JPH01301364A - Desensitizer composition for pressure sensitive copying paper - Google Patents

Abstract

PURPOSE:To obtain a desensitizer which has an extremely large desensitizing effect, can be printed with an offset press, and is excellent in hydrophobic property, by a method wherein the title desensitizer composition for pressure sensitive copying paper is an alkylene oxide adduct of a specific amine compound, having a compound of which the molecular weight is within a specific range. CONSTITUTION:A desensitizer composition is an alkylene oxide adduct of an amine compound as given in the general formula (1), having a compound of which the molecular weight is 500 to 3,000. In the formula, R1, R2, R5 and R6 are hydrogen or an alkyl radical and at least two radicals among them are hydrogen. R3 and R4 are a straight- chain or a branching alkylene radical of 2 to 4 in carbon number. Further, the alkylene oxide herein means propylene oxide, butylene oxide, styrene oxide, etc., which is a mixture of one or two or more kinds of alkylene oxide. The additional order of two or more kinds of alkylene oxide herein is not specifically limited, and either a block type or a random type may be preferable. The desensitizer composition is inferior in heat resistance and light fastness for that of under 500 in molecular weight, and the desensitizing effect is decreased for that of over 3,000 in molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a desensitizer for pressure-sensitive copying paper, and more particularly to a desensitizer for pressure-sensitive copying paper that has excellent storage stability.

[Conventional technology]

As is well known, pressure-sensitive copying paper contains colorless electron-donating dyes such as crystal violet lactone, mikite green, benzoylleucomethylene blue, 3-diethylamino-7-pendylaminofluoran, and benzo-β-naphthospiropyran. A contact reaction between microcapsules dissolved in a non-volatile oil and enclosing microdroplets of the solution, and an electron-accepting substance (hereinafter referred to as a color developer) that reacts with this colorless dye to develop color. It has been known for a long time that colored images can be obtained. Pressure-sensitive copying paper specifically utilizes this principle, for example, U.S. Pat.
No. 505,470, No. 2.505.489, No. 2.5
No. 05,471, No. 2,548,366, No. 2,71
No. 2,507, No. 2,730,456, No. 2,730
, No. 457, No. 3,418,250, No. 3,672,
There are some related to No. 935, etc.

When such copy paper is used for slips, etc., make sure that the characters written on the first sheet of multiple stacked slips are not copied onto the lower part of the paper. is often required. Conventionally, in order to prevent color development in specific areas of pressure-sensitive copying paper, in order to prevent color development in specific areas of pressure-sensitive copying paper, printing machines, etc. A method of applying fJIi on a color developer sheet using fJIi is widely adopted.

Regarding desensitizers, see US Pat.
No. 6-22651, No. 46-29546, Japanese Unexamined Patent Publication No. 1973
-32915, Special Publication No. 47-38201, 4B
-4050, JP-A-48-6805, JP-A-49-
No. 4484, No. 49-19647, No. 49-2300
No. 8, No. 49-23850, No. 50-14571,
No. 50-29365, No. 53-23724, No. 61
-2515, JP-A No. 53-23724, JP-A No. 56-6
No. 7291, German Patent Application (OLS) 2.343.8
No. 00, No. 2,359,079, No. 2.361,85
Although detailed in No. 6, the following specific examples are given.

Quaternary ammonium salts such as dodecyltrimethylammonium chloride and octadecyl ammonium chloride, aliphatic amines such as dodecylamine, 2,4.4-1-
Substituted oxazolines such as dimethyl-2-oxazoline, reaction products of diamines or polyamine derivatives having a cyclic structure such as xylene diamine, N-aminopropylpiperidine, and alkylene oxide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene Glycol, polypropylene glycol, glycerin-propylene oxide adduct,
Examples include polyoxypropylene alkylamines, spiroacecool diamines, and glycidyl ether adducts of amines.

