DE2911945A1 - COLOR DEVELOPMENT COMPOSITION FOR PRESSURE SENSITIVE WRITING SHEET MATERIAL AND PROCESS FOR THEIR MANUFACTURING - Google Patents

Description

Applicant: Mitsui Toatsu Chemicals, Incorporated No. 2-5, Kasuraigaseki 3-chome, Chiyoda-ku
Tokyo, Japan

Color developing composition for pressure sensitive Writing sheet material and method for making them.

The invention relates to improved color developing compositions for pressure sensitive writing sheet material.

They generally contain pressure sensitive writing sheet materials a first sheet (known as a "backed sheet") coated with microcapsules, the one Contain electron donating organic compounds (which in general called "pressure-sensitive dye") dissolved in a non-volatile organic solvent, and a second sheet (referred to as the "top-coated sheet"

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is known), which with an aqueous coating composition, which contains an electron attractive color developer is coated, and these sheets lie so that their coated Surfaces butt against each other. If this is now done by means of a ballpoint pen, a typewriter or the like pressure is applied, the microcapsules lying in the corresponding areas are torn open and the pressure-sensitive dye solution that is thus released comes into contact with the color developer to produce the desired color.

Accordingly, pressure-sensitive writing sheet materials for making a variety of copies can be prepared by Layers of microcapsules and layers of color developer are properly placed against one another. In addition, it is also possible pressure sensitive recording or writing materials of the "self-supporting type" (i.e. on which all substances are contained at the same time).

In the above-described pressure-sensitive writing sheet materials One or more pressure-sensitive dyes are used, selected from (1) triphenylmethane dyes such as Crystal Violet Lactone, (2) methylene blue dyes such as benzoyl leucomethylene blue (Benzoyl Leucomethylene Blue), (3) fluoran dyes such as lthodamine lactam (rhodamine lactam), (4) leucoauramine dyes, (5) spiropyran dye Qi and the like are selected.

On the other hand, the electron attractive color developers used therein include (1) inorganic solid acids such as acid alumina and activated clay, (2) certain phenol-formaldehyde polymers, (3) metallic salts of substituted salicylic acids and the like. Be under these color developers certain phenol-formaldehyde polymers and particularly p-phenylphenol-formaldehyde polymers Widely used for (1) their excellent color developing performance, (2) the good application properties (or rheological properties) of the aqueous coating paints made from them

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(3) the good water resistance of paper sheets that coated therewith, and (4) their low price.

Pressure sensitive writing sheet materials that employ a phenol-formaldehyde polymer is used as a color developer, but have the disadvantage that, be it before or after color development, tend to yellow during long-term storage and thereby lose their commercial value. Accordingly, there is there is a strong growing need for pressure sensitive writing sheet materials that are not only improved

Whiteness but also improved resistance to yellowing during storage and yellowing when influenced by Own light.

It is therefore an object of the present invention to provide a new color developing composition for pressure-sensitive recording or writing sheet material, the improved durability against yellowing and excellent in color developing performance.

Another object of the present invention is to provide a To provide a color developing composition for pressure-sensitive recording or writing sheet material which is subject to yellowing is effectively prevented by exposure to light, during storage and in an oxidizing atmosphere.

It is a further object of the present invention to provide a color developing composition for pressure-sensitive recording or to provide writing sheet material which, when applied to color developing sheets, will reduce the cost for the color developer required for the production of pressure-sensitive recording or writing sheet materials are to be reduced and the whiteness or whiteness of the color developing sheets to improve.

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It has now been found that the above objects of the invention can be solved by a color developing composition comprising a p-substituted phenol-formaldehyde polymer and comprises an additive selected from (a) a particular benzotriazole compound, (b) a particular hindered phenolic Compound, (c) a combination of the benzotriazole compound and the hindered phenolic compound, (d) a combination the benzotriazole compound and a certain dialkyl thioether derivative, (e) a combination of the hindered phenolic compound and the dialkyl thioether derivative and Cf) a combination the benzotriazole compound, the hindered phenolic compound and the dialkyl thioether derivative is selected, wherein the p-substituted phenol-formaldehyde polymer and the additive are homogeneously dissolved in mutual solution.

According to the present invention, there is provided a color developing composition for pressure-sensitive recording or writing sheet material comprising (A) 100 parts by weight of a p-substituted Phenol-formaldehyde polymers and (B) a specific amount of an additive selected from the group is composed of

(a) 1 to 10 parts by weight of a benzotriazole compound having the general formula

HO

^NY 2

where X represents a hydrogen, chlorine or bromine atom, Y ₁ and Y _{2 represent} hydrogen atoms, alkyl radicals with 1 to 12 carbon atoms, alkoxy radicals with 1 to 12 carbon atoms, aryl radicals with 6 to 15 carbon atoms or aralkyl radicals with 7 to 15 carbon atoms and the by Y- and Yg radicals shown can either be the same or different from one another,

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(b) 1 to 20 parts by weight of a hindered phenolic compound, as a phenol derivative with an alkyl, alkylene or hydroxy substituent radical in the 2- or 6-position or is defined in both of the benzene ring,

(c) a combination of 1 to 10 parts by weight of said Benzotriazole compound and 1 to 10 parts by weight of said hindered phenolic compound,

(d) a combination of 1 to 10 parts by weight of said benzotriazole compound and 0.5 to 10 parts by weight of one Dialkyl thioether derivative having the general formula

^ R ₁ COOR ₃

where R _{1 represents} an alkylene radical with 1 to 6 carbon atoms, R ₂ and R _{3 represent} alkyl radicals with 8 to 22 carbon atoms and the radicals represented by R 1 and R 1 can be the same or different from one another,

(e) a combination of 1 to 10 parts by weight of said hindered phenolic compound and 0.5 to 10 parts by weight of said dialkyl thioether derivative and

(f) a combination of 1 to 10 parts by weight of said benzotriazole compound, 1 to 10 parts by weight of said hindered phenolic compound and 0.5 to 10 parts by weight of said dialkyl thioether derivative in which the total The amount of these three components is not greater than 20 parts by weight,

wherein the p-substituted phenol-formaldehyde polymer and said Additive are homogeneously dissolved in mutual solution.

The above-described composition is pulverized and then mass-milled in the presence of a surfactant subject. To the resulting aqueous suspension, various components are added that are necessary to to provide the properties desired for the color developing sheets. The aqueous coating paint produced in this way is applied

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Paper sheets are applied and then dried to make the color developing sheets for use in pressure sensitive writing sheet materials to obtain.

The p-substituted phenol-For aldehydpelymere ^, which may be used in the practice of the invention are polymers which eiaes by reacting one or more p-substituted phenols with formaldehyde or a forr; u ^T .ldohyderaeugenden compound. The p-subst: -tui © rten phenols that are useful for this purpose include (1) ρ-ΛIKy! Phenols bit an alkyl portion of 1 to 15 carbon atoms τΛ <*? - ~ € ί? Θ® & Ι _} ρ- Ethylphenol, p-Isopropylphenol, p-tert-Butylphenol ,, s-tert-Itst ^! Phenol, p-tert-Octylphenol, p-NonyTphonol "nd ζ-Ί-c ■,>Gi3i" l _i v ---- eL _i , (2) p-Cyeloalkylphenols such as p-Cyclohexyl ^ henol- (3> ^ lalessttp ^ aSiJo they p-Ghlorphenol and p-Bromphenv>^.;(4> p-liäylpueuolc vio p-Mtee *? ! phenol and (5) p-aralky! phenol "- as *> c -Ii ^ vir." ΐfc ^ rsylpitGET-Z ii: yl CC _} o € dimethylbenzy! phenol. Uirr ^ r aiicferGr. ⁷ iiti7 "Wz p -FüGriviylEeaol formaldehyde polymers, which are made from ^ -PLv-u ^ j. ^ Glig-I :: · ~ Δ Wo-varitueh ^ u , because of their compatibility 'old 7?. · " ^: ^ ^Τ ΐϊ = ΐ ^α Γ ^:: '"Λ""3" ^τ "" · _nuvF./ja.n:

hindered phen ·) HsHEN

preferred for their ability to

The benzotriazo compounds - the be tion of the invention uses ie? SG3 the general η form

aMisc ^ aii Durchfühsi? 5-s ^ srlilEdiiBfen mit

Γ il ι

JsJ

CD

where X is a hydrogen _s chlorine - Yg hydrogen atom, Älicylreste «ii (eg methyl, ethyl, isopropyl, etc.), alkoxy with 1 to 12 Γ

r ^ rstell, T- ®ηά ^ i lenstof'fatomen

-Amyl, tert-octyl uiG "(e.g. methoxy,

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Xthoxy, butoxy, octoxy, etc.), aryl radicals with 6 to 15 carbon atoms (e.g. phenyl, tolyl, naphthyl, etc.) or aralkyl radicals with 7 to 17 carbon atoms (e.g. benzyl, oC-methylbenzyl, OC, OC -dimethylbenzyl, etc.) ) and the radicals represented by Y- and Y "can be either identical to or different from one another.

