JPH10297084A - Desensitizer for pressure-sensitive copy paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain superior desensitization effect and print suitability to offset printing, etc., by adding and reacting in the same system a specific amount of alkylene oxide and a specific amount of glycydil ether to active hydrogen of a specific amine such as diethylene triamine, triethylene tetramine or the like. SOLUTION: 2-30 mol (preferably 4-24 mol) of alkylene oxide and 2-30 mol (preferably 4-24 mol) glycydil ether expressed by a formula II wherein R is an alkyl group, an alkenyl group or aryl group of C3 ) or more are reacted to one mol of an amine expressed by a formula I wherein (n) is an integer 1-5. A mixed addition substance of the amine resulting from the competitive addition of the above two to active hydrogen of the amine is made an effective component. When an addition amount of the alkylene oxide and a mixture ratio to the glycydil ether are changed, physical properties such as a viscosity, a hydrophobic feature, etc., can be suitably adjusted in accordance with a use purpose. The above two can be used singly or together.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a desensitizer for pressure-sensitive copying paper, which has a high desensitizing performance and is excellent in various printing suitability such as offset printing and set-off property. .

[0002]

BACKGROUND OF THE INVENTION In a pressure-sensitive copying paper, a color former (leuco dye, a so-called coloring agent as a dye precursor) in a microcapsule jumps out under the external pressure of a writing pressure, a typewriter, etc. Contact with and react with a color developer consisting of a solid acid such as an aromatic carboxylic acid or a polyvalent metal salt thereof (e.g., a zinc salt of a salicylic acid derivative), zeolite, or activated clay, thereby forming a color from the colorless state itself. The basic principle is to take a structure.

[0003] As a specific usage form, a microcapsule containing a coloring agent is applied to one surface of each sheet which comes into contact with the top and bottom, and a color developing agent is applied to the other surface. Paper (n sheets)-layered in order like lower paper,
Alternatively, by a self-contained system in which a color developer layer and a microcapsule layer are laminated and applied on the same surface, when an external pressure is applied, a reaction occurs on the contact surface to cause color development.

However, when such pressure-sensitive copying paper is used for a slip or a form, a portion that does not need to be partially copied is required. However, the purpose of preventing color formation at an unnecessary portion of the copying is required. Is a desensitizer. The desensitizer uses the reversible reaction of the color development reaction to inhibit the electron accepting action of the color developer, and the electron donor uses the chromogen to try to take a conjugated double bond system in the molecular structure. The main principle is to separate the color with a desensitizer to make it colorless, and in actual use, the desensitizer is made into an ink with a suitable binder and printed on the surface coated with the color developer. It is widely done.

[0005]

2. Description of the Related Art As a prior art 1 of a desensitizer for pressure-sensitive copying paper, Japanese Patent Application Laid-Open No. 2-84470 discloses a method in which an alkylene oxide is added to a predetermined amine such as N-aminopropylcyclohexylamine. A desensitizing ink containing an adduct in which at least 40% of the alkylene oxide is butylene oxide is disclosed. Conventional technology 2
JP-B-58-38119 discloses a desensitizer in which an alkylene oxide containing butylene oxide is added to a predetermined amine. As prior art 3, Japanese Patent Application Laid-Open No. 2-47082 discloses an adduct in which an alkylene oxide is added to a predetermined amine, and at least 40 mol% of the alkylene oxide is butylene oxide (in the examples of the same publication, a predetermined adduct is used). A desensitizer containing an amine adduct of butylene oxide and propylene oxide) is disclosed. The above prior arts 1-3 are all
An object of the present invention is to increase the rate of addition of butylene oxide having a relatively large hydrophobic group, modify the desensitized ink into a hydrophobic state, and improve the suitability for offset printing.

On the other hand, as prior art 4, Japanese Patent Publication No.
No. 515 discloses the addition of ethylene oxide (EO) and / or propylene oxide (PO) to amines and ammonia until active hydrogen disappears, and glycidyl ether, glycidyl ester, at least 25% of the hydroxyl groups at the terminal of the addition chain. A desensitizer mainly containing a reaction product etherified or esterified with an oxirane derivative such as an alkylene oxide having ₄ or more carbon atoms, an alkyl halide, or an acyl halide is disclosed. Prior art 4
Is composed of a combination of addition of an alkylene oxide (EO or PO) to an amine and blocking of the chain end of the adduct. The purpose of this combination is to improve both the desensitizing effect and the compatibility with the oil-based vehicle. I have.