[Problem to be solved by the invention]

However, when these desensitizers are used, various practical problems occur. In other words, the desensitizing ability may decrease under various conditions such as heat, humidity, and light, or the desensitizer applied to a specific portion of a desired sheet of paper may deteriorate due to heat or moisture on the desired portion of another sheet of adjacent paper. There is a phenomenon in which the desensitizing effect spreads to unnecessary areas. Furthermore, there is a phenomenon in which the area where the desensitizer is applied turns brown over time. Furthermore, most of these desensitizers have insufficient desensitizing effect, and in particular, they are not effective to the same extent for all types of color developers. Furthermore, it is inferior to hydrophobicity, so it is difficult to interact with water.
When a desensitizing agent is applied to a desired area using an off-cent printing method that utilizes the B property, problems such as water erosion of the desensitizing ink and plate staining occur, making it impossible to obtain stable printing.

Therefore, the purpose of the present invention is to
The object of the present invention is to provide a novel desensitizing agent that has an extremely large desensitizing effect, can be printed on an offset printing machine, and has excellent hydrophobicity.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors have conducted intensive research and have developed an alkylene oxide adduct of an amine compound represented by the following general formula, which is characterized by containing a compound having a molecular weight of 500 to 3000. A desensitizer composition for pressure-sensitive copying paper is provided.

(In the formula, Rl+ Rz, Rs, Rh are hydrogen or alkyl groups (methyl, ethyl, propyl, etc.), and at least two of them are hydrogen. Rz, R4 have 2 to 4 carbon atoms.
is a straight-chain or branched alkylene group. Further, alkylene oxide includes propylene oxide, butylene oxide, styrene oxide, etc., and is a mixture of one or more alkylene oxides. Here, the order of addition of two or more alkylene oxides is not particularly limited, and may be either a block type or a random type.

) [Function] Since the desensitizer composition of the present invention is an alkylene oxide adduct of an amine compound, it has a desensitizing effect on all types of color developers. Furthermore, since it has excellent hydrophobicity, it has good suitability for offset printing, and problems such as water loss and plate staining do not occur. The undiscovered desensitizer composition has a molecular weight of 5
00 to 3000, it has a high desensitizing effect and at the same time has excellent heat resistance and light resistance. Because the molecular weight is 50
If the molecular weight is less than 0, the heat resistance and light resistance will be poor, and if the molecular weight exceeds 3,000, the desensitizing effect will decrease.

[Specific structure of the invention]

The desensitizer composition of the present invention contains an alkylene oxide adduct of the above-mentioned amine compound having a molecular weight of 500 to 3,000 as a desensitizer component, and contains various other components as necessary. As these components, natural or synthetic polymer compounds, inorganic compounds, vegetable oils, organic solvents, waxes, etc. are used.

Examples of natural or synthetic polymer compounds include ketone resins,
Polyamide resins, maleic acid resins, phenolic resins, epoxy resins, alkyd resins, melamine resins, urea resins, nitrocellulose, ethylcellulose, butyral resins, polyvinyl alcohol, gelatin, shellac, etc. are included, and these are present in the desensitizer composition with 0 to It is used in a proportion of 40%, preferably 5-25%. Examples of inorganic compounds include titanium oxide, zinc oxide, barium sulfate, potassium carbonate, barium carbonate, magnesium hydroxide, silicon dioxide,
Examples include talc, which accounts for 0 to 50% of the desensitizer composition.
, preferably in a proportion of 0 to 40%. Examples of vegetable oils include linseed oil, tung oil, soybean oil, cottonseed oil, etc., which contain O to 50%, preferably 0, in the desensitizer composition.
Used at a rate of ~20%. Examples of organic solvents include methanol, ethanol, ethyl acetate, impropatol, toluene, hexane, methyl ethyl ketone, methyl isobutyl ketone, etc., which are present in the desensitizer composition.
- IQ%, preferably 0-5%.

The desensitizer composition of the present invention can be easily prepared by mixing and dissolving the above-mentioned components, or by kneading them using a three-roll mill, a sand mill, a dyno mill, etc. as necessary. The desensitizer composition is often applied to the developer sheet by using a printing machine, but it may also be applied by spraying, or by handwriting with a crayon or eraser-like substance.

The application amount of the desensitizer composition is 0.5 g/m to 10.0
g/d, preferably 1.0 g/rrr to 5. Og/r
It is rr.