Specific examples of the benzotriazole compounds include:

2- (2§-Hydroxy-5'-methylpheny-dbenzotriazole, 2- (2 ^f -hydroxy-5'-isopropylphenyl) benzotriazole, 2- (2 ^f -hydroxy-5 ^f -tert-butylphenyl) benzotriazole, 2- ( 2'-Hydroxy-5 ^f tert-amylphenyl) benzotriazole, 2- (2 ^l -hydroxy-5 ^t tert-octylphenyl) benzotriazole, 2- (2'-HyUrOXy-S ', 5'-di-isopropylphenyl) benzotriazole, 2 - (2 * -Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy -3 ', 5'-di-tert-octylphenyl) benzotriazole,

2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2 -hydroxy- 3'-methy1-5'-tert-butylpheny1 ) benzotriazole , 2- (2 * - Hydroxy-3'-tert-amy 1-5'-methylpheny dbenzotriazole,

2- (2'-Hydroxy- 4'-ethoxyphenyl) benzotriazole, 2- (2'-Hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-Hydroxy-5'-octoxyphenyl) benzotriazole,

2- ^(2-hydroxy-1 · 3, 5'-di-tert-butylphenyD-5-chlorobenzotriazole, 2- (2 x ^3-hydroxy-1, 5'-di-tert-amylphenyl) -5-bromobenzotriazole, 2 - (2 * -Hydroxy-3'-tert-buty1-5'-methylphenyl) -5-chlorobenzotriazole,

2- (2'-Hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole,

2- (2'-Hydroxy-5'- ® £, C 1-4 dimethylbenzylphenyl) benzotriazole, 2- (2'-Hydroxy-4'-octoxyphenyl) -5-chlorobenzotriazole and the like.

Among these benzotriazole compounds are 2- (2'-hydroxy-5'-methylphenyDbenzotriazole, 2- (2'-Hydroxy-ö'-tert-amylphenyI) -benzotriazole, 2- (2'-Hydroxy-5'-tert-octylphenyDbenzotriazole, 2- (2'-Hydroxy-3 ', 5'-di-tert-butylphenyDbenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-Hydroxy-3, 5 * -di-tert-amylphenyl) benzotriazole, 2- (2'-Hydroxy-3'-tert-buty1-5'-methylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-

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4'-octoxyphenydbenzotriazole is particularly effective.

The hindered phenolic compounds involved in practical Phenol derivatives can be used to carry out the invention with an alkyl, alkylene or hydroxy substituent radical in the 2- or 6-position or in both of the benzene ring. It is but not excluded that one or more such substituent radicals in positions other than «Jen 2- and 6-positions available. These compounds can be divided into three groups: (A) di-, tri-, or higher phenol derivatives (B) monophenol derivatives and (C) other phenol derivatives not belonging to the above two groups.

(A) The di-, tri-, or higher phenol derivatives include:

(1) alkylidenediphenols such as

2,2'-methylenebis (4-methyl-6-tert-buty! Phenol), 2,2'-methylenebis (4-ethy1-6-tert-buty! Phenol), 2,2'-methylenebis (4,6-di-tert-butylpnenol), 4,4'-methylenebis (3-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-buty! Phenol), 4,4'-methylenebis (2-methyl-6-tert-buty! Phenol),

2, 2 '-'Η? Hylenbis (6- (l-methylcyclohexyl) -4-raethy! Phenol),

4,4'-butylidenebis (3-methyl-6-tert-buty! Phenol), 4,4'-propylidenebis (2,6-di-tert-butylphenol), 4,4'-cyclohexylidenebis (2,6-di-tert-butylphenol),

4,4'-bis (2,6-di-tert-butylphenol) and the like;

(2) thiobisphenols such as

4,4'-thiobis (3-methy1-6-tert-butylphenol), 4,4'-thiobis (2,6-di-tert-butylphenol),
4,4'-thiobis (2-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,2'-thiobis (4,6-di-tert -buty! phenol),
2,2'-thiobis (4,6-di-tert-butylresorcinol), 1,1'-thiobis (2-naphthol), and the like;

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(3) tri- or tetraphenol derivatives such as

1,3,5-Trimethy1-2,4,6-tris (3,5-di-tert-buty1-4-hydroxybenzyl) -

benzene,

1, l, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,3,5-tris (3,5-di-tert-buty1-4-hydroxybenzyl) isocyanurate, Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane and the like, and

(4) other diphenols like

2,2'-ThiodiethyIbis (3- (3,5-di-tert-buty1-4-hydroxyphenyI) -

propionate),

K, lf-hexamethylene bis (3,5, -di-tert-butyl-4-hydroxyhydrocinnamide), 1,6-hexanediol bis (3- (3,5, -di-tert-buty1-4-hydroxyphenyl) propionate, and the same.

(B) the monophenol derivatives include:

(1) alkyl-substituted phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-p-cresol, 3-methyl-e-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butyl-p-cresol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-buty1-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, and the like;

(2) Divalent phenol derivatives such as catechol, p-tert-butylcatechol, 4,6-di-tert-butylresorcinol, 4,6-di-tert-amylresorcinol, 3-tert-buty! Hydroquinone, 3,5-di-tert-buty! Hydroquinone, 3,5-di-tert-amyhydroquinone, and the like, and

(3) other monophenols such as

Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

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6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bis (n-octylthio) -

1,3,5-triazine,

4-hydroxy-3,5-di-tert-butylbenzyl ethyl phosphate, 4-hydroxy-3,5-di-tert-butylbenzyloctadecyl phosphate, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, Butyl hydroxyanisole, and the like.

(C) The other phenol derivatives other than the aforementioned two Groups include, for example, 2,4-di-tert-butyl- o £ -naphthol, 2-tert-butyl-OC-naphthol, condensation products of p-tert-butylphenol with acetaldehyde, condensation products of p-tert-butylphenol with formaldehyde, styrenated phenol and the like.

These hindered phenolic compounds are all effective in preventing the p-substituted phenol-formaldehyde polymer, especially the p-phenylphenol-formaldehyde polymer, the inventor yellowing during storage. However, the di-, tri or higher phenol derivatives belonging to the above group (A) belong, because of their compatibility with p-substituted phenol-formaldehyde polymers, their little influence on the softening point of a color developing composition containing a p-substituted Phenol-formaldehyde polymer, and the low degree of decrease in its preventing effect on yellowing of a p-substituted phenol-formaldehyde polymers are preferred due to their sublimation during storage. Among the di-, triaders higher phenol derivatives are alkylidene diphenol derivatives and thiobisphenol derivatives particularly effective.

The dialkyl thioether derivatives used in practice of the invention are compounds having the general formula

(II)

R ₁ COOR ₃

where R _{1 represents} an alkylene radical having 1 to 6 carbon atoms,

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R ₂ and R _{3 represent} alkyl radicals having 8 to 22 carbon atoms and the radicals represented by R ₁ and R 3 can be identical to or different from one another. Specific examples of the dialkyl thioether derivatives include dilauryl thiodipropionate, dimyristyl thiodipropionate, dicety1-thiodipropionate, ditridecyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl- Q _f β'-thiodibutyrate and the like.

When the color developer contains a p-substituted phenol-formaldehyde polymer, color developing sheets for use in pressure-sensitive writing sheet materials tend to yellow during storage and when exposed to light. It is believed that this phenomenon is attributable to the formation of colored products, namely by:

(1) the oxidation reaction in which molecules of the p-substituted Phenol-formaldehyde polymers activated by the energy of light, especially ultraviolet light, and then activated by atmospheric oxygen to be oxidized;

(2) the oxidation reaction in which the p-substituted phenol-forraaldehyde is gradually oxidized by atmospheric oxygen when the color developing sheets are stored in air and especially at elevated temperatures;

(3) the oxidation reaction in which the p-substituted phenol-formaldehyde polymer is replaced by oxidizing gases such as NO, ozone, SO etc. existing in the storage environment is oxidized, and the like.

In practical cases, the yellowing phenomenon is related to two or for the above possible cases. Accordingly no complete countermeasures to prevent yellowing could be taken in the past.

The inventors of the present invention made a series of studies for the prevention of yellowing of pressure-sensitive writing sheet materials in which a p-substituted Phenol-formaldehyde polymer used as a color developer, have persisted and found that a composition that

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a homogeneous mutual solution of a p-substituted phenol-formaldehyde polymer, in particular a p-phenylphenol-formaldehyde polymer, and a benzotriazole compound as defined above is excellent in resistance to yellowing by light and that a composition which is a homogeneous mutual solution of a p-substituted phenol-formaldehyde polymer, in particular a p-phenylphenol-formaldehyde polymer, and a hindered phenolic compound as mentioned above is excellent in resistance to yellowing during storage and against yellowing in an oxidizing atmosphere.

In addition, it was found that a composition that a homogeneous mutual solution of a p-substituted phenol-formaldehyde polymer, in particular a p-phenylphenol-formaldehyde polymer, a benzotriazole compound as defined above and a hindered phenolic compound as defined above includes, excellent resistance to yellowing due to Light, against yellowing during storage and against yellowing in an oxidizing atmosphere.

In addition, it has been found that when a dialkyl thioether derivative, as defined above, in combination with the benzotriazole compound and / or the hindered phenolic Compound is used, then the resulting composition has remarkably improved resistance to yellowing . In this way, the combined use of the dialkyl thioether derivative enables the total amount of the Benzotriazole compound and / or the hindered phenolic compound which is needed to achieve practically sufficient resistance against yellowing by light and against yellowing during storage, thereby reducing the cost of the color developer, that for the manufacture of pressure sensitive writing sheet materials is required.

Ia was also found that by adding a dialkyl thioether derivative as defined above, a composition according to

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can be produced by the process of the invention which has a markedly improved whiteness content. Thus, the combined use of the dialkyl thioether derivative also, the whiteness of aqueous coating paints and paper sheets, coated therewith, and to further improve the quality of the pressure-sensitive writing sheet materials.