[0007]

However, in the prior arts 1 to 4, the desensitizing effect is not at a satisfactory level, or the hydrophobicity is insufficient, so that the compatibility with an oil-based vehicle is difficult. Good printability due to soiling etc.
Actually, there is a problem that (particularly, suitability for offset printing) cannot be obtained.

It is a technical object of the present invention to develop a new desensitizer for pressure-sensitive copying paper which is excellent in both desensitizing effect and various printing suitability including offset printing.

[0009]

SUMMARY OF THE INVENTION The present inventors have focused on the difference in the affinity between alkylene oxides such as ethylene oxide and propylene oxide and glycidyl ether, and have studied the activity of specific amines such as diethylenetriamine and triethylenetetramine. It has been found that when hydrogen is subjected to an addition reaction of a predetermined alkylene oxide and a predetermined glycidyl ether in the same system, an appropriate balance between hydrophilicity and lipophilicity can be imparted without being affected by water, thereby completing the present invention.

That is, the present invention 1 is represented by the following general formula (1) H- [NH- (CH ₂ ) ₂ ] _n -NH ₂ (1) (n is an integer of 1 to 5). (A) 2 to 30 alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide and styrene oxide per mole of the amines
And (B) the following general formula (2)

Embedded image (R is C ₃ or more alkyl, alkenyl, or aryl group) is reacted with a glycidyl ether 2-30 mol represented by an alkylene oxide and (B) glycidyl ethers active hydrogen of the amine of (A) Is a desensitizer for pressure-sensitive copying paper containing, as an active ingredient, a mixed adduct of an alkylene oxide of an amine and a glycidyl ether obtained by competitively adding the compound.

[0011] The present invention 2 is characterized in that, in the above-mentioned present invention 1, the amines are diethylenetriamine and triethylenetetramine.

The present invention 3 is characterized in that, in the above-mentioned present invention 1 or 2, the alkylene oxide of (A) is butylene oxide.

The present invention 4 is characterized in that in any one of the above-mentioned present inventions 1 to 3, the glycidyl ether of (B) is n-butyl glycidyl ether.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The amines of the above formula (1) are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, preferably diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Diethylenetriamine and triethylenetetramine are more preferred.

The alkylene oxide (B) is ethylene oxide, propylene oxide, butylene oxide, or styrene oxide, but is preferably butylene oxide, propylene oxide, or styrene oxide, and more preferably is butylene oxide. Butylene oxide includes 1,2-, 2,3-butylene oxide.

[0016] In the glycidyl ether of the formula (2), R represents C ₃ or more alkyl, alkenyl, and aryl groups, the alkyl groups, isopropyl, n- propyl, n- butyl, isobutyl, sec- butyl, n
-Pentyl, isopentyl, 2-ethylhexyl, n-
Hexyl, cyclohexyl, 2-methyloctyl, n-
Octyl, decyl, dodecyl, hexadecyl, octadecyl and the like can be mentioned. The alkenyl group is allyl,
1-propenyl, isopropenyl, butenyl, butadienyl, oleyl, linoyl and the like. The aryl group includes phenyl, benzyl, phenethyl, tolyl, xylyl, cinnamyl, styryl, o-phenylphenyl, naphthyl and the like. Therefore, typical examples of the glycidyl ether are isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, hexadecyl glycidyl ether, cyclohexyl glycidyl ether, allyl glycidyl ether, Phenylglycidyl ether,
o-phenylphenyl glycidyl ether, benzyl glycidyl ether, cinnamyl glycidyl ether, etc., among which n-butyl glycidyl ether, 2
-Ethylhexyl glycidyl ether, phenyl glycidyl ether and the like are preferable, and n-butyl glycidyl ether is more preferable.

The addition amount of the alkylene oxide is 2 to 30 moles, preferably 4 to 24 moles per mole of the amines.
The amount of addition of the glycidyl ether is 2 to 30 mol, preferably 4 to 10 mol. When the addition amount of the alkylene oxide and the mixing ratio with the glycidyl ether are changed, the viscosity and the hydrophobicity are changed depending on the purpose of use. Physical properties such as can be appropriately adjusted. However, the alkylene oxide and the glycidyl ether can be used alone or in combination. For example, a plurality of alkylene oxides can be added to the specific amines and a plurality of glycidyl ethers can be competitively added.

