FI102598B - recording Material - Google Patents

Abstract

Thermally- or pressure-sensitive record material comprises a substrate and a substituted phenol color developer material of the formula <CHEM> wherein: n is independently an integer from 1 to 4; m is independenty an integer from 1 to 4; each of R<1> amd R<2> is independently hydrogen, C1-C8 alkyl, or halogen; R<3> is allyl, benzyl or C1-C4 alkyl, preferably methyl; and either each of R<4> and R<5> is independently hydrogen or C1-C8 alkyl, or R<4> and R<5> together form a 5 or 6 membered alkyl ring.

Description

102598

RECORDING MATERIAL This invention relates to a type of recording material which can develop dark colored markers by reactive contact with one or more colorless basic chromogenic (also called color former) agents. The invention may be used in particular in heat-sensitive recording materials and systems and in pressure-sensitive recording materials and systems (also referred to as carbon-free copy papers).

The heat-sensitive recording material typically consists of one or more substrate sheets or rolls coated with color-forming agents formed from a chromogenic material and an acidic color development agent.

Thermosensitive recording media systems are well known in the art and have been described in many patents, e.g. In these systems, the basic chromogenic agent and the acidic color developer are contained in one or more substrate coatings which, when heated to a suitable temperature, melts, softens or sublimates, thereby allowing the reaction of these agents to produce a colored trace. Such systems are heat-responsive in nature and generate a sufficiently strong color image by selective heat exposure.

The transfer type pressure-sensitive carbon-free braiding paper typically comprises a plurality of overlapping 35 layers consisting of sheets of paper coated on one surface of one such layer by pressure breakable microcapsules containing a solution of one or more colorformers (hereinafter referred to as 102598). a second sheet having a coating containing one or more color enhancers (hereinafter CF sheet). The uncoated side of the CF sheet may also be pressurized with a rupture wool microcapsule containing a solution of the color former, thereby forming a pressure-sensitive sheet coated on both the front and the back (CFB sheet). When these layers are superimposed so that the microcapsules of one layer are adjacent to the color development paths of the second layer, release, for example by a typewriter or printing device, sufficient pressure to break the microcapsules onto the CF sheet of solution with. Such transfer systems and their manufacture are described in U.S. Patent No. 2,730,456.

The recording material of this invention uses a phenol derivative as a color developer.

Certain biphenol compounds have previously been proposed as developing agents, such as 2,2-bis (4-hydroxyphenyl) -5-methylhexane (U.S. Patent 4,551,739). Other biphenol compounds, such as 2,2'-methylene-bis (4-tert-pentylphenol), have been proposed in U.S. Patent 3,244,550; 4,4'-sec-butylidene diphenol and 4,4'-isopropylidenediphenol.

U.S. Patent 4,880,766 describes a number of known and novel developmental compositions which include phenol and diolefinic alkylated or alkenylated ring hydrocarbon addition products; a zinc-modified addition product of phenol and diolefinic alkylated or alkenylated ring hydrocarbon; mixtures of an acidic polymer with an organic carboxylic acid or a metal salt thereof; polyvalent carboxynaturated turpentine phenol resins; and alloys containing a certain percentage by weight of a phenolic group, a divalent zinc and an aromatic carboxylate compound.

It is an object of the present invention to find recording materials having improved thermal sensitivity or faster or more intense imaging.

According to the invention there is provided a recording material comprising a substrate and a color developer, characterized in that the color developer contains a substituted phenol of the formula io (R *) 4 (R 2) 4 K ° - (5) - = - ( i) ~ ° ηϊ wherein: both R 1 and R 2 are independently hydrogen, C 1 -C 4 alkyl, or halogen; R3 is allyl, benzyl or C1-C alkyl, preferably -20 methyl; and either R 4 and R 5 are independently hydrogen or C 1 -C 6 alkyl, or R 4 and R 5 together form a 5- or 6-membered alkyl ring, provided that when R 4 and R 5 are both methyl and R 1 and R 2 are both hydrogen, R 3 is not benzyl. 25

It is preferred that R4 and R5 are not simultaneously hydrogen. It is preferred that R 1 and R 2 are each independently hydrogen or halogen. Chlorine and bromine are preferred halogens for R3 and R2. Chlorine or bromine 30 may preferably be used up to two for each · phenyl or its hydrogen substitution. Methoxyphenyl. Alkylphenols are preferred.