The benzotriazole compounds described above were previously known to be used as ultraviolet stabilizers for plastics for general purposes such as polyethylene, polypropylene, polystyrene, etc. are useful. However, it was completely unknown in the past that they could also be used as anti-yellowing agents for p-substituted phenol-formaldehyde polymers, and particularly as anti-yellowing agents for pressure-sensitive ones Writing sheet materials are useful having a substantial amount of such p-substituted phenol-formaldehyde on it in Form of finely divided particles is applied.

It was previously known that the hindered phenolic compounds described above can be used as antioxidants for General purpose plastics such as polyethylene, polypropylene, polystyrene, etc. and high molecular compounds such as synthetic Rubber, polyurethane, polyamide, polyacetal, etc. are useful. However, since these compounds are phenol derivatives with chemical structures analogous to those of p-substituted phenol-formaldehyde polymers, it has been perfect in the past unknown to be useful as yellowing inhibitors for p-substituted phenol-formaldehyde polymers and particularly as yellowing inhibitors for pressure sensitive writing sheet materials are coated with a considerable amount of such p-substituted phenol-formaldehyde polymer in the form of finely divided particles.

It was previously known that the dialkyl thioether derivatives described above as additive antioxidants for polyolefins, and generally used in combination with phenolic antioxidants are useful. However, it was completely unexpected

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that when used in combination with a benzotriazole compound

ge hindered , dung as defined above, and / or a / pnenoiischen compound as defined above, are used as yellowing inhibitors for p-substituted phenol-formaldehyde polymers and in particular as yellowing inhibitors for pressure-sensitive writing sheet materials, on the one considerable amount of such p-substituted phenol-formaldehyde polymer is applied in the form of finely divided particles, the resulting composition being effectively prevented from yellowing during storage and when exposed to light.

In the manufacture of pressure sensitive writing sheet materials becomes an additive as defined above together with a p-substituted phenol-formaldehyde polymer on paper sheets upset. There are a number of possible methods to do this: (1) An aqueous suspension is prepared from the p-substituted phenol-formaldehyde polymer and then mixed with a separately prepared aqueous suspension of the additive to give an aqueous coating color form. Alternatively, (2) the additive is added to the p-substituted phenol-formaldehyde polymer and the resulting Mixture suspended in water by wet milling. Further alternatively, (3) a resin composition which a homogeneous mutual solution of the p-substituted phenol-formaldehyde polyraeren and the additive, prepared and then suspended in water.

According to these three methods, pressure-sensitive writing sheet materials containing an identical additive in an equal amount were prepared and then tested for resistance to yellowing when exposed to light and to yellowing during storage. As a result, it was found that the method (3) is the most effective in improving the resistance to yellowing. The results obtained with the methods (1) and (2) were less desirable than the-

§09840 / 078

those obtained by the method (3).

Therefore, when preparing pressure-sensitive writing sheet materials having a composition containing a p-substituted one Phenol-formaldehyde polymer and an additive as defined above becomes a satisfactory improvement in the resistance to yellowing not by simply using a uniform mixture of finely divided particles of the p-substituted phenol-formaldehyde polymer and finely divided particles achieved by the additive, rather than by finely divided Particles of a resin composition are used which are a homogeneous mutual solution of the p-substituted phenol-formaldehyde polymer and the additive.

Based on these findings, the inventors of the present Invention carried out a further study on the preparation of a color developing composition which has a homogeneous mutual solution of a p-substituted phenol-formaldehyde polymer and an additive as defined above and invented a new process for the preparation of such a composition therefrom.

More specifically, a resin composition having a homogeneous mutual Solution of a p-substituted phenol-formaldehyde polymer, especially a p-phenylphenol-formaldehyde polymer, and one Additive, which is as defined above, can be prepared by one of the following two processes:

(1) A p-substituted phenol, preferably p-phenylphenol and formaldehyde or a formaldehyde generating compound are dissolved in water or an organic solvent and then subjected to a condensation reaction in the presence of an acidic catalyst. An additive as defined above is added either to the aforementioned starting materials or to the reaction mixture at the end of the condensation reaction. After the condensation reaction has ended, the water or organic solvent is removed by heating and the residue is removed

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is cooled to obtain a homogeneous and clear resin composition.

(2) A p-substituted phenol, preferably p-phenylphenol, and formaldehyde or a formaldehyde-generating compound are dissolved in a water-repellent organic solvent that is mixed with Water can form an azeotropic mixture, dissolved and then undergo a condensation reaction in the presence of an acidic catalyst subject. An additive as defined above becomes either the aforementioned starting materials or the Reaction mixture added at the end of the condensation reaction. After the condensation reaction has ended, the resulting Solution of a p-substituted phenol-formaldehyde polymer and the additive in the organic solvent with an aqueous one mixed alkaline solution. This mixture is steam distilled to remove the organic solvent and thereby a to leave a homogeneous aqueous solution of the corresponding alkaline metal phenates. Eventually it becomes a finely divided homogeneous resin composition collected by precipitation with an acid .

Although either method can provide the color developing composition of the invention, method (2) is more favorable than that Method (1) because the resulting composition can be easily dispersed in water without being pulverized beforehand must and because pressure-sensitive writing sheet materials provided therewith exhibit excellent color developing performances.

Therefore, according to the present invention, includes a process for the preparation of a color developing composition for pressure sensitive Recording or writing sheet materials the provision of a mixture of a p-substituted phenol, preferably p-phenylphenol, formaldehyde or a formaldehyde-generating one Compound and a hydrophobic organic solvent capable of forming an azeotropic mixture with water, and the Subjecting this mixture to the condensation reaction in the presence of an acidic catalyst. An additive as defined above

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becomes either the above starting materials or the reaction mixture at the end of the condensation reaction added. The resulting solution of a p-substituted phenol-formaldehyde polymer and the additive in the organic Solvent is mixed with an aqueous alkaline solution. This mixture is steam distilled to the organic To remove solvents and leave a homogeneous aqueous solution of the corresponding alkaline metal phenates. Finally, a finely divided powdery composition is which comprises a homogeneous mutual solution of the p-substituted phenol-formaldehyde polymer and the additive, collected by precipitation with an acid.

In the process of the invention, a water-repellent or hydrophobic organic solvent is used which is mixed with water can form an azeotropic mixture. The organic solvents usable for this purpose include aromatic ones Hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as pentane, heptane, hexane, etc., alicyclic ones Hydrocarbons such as cyclohexane, etc., halogenated hydrocarbons and the like, and these can either be used alone or in Combination can be used. The hydrophobic organic solvent is used in an amount sufficient to azeotropically remove the water formed by the condensation reaction, and it is preferably used in an amount used which is equal to make 0.5 to 2.0 times the volume of p-substituted phenol used.

In the aforementioned organic solvent, a p-substituted one Phenol, formaldehyde or a formaldehyde-generating compound and an additive as defined above, dissolved. An acidic catalyst is also added to accelerate the condensation reaction. The ones useful for this purpose acidic catalysts include inorganic acids such as hydrochloric acid, Sulfuric acid, phosphoric acid, etc. and organic acids such as formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid etc., and they can either be used alone or in combination

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be used.

The p-substituted phenol and the formaldehyde or the formaldehyde generating Compounds can be used in proportions of 0.6 to 0.9 moles of formaldehyde for each mole of the p-substituted phenol will.

The condensation reaction for the formation of a p-substituted phenol-formaldehyde polymer is carried out at the temperature in the azeotropic distillation of the organic solvent and the water formed by the condensation reaction takes place. When the azeotropic mixture is removed from the reaction system and condensed to separate it into two layers and only the organic solvent layer is returned to the reaction system, the condensation reaction can be terminated

can easily be demonstrated by the facts »- {that

Water ceases to be present in the distillate and that the temperature rises and at the boiling point of the solvent used comes to equilibrium.

The amounts of the various additives used in the color developing composition of the invention are as follows: The amount of a benzotriazole compound should be 1 to 10 parts by weight per 100 parts by weight of the p-substituted phenol-formaldehyde polymer be. The amount of a hindered phenolic compound should be 1 to 20 parts by weight when used alone is used, or 1 to 10 parts by weight when used in combination with at least one other additive, per 100 parts by weight of the p-substituted phenol-formaldehyde polymer. The amount of a dialkyl thioether derivative should be 0.5 to 10 parts by weight per 100 parts by weight of the p-substituted one Be phenol-formaldehyde polymers. When the amount of additive used is less than the corresponding lower limit is, the resulting color developing composition fails to provide pressure-sensitive writing sheet materials which have sufficient durability against yellowing, if, on the other hand, it is greater than the corresponding upper limit, the p-substitute

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. 30 -

ated phenol-formaldehyde polymer and the additive if they should form a homogeneous mutual solution so that no further improvement in the resistance to yellowing is observed can be. In addition, if the additive should consist of a combination of a benzotriazole compound, a hindered phenolic compound and a dialkyl thioether derivative, the total amount of these three components is not greater kls 20 parts by weight per 100 parts by weight of the p-substituted one Phenol-formaldehyde polymers in terms of performance and the cost of the color developing composition thus obtained.

After the condensation reaction has ended, the resulting solution is mixed with an aqueous alkaline solution. This mixture is steam-dried in order to completely remove the organic solvent and thereby leave an aqueous solution in which the p-substituted phenol-formaldehyde polymer and the additive are dissolved in the form of the corresponding alkaline Metallphe-Bolato.