The reaction for adding the alkylene oxide and the glycidyl ether to the above-mentioned specific amines is not particularly limited, and a conventionally known method may be used. For example, in a solvent or without solvent, amines and alkylene oxide,
It is carried out by a method of mixing and heating glycidyl ether, or a method of adding an alkylene oxide and glycidyl ether little by little to amines melted by heating. As the catalyst, an alkali such as sodium hydroxide or potassium hydroxide is often used, but it may be used without a catalyst.
The order of the addition may be such that the alkylene oxide and the glycidyl ether are added to the specific amine at the same time, or the alkylene oxide is added to the specific amine before adding the glycidyl ether, or vice versa. The reaction product thus obtained is a light-colored or light-yellow liquid and has a low affinity for water, so that when applied to various pressure-sensitive copying paper developers, an excellent desensitizing effect is obtained. be able to.

To produce a desensitizing ink for pressure-sensitive copying paper using the desensitizing agent of the present invention, (1) a pigment and / or a filler,
What is necessary is just to mix (2) a vehicle and (3) a desensitizer. The mixing ratio of these components can be appropriately selected, but usually, (1) 10 to 30% by weight of pigment and / or filler, and (2) 1% of vehicle.
0 to 30% by weight, and (3) the desensitizer in the range of 30 to 70% by weight.

The pigment or filler of the above (1) may be selected from inorganic compounds such as calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, magnesium hydroxide, barium sulfate and silicon dioxide, or styrene resin, acrylic resin, melamine resin and the like. Organic compounds such as urea resins can be used,
It can also be used as a regulator of printability, viscosity, matteness, opacity, or whiteness. The vehicle of the above (2) is
As in the case of ordinary paints, it is used for the purpose of uniform dispersion of pigments, adjustment of ink fluidity, and fixation of pigments on the printing surface, and specifically, vegetable oil, mineral oil, linseed oil, soybean oil, alcohol Solvents, organic solvents such as ketones, phenolic resins, epoxy resins, polyamide resins, alkyd resins, ketone resins, urea resins, melamine resins, acrylic resins, terpene phenolic resins, rosin-modified phenolic resins, polyvinyl alcohol, or casein High molecular compounds can be used.

In preparing the above-mentioned desensitizing ink for pressure-sensitive copying paper, a conventionally known desensitizing agent is added in combination with the desensitizing agent as long as the properties of the desensitizing agent of the present invention are not impaired. Can be controlled. In addition, the desensitizing ink may include, if necessary, an organic solvent such as alcohols and ketones, an antioxidant, an ultraviolet absorber, a fluorescent brightener, a viscosity modifier, or paraffin for improving friction resistance. Various additives such as waxes such as silicone, fluorine and polyethylene may be added in combination.

The above-mentioned desensitizing ink is manufactured by a usual printing ink manufacturing method. For example, various components such as a desensitizing agent, a pigment and a vehicle of the present invention are mixed and dissolved, or if necessary, a three-roll mill. It can be easily prepared by grinding using a sand mill, a Dyno mill or the like.

The above desensitizing ink is applied to a developing paper or the like by using various printing machines, spraying with a spray or the like, or writing by hand with a crayon or an eraser-like substance. For the printing method, letterpress gravure, flexo, UV printing, and the like can be applied, including offset printing.

When the desensitizing ink is applied, the amount applied (ie, the amount of the desensitizing agent of the present invention) varies depending on the type and amount of the developer, the type of the desensitizing agent and the method of application. is not particularly limited, usually, 0.05-5 g / m ² as a desensitizing agent component, preferably it is desirable to use at 0.1-2 g / m ^2. Incidentally, the amount used is 0.05 g / m ^2.
If the amount is smaller, the desensitizing effect cannot be sufficiently obtained, and conversely, even if the coating amount is increased more than necessary, a better desensitizing effect is not obtained, and excessive excess is uneconomical, Inconveniences occur such that the non-printing portion moves during storage and hinders the color forming ability of the non-printing portion adjacent thereto.