Particularly preferred color development agents within the above general formula and the preceding recommendations are those wherein both R 1 and R 2 are independently hydrogen or halogen and R 3 is C 1 -C 1 alkyl, preferably methyl.

102598 4

Illustrative examples of these compounds are: 1. Phenol, 4- [1- (4-methoxyphenyl) -1,3-dimethylbutyl] -?

M.p. 119-122 ° C

II

2. Phenol, 4- [1-Ethyl-1- (4-methoxyphenyl) propyl] -CH 3 - (O, R) - (O) -?

mp 124-126 ° C

3. Phenol, 4- [1- (4-methoxyphenyl) -1-methylpropyl] -20 ch3-CH3 m.p. 112-113 ° C 25-102598 δ 4-Phenol, 4- [1- (4-methoxyphenyl) cyclohexyl] -5 ™ -

Melting point 115-117 ° C

5. Phenol, 4- [1- (4-methoxyphenyl) -3-methylbutyl] -

B

15 ^ oV | - ^ 0 ^ -3 '-' CHj? I c / l \ H ch3 h ch3

mp 79-80 ° C

6. Phenol, 4- [1- (3,5-dibromo-4-methoxyphenyl) -1-methylethyl] -2,6-dibromo

Br CH3 Br 25 ypy j yp ^ ~ ° c>, y

Br CHj Br

mp 133-134 ° C

7. Phenol, 4- [1- (4-Allyloxyphenyl) -1,3-dimethylbutyl-30] -

B

Viscous liquid 102598 6 8. Phenol, 4- [1- (4-Benzyloxyphenyl) -1, CH2 -CH3 - (-) - (- (-) -) - OCH2CH = CH2 355 y. 3-dimethyl-but-tyyii] -

B

5 cHi I / CH5 »> / ö) -ch ^ / oV- ° cH! - (5) '-' 3 viscous liquid 10 9. Phenol, 4- [1- (4-ethoxyphenyl) -1,3-dimethylbutyl] -

B

CH, | CHS

These viscous liquids are typically coated. The invention is typically coated with i / \ / \ HO- <O) - C - ((~) V-OCH.-CH,., \ V_y / i \ V_y / <s. The substrate may either be provided with conventional CF pressure-sensitive recording media, or coated with the substrate in combination with a chromogenic compound to provide a heat-sensitive recording material having improved thermal sensitivity, or faster or more intense imaging.

The alkoxy group may optionally be replaced by ethoxy, propoxy, isopropoxy, isobutoxy, tert-butoxy, sec-butoxy, i.e. one to four to thirty carbon atoms in the alkoxy group may be preferred, with methoxy being preferred.

These compounds include the following: 4- [1- (4-ethoxyphenyl) -1,3-dimethylbutylphenol / 4- [1-ethyl-1- (4-ethoxyphenyl) propyl] phenol; 4- [1- (4-ethoxy-35-phenyl) -1-methyl-propyl] -phenol; 4- [1- (4-ethoxyphenyl) cyclohexyl] phenol; 4- [1- (4-ethoxyphenyl) -3-methyl-·. butyl] phenol; 4- [1- (3,5-Dibromo-4-ethoxyphenyl) -1-methylethyl] 2,6-dibromophenol; 4- [1- (4-isobutoksifenyy-1i) -1,3-dimetyy1ibutyyli] phenol; 4- [1- (4-propoxyphenyl) -1,3-dimethylbutylphenyl; 4- [1-ethyl-1- (4-propoxyphenyl) propyl] phenol; 4- [1- (4-propoxyphenyl) -1-methylprop-5-yl] phenol; 4- [1- (4-isopropoxyphenyl) cyclohexyl] phenol; 4- [1- (4-tertbutoksifenyyli) -3-methyl-butyl] phenol; 4- [1- (3,5-dibromo-4-butoxyphenyl) -l-methylethyl-yl] -2,6-dibromophenol; 4- [1- (4-tertbutoksifenyyli) -1,3-dimetyy1ibutyy1i] phenol; 4- [1-ethyl-1- (4-isopropoxy-phenyl) -propyl] -phenol and the like.

