure, and offset printing. be.

The desensitizing effect of the desensitizing 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 (acid site) of the acidic color developer, thereby inactivating the color developer.

The desensitizing ink of the present invention has an excellent desensitizing effect against clay-based developers (e.g. acid clay, activated clay, attapulgite), phenol-formaldehyde resin-based color developers, etc., but especially polyvalent metal salts of salicylic acid derivatives. , or polyvalent metal salts of salicylic acid cocondensation resin, etc.
Coupled with the excellent desensitization effect, changes in the desensitized printed area over time (
Coloring) is also extremely rare.

The desensitized ink of the present invention generally contains a pressure-sensitive dye (dye precursor).
It is applied to the developer surface and provides excellent desensitization for various fluorane-based, triallylmethanephthalide-based, pyridyl phthalide-based, acylleucophenothiazine-based, and rhodamine anilinolactam-based compounds that are widely used as Demonstrates the effect (coloring prevention effect).

The desensitizing agent used in the desensitizing ink of the present invention generally has low solubility in water, so it has excellent printability not only for G5 printing using gravure, flexo, and letterpress printing methods, but also for wet offset printing, and in small quantities. Since it has a sufficient desensitizing effect with a quantity of 1, it can cope with high-speed printing.

CF receipt and CFB coated with the desensitizing ink of the present invention
The sheet has no yellowing or odor over time, and a good printing surface can be obtained.

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 0.5 g/cd or more, preferably 1 to 5 g/cd.

〔Example〕

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

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

100 parts of a 10% aqueous solution of ethylene maleic anhydride and 240 parts of water were mixed, the pH was adjusted to 4.0 with a 10% aqueous sodium hydroxide solution, and 3-diethylamino-6-
After emulsifying 200 parts of alkylnaphthalene in which 5% by weight of methyl-7-ayurinofluorane was dissolved in a homomixer, a methylated methylolmelamine aqueous solution with a solid content of 50% (
Add 60 parts of Mitsui Toatsu Chemical's Neelamine T-5304) and hold at 55°C for 3 hours with stirring until the average particle size is 5.
A microcapsule liquid of 0μ was obtained.

To 100 parts of this microcapsule liquid, 20 parts of wheat starch granules, 20 parts of 20% oxidized starch powder, and 116 parts of water were added, stirred, and applied to 40 g/rrf so that the solid content was 5 g/d. I got the CB receipt.

Zinc salt of 3,5-dibenzylsalicylic acid of CF Kushi-A was wet-pulverized using a sand grinding mill in the presence of a small amount of polymeric anionic surfactant to obtain a solid content of 40% by weight.
An aqueous suspension was prepared.

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

Composition of water-based paint Solid weight part Light calcium carbonate 100 Color developer 20 Adhesive Oxidized starch 8 Synthetic latex 8 Preparation of CF sheet (B) 3. Salicylic acid-α, α° dimethoxy instead of zinc salt of 5-dibenzylsalicylic acid A CF receipt B) was prepared in the same manner using the zinc salt of -p-xylene-mesitylene cocondensation resin.

Synthesis Example 1 12.0 g of ethylenediamine and 20 g of octyl acetate bromide
1g of dimethylformamide 250+++f! 124 g of potassium carbonate was added. Add this solution to 90'
The mixture was stirred at C for 12 hours. After completion, the reaction solution was heated to 10001d.
, into semi-saturated brine and the organic layer was separated. The volatile components contained in the remaining organic layer were removed under reduced pressure, and the following compound (A
) 139g was obtained.

Compound (A) Synthesis examples 2 to 5 Compounds (B) to (E) were obtained in the same manner as in Synthesis Example 1.

Compound (B) R"-CHzCOOCItHts Compound (C) Compound (D) R'-CHtCOOCJb Compound (E) R'-CHtCOOCJ+ 3 Example 1 40 parts of the desensitizer obtained in Synthesis Example 1 and rosin-modified malein as a binder 40 parts of titanium oxide was added to a face prepared by heating and melting 30 parts of acid resin, and the mixture was kneaded with three rolls to obtain a desensitized ink.
3.5 g/l was printed on top using a letterpress printing machine.

A combination of each of the obtained desensitized printing papers and 08 paper was passed through a super calendar roll with a linear pressure of 100 kg/am to perform a coloring operation, and - the color density value after being left day and night (
The desensitization effect was evaluated by color measurement using the Macbeth density (Vis value).

Examples 2 to 5 Desensitizing effects were evaluated in the same manner as in Example 1, except that the desensitizers obtained in Synthesis Examples 2 to 5 were used.

Comparative Examples 1 to 3 The desensitizing effect was evaluated in the same manner as in Example 1, except that no desensitizer was used and a tertiary amine having two polyethyleneoxy groups and polypropylene glycol were used as the desensitizer.

The results obtained are summarized in Table 1.

Table 1 Note: 1 Compound without offset printability Compound (F) Compound (G) The numbers in Table 1 indicate the desensitizing effect, and the smaller the number, the stronger the effect.A value of 0.05 to 0.07 is completely It means being desensitized.

The desensitized ink of Comparative Example 2 using a tertiary amine having two polyethyleneoxy groups was not suitable for offset printing due to water loss.

Furthermore, the desensitizing ink using polypropylene glycol of Comparative Example 3 does not have a sufficient desensitizing effect on salicylic acid polyvalent metal salt and/or salicylic acid cocondensation resin polyvalent metal salt color developer.

In the examples, examples of offset ink and desensitized printing using the ink are shown, but the present application is not limited to offset ink, but also includes ink for letterpress printing, flexo printing, and gravure printing. be.

Applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) Partial structure (I) -CH_2CH_2N(CH_2COOR)_2(I
) (R represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group having 1 to 18 carbon atoms).