Examples of the color developing agent to which the desensitizer of the present invention can be applied include clays such as activated clay and acid clay, p-phenylphenol-formaldehyde resin, p-octylphenol-aldehyde resin, p-carboxyphenol-
P-substituted phenol-formaldehyde resins such as zinc salt of formaldehyde resin and polyvalent metal salts thereof, zinc salt of 3,5-di (α-methylbenzyl) salicylic acid, zinc salt of 3,5-di (tert-butyl) salicylic acid And a polyvalent metal salt of a nucleus-substituted hydroxycarboxylic acid compound such as a polyvalent metal salt of a carboxy-modified terpene phenol resin.

[0026]

The desensitizer of the present invention is a compound obtained by mixing and adding alkylene oxide and glycidyl ether to active hydrogen of a specific amine to control the amount of nitrogen and hydroxyl groups in the molecule. On the other hand, the desensitizer of the above-mentioned prior art 3 is a compound obtained by adding ethylene oxide and propylene oxide until the amines have no active hydrogen and blocking the terminal hydroxyl group of the addition chain with glycidyl ether or the like. Even if glycidyl ether is bonded to 25% or more, hydrophobicity can be imparted, but sufficient lipophilicity cannot be imparted. On the other hand, in the desensitizer of the present invention, the alkylene oxide and the glycidyl ether are mixed and added to the active hydrogen of the specific amine, so that the lipophilic glycidyl group and other ether groups in the molecule are appropriately added. It can be estimated that the presence of the compound significantly improves the lipophilicity as compared with the desensitizer of the above-mentioned conventional technology 3.

As described above, the desensitizer of the present invention greatly improves the lipophilicity, increases the affinity with the color developer, and reduces the amine nitrogen basicity of the desensitizer to an acidic substance. In order to effectively deactivate the activity of the color developer, the desensitizing effect is greatly increased, and set-off due to migration of the desensitizer can be effectively suppressed. In addition, since the desensitizer has a good balance between hydrophilicity and lipophilicity, the fountain solution in offset printing and the desensitizer of the present invention are easily harmonized.

[0028]

As described above, since the desensitizer of the present invention effectively deactivates the activity of the color developer, the desensitizing effect is greatly improved. In addition, glycidyl groups, which are lipophilic groups, and other ether groups are properly mixed in a molecule having a specific amine as a basic skeleton, and lipophilicity is greatly improved, so that compatibility with an oily vehicle is good. Thus, ink suitable for various printings can be formed, and the obtained ink has good stability.

In particular, in offset printing, the desensitizer of the present invention is in harmony with the fountain solution, so that even if continuous printing is performed for a long time on an offset printing machine, the non-desensitized portion of the plate stain and fountain solution can be removed. No desensitizer elution and no stain such as rolls, and shows good offset printing suitability. In addition, it can be applied sufficiently to letterpress gravure, flexo, and UV printing methods other than offset printing, and has excellent printability as a desensitizing ink for various printing methods to obtain a completely desensitized developer sheet. be able to.

That is, as is apparent from the test results described below, the desensitizer for pressure-sensitive copying paper of the present invention has excellent desensitizing performance as compared with the conventional desensitizer, and has the disadvantage of the conventional method. By improving the hydrophilicity of the ink, a desensitizing ink having good workability can be obtained.

[0031]

EXAMPLES Hereinafter, examples of the production of desensitizing agents and desensitizing inks using the desensitizing agents will be sequentially described, along with test examples of the obtained desensitizing inks such as desensitizing performance and printability. . However, the present invention is not limited to the following examples and the like, and it is needless to say that appropriate modifications can be made within the technical idea of the present invention.

Example 1 (1) Synthesis of Desensitizer In a 1-liter autoclave, 29.5 g (0.2 mol) of triethylenetetramine, 155.0 g (1.2 mol) of n-butylglycidyl ether, 1 , 2-butylene oxide 284.4 g (4.0 mol), 40% KOH 14.8 g (0.4%).
11 mol) and reacted at 110 ° C. for 6 hours. After the reaction is completed, transfer the reaction product to a 1 liter four-necked flask,
After adding 500 g of warm water and stirring at 80 ° C., the mixture was transferred to a 1-liter separating funnel, and the aqueous layer was separated. The oil layer was transferred to a one-liter four-necked flask, and 500 g of 10% saline was added.
After stirring at 80 ° C., the mixture was transferred to a 1-liter separating funnel, and the aqueous layer was separated. The same operation was repeated twice more with 500 g of 10% saline, and the oil layer was washed with water. This oil layer was transferred to a 1-liter eggplant flask, distilled on an evaporator in an oil bath at 110 ° C. for 30 minutes, and then reduced under reduced pressure (10%).
(20 mmHg) for 1 hour to distill off water and low-boiling substances to obtain 448 g of a reaction product. The reaction product is
Average molecular weight 1380 (measured by GPC), viscosity 375 cps
(20 ° C.), it was a pale yellow liquid having a hydroxyl value of 158. This compound is referred to as desensitizer A.