When the resulting materials are viscous oils at room temperature, chlorination or bromination in R * or R 2 increases the molecular weight and helps to provide solids. The oils may be used in powder form together with clays and other carriers. Methoxy versions are typically solids at room temperature and are preferred in temperature recording materials.

The substituted phenols and alkoxy-phenylalkylphenols used in the invention are prepared as follows: , (Λ. <£> · "* JL1 '"' '' n N 'Ka3csif donkey system

Bisphenols, also called biphenols, can be monoalkylated by selective treatment with an alkylating agent in a two-phase system. The two-phase system may comprise an aqueous alkali solution and a water immiscible solvent such as CH 2 Cl 2 or ethyl ether. The product is removed from the further reaction by extraction with solvent. Another method of synthesis is the treatment of bisphenol with an alkylating agent in an alkali-35L aqueous solution, whereby the product precipitates from an aqueous alkali solution. These methods appear to produce better ·. results than by treating with an alkylating agent in a single 102598 8 organic solvent to which the monoalkylated product is soluble.

4- [1- (4-Alkoxyphenyl) cyclohexyl] phenol can be reacted with 4- [1- (4-methoxyphenyl) cyclohexyl] phenol, which may be prepared by a condensation reaction.

OMc HO ° Me 10 011 LO) ΟΓ, -Η, ΡΟ, / q \ / q \

1 o] * f j rK

\ / H + by-products 15

Chemical Abstracts (CA 85 (19): 142743V) describes this synthesis in more detail. Example 29 also describes the synthesis of this type of compound.

Recording systems utilizing the alkoxyphenylalkylphenol enhancers of the invention have surprisingly been found to have improved imaging properties, such as improved thermal sensitivity or faster imaging, or stronger images in recording systems. In thermal recording systems, a recording system with improved thermal sensitivity can advantageously obtain an image with less energy, which makes the system usable in facsimile machines.

Compounds of different substitution patterns may also ·. daan used. The recommended melting point for compounds of this type for heating systems is in the range of 60-150 ° C.

Thermosensitive character formation systems are well known in the art and have been described in numerous patents. for example, U.S. Patents 3,539,375, 3,674,535, 3,746,675, 102598,9, 4,151,748, 4,1818,771, and 4,245,318. In these systems, the alkaline chromogenic agent and the acidic color developer are contained in the coating or coatings of the substrate which, when heated to a suitable temperature, melt or soften, thereby allowing an inter-agent reaction to produce a colored trace.

The recording material of the invention includes a substrate or a substrate, which is generally sheet-like. For the purposes of this invention, sheets can be considered as support bays, and are also meant webs, tapes, belts, transparencies, cards, and the like. Sheets refer to products with two large surface dimensions and a relatively small thickness dimension. Paper is recommended. The substrate or substrate material may be opaque, transparent or translucent and may itself be colored or colorless. It may be a film, including, for example, cellophane and synthetic polymer sheets, molded, extruded or otherwise formed.

