JPS63149185A - Desensitizing composition for pressure sensitive paper - Google Patents

Abstract

PURPOSE:To suppress a migration phenomenon on a printing surface and prevent discoloration, fading or bleeding of printed images, by using a specified ether as a desensitizing agent to prepare an ink from the micture of a desensitizing agent and a pigment, a binder, an organic solvent or the like. CONSTITUTION:A desensitizing composition for pressure sensitive paper comprises a compound of general formula (I), wherein n is an integer of 7-25, and R is an integer of 5-18 carbon atoms. As the compound, for example, at least one of polyoxyethylene amylmethyl ether, polyoxyethylene caprylmethyl ether and the like is preferably used in an amount of 25-80 wt.% as solid components in an ink. As a pigment, at least one of magnesium oxide, calcium oxide and the like is used. As a binder, at least one of a phenolic resin, a rosin- modified phenolic resin and the like is used. AS an organic solvent, at least one selected from alcohols such as methanol and ethanol and ketones such as acetone and methyl ethyl ketone is used.

Description

DETAILED DESCRIPTION OF THE INVENTION (A>Industrial Field of Application) The present invention relates to a combination of an electron-donating colorless organic compound and an electron-accepting compound for use in carbonless pressure-sensitive copying paper. The present invention relates to a desensitizer composition for inhibiting a color-forming reaction due to contact with a chemical compound.

(B) Conventional technology Normally, carbonless pressure-sensitive copying paper is made by dissolving electron-donating leuco dyes such as crystal violet lactone, benzoyl leucomethylene blue, malachite green, and rhodamidianilinolactam in a nonvolatile oil in fine capsules. A paper-like support is coated with a solid acid (i.e., acidic substance) such as acid clay, activated clay, attapulgite, various phenolic resins, and polyvalent metal salts of salicylic acid derivatives together with a suitable binder. When the coated sides of both papers are stacked facing each other and pressure is applied by writing or using a typewriter, the capsule in the pressure area is destroyed and the leuco dye and solid acid are released. Color develops on contact.

Furthermore, if a middle paper coated with a solid acid on the front surface and a leuco dye-containing capsule on the back surface is used by sandwiching it between the upper paper and the lower paper, an even larger number of copies can be obtained.

Desensitizers are used to prevent color development by pre-coating areas on the electron-receptive surface of carbonless pressure-sensitive copying paper that do not need color development, or to partially cover already colored surfaces to erase developed color images. be done.

Conventionally known desensitizers include, for example, Japanese Patent Publication No. 33-392
Cationic quaternary ammonium salts described in Publication No. 1 (e.g.
dodecyltrimethylanimonium chloride), aliphatic amine acetate (e.g. n-dodecylamine acetate), higher aliphatic amine (e.g. nidodecyldiamine), oxazoline derivative (e.g. 2.4.4-trimethyl-2-oxazoline), 2 described in the Special Publication Publication No. 1973 29546M
Tertiary amine having polyethylene oxide groups (
Examples: N,N-dipolyoxyethylene ethylamine), polyoxyethylene alkyl ester (general formula RCoo (C2H40) m
H and R are alkyl groups having 12 to 18 carbon atoms, e.g. polyoxyethylene oleyl ester), polyoxyethylene alkyl ether (general formula RO(CzH40)nH,R
is an alkyl group having 12 to 18 carbon atoms (e.g. polyoxyethylene lauryl ether), polyoxyethylene alkylphenyl ether (alkyl group having 1 to 3 carbon atoms), Japanese Patent Publication No. 49-23850@
Propylene oxide addition compound of alkyldiamine described in the publication (e.g. polyoxypropylene diethylamine)
, poly r-alkyl glutamate described in Japanese Patent Publication No. 49-4484M, polyamine-ethylene oxide adduct compound described in Japanese Patent Publication No. 49-23008, Japanese Patent Publication No. 49-23008,
9-72009@ Amine-glycidyl ester (or ether) addition compound described in the publication, JP-A-50-3750
Polypropylene glycol described in Publication No. 7, JP-A-1988
-Alkyl or arylamine propylene oxide/ethylene oxide addition compounds described in JP-A-84318, addition compounds of alkylene oxide and/or styrene oxide to alkylphenols or polycondensates of alkylphenols and formaldehyde described in JP-A-52-125108; A product obtained by reacting a rosin or a modified rosin having a carboxyl group with a polyalkylene glycol described in JP-A No. 57-25991,
Imidazole derivatives or their bis forms described in JP-A-57-69089, alkylene oxide or styrene oxide addition compounds to resin M reduced alcohols as described in JP-A-57-95493, JP-A-58-98282
Amine-based polyoxybutylene propylene copolymer polyols described in JP-A No. 58-51183, alkylene oxide addition compounds of rosin alcohol and alkylene oxide addition compounds of rosin amine, described in JP-A-59-209191. Examples include styrene oxide addition compounds of 3-alkoxypropylamine, alkylene oxide-styrene oxide coaddition compounds, and others, but most of them are relatively polyether chains containing polyether chains in the molecule, such as polyethylene oxide and propylene oxide. It is an organic compound with a high molecular weight (usually a molecular weight of several hundred or more).