(2) Preparation of desensitizing ink 25 parts of titanium oxide was added to a varnish obtained by heating and dissolving 50 parts of the above desensitizer A, 15 parts of a rosin-modified phenol resin as a binder, and 10 parts of polymerized linseed oil. The meat was kneaded to obtain a desensitizing ink.

Example 2 Based on the synthesis method of Example 1 described above, Example 3 differs from Example 1 in that three components of amines, alkylene oxide and glycidyl ether were simultaneously reacted. The procedure of the reaction of the components was changed, and other synthesis conditions were set as in Example 1. That is, after reacting triethylenetetramine and n-butyl glycidyl ether, 1,2-butylene oxide was gradually dropped under pressure and reacted for 3 hours under pressure. After completion of the reaction, the resultant was washed with water to synthesize a desensitizer, and a desensitizing ink was prepared under the same conditions as in Example 1.

Example 3 Based on Example 1 described above, the amount of 1,2-butylene oxide added was 115.4 g.
(1.6 mol), and other synthesis and ink preparation conditions were set in the same manner (the same in each of the following Examples and Comparative Examples), a desensitizer was synthesized, and a desensitized ink was prepared.

Example 4 Based on Example 1 described above, triethylenetetramine was replaced with diethylenetriamine2.
A desensitizer was synthesized by replacing 0.6 g (0.2 mol) with 130.2 g (1.0 mol) of n-butyl glycidyl ether and 144.2 g (2.0 mol) of butylene oxide. A desensitizing ink was prepared.

Example 5 Based on Example 1, the n-butyl glycidyl ether was changed to 298.1 g (1.6 mol) of 2-ethylhexyl glycidyl ether, and 144.2 g (2. 0 mol) to synthesize a desensitizing agent to prepare a desensitizing ink.

<< Example 6 >> Based on Example 1, the n-butyl glycidyl ether was changed to 150.2 g (1.0 mol) of phenyl glycidyl ether.
A desensitizer was synthesized by changing the butylene oxide to 230.7 g (3.2 mol) to prepare a desensitizing ink.

Example 7 A desensitizing ink was prepared by replacing 1,2-butylene oxide with 104.6 g (1.8 mol) of propylene oxide based on Example 1 described above to prepare a desensitizing ink. did.

Example 8 On the basis of Example 1 described above, n-butyl glycidyl ether was 223.6 g (1.2 mol) of 2-ethylhexyl glycidyl ether, and butylene oxide was 192.2 g (1.2 mol) of styrene oxide.
6 mol), and a desensitizing agent was synthesized to prepare a desensitizing ink.

Example 9 Based on Example 1 described above, triethylenetetramine was added to 37.9 g (0.2 mol) of tetraethylenepentamine, and 139.2 g of n-butylglycidyl ether was used for 139.2 g of isopropylglycidylether.
(1.2 moles) and butylene oxide was changed to 324.5 g (4.5 moles) to synthesize a desensitizer.
A desensitizing ink was prepared.

Comparative Example 1 A desensitizing ink was prepared based on Example 1 without using n-butylglycidyl ether to prepare a desensitizing ink.

Comparative Example 2 29.5 g (0.5%) of triethylenetetramine was prepared in a 500 g four-necked flask based on Example 1 without using an alkylene oxide.
2 mol), and 155.0 g (1.2 mol) of n-butyl glycidyl ether was added dropwise at 80 ° C. to synthesize a desensitizer to prepare a desensitized ink.

Comparative Example 3 Based on Example 1 described above, 20.6 g (0.2) of diethylenetriamine was placed in a 1-liter autoclave without using glycidyl ether.
Mol) and 14.8 g (0.11 mol) of 40% KOH, and propylene oxide 104.6 (1.8 mol.
Mol) and butylene oxide (130.0 g, 1.8 mol) were gradually added and reacted under pressure for 3 hours to synthesize a desensitizer to prepare a desensitized ink.