20

The compounds of the invention are more preferably and most preferably used in thermosensitive systems. In heating systems, the components of the color forming system (color former and developer of the invention) are substantially obtuse to one another and substantially uniformly distributed throughout the active coating material deposited on the substrate. In preparing the heat recording material, a coating composition is prepared which includes a fine dispersion of the components of the color forming system, a polymeric binder, surfactants, and other additives in an aqueous coating medium. The composition may further comprise inert pigments on the same or additional layers, such as clay, talc, aluminum hydroxide, calcined kaolinic clay and calcium 35 carbonate; synthetic pigments such as urea-formaldehyde resin pigments; natural waxes such as carnauba wax; synthetic waxes; lubricants such as zinc stearate; wetting agents; anti-foaming agents; sensitizers and antioxidants. Sensitizers may include, for example, acetoacetate-o-toluidine, phenyl-1-hydroxy-2-naphthoate, 1,2-diphenoxyethane and p-benzylbiphenyl. These materials can be coated in one or more layers. The different components may be in the same layer or separated by placing different components in different layers. For example, the chromogenic agent may be deposited as a topsheet. The developer and sensitizers may be arranged in a separate layer or in 10 layers such as a lower layer. One active layer containing chromogen, developer and sensitizers is recommended.

The components of the color forming system are substantially insoluble in the dispersion media (preferably water) and are ground to a single average particle size of about 1 micron to about 10 microns, preferably about 1 to 3 microns. The polymeric binder is substantially soluble in the medium, although latexes are suitable in some cases. Preferred water-soluble binders include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, starch, modified starch, gelatin and the like. Suitable latexes include polyacrylates, styrene-butadiene-rubber latexes, polyvinylacetates, polystyrene, and the like.

Suitable chromogenic compounds, such as the phthalide, leucuramine, spiropyran and fluorane compounds used in biscuit storage systems, are well known and color forming compounds. Examples of these compounds are crystal violet lactone (3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, U.S. Patent Re. 23,024); phenyl, indole, pyrrole and carbazole-substituted phthalates (e.g. U.S. Patents 3,491,111, 3,491,112, 3,491,116, 3,509,174); nitro, amino, amido, sulfonamido, aminobenzylidene, halo, anilino-substituted fluoranes 10259811 (e.g. U.S. Patents 3,624,107, 3,627,787, 3,641,011, 3,642,828, 3,681,390); spiro-dipyrans (U.S. Patent 3,971,808); and pyridine and pyrazine compounds (e.g., U.S. Patents 3,775,424 and 3,853,869). Other particularly suitable chromogenic compounds include, without limitation, the invention: 3-diethylamino-6-methyl-7-anilino-fluoran (U.S. Patent 3,681,390); 2-anilino-3-methyl-6-dibutylamino-fluorane (U.S. Patent 4,510,513), also known as 3-dibutylamino-6-methyl-7-anilino-10-fluorane; 3-dibutylamino-7- (2-chloroanilino) fluorane; 3- (N-Ethyl-N-tetrahydrofurfurylamino) -6-methyl-7- 3,5,5'6-tris- (dimethylamino) spiro [9H-fluorene-9,1 '(3R) -isobenzofuran] -31-one ; 7- (1-Ethyl-2-methylindol-3-yl) -7- (4-diethylamino-2-ethoxyphenyl-5,7-dihydrofluoro-3,4-b] pyridin-5-one (U.S. Patent 4,246,318); 3-diethylamino-7- (2-chloroanilino) fluorane (U.S. Patent 3,920,510); 3- (N-methylcyclohexylamino) -6-methyl-7-anilinofluorane (U.S. Patent 3,959,571); 7- (1-octyl-2-methylindol-3-yl) -7- (4-diethylamino-2-ethoxyphenyl) -20,5,7-dihydrofuro [3,4-b] pyridin-5-one; -diethylamino-7,8-benzofluorane; 3,3-bis (1-ethyl-2-methylindol-3-yl) - f-thalide; 3-diethylamino-7-anilinofluorane; 3-diethylamino-7-benzylaminofluorane; 3 1-Phenyl-7-dibenzylamino-2,2 * -spiro-di- [2H-1-benzopyran] and any mixtures thereof Fluorane compounds are preferred.