The alkalis that are useful for this purpose are sodium hydroxide and potassium hydroxide, and they are used in the form of a 5 to 20% aqueous solution. This aqueous solution is used in an amount of 0.6 to 1.2 moles of alkali per mole of the p-substituted phenol-formaldehyde polymer. Under these Conditions, a benzotriazole compound, a hindered phenolic compound and / or a dialkyl thioether derivative become homogeneous dissolved in the form of the corresponding alkali metal phenates as long as they are used in amounts falling into those given above Areas fall. More specifically, the solubility of the corresponding alkali metal phenates varies in an aqueous alkaline one Solution according to the position and type of the substituent radical or the radicals in the benzotriazole compound, the hindered phenolic compound and the dialkyl thioether derivative are included. Even if a small part of they remain unsolved is the decrease in their anti-yellowing effect of the p-substituted phenol-formaldehyde polymer so small that from a practical point of view

9098ΔΠ / 0784

- 31 from no problems arise.

The above-described aqueous solution containing the alkaline metal phenates is cooled and an acid is added to this solution with stirring. The acids used for this Useful purposes include inorganic acids such as hydrogen chloride acid, nitric acid, sulfuric acid, phosphoric acid, etc. and organic acids such as oxalic acid, acetic acid, p-toluenesulfonic acid etc. The resulting precipitate is collected by filtration, washed with water and dried to obtain a finely divided white powdery composition to obtain a homogeneous mutual solution of the p-substituted phenol-formaldehyde polymer and the additive.

Then, an aqueous coating paint for the formation of color developing sheets is used in the manner described above obtained color developing composition. More special the color developing composition of the invention, a dispersant and water in a suitable apparatus such as a sand mill (English: sand grinding mill), a ball mill, an attritor or an attritor etc. dispersed together, to form an aqueous suspension. Then an aqueous coating paint is produced by adding this aqueous suspension is mixed with various ingredients used to control the surface properties of the color developing sheets required are. For this purpose, (1) inorganic or organic pigments, (2) pigment dispersants, (3) coating compositions and (4) other additives are used. More specifically, (1) the inorganic or organic pigments include kaolin, Bentonite, talc, calcium carbonate, barium sulfate, aluminum oxide (Alumina), silicon oxide (silica; silicon dioxide, silicon IV oxide; Silica, etc.), satin white or plaster of paris, titanium oxide, polystyrene emulsion and the like; (2) which comprise pigment dispersants Phosphates such as sodium metaphosphate, sodium hexametaphosphate, Sodium tripolyphosphate, etc., polycarboxylates such as sodium polyacrylate etc., and the like; (3) the coating binders include modified starches such as oxidized starch, enzyme-modified

9098Λ0 / Π784

te starch, urea phosphate modified starch, alkylated Starch, etc., water-soluble proteins such as casein, gelatin, etc., synthetic rubber latexes such as styrene-butadiene latex, methyl methacrylate-butadiene latex etc, polyvinyl acetate emulsion, vinyl acetate ethylene copolymer emulsion, Polyvinyl alcohol, carboxymethyl cellulose, Hydroxyethyl cellulose, methyl cellulose and the like; and (4) the other additives include fluorescent whiteners, Antifoam agents, viscosity modifiers, anti-dust agents, slime control agents, lubricants, water repellants and the like.

In addition, other substances that have a color-developing effect can be used Have property to be used in the above-mentioned aqueous coating paint. The ones useful for this purpose Substances include inorganic solid acids such as activated clay or artificial clay etc., salicic acid derivatives such as zinc-3-phenyl-5-C *, Cxl-dimethylbenzyl salicylate, Calcium 3, 5-di-Oi "-methylbenzyl salicylate, Zinc 3,5-di-tert-butyl salicylate, etc., sulfenic acid derivatives such as polystyrene sulfonic acid, etc., and the like.

Color developing sheets in which the color developing composition of the invention are prepared by applying the aqueous coating paint described above a substrate or a support such as paper is applied. In general, the aqueous coating paint is used in such Amount applied so that it has a dry coating weight of

2 2

provides not less than 0.5 g / m and preferably 1 to 10 g / m. The performance of the color developing sheets thus obtained largely depends on the concentration of the color developing composition of the invention in the aqueous colorless coating paint. When the dry coating weight is greater than 10 g / m 2, there will be no further improvement in color developing performance observed, no additional effect on the resistance to yellowing when irradiated with light and against yellowing during storage, and only economic loss is caused.

909840/0784

In pressure-sensitive writing sheet materials containing the thus obtained Containing color developing sheets not only will their yellowing upon exposure to light and during storage (which is believed to be the p-substituted phenol-formaldehyde polymer is effectively prevented, but also excellent color developing performance becomes and achieved good water resistance. In this way, the color developing composition of the invention makes it possible to produce pressure sensitive recording or writing sheet materials of exceptionally high commercial value.

To further elucidate the finding, the following are provided Examples and comparative examples given. The results of evaluation of those obtained in these Examples and Comparative Examples Color developing compositions are shown in Table 1. The production of an aqueous coating paint, containing an aqueous suspension of a color developing composition, the manufacture of color developing sheets for use in pressure-sensitive writing sheet materials, the measurement of the whiteness of the color developing sheets, the determination the rate of color development and the evaluation of the resistance to yellowing by light ", against yellowing during Storage and anti-yellowing by NO were carried out according to the following procedures.

Preparation of an aqueous coating color and manufacture of color developing sheets.

Using a sand grinding mill, 80 g of a composition containing a p-phenylphenol-formaldehyde polymer and an additive as defined above or a p-phenylphenol-formaldehyde polymer alone, 1.6 g of one high molecular weight polycarboxylic acid surfactant (commercially available under the tradename "Orotan 731SD" from Rohm & Haas Co., U.S.A.) and 118.4 grams of water together dispersed to form an aqueous suspension. Then became

909840/0784

an aqueous coating paint containing the aqueous suspension described above and other necessary ingredients, prepared according to the formulation given below. Using a Meyer bar coater was This aqueous coating color is applied to sheets of quality paper so that it has a dry coating weight of

ο
Delivered 6.0 g / m. In this way, color developing sheets for use in pressure-sensitive writing sheet materials were obtained.

Component parts by weight

6th 5 13th 1 2 θ 15th 2, O, 13,

Aqueous suspension (42% dispersion in water)

Kaolin calcium carbonate oxidized starch (15% aqueous solution)

Styrene-butadiene latex (50% dispersion in Water) sodium metaphosphate water

A total of 52.5

Degree of whiteness of color developing sheets

Four color developing sheets made as indicated above were placed one on top of the other and the reflectance of the top sheet was determined by means of a Model TSS Hunter Colorimeters (manufactured and sold by Toyo Seiki Co., Japan) equipped with a blue filter was. The whiteness of the color developing sheets was expressed in terms of their reflection coefficient (F). Bigger ones Values for the reflection coefficient (F) represent higher degrees of whiteness Differences in the order of magnitude of 0.5 lines could be recognized by visual observation.

909840/0784

_ 35 Density and_Ra j ^ e_of color development

A back-coated sheet (commercially available under the trade name "NW-4OT" from Jujο Fapermaking Co., Japan) using Crystal Violet Lactone as the main pressure-sensitive dye is applied to a color developing sheet prepared as above placed with their two coated surfaces lying against each other. Then this set of sheets was typed on with an electric typewriter to develop a cobalt blue color. The reflectance of the color developing sheet was measured using a Model TSS Hunter Colorimeter fitted with an amber filter. This measurement of the density of the developed color was carried out twice, 1 minute and 20 hours after the writing. Then the initial color development rate (J-) and the final color development rate (J «) were ^{calculated from the} following equations:

OI

J _n = ^ux χ 100 (%)

¹ O

and j - j

j = _0- 2_ _{χ 100 (%)}

^{2 1} O

where I «, I ₁ and I _{0 are} reflection capacities, which were observed accordingly before the inscription, 1 minute after the inscription and 20 hours after the inscription. For both initial and final color development rates, higher values represent more desirable results.

Resistance to yellowing from light

A color developing sheet made as above (da but not yet subjected to color development) was exposed to sunlight for 12 hours. Using a Model TSS Hunter Colorimeters fitted with a blue filter ver was seen, the reflectance of the color developing sheet became measured before and after the test. Daaa became the degree aesg

909840/0784

Yellowing by light in values of the 2ει. . "/;.?:.: ■; I tsns of the power content (H), which is defined by the following equation:

^K 2 H = —— χ 100 (%)

^K l

where K- and Kg are those observed before and after testing, respectively Are reflectivities. Higher values for keeping of the whiteness represent lesser degrees of yellowing from light and are therefore more desirable results.

Resistance to yellowing on storage

A Far'o developing sheet (das but not yet subjected to color development) was attached to a wall of a room that is not directly exposed to sunlight was exposed and left there for two months. Using a blue filter, the reflectance of the color developing sheet measured before and after the test. Then the degree of yellowing during storage was expressed in values the whiteness retained (M) is expressed by the following equation:

^L 2

M = —-— x 100 (%)

^L l

where L- and L "are the reflectivities that correspond to observed before and after the test. Higher. ^ Values for maintaining whiteness, lower degrees of yellowing during storage represent and are therefore more desirable Results.