Comparative Example 4 Triethylenetetramine 2
9.5 g (0.2 mol) of 44.1 g (1
Mol) and propylene oxide (58.1 g, 1 mol) to completely (satisfactorily) add the two alkylene oxides to the active hydrogen of the amine, and then add n-butyl to the addition chain site. Glycidyl ether was reacted to synthesize a desensitizer to prepare a desensitized ink. In Comparative Example 4, the basic synthesis conditions and ink preparation conditions other than the above addition procedure were based on Example 1.

Comparative Example 5 In Comparative Example 5, 1,2-butylene oxide and n-butyl glycidyl ether were mixed and added to amines different from the present invention. That is, based on Example 1 above, 29.0 g (0.2 mol) of N-methyl-3,3'-iminobis (propylamine) was used instead of triethylenetetramine, and 2
-Butylene oxide and n-butyl glycidyl ether were mixed and added to synthesize a desensitizer, and a desensitizing ink was prepared.

<< Example of evaluation test of desensitizing ink >> Example 1 above
To 9 and Comparative Examples 1 to 5 to prepare pressure-sensitive paper, and the desensitizing effect, set-off property, seepage, hydrophilicity of the desensitizing ink, and The properties of the desensitizer for pressure-sensitive copying paper were examined by testing the quality of the roll for contamination. (1) Desensitizing effect Visually evaluate the degree of color development of the desensitized ink printing part when the lower paper and the upper paper printed with desensitizing ink are superposed on each other so that the color forming agent-coated surfaces face each other and printed with a typewriter. did.
The evaluation criteria are as follows. ◎: No color development ○: Very slight color development △: Slight color development ×: Clear color development

(2) Set-off property The coated part and the non-coated part are folded back so that they face each other.
The test was performed under the conditions of ° C., 30 g / cm ² and 72 hours. The judgment was made by spraying a desensitizing checker which reacts with the color developer and develops a color, and visually evaluates the degree of color development of the uncoated portion. The evaluation criteria are as follows. ◎: Uniform color development が あ る: Some areas do not develop color slightly △: Some areas do not develop color ×: Non-uniform color development

(3) Penetrating and penetrating A stretched material is sandwiched between unprinted medium sheets at 50 ° C.
The test was performed under the conditions of 30 g / cm ² and 72 hours. The judgment was made by spraying a desensitization checker, which reacts with the color developer, on the upper and lower sheets of the colored material to form a color, and visually evaluated the degree of coloring of the sheet. The evaluation criteria are as follows. ◎: Uniform color development が あ る: Some areas do not develop color slightly △: Some areas do not develop color ×: Non-uniform color development

(4) Hydrophilicity of desensitizing ink When the desensitizing ink was subjected to wet offset printing, the degree of contamination of the dampening solution was visually determined. The evaluation criteria are as follows. ：: The dampening solution is not stained at all. ○: The dampening solution is very slightly clouded. △: The dampening solution is slightly clouded. ×: The dampening solution is clouded, and the ink adheres to the roll.

(5) Staining of Plate and Roll At the time of wet offset printing of the desensitizing ink, the degree of adhesion of ink on the non-image area of the PS plate and the adhesion of ink on the feed roll were visually determined. The evaluation criteria are as follows. ◎: Both PS plate and roll are not dirty at all ○: Both PS plate and roll are very dirty △: Both PS plate and roll are slightly dirty ×: Both PS plate and roll are dirty and cannot be used

<< Evaluation in Each Test >> The results of the above tests are shown in FIG. FIG. 2 summarizes the ratio of addition of reactants when synthesizing each desensitizer. Looking at the results in FIG.
In Examples 1 to 9, all evaluations were ◎ to ○,
All the comparative examples were x to △. In particular, in Examples 1 to 4, all evaluations were ◎. In the case of a desensitizer obtained by combining butylene oxide and n-butyl glycidyl ether with specific amines of triethylenetetramine or diethylenetriamine, the desensitizing effect and offset printing were obtained. It was recognized that the suitability, set-off property (migration resistance), balance between hydrophilicity and lipophilicity, etc., were both extremely excellent. Also, triethylenetetramine, styrene oxide and 2
The desensitizer of Example 8 consisting of a combination of -ethylhexyl glycidyl ether was highly evaluated after the above Examples 1-4.