These agents can be used alone and in mixtures of two or more.

Examples of suitable acidic developers that can be used in temperature recording systems in admixture with the new inventors are the compounds listed in U.S. Patent 3,539,375 as a phenolic reactant, in particular monophenols and diphenols. Suitable acidic developing agents include, but are not limited to, the following compounds, which may be used alone or in mixtures: 4,4'-isopropylidinediphenol (bisphenol A); hydroksibentsalde-p-formaldehyde; p-hydroxybenzophenone; p-hydroxypropiophenone; 2,4- "102598 dihydroxybenzophenone; 1,1-bis (4-hydroxyphenyl) cyclohexane; salicyanilide; 4-hydroxy-2-methylacetophenone; 2-acetylbenzoic acid; m-hydroxyacetanilide; p-hydroxy-acetanilide; 2,4-dihydroxyacetophenone; 4-hydroxy-4 '-5 methylbenzophenone; 4,4'-dihydroxybenzophenone; 2,2-bis (4-hydroxyphenyl) -4-methylpentane; benzyl 4-hydroxyphenyl ketone; 2,2-bis (4-hydroxyphenyl) -5-methyl-liheksaani; ethyl-4,4-bis (4-hydroxyphenyl) -pentanoaat-phosphate; isopropyl-4,4-bis (4-hydroxyphenyl) pentanoate; Methyl 4,4-bis (4-hydroxyphenyl) pentanoate; allyl 4,4-bis (4-hydroxyphenyl) pentanoate; 3,3-bis (4-hydroxyphenyl) pentane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) -1-phenylpropane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-methylene-bis (4-ethyl-6-tertia-15-ributylphenol); 4-hydroxycoumarin; 7-hydroxy-4-methyl-ticarin; 2,21-methylene-bis (4-octylphenol); 4,4'-sulfonyldiphenol; 4,4'-thio-bis (6-tertiary-butyl-m-cresol); methyl-p-hydroxybenzoate; n-propyl p-hydroxybenzoate; benzyl-p-hydroxybenzoate. Of these, phenolic developmental compounds are preferred. Of the phenolic compounds, 4,41-isopropylidinediophenol, ethyl 4,4-bis (4-hydroxyphenyl) pentanoate are preferred; n-propyl-4,4-bis (4-hydroxyphenyl) pentanoate, isopropyl-4,4-bis (4-hydroxyphenyl) pentanoate, methyl 4,4-25 bis (4-hydroxyphenyl) pentanoate, 2,2 -bis (4-hydroxyphenyl) -4-methylpentane, p-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, and benzyl p-hydroxybenzoate. Other types of acidic compounds are also suitable.

30

In pressure sensitive recording systems, for example, a typewriter-pressurized pressure sufficient to break the microcapsules releases the solvent containing the dissolved color former and reactively contacts it with a color developer coated on the other substrate, thereby producing a pattern similar to that of the other substrate.

The development compounds of the present invention are suitable for use in 13,102,598 pressure-sensitive and heat-sensitive characterization systems. The pressure-sensitive label forming systems provide a imprinting system in which unreacted residual forming portions and solvent liquid are disposed on the sheet-like base material and / or material, wherein one or both of the imprinting components are soluble in the the alignment causes the barrier layer to break in the region constrained by the pressure pattern. The imprinting components then reactively contact to produce a visible imprint.

Within the scope of the present invention, the color former may consist solely of solid color-forming particles or color-forming particles dispersed or dissolved in a resin.

The developer composition may be used in either the carbonless transfer paper system described above or the carbonless carbonless paper system as described in U.S. Patent Nos. 2,730,457 and 4,167,346. U.S. Patent 3,672,935 discloses examples of a plurality of carbonless paperless paper systems of each type.

The transfer-type carbonless storage system uses a bottom-coated (CB) and a top-coated 30 (CF) sheet.

