JPS60131289A - Desensitizer composition - Google Patents

Abstract

PURPOSE:To enhance a desensitizing effect and bleeding resistance, by incorporating a substance obtained by the reaction of a diamine such as an aromatic diamine of a specified general formula with a compound having at least one oxysilane group. CONSTITUTION:A developer composition forming no color is prepared by incorporating a substance obtained by the reaction of one or more in mixture of aromatic diamines, cyclohexyl diamines and perhydronaphthalene diamines of formulas I , II, III, IV, V and VI, wherein each of R1 and R2 is a hydrogen atom or a 1-2C alkyl group, with a compound having at least one oxysilane group. In this case, in addition to a binder such as a ketone resin and a polyamide resin, an additive for enhancing printing adaptability or brightness, e.g., titanium oxide or zinc oxide, is added to the composition.

Description

[Detailed description of the invention] The present invention relates to a desensitizer for carbonless paper.

More specifically, the present invention relates to a desensitizer having the ability to suppress or block the coloring function of an electron-accepting compound or solid acid for changing color from colorless to carbonless pressure-sensitive copying paper.

In general, pressure-sensitive copying paper is made by dissolving a pressure-sensitive dye such as an electron-donating phenylmethane compound or a leuco substance in a non-volatile oil, micro-encapsulating it with a capsule shell-forming substance, and applying it to the paper and electron-accepting material. The paper coated with a chemical substance or a solid acid, etc., is stacked on top of each other, and when pressure is applied, capsule rupture occurs at the pressurized area, and phenylmethane-based Color is generated by the coloring mechanisms of compounds and leuco substances. A desensitizer is a substance used for the purpose of suppressing or preventing color development by applying it in advance to areas where color development is unnecessary on either side of the surface coated with an electron-accepting substance or an electron-donating substance. be. □ The microcapsules containing the pressure-sensitive dye, which is an electron-donating substance, or the electron-accepting substance are each applied to the entire surface of the paper, so a desensitizer is applied to areas where color development is not required by printing or coating. There are widely used methods to do this.

Color developers are electron-accepting substances such as reed; solid acids of clay minerals include acid clay, bentonite, attapulgide, zeolite, and kaolin; examples of organic acids include tannic acid, gallic acid, and pro-gallic acid. Also known are aromatic carboxylates such as zinc salicylate, tin salicylate, and zinc 3.5-tert-butylsalicylate.

The developer may be used alone or as a mixture, and the developer may be applied to paper or other support together with a binder, such as styrene-butadiene latex.

The other coloring agent is an electron-donating substance that develops color by reacting with the color developer, and is a colorless organic compound such as crystal violet lactone, rhodamine anilinolactone, malachite green lactone, pensoyl leucomethylene blue, Michler's human roll, N-allyl leukoolamine, etc. are known.

The coloring agent is dissolved in synthetic or natural oil such as chlorinated diphenyl, chlorinated terphenyl, chlorinated halaffin, chlorinated naphthalene, alkylated naphthalene, kerosene, paraffin and naphthenic oil, and applied to the support together with a binder. Alternatively, they are encapsulated by the method described in US Pat. No. 4,800,457 and coated onto a support, optionally with additives such as anti-smudging agents such as starch particles.

These color reactions are described, for example, in U.S. Pat. No. 2,505,470.
No. 40732, UK Patent No. 825354
In addition to the recording materials exemplified in the specifications of this issue, it is also used for recording materials such as spirit printing, stencil printing, automatic ticket vending systems, fingerprint collection systems, and letter writing systems.

Conventionally, known desensitizers include tertiary amines obtained by addition polymerization of ethylene oxide to monoalkylamines, aralkylamines, or ethanolamines (Japanese Patent Publication No. 46-2954
Polymeric primary alkyl amines such as dodecylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, alkyl or arylamine acetates (Japanese Patent Publication No. 35697/1983), average molecular weight 400 to 5,000 of polypropylene glycol (%
public t+]s.

-27732), spiroacetal diamine (% 1975-4370v, by reacting spiroacetal diamine with a compound containing an oxy2 group, most of which are strongly hydrophilic substances, so Toppan Printing Printing using a printing machine other than a letterpress printing machine is prohibited.
It was difficult to The ability to use desensitizers for printing in printing formats other than letterpress presses provides a number of benefits. For example, if you can print with an offset lithographic printing machine, you will be able to print at (1
) Since it is offset, the ink buildup is uniform (2
) Since the printing pressure is applied uniformly over the printing surface, there is less destruction of the paper microcapsules (3) Easy plate making (4) Fast printing speed (5) Beautiful print finish (6) The printing machine is Since it is widely used, it is expected to have advantages such as high demand.

Attempts have been made to print a desensitizer using a wet offset printing machine, for example, using a carbonaceous compound as the desensitizer, but conventional desensitizers have poor printability and bleed resistance. The desensitization effect was also not sufficient.

Although attempts have recently been made to print desensitizers by waterless lithographic printing, it has been strongly desired that desensitizers that can be printed using conventional wet offset printing machines have been widely used.

The present inventors have previously used compounds described by the general formula in the claims as desensitizer components, such as tolylenediamine,
It was disclosed that xylerine diamine, monomethylcyclohexyldiamine, dimethylcyclohexyldiamine, diaminophenylmethane, diaminocyclohexylmethane, diaminonaphthalene, diaminoperhydronaphthalene, etc. have excellent desensitizing effects.

