JPS581591A - Color developing paper for no carbon copying paper using paraphenylphenol resin with a higher solubility - Google Patents

Abstract

PURPOSE:To provide a color developing paper with a better color developing property and a higher color developing rate, by coating a paper sheet with a p-phenylphenol (PPP) resin obtained by the reaction of p-phenylphenol (PPP), other substituted phenols and formaldehyde under a specific condition. CONSTITUTION:100pts.wt. PPP, 0-30pts.wt. one or more of substituted phenols (e.g., p-t-butylphenol) and formaldehyde are caused to react in the presence of a catalyst in a quantity enough to control the pH of the system below 1.9 together with a monohydric alcohol with a boiling point of 80-170 deg.C (e.g.: n- propanol) to obtain a PPP resin. The resin thus obtained is applied on a paper by wate coating or the like to produce a color developing paper as expected.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a rose phenylphenol resin with improved solubility and a color paper for carbonless copying paper made from the resin.

Carbonless pressure-sensitive copying paper is usually used in combination with paper coated with microcapsules containing a colorless color-forming basic dye dissolved in oil and paper coated with an acidic substance (color paper). Recently, the usage has increased and it is widely used for general slips.

Activated clay has traditionally been used as an acidic substance, but
In recent years, a synthetic phenolic resin has been developed, and due to its deep color, it is replacing activated clay. Another advantage of phenolic resins over activated clay is that they are soluble in solvents, so they can be dissolved in solvents to form spot inks and applied to colored areas by printing.

Various studies have been conducted on phenolic resins, but due to the depth of their color development, rose phenylphenol resins (hereinafter referred to as P
It is called PP resin. ) is generally widely used. This PPP resin has a deep color, but its solubility in solvents is insufficient, and getones such as methyl ethyl ketone and acetone are good bathing agents.For example, PPP resin is used as a spot ink for flexo and gravure. In some cases, a ketone solvent must be used, and the ink prepared in this manner is unsatisfactory in that it has a strong odor and there are restrictions on the materials that can be used.

The present invention relates to improvements in PPP resins. With this improvement, when used as a carbonless pressure-sensitive copying paper, it is possible to obtain a colorant with good color development properties, and also to make it possible to create an excellent spot ink with good stability. The present invention will be described in detail below.

The PPP resin of the present invention is first characterized by its manufacturing method. That is, it is produced by reacting paraphenylphenol and one or more other substituted phenols with formaldehyde in the presence of a catalyst and in the coexistence of a -hydric alcohol under conditions of 19 or less. It is characterized by Other substituted phenols include vala-cresol, para-butylphenol, vara-amylphenol, vara/chlorohexylphenol, parahebutylphenol, vara-octylphenol, paracumylphenol, balanonylphenol, ornophenylphenol, halachlorphenol, varabrome. For example, phenol can be added in an amount of 0 to 30 parts per 100 parts of paraphenylphenol. Addition of other phenols in excess of this lowers the coloring properties and is not suitable for use in carbonless copying paper.

As formaldehyde, formaldehyde aqueous solution,
Paraformaldehyde and other formaldehyde producing compounds are used.

There are two methods for producing the PPP resin of the present invention; one is to carry out the reaction in an acidic environment using an acidic catalyst, and the other is to carry out the primary reaction under an alkaline catalyst, and then carry out the reaction under an acidic catalyst. This is a method of performing a secondary reaction. As a catalyst,
Sodium hydroxide, potassium hydroxide, barium hydroxide, etc. are used as alkaline catalysts, and hydrochloric acid, phosphoric acid, phosphoric acid, para-toluenesulfonic acid, etc. are used as acidic catalysts.
Commonly used catalysts can be used. The molar ratio of phenol and formaldehyde is 1 mole of phenol when formaldehyde is used at a ratio of 0.3 to 10 moles when using only the acidic catalyst described above, and from 0.5 to 0 mole when carrying out the above two-stage process. do. When using an acidic catalyst, it is necessary to keep the pH below 9.