The CB sheet coating may contain a color developer and microcapsules containing a solvent liquid for a color former coated on the CF sheet. In addition, the CB coat-35 te preferably contains a protective backing material such as uncooked starch particles as described in GB patents 1232347 and 1252858.

102598 14

When the color former used is a basic chromogenic agent, the acidic developer may be used in the coating of another base material, such as clays; treated clays (U.S. Patents 3,62,364 and 3,753,761); aromatic carboxylic acids such as salicylic acid; derivatives of aromatic carboxylic acids and their metal salts (U.S. Patent 4,022,936); phenolic developers (U.S. Patents 3,244,550 and 4,573,063); acidic polymers such as phenol-formaldehyde polymers, etc. (U.S. Patent Nos. 3,455,721 and 3,672,935); and metal-modified phenolic resins (U.S. Pat. Nos. 3,732,120; 3,737,410; 4,165,102; 4,165,103; 4,166,644 and 4,188,456).

Microcapsules for use in CB sheet coating can be prepared by any of several methods well known in the art, eg, in U.S. Patents 2,800,457; 3,533,958; 3,755,190 of gelatin as described in U.S. Patent Nos. 3,800,457 and 3,041,289, or more preferably urea formaldehyde resin and / or melamine formaldehyde resin as disclosed in U.S. Patent Nos. 4,001,140; 4,081,376; 4,089,802; 4,100,103; 4,105,823; 4,444,699; or 4,552,811.

The solvent liquid used in the microcapsules may be any material to which the colorant has sufficient solubility, which is a liquid within the temperature range in which carbonless stiffener paper is normally used and which does not prevent or otherwise interfere with the coloring reaction. Examples of suitable liquids include, but are not limited to, solvents commonly used in carbon-free copy papers, such as ethyl diphenylmethane (U.S. Patent 3,996,406); benzyl xylenes (U.S. Patent 4,130,299); alkyl biphenyls such as propyl biphenyl (U.S. Patent 3,627,581) and butyl biphenyl (U.S. Patent 4,287,074); Dialkyl phthalates having 4 to 13 carbon atoms in alkyl groups, e.g. dibutyl phthalate, dioctyl phthalate, dionyl phthalate and ditridecyl phthalate; 2,2,4-trimethyl-10,259,811 -1,3-pentanediol diisobutyrate (U.S. Patent 4,027,065); C10-C14 alkylbenzenes such as dodecylbenzene; alkyl or aralkyl benzoates such as benzyl benzoate; alkylated naphthalenes such as dipropylnaphthalene 5 (U.S. Patent 3,806,463); partially hydrogenated terpenyl; high boiling straight or branched hydrocarbons; and mixtures thereof.

The following examples are intended only to illustrate the invention and should not be construed as limiting in any way. All numerical values, percentages, and parts of this document are by weight and are based on the metric system unless otherwise stated.

The color development of the compounds is tested in thermal systems by heating the same amount of chromogenic compound and test developer with slide and observing dye, Table 1. Some of the compounds were also tested as paper coatings. Separate dispersions of chromogenic material and developer were prepared (Table 2) and mixed in different ratios. Additives such as filler, lubricant and sensitizer, Table 3 were added. The thermal sensitivities of the coatings were tested by touching them with a hot metal piece for 5 seconds and measuring the color result on a Macbeth densitometer, Table 4.

The results of Tables 4 and 5 show that the compounds of the invention, Examples 1-4, are as good as or better than. two generic developmental compounds, Controls 1 and 2. Example; Results 5 to 12 show the improved thermal sensitivity obtained with a mixture of the compounds of the invention and commercial compounds. The results of Examples 14-19 show the improved thermal sensitivity obtained with a commercial sensitizer. Example 13 is a control. Examples 20-25 illustrate recommended combinations.