As a result of further research, the present inventors have found that by reacting a compound having at least one oxirane group during the dispensing of the diamine, the desensitizing effect and resistance of aromatic diamines and hydrogenated aromatic diamines can be improved. It has been found that the bleedability is improved and the above conditions are completely achieved. These aromatic diamines and perhydro aromatic diamines are known compounds, and specific examples include tolylene-2,3-diamine, tolylene-2,4-cyamine, tolylene-45
-diamine, tolylene-2,6-diamine, ortho-xylene-3,4-diamine, ortho-xylene-3,5-diamine, ortho-xylene-3,6-diamine, meta-xylene-2,4-diamine, meta-xylene- 2,5-diamine, meta-xylene-2,6-diamine, meta-xylene-5,6-diamine, laxylene-2,3-diamine, para-xylene-45-diamine, para-xylene-2
, 6-diamine, hydrogenated compounds of the above compounds, i.e. monomethylcyclohexyldiamine, dimethylcyclohexyldiamine, diphenylmethane-4,4'-diamine, dicyclohexylmethane-4,4'-diamine, naphthalene-1,5-diamine, Examples include perhydronaphthalene-1,5-diamine.

On the other hand, examples of compounds containing at least one oxirane group in the molecule are as follows.

Examples include alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide, arylene glycidyl ethers such as Epico) 828, Epico) 834, and Epicoat 1oo1.

It is easy to react an aromatic diamine with a compound containing a perhydro aromatic cyanmint oxirane group, and addition polymerization is generally carried out in a pressure cooker. Addition polymerization of 4 mol of monoepoxide per 1 mol of aromatic diamine or perhydro aromatic diamine can be carried out without a catalyst. To obtain an epoxide addition polymer of 4 moles or more,
Caustic alkali is commonly used as a catalyst, but
In some cases, it is also possible to use a commercially available inorganic acid.

The desensitizer composition of the present invention contains as a total desensitizing component a substance reacted with at least one of the aromatic diamines, cyclohexyl diamines, and perhydronaphthalene diamines and a compound having one or more oxirane groups in the molecule. Generally, the following substances are added to the other ingredients. One is that those often used as binders include ketone resins, polyamide resins, maleic resins, phenolic resins, epoxy resins, fumar resins, urea resins, melamine resins, alkyd resins, acrylic resins, nitrocellulose, Commercial molecular compounds include methylcellulose, cellulose acetate butyrate, butyral resin, casein, gelatin, polyvinyl alcohol, etc.

Secondly, materials such as titanium oxide, zinc oxide, barium sulfate, magnesium hydroxide, and talc are used to improve printability, whiteness, and hiding power. Third, as a solvent, glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, and polypropylene glycol, or alcohols are used. Additionally, in order to increase the abrasion resistance, parafille and wax are used in combination, as well as drying oils such as oil, tung oil, and soybean oil, and semi-drying oils such as cottonseed oil, rapeseed oil, and rice bran oil. Ru. This does not preclude the use of starch or the like as an anti-fouling agent in some cases. Other desensitizers can also be used in combination.

The present invention will be specifically explained below with reference to examples.
It can be seen that excellent effects can be obtained by using the product of the present invention.

Preparation of desensitizing ink and production of printed matter> 60 parts of the desensitizer shown in the table below and 32 parts of rosin-modified maleic acid resin (trade name: Hitarakku = After kneading 2 parts of titanium oxide at 3 bottles/-1 mil, polyethylene glycol (5++-1jk4o o) tse7+ was obtained. A y-++i**.

The ink of the present invention and the ink of the comparative example were printed on inner sheets of commercially available carbonless pressure-sensitive copying paper at a density of 3.0 f/♂.

<Test method> ■Color development test Using the above printed paper, apply 1001 to a sphere with a diameter of 0.8 mm.
A coloring operation was carried out by applying a load of 100 mL and moving at a speed of 5 m/min. The results are summarized in the table below. The numerical values indicate reflective visual density values (visual density, Vis, D) measured with a microdensitometer.

■Bleed resistance test The above printed material and non-desensitized carbonless pressure-sensitive copying paper were stacked together, a load of 10 f/cd was applied, and the temperature was left in a constant temperature and humidity room at a relative humidity of 90 degrees and a temperature of 20 degrees Celsius for days in the garden. Then, a color development test was conducted on the above-mentioned printed matter and non-desensitized carbonless pressure-sensitive copying paper. The results are shown in the table.

The effectiveness of the desensitizing effect of the compounds of the invention is clear from the table.

That is, regarding the desensitizing effect in the table, the smaller the numerical value, the greater the effect, and the numerical value of 0.05 or less indicates that the desensitizing effect is significant.

The difference in desensitization effect between areas coated with the composition of the present invention and areas not coated will be apparent in the bleed resistance test results section.

That is, the fact that is clear in each example is that the bleed resistance when coated is 1/100 of the density when not coated, indicating complete desensitization.

Furthermore, by reacting an aromatic diamine or a perhydro aromatic compound with a compound having an owaritane group, the desensitization effect is approximately twice as high as that obtained when no reaction is performed.

(Clothing) Color development test and bleed resistance test results 14- 1
Representative view l- λ Special IFF Claims Represented by the following general formulas (1) to [Vl] The invention is characterized by containing a substance obtained by reacting one or a mixture of aromatic group diamines, cyclohexyl diamines, and Bercht's 7-talene diamines with a compound containing at least one of the above oxirane groups. A color developer composition that transforms a colorless color into a color.

[In the formula, turtle and 14 are hydrogen atoms and/or carbon atoms 1 to 2
represents an alkyl group. ] A7^

Claims (1)

[Claims] Reaction of one or a mixture of aromatic diamines, cyclohexyl diamines, and perhydronaphthalene diamines represented by the following general formulas CI) to (Vl) with a compound containing at least one individual oxirane group. 1. A composition for a color developer capable of producing a colorless color, characterized in that it contains a substance obtained by the above process. [In the formula, Tomo and Tori represent a hydrogen atom and/or an alkyl group having 1 to 2 carbon atoms. ]