Resistance to yellowing by NO

Pressure-sensitive writing sheet materials · ::, bsi those a p-substituted Phenol-formaldehyde polymer, vc-ri ^ 'jgweise a p-phenylphenol-formaldehyde polymer, as a color developer? r is used,

9 0 SS i: ■ ·. G 7 B! ■

j, E-

subject to boknnni "in .: ^, the Ve *." r :: 1 lbc-ii £ σ; siziar oxidizing atraosphere, therefore '.Vuroc ¹ the base of the fawn-like Vss'gilbeEE measured in accordance with JIS-1055 (method toia T ^ ssien der EeMiieit of colored materials and dyes against nitrogen oxide gas). A Farfoe Biological Leaf (which, however, had not yet undergone color development) recovered as described above was placed in a sealed container, exposed to nitric oxide gas for 50 meows, and then compared to a standard dyed fabric treated in the same way Blue filter was the reflectivity of the color developing sheet before and naefo €% * «? Test gisraessen. The degree of yellowing was then expressed by NG _V ± n values of the retained white content (Fi, which was defined by the following equation ¹ ,

^N 2 P - - - χ 100 (%)

^N I

where N ₁ and N “are the healing abilities before and after

Jl. ώ

Test were. Greater values for the maintenance of the white content provide lesser degrees of yellowing in an oxidizing atmosphere is NO and ₅ indicate that the oxidation of the

p-substituted Phono 1-formaldehyde polymers and soiait the yellowing of the color developing sheet for a long period of time

Storage had been prevented.

When the ability to resist yellowing by light, yellowing during storage and yellowing by NO are expressed in terms of the retention of whiteness of the color developing sheet, differences on the order of 2% can be recognized by visual observation.

example 1

In a glass reactor 170 g of p-pheny! Phenol, 22.5 g of 80% paraformaldehyde, 3.4 g of 2- (2 ⁱ -hydroxy-5 ⁱ -i-methylphenyl) benzotriazole, 8.5 g of 4, -f * Bü'ν ';; ■. ^: .:? ubis (3-a ₁ ethyl-6-t ^; .-.- L ⁱ -i: -. butyl-phenol), 1.7

Entered dilauryl thiodipropionate, 2.0 g of p-toluenesulfonic acid and 200 g of benzene. This mixture was heated to 70 to 80 ^° C. for two hours with stirring, during which time the water formed by the reaction was removed from the reaction system by azeotropic distillation with benzene. The resulting homogeneous benzene solution of a p-phenylphenol-formaldehyde polymer and various additives was mixed with 320 g of a 10% aqueous solution of sodium hydroxide and steam distilled in order to remove the benzene and thereby leave a yellow-green and clear homogeneous aqueous solution of sodium phenolates. Then, dilute sulfuric acid was added dropwise to this solution with stirring. As a result, a homogeneous resin composition composed of the aforementioned p-phenylphenol-formaldehyde polymer, 2- (2 ^l -hydroxy-5'-methylpheriyl) benzotriazole, 4,4 ^f -butylidenebis (3-methyl-6-tert-butylphenol) and dilauryl thiodipropionate, precipitated. This precipitate was collected by filtration, washed with water and dried to obtain 188 g of a finely divided powdery composition having a high whiteness.

Example 2

The procedure of Example 1 was repeated with the exception that 5.1 g of 2- (2 ^f -hydroxy-3 ·, S'-tert-butylphenyD-ö -chlorobenzotriazole, 4.2 g of tetrakis (methylene (3.5 -di-tert-butyl-4-hydroxyphenyl) propionate) methane and 2.25 g of dimyristylthiodipropionate were used as the benzotriazole compound, the hindered phenolic compound and the dialkylthioether derivative, respectively, thus giving 184 g of a finely divided powdery composition having a high whiteness The aqueous solution of sodium phenates obtained in between looked pale yellow and clear.

Example 3

The procedure of Example 1 was repeated with the exception that 4.25 g of 2- (2 ^f -hydroxy-3 ^f -tert-butyl-5 ^f -methylphenyl) -5-chloro-

909840/0784

Q 1

benzotriazole 2.55 g 1,3,5-tri5ietii7l »2 ₅ 4, 6-tris (3, 5-di butyl-4-hydroxybenzyl) benzene and 3.4 g bistearylthiodiproploHsi: correspondingly, as the benzotriazole compound, the hindered phenolic compound and the dialkyl thioether derivative were used. In this way, 183 g of its finely divided powdery composition having a thick degree of whiteness was obtained. The intermediate aqueous solution of sodium phenates looked yellow and clear.

Example 4

The procedure of Example 1 was repeated with the exception that 3.4 g of 2- (2'-hydroxy-3 *, 5 * -di-tert-amylphenyl) benzotria3Gl and 5.1 g of 1,3,5-Tris ( 3,5-tert-butyl-4-hydroxybenzyl) isoeyaziU2'at were used as the benzotriazole compound and the hindered® phenolic compound, respectively. In this way 186 g of a finely divided powdery composition six were obtained with a high degree of whiteness. The aqueous intermediate solution 7 © e> sodium phenolates looked pale yellow-green and clear.

Example 5

A glass reactor was charged with 170 g of p-phenylphenol, 52.7 g of 37% formalin, 10 g of concentrated (35%) hydrochloric acid, 1 g of ossial anhydride and 250 g of toluene. This mixture was heated at 70 to 110 ° C for 6 hours with stirring, during which time the water formed by the reaction was removed from the reaction system by azeotropic distillation with toluene. To the resulting homogeneous toluene solution of a p-phenylphenol-formaldehyde polymer ¥ / ere 2.55 g of 2- (2 * -Hydi ^a osy ~ 3 ', ^5! -Di-tert-butylphenyl) benzotriazole, 6.8 g of 4j, 4' ~ Thiobis (3 = methyl-6-tert-butylphenol) and 2.55 g of distearyl S, ß »-thiedibutyrate were added, all of which dissolved in it homogeneously Sodium hydroxide mixed and steam distilled to remove the toluene, creating a pale gel?: / 3 and clear homogeneous aqueous solution of NatriMaphs-nolatoa m? I. ' : t he leave. Then this solution became drop by drop © sa ve ^ rlSsEv ~ ;. ⁼

90984 0/0734

Sulfuric acid added. As a result, a homogeneous resin composition 1-6 was precipitated from the above-mentioned p-phenylphenol-formaldehyde polymer, 2- (2'-hydroxy-3 ^l, 5'-di ~ tertbutylphenyDbenzotriazol, 4,4'-thiobis (3-methyl- -tert-buty 1-phenol) and distearyl-ß, ß'-thiodibutyrate, This precipitate was collected by filtration, washed with water and dried to obtain 183 g of a finely divided powdery composition having a high degree of whiteness.

Example 6_

The glass reactor was charged with 170 g of p-phenylphenol, 25.3 g of 80% paraformaldehyde, 1.5 g of p-toluenesulfonic acid and 300 g of benzene. This mixture was heated at 70 to 80 ° C for 3 hours with stirring, during which time the water generated by the reaction was removed from the reaction system by azeotropic distillation with benzene. 6.8 g of 2- (2 ^t -hydroxy-3 ^t , 5'-di-tert-amylphenyl) benzotriazole, 6.8 g of octadecyl 3- (3 ', 5 '-di-tert-butyl-4 ^f -hydroxyphenyl) propionate and 2.55 g of dilauryl thiodipropionate were added, all of which dissolved in it homogeneously. The homogeneous benzene solution thus obtained was mixed with 370 g of 15% aqueous solution of potassium hydroxide, and the benzene was stripped to leave a pale yellow-green and clear homogeneous aqueous solution of potassium phenates. Then this solution was added dropwise to dilute sulfuric acid. As a result, a homogeneous resin composition composed of the aforementioned p-phenylphenol-formaldehyde polymer, 2- (2'hydroxy-3 ', 5'-di-tert-amylphenyDbenzotriazole, octadecyl 3- (3', 5'-di-tert -butyl-4-hydroxyphenyl) propionate and dilauryl thiodipropionate, These precipitates were collected by filtration, washed with water and dried to obtain 190 g of a finely divided powdery composition having a high whiteness.

9 0 9 8 * Ο / 0 ^

Q Ί

Example 7

A glass reactor was charged with 170 g of p-Ffee _£ : ;; LpfcsHOl ₅ 2 ©, 6 g of 80% paraformaldehyde, ^{4.25 g of 2- (2 t} -HydrGxy-4 ^c -o & i-oicy-phe & yl) benzot ?: ⁱ iazol , 3.4 g of 2,2'-methylenebis (6- (l-methyicyelohexyD-p-eresol), 4.25 g of lauryl stearyl thiodipropionate, 0.5 g of orral acid hydrate ^ IG g of 35% hydrochloric acid and 200 g of toluene fecssehiokt. This mixture was heated for 10 hours under stirring a ^ f IG to 116 ° C, and during this 7, the water formed by dis Renkt ion was removed from the reaction system by azeotropic distillation with toluene. The resulting homogeneous toluene was dissolved by the toluene Heating the solution to ITO "G ufid KrK lowering the pressure to 20 mm Hg over a period of 2 hours. In this way 185 g of a pale yellow and clear homogeneous resin composition were obtained, which consists of a p-phenylphenol-formaldehyde polymer, 2- ( 2 * -Hydx'oxy-4'-octoxyphenyl) -benzotriazole, 2,2'-methyleneMs (6- (l-fii9 "!. 'Hylcyclohexyl) -p-cresol) and Laury 1stearylthiodipropionate consisted of. Using a small size grinder, this composition was ground to a finely divided white powder which completely passed through a 50 mesh sieve (ASTM).

Example 8

The procedure of Example 3 was repeated except that the distearyl thiodipropionate was omitted. To this Way were 180 g of a finely divided white powdery

Composition obtained, Bei , a pie I 9

The procedure of Example 1 would be repeated except that each of the 2- (2 '-hydroxy-S'-methy IpheayDbeiazotriazole and

the 4,4 'bi! tylic! enbis (3-! nethyl ~ 6-tert ™ bi! tylpiienol) by 6.8 g

2- (2'-Hydrojty-3 ', 5'o-tert-amylphenyDbenzotriazole and 6.8 g

Octadecyl 3 (3, * ύί -tert-butyl-4-hydrous: _f * iJhenyDpropionat replaced

“'JViien'. Never! ias ■: · ;;; ■■:; ■ vltliiOiiir-ifopionK ": 7'V-gge-lasse n " swrde. On '1, IvSe v / eis · ¹ · ΐ · \: v ■':. ■■ ■;. "'■' ς ^: a finely v-sr-divided '.ieisseE powder-coated

9 0 9 S L Π / 0 "■ *>:

- 42 migen composition obtained.