1β 102598

The examples provided are merely illustrative and other coloring agents, developers and sensitizers could be used with the compounds of the invention; for example, the sensitizer may alternatively be acetoacetate-o-toluidine or phenyl-1-hydroxy-2-naphthoate.

Efficacy in pressure-sensitive systems is demonstrated by coating the substrate with a developer dispersion and dripping a color former solution onto its surface, Table 6.

10

Table 1: Melt Color Color Formation Developer Detected Color N-102 Bisphenol A (Contrast) Black 15 N-102 AP-5 (Cont.) Black N-102 # 1 Black N-102 # 2 Black N-102 # 3 Black N -102 # 4 black 20 N-102 # 5 black N-102 # 6 reddish brown

Table 2: Dispersions 25 Dispersion A Chromogenic Components chromogenic 94.95 binder, polyvinyl-81.00 alcohol 20% solution in water (Vinol 203) 30 antifoam and dispersants 1.36 water 122.69

Dispersion A-1 The chromogenic substance is N-102 3-diethylamino-6-methyl-7-anilinofluoro-35ane

Dispersion A-2 The chromogenic substance is Bu N-102 3-dibutylamino-6-methyl-7-anilinofluorane 102598 17

Dispersion B Color developer parts developer 17.00 binder, polyvinyl alcohol 14.50 20% solution in water (Vinol 205) 5 antifoam and dispersants 0.12 water 63.38

Dispersion B-1 The developing agent is Bis-A

4,4'-isopropylidenediphenol 10

Dispersion B-2 The developing agent is AP-5 2.2-bis (4-hydroxyphenyl) -4-methylpentane 15 Dispersion B-3 The developing agent is compound # 1 phenol, 4- [1- (4-methoxyphenyl) -1,3-dimethylbutyl) -

Dispersion B-4 The developing agent is compound # 2 phenol, 4- [1-ethyl-1- (methoxyphenyl) propyl] -

Dispersion B-5 The developing agent is compound # 3 phenol, 4- [1- (4-methoxyphenyl) -25'-methylpropyl] -

Dispersion B-6 The developing agent is compound # 4 phenol, 4- [1- (4-methoxyphenyl) -cyclohexyl] -30

Dispersion B-7 The developing agent is BisM

• 4.41 - [1,3-Phenylenebis (1-methylethylidene] bisphenol) Dispersion B-8 The developing agent is D-8 4 - [(4- (1-methylethoxy) phenyl) sulfonylphenol 102598

Dispersion C Sensitizer parts Sensitizer 17, o binder, polyvinyl alcohol 14.50 20% solution in water 5 antifoam and dispersants 0.12 water 63.38

Dispersion C-1 The sensitizing agent is DPE

1,2-diphenoxyethane 10

Dispersion C-2 The sensitizing agent is pBB

p-benzylbiphenyl

Dispersion C-3 The sensitizing agent is DBT

15 dibenzyl terephthalate

Dispersion C-4 The sensitizing agent is DBO

dibenzyloxalate 20 Table 3: Test compositions

Material parts

Control-1 Dispersion Al 0.53 Dispersion B 7.00 25 Filler 0.40 Zinc Stearate (23%) 1.00 PVA (Vinol 325 10%) 2.80 Water 0.60 30 Control-2 Same as Control 1 but B1 replaced by B-2

Example-l Same as control 1 but replacing B-1 with B-3 35

Example-2 Same as control-1, but B-1 replaced by B-4 102598 19

Example-3 Same as control-1, but B-1 replaced by B-5

Example-4 Same as control-1, but B-15 replaced by B-6

Example-5 Same as control-1 but B-1 replaced by 1: 1 with B-1 / B-3 10 Example-6 Same as control-2 but B-2 replaced by 1: 1 with B-2 / B-3