As shown in FIG. 2, it can be seen from Examples 1 and 2 that the glycidyl ether was added to the specific amines even when the specific amines of the present invention were subjected to the addition reaction of alkylene oxide and glycidyl ether simultaneously. Subsequent addition of the alkylene oxide did not change the properties of the resulting desensitizer. As can be seen from Examples 1 and 3, even if the butylene oxide content was changed from 4.0 mol to 1.6 mol, there was no change in the properties of the obtained desensitizer. Therefore, triethylenetetramine and n It can be seen that the combination of -butyl glycidyl ether does not require much butylene oxide. Looking at Examples 1 and 4, when the specific amines are changed from triethylenetetramine to diethylenetriamine, the characteristics of the desensitizer become the same even if the added amounts of butylene oxide and n-butylglycidyl ether are reduced. Also, when looking at Examples 5 to 8, when the specific amine is 0.2 mol of triethylenetetramine, it is naturally obtained by changing the type of alkylene oxide to be added, the type of glycidyl ether, and the amount of addition. Desensitizing effect of desensitizer, suitability for offset printing,
It can be seen that the balance between set-off property, hydrophilicity and lipophilicity is different.

In particular, the desensitizer of the present invention is obtained by mixing and adding a specific alkylene oxide and a specific glycidyl ether to a specific amine, and a glycidyl group and another ether group are appropriately mixed in the molecule. The balance between the lipophilicity and the lipophilicity is particularly good, and as shown in the hydrophilicity test of the desensitizing ink, during the wet offset printing, neither the PS plate nor the roll is stained at all, or only a slight stain is observed. The point is also a remarkable feature.

On the other hand, in Comparative Examples 1 to 3, even when the specific amines of the present invention were used, only the alkylene oxide was added to the amines without using glycidyl ether, or Even if only glycidyl ether is added without using an oxide, not only is the desensitizing effect insufficient, but also the balance between hydrophilicity and lipophilicity is poor, and offset printing suitability and set-off property are hardly practical levels. I understand.

The desensitizer of Comparative Example 4 was obtained by completely adding ethylene oxide and propylene oxide until the active hydrogen of the specific amine of the present invention disappeared, and blocking the addition chain end with glycidyl ether. Since the addition site in the amine molecule attacked by glycidyl ether is different from the desensitizer of the present invention in which alkylene oxide and glycidyl ether are mixed and added to the compounds,
The desensitizing effect, suitability for offset printing, set-off property, etc. were all low evaluations. Further, the desensitizer of Comparative Example 5 is obtained by mixing and adding butylene oxide and glycidyl ether to a predetermined amine different from the present invention, and also has the same desensitizing effect, suitability for offset printing, set-off property, etc. It was a low rating. According to the test results of Comparative Example 5, when the alkylene oxide and glycidyl ether are mixed and added to the amines, the amines of the basic skeleton to be added are different from each other. It turned out to bring.

[Brief description of the drawings]

FIG. 1 is a table showing test results of Examples 1 to 9 and Comparative Examples 1 to 5.

FIG. 2 is a table showing the addition ratio of reactants when synthesizing each of the desensitizers of Examples 1 to 9 and Comparative Examples 1 to 5.

Claims (4)

[Claims] 1. One mole of an amine represented by the following general formula (1) H- [NH- (CH ₂ ) ₂ ] _n —NH ₂ (n is an integer of 1 to 5) (A) 2 to 30 mol of at least one alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide and styrene oxide; and (B) the following general formula (2): (R is C ₃ or more alkyl, alkenyl, or aryl group) is reacted with a glycidyl ether 2-30 mol represented by an alkylene oxide and (B) glycidyl ethers active hydrogen of the amine of (A) A desensitizer for pressure-sensitive copying paper, comprising, as an active ingredient, a mixed adduct of an alkylene oxide of an amine and a glycidyl ether obtained by competitively adding the compound. 2. The desensitizer for pressure-sensitive copying paper according to claim 1, wherein the amines are diethylenetriamine and triethylenetetramine. 3. The desensitizer for pressure-sensitive copying paper according to claim 1, wherein the alkylene oxide of (A) is butylene oxide. 4. The glycidyl ether of (B) is n-butyl glycidyl ether.
3. The desensitizer for pressure-sensitive copying paper according to any one of the above items 3.