Example 10

The procedure of Example 3 was repeated except that the 2- (2 ^L -hydroxy-3'-tert-butyl-5 ^f -methylphenyl) -5-chlorobenzotriazole was omitted. In this way, 179 g of a finely divided white powdery composition was obtained.

Example 11

The procedure of Example 3 was repeated except that the 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-buty1-4-hydroxybenzyl) benzene has been omitted. In this way, 180 g of a finely divided white powdery composition was obtained.

Example 12

The procedure of Example 3 was repeated except that the 1,3,5-trimethy1-2,4,6-tris (3,5-di-tert-buty1-4-hydroxybenzylbenzene and the distearyl thiodipropionate have been omitted. In this way, 178 g of a finely divided white powdery composition obtained.

Example 13

The procedure of Example 12 was repeated with the exception that the 2- (2 ^t -hydroxy-3 ^f -tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole was replaced by 8.5 g of 2- (2'-hydroxy- 5'-tert-octylphenyl) benzotriazole was replaced. In this way, 182 g of a finely divided white powdery composition was obtained.

Example 14

The procedure of Example 3 was repeated with the exception that the 2- (2 ^f -hydroxy-3'-tert-butyl-5 ^f -methylphenyl) -5-chloro-

909840/0784

2311943

benzotriazole and the distearyl thiodipropicnate have been omitted. In this way, 177 g of a finely divided white powdery Preserved composition.

Example 15

A glass reactor was charged with 170 grams of p-phenylphenol, 52.7 grams of 37% formalin, 10 grams of concentrated (35%) hydrochloric acid, and 250 grams of benzene. This mixture was heated at 70 to 80 ° C for 6 hours with stirring, during which time the water generated by the reaction was removed from the reaction system by azeotropic distillation with benzene. 8.5 g of 4,4 ^i- thiobis (3-methyl-6 ~ l- @ rt-butylpheiaol> (commercially available under the name "Yoshinox SE" from Yoshitomi Pharmaceutical Co., Japan), which were homogeneously dissolved therein. The homogeneous benzene solution thus obtained was mixed with 253 g of a 15% aqueous solution of sodium hydroxide and steam distilled to remove the benzene and thereby a yellow and clear homogeneous aqueous solution of sodium phenolates Then this solution was added dropwise to dilute sulfuric acid. As a result, a homogeneous resin composition composed of the above-mentioned p-phenylphenol-formaldehyde polymer and 4,4'-thiobis (3-methyl-6- 'tert-butylphenol) was precipitated. This precipitate was collected by filtration, washed with water and dried to obtain, among other things, 183 g of a finely divided white powdery composition,

Example 16

The procedure of Example 3 was repeated except that the 4,4 'thiobis (3-methyl-6-tert-butylphenol) was replaced by 6.8 g 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) was replaced. on in this way, 180 g of a finely divided white powdery composition was obtained. The aqueous interim solution of sodium phenates looked pale yellow-green and clear.

S09840 / 07R4

Comparative example 1

The procedure of Example 3 was repeated with the exception that the 2- (2 ^t -hydroxy-3 ^f -tert-butyl-5 ^f -methylphenyl) -5-chlorobenzotriazole, the 1,3,5-triraethyl-2,4 , 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the distearyl thiodipropionate have been omitted. In this way, 175 g of a finely divided white powder consisting of a p-phenylphenol-formaldehyde polymer alone was obtained.

Comparative example 2

The procedure of Example 2 was repeated except that the 10% aqueous solution of sodium hydroxide was replaced with 157.6 g of a 33% aqueous solution of sodium hydroxide. In this way, 184 g of a finely divided white powdery composition was obtained. The aqueous solution of sodium phenates obtained after removing the benzene by steam distillation, however, looked cloudy because one or more of the additives, i.e. 2- (2 ^f -hydroxy-3. ', 5'-di-tert- butylphenyl) -5-chlorobenzotriazole, tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane and dimyristylthiodipropionate. Accordingly, the. finely divided white powdery composition collected by precipitation with an acid, not as a homogeneous mutual solution of a p-phenylphenol-formaldehyde polymer, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -chlorobenzotriazole, tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane and dimyristylthiodipropionate can be considered.

Comparative example 3

Using a sand grinding mill, 75.99 g of the p-phenylphenol-formaldehyde polymer described in Comparative Example 1 had been obtained, 1.46 g of 2- (2'-hydroxy-3 ', ö'-di-tert-amylphenyDbenzotriazole, 1.46 g 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1.09 g dilaurylthio

909840/0784

2811

dipropionate, 1.6 g of an oiierf lSeii € iiakti7CE; By means of the high molecular weight polycarboxylic acid type (commercially available under the trade name "Orotan 731SD" from Rohm & Haas Co., USA) and 118.4 g of water are dispersed together to form a watery suspension with a white color. This aqueous suspension consisted of the same components as the aqueous suspension obtained by subjecting the composition of Example 4 to wet milling according to the procedure described under the heading "Preparation of Aqueous Coating Paint and Preparation of Color Developing Sheets". However, the homogeneity of the p-phenylphenol-formaldehyde ^{polymer, the 2- (2 s} -HycliOxy-3 *, S'-di-tertaraylphenyDbenzotriazole, the 1,3,5-tris (3,5-di-tert-butyl-4 Hydroxybenzyl) iaocyanurate and dllaurylthiodipropionate in the former aqueous suspension worse than in the latter.

Comparison with is ρie 1 ■ '!

The procedure of Example 3 was repeated with the exception that 2- (2'-hydroxy-3'-tert-butyl-5 ^t -methylphenyl) -5-chlorobenzotriazole and the ϊ, 3,5-trimethyl-2,4, 6 ~ tris (3,5 »di-tert-butyl-4-hydroxybenzylbenzene were omitted. In this way 178 g of a finely divided white powdery composition were obtained.

t, Γ / 0784

Tabel Benzotriazole compound 1 Dialkyl thioether
derivative I.
Oi
i 2- (2'-Hydroxy-5 ^f -methylpheny1) -
benzotriazole
(2.0%) hindered phenolic
link Dilaurylthiodi-
propionate
(1.0%) example
1 2- (2'-hydroxy-3 ', 5'-di-tert-
butylphenol) -5-chlorobenzotri-
azole
(3.0%) 4,4'-butylidenebis (3-
methyl-6-tert-butyl-
phenol
(5.0%) Dimyristylthiodi-
propionate
(1.5%) example
2 2- (2 -hydroxy-3'-tert-buty1-
5'-methylphenyl) -5-chlorobenzo-
zotriazole
(2.5%) Tetrakis (methylene (3.5-
di-tert-butyl-4-hydroxy
phenyDpropionate) methane
(2.5%) Distearylthiodi-
propionate
(2.0%) 2911945 2 example
30 3
O 2- (2-hydroxy-3 ', 5'-di-tert-
amylphenyl) benzotriazole
(2.0%) l, 3,5-triraethyl-2,4,6-
tris- (3,5-di-tert-bu-
tyl-4-hydroxybenzy1) -
benzene
(1.5%) Dilaurylthiodi-
propionate
(2.0%) ca example
* ^ 4 2- (2'-hydroxy-3 ', 5'-di-tert-
butylpheny1) benzotriazole
(1.5%) 1,3,5-tris (3,5-di-tert-
butyl-4-hydroxybenzyl) -
isocyanurate
(2.0%) Distearyl-ß _t ß -.
thiodibutyrate
(1.5%) example
5 2- (2'-Hydroxy-5 ^f -tert-amyl ~
phenyl) benzotriazole
(4.0%) 4,4'-thiobis (3-methy1-
6-tert-butyl phenol )
(4.0%) Dilaurylthiodi-
propionate
(1.0%) example
6th Octadecyl 3- (3,5-di-
tert-butyl-4-hydroxy
phenyD propionate
(4.0%)

Table 1 (continued)

example
7th Benzotriazole compound hindered phenolic
link Dialkyl thioether
derivative Ü 29119A example
8th 2- (2'-hydroxy-4'-octoxy-
phenyDbenzotriazole
(2.5%) 2,2'-methylenebis (6- (l-
methylcyclohexy1) -p-
cresol)
(2.0%) Laurylstearylthio
dipropionate
(2.5%) example
9 2- (2'-hydroxy-3'-tert-butyl-
5 * -methylpheny1) -5-chlorobene-
zotriazole
(2.5%) l, 3,5-trimethyl-2,4,6-
tris (3,5-di-tert-butyl-
4-hydroxybenzyl) benzene
(1.5%) / 0786Qi example
10 2- (2'-Hydroxy-3 ♦, 5 ^f -di-tert-
amy lpheny dbenzotriazole
(4.0%) Octadecyl 3- (3,5-di-tert-
butyl-4-hydroxyphenyl) -
propionate
(4.0%) 3
-3
CO example
11 1,3,5-trimethy1-2,4,6-
tris (3,5-di-tert-buty1-
4-hydroxybenzyl) benzene
(1.5%) Distearylthiodi-
propionate
(2.0%) example
12th 2- (2 ^f -hydroxy-3'-tort-butyl
s' -methy lpheny l) -5-chlorobenzene-
zotriazole
(2.5%) Distearylthiodi-
propionate
(2.0%) 2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-chlorobenzo-
zotriazole
(2.5%)