Specific examples of color developers to which the desensitizer composition of the present invention can be applied include:
Inorganic color developers such as kaolin, bentonite, acid clay, zeolite, activated clay, acpal guide, etc., phenolic aldehyde polymer, phenolacetylene polymer, polyvalent metal salt of phenol polymer, salicylic acid, aromatic carboxylic acid, zinc , polyvalent metal salts of aromatic carboxylic acids and metals such as tin and aluminum, and organic color developers such as polymers of aromatic carboxylic acids and aldehydes or acetylene.

These color developers are applied to a support such as paper along with a binder such as styrene-butadiene latex or starch.

On the other hand, examples of colorless dyes (color formers) that cause a color reaction with a color developer include diphenylmethane compounds, triarylmethane compounds, xanthine compounds, spiropyran compounds, and thiazine compounds. These are either dissolved in a solvent and encapsulated, or dispersed in a binder solution, and applied to a support such as paper. Solvents include cottonseed oil, kerosene, paraffin, naphthenic oil, alkylated biphenyls,
Natural or synthetic oils such as alkylated terphenyl, chlorinated paraffin, and alkylated naphthalene may be used, and these oils may be used alone or in combination. For information on how to make capsules,
U.S. Patent No. 2,800,457, U.S. Patent No. 2.800.458
A method using coacervation of hydrophilic colloids described in British Patent No. 867, 797, British Patent No. 950,
Interfacial polymerization method described in No. 443, etc., JP-A-56-1
No. 02934, No. 57-71634, No. 57-105
No. 236 1. There is an in-situ (in-5-itu) polymerization method described in No. 57-110332 and the like.

〔Example〕

The desensitizing effect of the desensitizer composition of the present invention was confirmed using the following color developer sheet and color former sheet.

(Color developer sheet A) 200 g of activated clay was dispersed in 800 parts of water (parts by weight, hereinafter the same), and then the pH of the dispersion was adjusted to 10.0 with a 20% aqueous sodium hydroxide solution. Add to this 40 parts of styrene-butadiene copolymer latex and 20% solid content.
A coating solution was prepared by adding 30 parts of a starch aqueous solution. 40g/n of this coating liquid? The color developer sheet A was obtained by coating the base paper with a coating rod to a solid content of 5 g/m and drying.

(Developer sheet B) 700 parts of water, 20 parts of zinc oxide, 180 parts of calcium carbonate, and 4 parts of zinc 3,5-di-α-methylbenzylsalicylate.
0 parts were added and mixed, and dispersed for 30 minutes using an attritor. To this liquid were added 25 parts of styrene-butadiene copolymer latex in solid form and 60 parts of a 20% starch aqueous solution, and the mixture was uniformly stirred to prepare a coating liquid. 40 g/r of this coating liquid
A developer sheet B was obtained by coating the base paper of d with a coating rod to a solid content of 4 g/rd and drying.

(Developer Sheet C) 200 parts of calcium carbonate and 40 parts of rose phenylphenol-formalin condensate were added and mixed to 700 parts of water, and dispersed for 30 minutes using an attritor. Add 25 parts of styrene-butadiene copolymer latex in solids to this liquid, and
60 parts of 0% starch aqueous solution was added and stirred uniformly to prepare a coating solution. Apply this coating liquid to 40 g/rd base paper with a solid content of 4
It was coated with a coating rod and dried to obtain a color developer sheet C so as to give a color developer sheet of g/lri.

(Color forming agent sheet A) 10 parts of acid-treated gelatin having an isoelectric point of 8.0 and 10 parts of gum arabic were dissolved in 60 parts of water at 40°C, and 0.2 parts of sodium alkylbenzenesulfonate was added as an emulsifier. 50 parts of color former oil was added to this and emulsified. The color former oil was prepared by dissolving 3.5% by weight of crystal violet lactone and 15% by weight of benzoyl leucomethylene blue in 5 parts of diisopropylbiphenyl oil. 4 when the average size of the emulsified droplets reaches 8 microns.
100 parts of water at 0°C was added to suppress the progress of emulsification, and while stirring was continued, 210 parts of water at 30°C was added, and 20% hydrochloric acid was added to adjust the pH of the system to 4.4.