The monohydric alcohol coexisting has a boiling point of 80 to 170.
°C alcohol is used. Specific examples include n-propatool, inopropatool, n-butanol, inobutanol, n-amyl alcohol, isoamyl alcohol, etc., and it is also possible to use one or a mixture of two of these. good. Methanol, ethanol, etc. that are compatible with water cannot be used. However, it may be used by adding a small amount to the above-mentioned high boiling point alcohols. The resin produced is preferably solid when it is processed into paper as an aqueous coating liquid and used to produce color paper for carbonless copying paper, but it does not need to be solid when it is dissolved to make ink. .

The resin of the present invention has a second characteristic when used as a coloring paper for carbonless copying paper, and it can be used as a product with a particularly fast coloring speed compared to conventional PPP resins. This is considered to be because the resin of the present invention has excellent solubility in the oil in the capsule.

Furthermore, when an ink is prepared, the third characteristic is that the stability of the ink can be improved due to its good solubility in various solvents. According to the present invention, it is possible to produce a resin soluble in ethyl acetate, and when producing a flexographic/gravure type spot ink, the solvent can be changed to, for example, methyl ethyl keto/or acetone J:ethyl acetate. In this case, not only does the odor improve, but these ketone solvents have a strong tendency to destroy capsules, making them unsuitable as inks for carbonless paper.
Ethyl acetate is preferable because it has a weak property of destroying capsules, and it has become possible to significantly reduce the problems caused by capsule destruction during printing. When manufactured as an ink, an m resolution of 40% or more is required. It also has good dissolubility into polyethylene glycols (ethylene glycol ethers), making it possible to create spot inks for letterpress or offset with excellent stability.

It is not clear why the resin according to the present invention is so good, but it is probably because the molecular weight distribution is suitable for color development and solubility, and because a small portion of the alcohol has an ether bond. It will be done.

This will be described in detail below with reference to Examples.

Example j 4 solo flasks with temperature side, condenser and stirrer Niva phenylphenol 500r, 37% formalin 115
f? , Isobutyl alcohol 2502 Hydrochloric acid 1.5C
Insert 11. The pH at this time was 05. A rapid reaction was carried out at 95 to 100°C for 5 hours with stirring, then concentrated and dehydrated, heated to 150°C, and the melting point was 100°C.
A white resin was obtained.

Example 2 Rose phenylphenol 5002 was prepared in the same manner as in Example 1.
．． 37% formalin 12o2, oxalic acid 57, and n-butanol 2001i' were added, reacted at 98 to 100°C for 5 hours, and concentrated and dehydrated at 135°C. The melting point of the resin produced was 110°C. (ljl), C0 analysis showed that the monomer content was 35% and the average molecular weight was about 3001
Example 3 In addition to Example 1, 450 g of balaphenylphenol, 507 g of balater/yari-methylphenol, 300 S' of robetanol, 37% hol-71 Noah 170 y,
A slightly brown resin with a melting point of 80° C. was obtained by applying / oxalic acid ray.

Example 4 Actual example 1,! 1m Similarly, rose phenylphenol 5009.37% formalin 160%, sulfuric acid 5?
, 98-100 with the addition of Normal Octa Tool 2007
The mixture was reacted at ℃ for 5 hours and heated to 135℃. The melting point of the resin produced was 75°C. According to the analysis of Q, p, C, the monomer content is 14% and the 1F average molecular weight is about -
1 (it was 10)

9- Comparative Example 1, methanol 2002 and water [00f] were added to the n-butanol 2002 of Example 2, and the mixture was refluxed at 77 to 81°C for 5 hours and heated to 135°C. The melting point of the obtained product was 165°C.

Comparative Example 2 Example 1 Same as above, rose phenylphenol 500r
, 80% paraformaldehyde 552, and 2.5 ft' of paratoluenesulfonic acid 2002 were added to obtain a slightly brown transparent resin with a melting point of 73°C.