By appropriately blending these desensitizer compounds with vehicles, binders, pigments, etc. that are known and used in the printing ink technical field, the desensitizer content in the ink can usually be reduced to 30 to 80%. It has already been widely used to print patterns on the colored surface of carbonless pressure-sensitive copying paper using an appropriate printing method using various types of printing ink.

(C) Problems to be Solved by the Invention In conventionally known desensitized ink printing methods (for example, flexo, gravure, offset, letterpress printing, etc.), in flexo and gravure printing, drying of the ink is mainly due to the removal of organic solvents in the ink. This was achieved by ``evaporation,'' while offset and letterpress printing were achieved by ``permeation of the ink composition into the printing surface or paper''.

However, even if it appears to be dry, liquid substances in the ink composition, such as vehicles, binders, and desensitizers, exist in liquid form on the printed surface and in the paper. While pressure copying paper is stacked or rolled up and stored, it gradually migrates (migrate), destroying adjacent microcapsules or making it impossible to develop color in areas where color development is required. . That is, in desensitizing printing on carbonless pressure-sensitive copying paper, this migration phenomenon of desensitizing ink is an extremely troublesome problem. Furthermore, in recent years, advances in dyes and solid acids have significantly improved coloring ability, so when printing with desensitizing ink, the desensitizing effect is less likely to occur than before. There is a tendency that a sufficient effect cannot be obtained unless the amount of ink is increased, and if the amount of ink applied is increased, the ink drying speed is further slowed down, which tends to cause many troubles in the printing process.

Yet another problem is that when the amount of desensitizing ink increases, when writing or printing with colored ink on the surface printed with desensitizing ink, the printed area of the colored ink may noticeably change color, fade, or bleed. As a way to improve these problems, attempts were made to increase the amount of pigments and binder, but the ink drying properties were not very fast, and increasing the amount of pigments and binder decreased the proportion of desensitizer in the ink, resulting in less drying. It was not a practical improvement because a sufficient sensory effect could not be obtained.
In addition, cobalt naphthenate, cobalt oleate, or manganese, which are ink dryers used in film-colored inks (M polymerized inks), were added to the desensitizing ink, but no great effect was obtained. There wasn't.

The purpose of the present invention is to print desensitized ink on the colored surface (solid acid coated surface) of the lower paper in pressure-sensitive copying paper, and to maintain the ink drying properties of the desensitized ink even if the paper is stacked or rolled up and stored. It is fast and has no migration phenomenon, and also prevents color change and fading of colored ink.
It is an object of the present invention to provide a desensitizer that does not bleed and, most importantly, has a desensitizing effect.

(D>Means for Solving the Problems) As a result of extensive research, the present inventor has succeeded in developing a desensitizing ink that is particularly suitable for use in flexo and gravure printing.

That is, the present inventor uses the following general formula (1) as a desensitizing agent for flexo and gravure printing (n is an integer of 7 to 25, and R is an integer of carbon number 5 to 18). . By using the compound shown as a desensitizer and forming it into an ink together with pigments, binders, organic solvents, etc., it exhibits an excellent desensitizing effect, and there is little migraine phenomenon on the printed surface, and furthermore, even when colored ink is printed, it does not change color or fade. The present invention was based on the knowledge that it was an excellent desensitizer as there was no bleeding.

Specifically, the desensitizer of the present invention of formula (I) is, for example, polyoxyethylene amyl methyl ether, polyoxyethylene capryl methyl ether, polyoxyethylene hebutyl methyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl methyl Ether, polyoxyethylene undecyl methyl ether, polyoxyethylene lauryl methyl ether, polyoxyethylene trizosyl methyl ether, polyoxyethylene myristyl methyl ether, polyoxyethylene pentadecyl methyl ether, polyoxyethylene cetyl ether, polyoxyethylene One type from stearyl methyl ether, polyoxyethylene oleyl methyl ether, etc. and/or
Or, it is preferable to use two or more types, and among them, R is an alkyl group having 12 to 18 carbon atoms, and the number of n moles of ethylene oxide + CH2CH20 + r+ is 10
20 moles.