The liquid was further cooled to 8°C while stirring, and then heated to 20°C.
% geltaraldehyde is added followed by lO
% carboxymethyl starch solution was added, 25% caustic soda was added dropwise, the pH was adjusted to 8.5, and the liquid temperature was adjusted to 40%.
Microcapsules with hardened walls were obtained by heating to .degree.

10 parts of wheat starch was dispersed in this liquid, and the mixture was coated on 40 g/rd paper at a solid content of 5 g/rd and dried to obtain color former sheet A.

(Coloring agent sheet B) 1% by weight of crystal violet lactone in 4 parts of diisopropylbiphenyl, 4% by weight of 3-diethylamino-7-phenylaminofluoran, 3% by weight of 3-diethylamino-7,8-benzofluorane, 3. 0.5% by weight of 6-bismethoxy-fluorane and 2% by weight of benzoylleucomethylene blue are dissolved to form a color former oil,
Produced in the same manner as color former sheet A using 50 parts of this,
Color former C) B was obtained.

(Preparation of a $i sensitizer composition) 60 parts of the desensitizer of Examples (11 to (5)) shown in Table 1 and Comparative Examples (1) to (4) shown in Table 2, and rosin as a binder. Modified maleic acid resin (softening point 120'C).

Oxide 30) Add 1 part of titanium oxide to the face made by heating and melting 30 parts of titanium oxide.
0 parts was added and kneaded using a three-roll mill to obtain a desensitizer ink.

(: Evaluation of $i sensitizer composition) Evaluation of the desensitizer composition was performed by the method shown below.

(1) Suitability for offset printing Lightweight offset printing a (manufactured by Ryobi,
50ON) and each developer sheet A.

Printing was applied on B and C. The evaluation includes visual observation of the staining of the printing plate during printing, ink transferability, and water erosion of the ink.
The suitability for offset printing was determined.

(2) Desensitizing effect In order to evaluate the color development prevention effect of the desensitizer, each desensitizer ink was placed on the developer sheets A, B, and C using an RI tester ■
Printing was applied using a mold (manufactured by Mei Seisakusho) at a concentration of 2 g/rrl. Next, these sheets and the color former sheet)
The coated surfaces of A and B were combined and printed using an electric typewriter, and the presence or absence of disappearance of the colored characters was visually determined.

(Heat Resistance of 31M Sensitizing Effect) The color developer sheet on which the desensitizing effect was evaluated was treated in a hot air dryer (100° C., 2 hours), and whether or not the desensitizing effect disappeared due to heat was visually determined.

(4) Light resistance of desensitizing effect The color developer sheet on which the desensitizing effect was evaluated was exposed to direct sunlight for 48 hours, and whether or not the desensitizing effect disappeared due to light was visually determined.

These evaluation results are shown in Table 3. The evaluation criteria were: ○ when no color developed, Δ when slight color developed, and × when color clearly developed. In Table 3, Examples (11 to (7)) are examples using the desensitizing ink of the present invention, and Comparative Examples (11 to (4) are examples using the known desensitizing ink. It is.

(Effects of the Invention) As described above, according to the present invention, since the alkylene oxide adduct of an amine compound is used as the desensitizer composition,
It has a desensitizing effect on all types of color developers, and has excellent printability and storage stability.

Claims (1)

[Scope of Claims] A desensitizer composition for pressure-sensitive copying paper, which is an alkylene oxide adduct of an amine compound represented by the following general formula, and contains a compound having a molecular weight of 500 to 3,000. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_5, R_6 are hydrogen or alkyl groups (methyl, ethyl, propyl, etc.), and at least two of them are hydrogen. R_3, R_4 is a straight chain or branched alkylene group having 2 to 4 carbon atoms.Alkylene oxide includes propylene oxide, butylene oxide, styrene oxide, etc., and is a mixture of one or more alkylene oxides. (Here, the order of addition of two or more alkylene oxides is not particularly limited, and may be either a block type or a random type.)