Example 5 100 fi' of the resin of Example 1, 200 g of water, and 03 f of sodium silicate were placed in a ball mill and pulverized until the particle size was 51 or less. This dispersion liquid 301 is added with water 2007
, kaolin 30 fluorinated starch (10% aqueous solution) 25? , Dow Latex 62U (Dow Chemical Company S, B, I”L
, latex) and applied about 52 coats of the same to high-quality paper (Mitsubishi Diaform), a bottom sheet for non-carbon paper with good color development was obtained.

Comparative Example 3 Instead of the resin of Example 1 used in Example 5, Comparative Example 1
The reactants were used. The paper obtained by coating showed almost no color development.

Also, shiny crystalline powder was observed on the surface of the paper. It is considered that most of the reactants in Comparative Example 1 were unreacted substances.

Example 6 60 parts of ethyl acetate was added to 740 parts of the cash register of Example 2 and dissolved. To this, 5 parts of maleic acid resin (Aurayorinsan Marquid Nα32) dissolved in 5 parts of ethyl acetate was added, and the titanium oxide was dispersed and ground for 8 hours in a ball mill with 30 parts of titanium oxide to form a spot ink for flexi-gravure. It was created. When printed on two-leaf paper (Mitsubishi NOR paper 1N-40) using a flexible printing machine (manufactured by Miyakoshi), a spot-printed middle-leaf paper was successfully produced.

Comparative Example 4 The same procedure as in Example 6 was carried out using Hytanol X712 (paraphenylphenol resin manufactured by Hitachi Chemical Co., Ltd.) in place of the cash register in Example 2, but Hytanol X712 did not dissolve in ethyl acetate. , it was difficult to make into ink. A spot ink was prepared using methyl ethyl keto/in place of ethyl acetate. When flexible printing was performed in the same manner as in Example 6, color blurring occurred in the spot printed area in blue. Further, when comparing the color development properties, the color development speed was slower and the color development density was lower than that of the printed matter of Example 6.

Example 7 P, It, G, 40 for 100 parts of the resin of Example 4.

(Polyethylene glycol) was dissolved in 100 parts, 100 parts of titanium oxide was added and mixed, and a letterpress letterpress was prepared using a three-roll mill. When printed on high-quality paper using a rubber letterpress using an ordinary letterpress printing machine (manufactured by Mei Seisakusho), a good carbonless copy paper F sheet was obtained.

Comparative Example 5 An ink was prepared in the same manner as in Example 7 using the resin of Comparative Example 2 instead of the resin of Example 4. N P , E,
Since the solubility was not sufficient for 0.400, the resin precipitated and a good ink could not be obtained. Printing was performed in the same manner as in Example 7. Good printed matter was not obtained. Further, when comparing the color development, both the color development speed and density were compared to Example 7.
was inferior compared to

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Claims (1)

[Scope of Claims] 1. Presence of a catalyst in an amount sufficient to achieve a PII of 10 or less V of 1 (Φ or less) and formaldehyde of 1. and,
A colored paper for copying paper made by coating a phenylphenol resin obtained by reacting in the coexistence of a monohydric alcohol F with a boiling point of 80 to 170°C on paper. 2. The colored paper for carbonless copying paper according to claim 5, wherein the ratio of the substituted phenol to the phenylphenol resin is 100:0 to 100:30. 3. The color paper for carbonless copying paper according to claim 5, wherein the other substituted phenols are para-butylphenol and para-octylphenol. -1-4 The colored paper for carbonless copying paper according to claim 5, wherein the coating method is an aqueous coating. 5. The colored paper for carbonless copying paper according to claim 5, wherein the coating method is flexographic printing or gravure printing. 6. The colored paper for carbonless copying paper according to claim 9, which uses a solvent containing ethyl acetate as a main component in flexographic printing or gravure printing. 7. The color paper for carbonless copying paper according to claim 5, wherein the coating method is letterpress printing or offset printing.