The desensitizer of the present invention is preferably added in an amount of 25 to 80 percent by weight, particularly preferably 30 to 75 percent by weight, based on solid weight in the ink.

If it is less than 25% by weight, a sufficient desensitizing effect cannot be obtained, and if it is more than 80% by weight, the amount of pigment and/or binder added will decrease, and when printing on a support such as paper, the desensitizing ink printed area will become transparent and will not be attached. The adhesion force (adhesion force) decreases, and furthermore, the adhesion force (adhesion horn) decreases when printing with colored ink.

As the pigment used in the present invention, one and/or two types from magnesium oxide, calcium oxide, zinc oxide, titanium oxide, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, barium sulfate, kaolin, talc, etc. Use more than that.

The binder used in the present invention includes phenolic resin, rosin-modified phenolic resin, butyral resin, polyamide resin, ketone resin, mylene resin, acrylic resin,
One and/or two or more of urea resins, melamine resins, epoxy resins, nitrocellulose, ethylcellulose, etc. are used.

Examples of organic solvents used in the present invention include alcohols such as methanol, ethanol, and isopanol, acetone,
One and/or two or more of ketones such as methyl ethyl ketone and esters such as ethyl acetate are used.

Furthermore, in the present invention, naturally occurring animal and vegetable oils such as linseed oil, tung oil, soybean oil, cottonseed oil, and whale oil, or modified products thereof, may be used as vehicles for ink properties (improving ink viscosity (flow), binder solubility, etc.), if desired. Can be used.

By forming the desensitizer of the present invention as described above into an ink together with conventionally known pigments, binders, and organic solvents, the desensitizing effect is greatly superior, so the amount of ink applied is small, and the ink drying properties are extremely high. As a result, the speed of the printing press was increased, which greatly contributed to improving productivity.

Hereinafter, preferred embodiments and excellent effects of the present invention will be specifically explained using the most representative examples. All parts below represent parts by weight.

(E) Examples Example 1 Polyoxyethylene amyl methyl ether (7 moles of ethylene oxide > 30 parts titanium oxide
10 parts butyral resin
7 parts ketone resin 6 parts methanol 17.5 parts ethanol 17.5 parts were mixed to prepare a desensitizing ink for flexography and gravure with an ink solid content concentration of 60%. This ink was applied to commercially available Mitsubishi NCR Paper Shimokawashita Paper-40 using a flexo printing machine (manufactured by Miyakoshi Seisakusho).
Printing was carried out so that the ink coverage (solid content coverage) was 1.0 g/m on the coated surface of the solid acidic phenolic resin).

Example 2 Polyoxyethylene amyl methyl ether of Example 1 (
(7 moles of ethylene oxide) to (1 mole of ethylene oxide)
An ink was formed and printed in the same manner except that the same amount was replaced with 5 mol).

Example 3 Polyoxyethylene amyl methyl ether of Example 1 (
(7 moles of ethylene oxide) to (2 moles of ethylene oxide)
An ink was formed and printed in the same manner except that the same amount was replaced with 5 mol).

Example 4 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene octyl methyl ether (7 moles of ethylene oxide) was replaced with 7 moles of ethylene oxide.

Example 5 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene nonyl methyl ether (7 moles of ethylene oxide) was replaced with polyoxyethylene nonyl methyl ether (7 moles of ethylene oxide).

Example 6 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene lauryl methyl ether (10 moles of ethylene oxide) was substituted for 7 moles of ethylene oxide.

Example 7 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene oleyl methyl ether (10 moles of ethylene oxide) was substituted for 7 moles of ethylene oxide.

Example 8 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene oleyl methyl ether (ethylene oxide 25 moles) was substituted for 7 moles of ethylene oxide.

Comparative Example 1 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene butyl methyl ether (10 moles of ethylene oxide) was substituted for 7 moles of ethylene oxide.

Comparative Example 2 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene lauryl methyl ether (6 moles of ethylene oxide) was substituted for 7 moles of ethylene oxide.

Comparative Example 3 Polyoxyethylene amyl methyl ethyl of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene lauryl methyl ether (ethylene oxide 26 moles) was substituted for 7 moles of ethylene oxide.

Comparative Example 4 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene oleyl methyl ether (ethylene oxide 28 moles) was substituted for 7 moles of ethylene oxide.

Comparative Example 5 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxynonyl ether (10 moles of ethylene oxide) was substituted for 7 moles of ethylene oxide.