Table 1 (continued)

Benzotriazole compound

hindered phenolic compound

Example 2- (2'-Hydroxy-5 ^f -tert-octyl-13 phenyl) benzotriazole

(5.0%)

example

14th

ο example

to 15

° example

o ¹⁶

oo ■

* "" · *, VlQ "Sf * € F" \ ■ »» «H K-« Μ · Η * I ^ B · ^

1,3,5 ~ trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (1.5%)

Dialkyl thioether derivative

4,4'-thiobis (3-methy1-6-tert-buty! Phenol)

(5.0%)

2,2 »-Methylene bis (4-ethy1-6-tert-butylphenol)
(4.0%)

^ 1. 2- (2 ^t -hydroxy-3 ^t , 5 ^f -di-tert-

'. p.2 butylphenyl) -5-chlorobenzotriazole

(3.0%)

ßisp.3

Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane
(2.5%)

Dimyristyl thiodipropionate

(1.5%)

2- (2 ¹ -hydroxy-3 ', 5 ^f -di-tertamylphenyD-benzotriazole

(2.0%) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

(2.0%)

Dilauryl thiodipropionate

(1.5%)

Cf.
Example 4

Distearyl thiodipropionate (2.0%)

Table 1 (continued) Test results

Degree of whiteness Color development rate Resistance to Resistance to Resistance to (F) At the beginning At the end Yellowing through yellowing through N0_gen yellowing select-

(J ₁ )

At- 82, H.

■ 10, f.

(J ₂ )

Light (H)

47.7

94.4

95.2

rend storage (M)

94, 8

H 2 . V

(O,

Λ 7 - \

94.0

92, 8

;> 3,

game 82.8

40, (3

47.7

93.5

1) 2.8

'·' 9 Λ

Ee i -

s-niel 82.8

40.4

47.4

93.0

Example 82.7 5

40.6

47.8

92.9

94.4

94 "Ö

Example 82.8

40.2

46.9

94.0

94, i

95.0

Table 1 (continued) Test results

Degree of whiteness Color development rate Resistance to Resistance to Resistance to (F) At the beginning At the end yellowing by yellowing by NO against yellowing

(J ₁ )

(J ₂ ) light (H)

rend storage (M)

example
7th

82.8

40.5

47.7

93.5

94.5

94.0

example
8th

O Γ;

82.1 40.8

47.6

91.3

Example 82.0 39.9 46.5

f-3.4

90.1

91.9

03.0

At- '82.7
game
10

40.6

47.7

80.9

90.0

91.8

Example 82.8 40.2 47.4 11

89.9

80.2

85.4

Example 82.0
12th

40.3

47.6

89.0

79.8

86.1

Table 1 (continued) Test results

Degree of whiteness Color development rate Resistance to Resistance to Resistance to (F) At the beginning At the end yellowing by yellowing by NO against yellowing

(J ₁ )

(J ₂ ) light (H)

rend storage (%)

.niel 81, «J

10.4 17.2

12.1

7 ^, 8

86.1

Example 82.0

14th

! 0.3 47, G.

81.0

87.3

K), L

to - -

S

oo game

* ■ * 15

^ - at-

° game

40, β 47.2

40.8 47.4

80, ίί

80.8

5-2.1

CO, 3

94.1

92.5

W ₄ ! "Ex.

82.0

40.7 47.7

80.5

79.3

85.5

See Ex.

82.7

40.4 47.4

90.7

85.2

90.2

VgI.Bsp.

81.9

40.5 47.6

81.0

80.9

86.1

82.5

40.4 47.8

80.5

7 &, 4

85.7

Claims (22)