Comparative Example 6 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene oleyl ether (15 moles of ethylene oxide) was substituted for 7 moles of ethylene oxide.

Comparative Example 7 Polyoxyethylene amyl methyl ether of Example 1 (
An ink was formed and printed in the same manner except that the same amount of polyoxyethylene oleyl ether (ethylene oxide 20 moles) was substituted for 7 moles of ethylene oxide.

Test method The printed paper thus obtained was tested and measured in the following manner, and the results are shown in Table 1.

The degree of color development and decolorization of the ink printed area was observed when the bottom paper printed with 0 desensitization effect was printed with a commercially available 3H', ICR paper black coloring top paper (N-40) and printed with a dot printer. The degree was marked as ◎, ○, △, and X.

(◎ mark: Completely erased, ○ mark: Should be erased, △ mark: Slightly erased, × mark: No eraser effect ) 0 ink drying property Combine the printed side of the printed bottom paper with the solid acid coated side of the bottom paper before printing, place a 'j/'III weight on 50, and press 1.
After leaving it for a week (indoors at 25 degrees Celsius), remove the weight, and pass the solid M-coated surface of the lower paper before printing and the upper Mitsubishi NCR paper Bushi Blue coloring paper together through a calendar to develop color, and the color develops by migration of the desensitized ink. The degree of decolorization (the area in contact with the desensitized ink printed area) was measured using a color difference meter, and the re-ink drying property (rate) was determined using the following formula. The larger the number, the higher the ink drying rate (percentage).

Ink drying rate (percent) = Color development reflectance of areas in contact with desensitized ink printed areas Color development rate of areas not in contact with desensitized ink printed areas O Adhesion resistance and bleeding of colored ink Immediately after desensitizing ink printing Print letterpress colored ink (blue) on the desensitized ink printed area, observe the adhesion and bleeding of the colored ink = 18-, and evaluate the degree of Q, ■, Δ.
It was marked as a mark. (○ mark: good, ■: poor, 1: poor, △: poor) (blank below) Test results (F') Effects As shown in Table 1, the present invention The desensitizing agent polyoxyethylene alkyl methyl ether has a great desensitizing effect and also dries the ink very quickly.As a result, the adhesion of the colored ink is good, there is no bleeding, and the coloring of the colored ink does not change or fade after printing. It achieved the excellent effect of not having any problems, speeding up printing presses, improving productivity, and was recognized as having great value as a practical product.

Procedure Neho Seisho (self-motivated) February 76, 1988 1, Incident Indication 1985 Patent Application No. 296381@
2. Name of the invention: Desensitizer composition for pressure-sensitive copying paper 3. Relationship with the case of the person making the amendment Patent applicant: ffi (600) 2111 4. Subject of the amendment (1) Items 5 to 5 from the bottom of the specification No. 9 Correct "polyoxyethylene octyl ether" in line 4 to "polyoxyethylene octyl methyl ether".

(2> Correct "polyoxyethylene cetyl ether" to "polyoxyethylene cetyl methyl ether" on page 10, lines 3 and 4.

(3) Page 18, lines 12-16 "Ink drying rate (percent) = Color reflectance of the area in contact with the desensitized ink printed area xlooo J is corrected as follows.

"Ink drying rate (percentage) = rate of color development of the area that came into contact with the desensitized ink printed area" Procedure Neho Seisho (self-motivated), Q/D 1, 1988, of the incident. Display 1986 Patent Application No. 296381 2,
Name of the invention: Desensitizer composition for pressure-sensitive copying paper 3, relationship with the amended case Patent applicant address: 3-4-2 Marunouchi, Chiyoda-ku, Tokyo Name (598) Mitsubishi Paper Mills Co., Ltd. e (600) ) 2481 4. "Claims" column and "Detailed Description of the Invention" column of the specification to be amended (1) The scope of claims is amended as shown in the attached sheet.

(2) "Represents an integer" on page 9, line 6 of the specification is corrected to "represents an alkyl group."

Attachment 2, Claims ``A desensitizer composition for pressure-sensitive copying paper containing a compound represented by the following general formula [I].

R-0+CH2Chi 20wn CHa (I)
(n is an integer of 7 to 25, R represents an alkyl group having 5 to 18 carbon atoms). ”

Claims (1)

[Scope of Claims] Desensitizer composition for pressure-sensitive copying paper R-O-(CH_2CH_2O)-_nCH_3 [I] containing a compound represented by the following general [I]
] (n represents an integer of 7 to 25, R represents an integer of carbon number 5 to 18).