Dr. rer. not. Horst Schüler PATENTANWALT 6000 Frankfurt / Main 1, 26.3.1979 Kaiserstraße 41 Dr.HS / ki Telephone (0611) 235555 Telex: 04-16759 mapat d Postscheck-Kontos 282420-602 Frankfurt-M. Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M. M / 195O Applicant: Mitsui Toatsu Chemicals, Incorporated, No. 2-5, Kasumigaseki 3-chome, Chiyoda-ku Tokyo, Japan claims 1.' Color developing composition for printing Writing sheet material, characterized in that it (A) 100 parts by weight of a p-substituted phenol-formaldehyde polymers and (B) a certain amount of an additive comprising the Is selected from the group consisting of the following; (a) 1 to 10 parts by weight of a benzotriazoi compound having the general formula where X represents a hydrogen, chlorine or bromine atom, Y and Y represent ₂ hydrogen atoms, alkyl radicals with 1 to 12 carbon atoms, alkoxy radicals with 1 to 12 carbon atoms, aryl radicals with 6 to 15 carbon atoms or aralkyl radicals with 7 to 15 carbon atoms and those with Y and Y ₂ denoted residues 9098 ^ 0/0784 cannot be the same or different from each other, (b) 1 to 20 parts by weight of a hindered phenolic compound which is used as a phenol derivative with an alkyl, Defined alkylene or hydroxy substituent radical in the 2- or 6-position or in both of the benzene ring is, (c) a combination of 1 to 10 parts by weight of the specified benzotriazole compound and 1 to 10 parts by weight of the specified hindered phenolic compound, (d) a combination of 1 to 10 parts by weight of the specified benzotriazole compound and 0.5 to 10 parts by weight of a dialkyl thioether derivative. with the general formula R ₁ COOR ₂ R ₁ COOR ₃ where R _{1 represents} an alkylene radical with 1 to 6 carbon atoms, R ₂ and R _{3 represent} alkyl radicals with 8 to 22 carbon atoms and the radicals represented by R ₂ and R ₃ can be either the same or different from one another, (e) a combination of 1 to 10 parts by weight of the hindered phenolic compound and 0.5 to 10 parts by weight of said dialkyl thioether derivative and (f) a combination of 1 to 10 parts by weight of said benzotriazole compound, 1 to 10 parts by weight of said hindered phenolic compound and 0.5 to 10 parts by weight of said dialkylthiofther derivative in which the total amount of these three Components not greater than 20 parts by weight let wherein the p-substituted phenol-formaldehyde polymer and the said additive are homogeneously dissolved in mutual solution. S09840 / 0784 2. Color developing composition according to claim 1, characterized in that the p-substituted phenol-formaldehyde polymer is a p-phenylphenol-formaldehyde polymer is. 3. Color developing composition according to claim 1, characterized in that the benzotriazole compound 2- (2 * -hydroxy-5'-methylphenyl) benzotriazole, 2- (2 * -hydroxy-5 * -tert-octylphenyl) -benzotriazole, 2- (2 '-Hydroxy-5 · -tert-octy! Phenyl) benzotriazole, 2- (2 · - Hydroxy-3 ·, 5'-di-tert-butylphenyl) & enzotriazole, 2- (2' ~ hydroxy-3 ¹ , ö ' -di-tert-butylphenyD-S-chlorobenzotriazole, 2- (2 * -hydroxy-3 ·, 5 '-di-tert-amylphenyDbenzotriazole, 2- (2' -hydroxy-3 · -tert-buty 1-5 '- methylpheny 1) -5-chlorobenzotriazole or 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole 1st. 4. color development composite icing according to claim 1, characterized in that the hindered phenolic compound is a di-, tri- or Is tetraphenol derivative. 5. Color developing composition according to claim 4, characterized in that the diphenol derivative is an alkylidenediphenol derivative or a Is thiobisphenol derivative. 6. color developing composition according to claim 5, characterized in that the Alkylidendiphenolderivat 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2 ^{1-methylenebis} (4-ethyl-6-tert-butylphenol), 2,2 '-Methylene bis (4,6-di-tert-butylphenol), 4,4 "-methylene bis (3-methy1-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4 , 4'-methylenebis (2-methy1-6-tert-butylphenol), 2.2 ^t -methylene bis (6- (1-methylcyclohexyl) -4-methylphenol), 4,41-butylidene1) is (3-methyl-6-tert -butylphenol), 4,4'-propylidenebi (2,6-di-tert-ljutylphenol), 4,4'-cyclohexylidenebis (2,6-ai * tert <-butylphenol) © äer 4,4'-Bi β ( 2 ₁ 6-di-1 is t-butylpienol); S09840 / 0784 -A- 7. color developing composition according to claim 5, characterized in that the thiobisphenol derivative 4,4'-thiobis (3-methy1-6-tert-buty1-phenol), 4,4'-thiobis (2,6-di-tert-butylphenol), 4,4'-thiobis (2-methy1-6-tert-butylphenol), 2,2'-thiobis (4-methy1-6-tert-butylphenol), 2,2'-thiobis (4,6-di-tert-butyl-phenol), 2,2'-thiobis (4,6-di-tert-butylresorcinol) or 1,1'-thiobis (2-naphthol). 8. color developing composition according to claim 1, characterized in that the dialkyl thioether derivative dilauryl thiodipropionate, dimyristyl thiodipropionate, Distearyl thiodipropionate, distearyl ß _f ß'-thiodibutyrate or lauryl stearyl thiodipropionate. 9. Color developing composition for pressure sensitive materials Writing sheet material, characterized in that it is (A) 100 parts by weight of a p-substituted phenol-formaldehyde polymers, (B) 1 to 10 parts by weight of a benzotriazole compound with the general formula HO " ^Y l where X represents a hydrogen, chlorine or bromine atom, Y ₁ and Y _{2 represent} hydrogen atoms, alkyl radicals with 1 to 12 carbon atoms, alkoxy radicals with 1 to 12 carbon atoms, aryl radicals with 6 to 15 carbon atoms or aralkyl radicals with 7 to 15 carbon atoms and the radicals represented by Y ^ and Y ₂ may be either the same or different from each other, (C) 1 to 10 parts by weight of a hindered phenolic compound which is used as a phenol derivative with an alkyl, alkylene or 909840 / 078Ä Hydroxyl substituent radical in the 2- or 6-position or is defined in both of the benzene ring, and (D) 0.5 to 10 parts by weight of a dialkyl thioether derivative having the general formula R ₁ COOR ₂ comprises, where R- represents an alkylene radical with 1 to 6 carbon atoms, R "and R _{3 represent} alkyl radicals with 8 to 22 carbon atoms and the radicals represented by R" and R ₃ can be the same or different from one another, and the total amount of this benzosotriazole compound, this hindered phenolic bond and this Dialkylthioätiierderivats is not greater than 20 parts by weight and all these four components are homogeneously dissolved in mutual solution. 10. Farbentwlcklungszusammeiisetsiiag na cn claim 9, characterized in that the p-substituted phenol-iOrEaLdehydpolyiaer a p-Piieaylphenoi-formaldehyde polymer is. 11. color development kit according to claim 9, characterized in that the Benzotriazole compound 2- (2 '-Hyäroxy-5 ^l -tBethylphenji} bensotriaaol _t 2- (2' -Hydroxy-5 ^f -tert-affiylpfees3iyl) -b © naot2? Ias8ol, 2- (2'-Hydroxy-5 ^f -tert ~ octylpiienyl} faenzotriazole _> 2- (2'-hydroxy-3 ', 5'-di-tert -utylphenyl) benzotriazole, 2- (2'-HyUrOXy-S ', 5 ^! -Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-Hydroxy-3 ', 5 ^t -di-tert-amylphenyl) benzotriazole, 2- (2 ^l hydroxy-3 ^I -tert-butyl-S ^: -! BethylpheHyl) -5-chlorobenzotriazole, or Is 2- (2'-hydroxy-4 * -octoxyphenyl) benzotriazole. 909840/0784 12. The color developing composition of claim 9, characterized in that the hindered phenolic compound is a di-, tri- or tetraphenol derivative is. 13. The color developing composition of claim 12, characterized in that the diphenol derivative is an alkylidenediphenol derivative or a Is thiobisphenol derivative. 14. The color developing composition of claim 13, characterized in that the alkylidenediphenol derivative 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2 -Methylene bis (4-ethy1-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 4,4? -Methylene bis (3-methy1-6-tert-butylphenol), 4,4-methylenebis (2,6-di-tert-butylphenol), 4,4 * -Methylene bis (2-methy1-6-tert-butylphenol), 2,2'-methylenebis (6- (l-methylcyclohexyl) -4-methylphenol, 4,4 ^l -butylidenebis (3-methy1-6-tert-butylphenol), 4,4 * -propylidenebis (2,6-di-tert-butylphenol), 4,4'-cyclohexylidenebis (2,6-di-tert-butylphenol) or 4,4 · -Bis (2,6-di-tert-butylphenol). 15. Color developing composition according to claim 13, characterized in that the Thiobisphenol derivative 4,4'-thiobis (3-methy1-6-tert-buty1-phenol) , 4,4'-thiobis (2,6-di-tert-butylphenol), 4,4'-thiobis (2-methy1-6-tert-butylphenol), 2,2'-thiobis (4-raethy1-6-tert-butylphenol), 2,2'-thiobis (4,6-di-tert-butylphenol), 2,2'-thiobis (4,6-di-tert-butylresorcinol) or Is 1,1'-thiobis (2-naphthol). 16 «color developing composition according to claim 9, characterized in that the 909840/0784 Dialkylthloätherderivat dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, distearyl ß -thiodibutyrat 'or laurylstearylthiodipropionate is. 17. Process for the preparation of a color developing composition for pressure-sensitive writing sheet material, characterized in that (A) a Mixture of at least one p-substituted phenol, Formaldehyde or a formaldehyde-generating compound, at least one additive and one water-repellent organic solvent is provided, wherein the additive is selected from the group consisting of (a) a benzotriazole compound having the general formula HO V ^Y where X represents a hydrogen, chlorine or bromine atom, Y and Y ₂ hydrogen atoms, alkyl radicals with 1; 12 carbon atoms, alkoxy radicals with 1 to 12 carbon atoms, aryl radicals with 6 to 15 carbon atoms or aralkyl radicals with 7 to 15 carbon atoms and the radicals represented by Y ^ and Y ₂ can be either the same or different from one another, and the amount of this benzotriazole compound 1 to 10 Parts by weight per 100 parts by weight of the p-substituted phenol-formaldehyde polymer to be formed, (b) a hindered phenolic compound acting as a phenol derivative having an alkyl, alkylene or hydroxy substituent group is defined in the 2- or 6-position or in both of the benzene ring, the amount this hindered phenolic compound is 1 to 20 parts by weight when used alone, or 1 to 10 parts by weight if they are combined 909840/0784 nation is used with at least one other additive per 100 parts by weight of that to be formed p-substituted phenol-formaldehyde polymers, and (c) a dialkyl thioether derivative having the general formula R ₁ COOR ₂ where R _{1 represents} an alkylene radical having 1 to 6 carbon atoms, R ₂ and R _{3 represent} alkyl radicals having 8 to 22 carbon atoms and the radicals represented by R ₂ ^{and R} 3 can be either the same or different from one another, and the amount of the dialkylthioether derivative is 0.5 up to 10 parts by weight per 100 parts by weight of the p-substituted phenol-formaldehyde polymer to be formed, the total amount of this benzotriazole compound, this hindered phenolic compound and this Dialkylthioether derivative not greater than 20 parts by weight per 100 parts by weight of the p-substituted to be formed Phenol-formaldehyde polymer, (B) the mixture is subjected to a condensation reaction in the presence of an acidic catalyst to obtain a Solution of a p-substituted phenol-formaldehyde polymer and to form this additive in said organic solvent, (C) this solution with an aqueous one alkaline solution is mixed, (D) the resulting mixture is steam distilled to make this organic To remove solvents and thereby leave an aqueous solution of the corresponding phenolates, and (E) a composition consisting of said p-substituted phenol-formaldehyde polymer and said additive is collected by means of precipitation with an acid. 909840/0784 ■ y "■ 18. The method according to claim 17, characterized in that the p-substituted phenol p-phenyl is phenol. 19. The method according to claim 18, characterized that the aqueous alkaline solution is a 5 to 20% aqueous solution of sodium hydroxide or Potassium hydroxide and in an amount of 0.6 to 1.2 moles Alkali is used per mole of this p-phenylphenol. 20. A method for preparing a color developing composition for pressure-sensitive writing sheet material, characterized in that (A) a mixture of at least one p-substituted one Phenol, formaldehyde or a formaldehyde-generating compound and a water-repellent organic solvent a condensation reaction in the presence of an acidic catalyst is subjected to a Solution of a p-substituted phenol-formaldehyde polymer in this organic solvent ειι form, (B) at least one additive is added to this solution selected from the group consisting of (a) a benzotriazole compound having the general formula where X represents a hydrogen, chlorine or bromine atom, Y ₁ and Y _{2 represent} hydrogen atoms, alkyl radicals with 1 to 12 carbon atoms, alkoxy radicals with 1 to 12 carbon atoms, arylresx © with β to 15 carbon atoms or aralkyl radicals with 7 to 15 carbon atoms and the residues represented by Y and Y ₂ 909840/0784 may be either the same or different from each other, and wherein the amount of this benzotrlazole compound 1 to 10 parts by weight per 100 parts by weight of the p-substituted phenol-formaldehyde polymer, (b) a hindered phenolic compound acting as a phenol derivative having an alkyl, alkylene or hydroxyl substituent group is defined in the 2- or 6-position or in both of the benzene ring, the amount this hindered phenolic compound is 1 to 20 parts by weight when used alone, or 1 to 10 parts by weight when in combination with at least one other additive per 100 parts by weight of the p-substituted phenol-formaldehyde polymer is used, and (c) a dialkyl thioether derivative having the general formula R ₁ COOR ₂ R ₁ COOR ₃ where R- represents an alkylene radical having 1 to 6 carbon atoms, R ₂ and R _{3 represent} alkyl radicals having 8 to 22 carbon atoms and the radicals represented by R ₂ and R ₃ can be either the same or different from one another, and the amount of this dialkylthioether derivative is 0.5 to 10 parts by weight per 100 parts by weight of the p-substituted phenol-formaldehyde polymer, being the total amount of said benzotriazole compound, said hindered phenolic compound and the dialkyl thioether derivative not greater than 20 parts by weight per Parts by weight of the p-substituted phenol-formaldehyde polymer is, (C) the resulting solution is mixed with an aqueous alkaline solution, (D) the resulting Mixture is steam distilled to this organic solvent to remove and thereby an aqueous solution 909840/0784 of the corresponding phenates, and (E) a composition consisting of this p-substituted Phenol-formaldehyde polymers and the said additive, collected by precipitation with an acid will. 21. The method according to claim 20, characterized that the p-substituted phenol is p-phenylphenol. 22. The method according to claim 21, characterized by d a el u r c h That the aqueous alkaline solution is a 5 to 20% aqueous solution of sodium hydroxide or potassium hydroxide and in an amount from 0.6 to 1.2 moles of alkali are used per mole of this p-phenylphenol will. 909840/0784