Example-7 Same as control-1 but B-1 replaced by 1: 1 with B-1 / B-4

Example-8 Same as control-2 but replacing B-2 with 1: 1 mixture B-2 / B-4

Example-9 Same as control-1 but replaced B-1 20 with 1: 1 mixture B-1 / B-5

Example-10 Same as control-2 but B-2 replaced by 1: 1 mixture of B-2 / B-5 Example-11 Same as control-1 but B-1 replaced by 1: 1 of B-1 / B-6

Example-12 Same as control-2 but replacing B-2 with 1: 1 mixture B-2 / B-6

Example-13 Same as control-2, but B-2 replaced by 1: 1 with B-2 / C-1

Example-14 Same as control-2 but B-2 replaced by 1: 1 with B-3 / C-1

Example-15 Same as control-2 but B-2 102598 replaced 1: 1: 2 with B-2 / B-3 / C-1

Example-16 Same as control-1 but B-1 replaced by 1: 1: 2 with B-1 / B-3 / C-15

Example-17 Same as control-2, but B-2 replaced 1: 1: 2 with B-2 / B-4 / C-1

Example-18 Same as control-2, but B-2 10 replaced by 1: 1: 2 with B-2 / B-5 / C-1

Example-19 Same as control-2 but B-2 replaced by 1: 1: 2 with B-2 / B-6 / C-1 Example-20 Same as control-1 but A1 replaced by A-2 and B1: 1: 2 with B-2 / B-3 / C-2

Example-21 Same as Example-20 but replaced with C-3 in C-2 20

Example-22 Same as Example-20 but in C-2 mixture replaced by C-4

Example-23 Same as control-1 but A-1 replaced by 25-A-2 and B-1 1: 1: 2 by B-1 / B-3 / C-1

Example-24 Same as Example-23, but B-1 replaced by B-7 in Example 30 Example-25 Same as Example-23, but B-1 replaced by B-8 102598

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Table 6: Color of solvent

Develop Color Shape / Format

solvent color 5 1. B-3: Phenol, 4- [1- N-102 / acetone black (4-methoxyphenyl) -1,3-dimethylbutyl] -10 2. B-3 Bu N-102 / acetone black 3. B-3 Crystal Violet Lactone (CVL), Acetone Blue 15

Example 26 Synthesis of 4- [1- (4-methoxyphenyl) -1,3-dimethylbutyl] phenol

NaOH (6.0 g, 0.15 mol) was dissolved in water (300 ml).

Then, 2,2-bis (4-hydroxy-phenyl) -4-methyl-pentane (13.5 g, 0.05 mol) was dissolved in aqueous NaOH.

CH3 CHJ

25 “YoV- | - / öYm

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Dimethyl sulfate (9.5 mL, 0.1 mol) was dissolved in CH 2 Cl 2 (300 mL).

The two solutions were mixed together at room temperature in a 1 L Erlenmeyer flask for 22.5 hours.

35 The organic layer was separated. The aqueous layer was extracted with CH 2 Cl 2. The combined organic layers were concentrated under reduced pressure to give a white solid (13.1 g).

102598 26

The white solid was mixed with water and then extracted with diethyl ether. The ether extract was washed with 2N ammonia (aq), 2N NaOH (aq) and saturated aqueous NaCl solution. The ether extract was then dried over drier, filtered and concentrated under reduced pressure to give a white solid. The solid was dried in an oven at 70 ° C for 22 hours to give 11.4 g of 4- [1- (4-methoxyphenyl) -1,3-dimethylbutyl] phenol (80% yield, mp 119-122 ° C).

Example 27 Synthesis of 4- [1-Ethyl] -1- (4-methoxyphenyl) -propyl] -phenol Cu, CH, 15 and CH2

Sp ;; CH3 Ci133 20

Dimethyl sulfate (8 mL, 0.08 mol) was dissolved in ethyl ether (350 mL). NaOH (5.3 g, 0.13 mol) was dissolved in water (350 mL). 4- [1-Ethyl-1-25 (4-hydroxyphenyl) propyl] -phenol (11.0 g, 0.043 mol) was dissolved in NaOH solution.

The two solutions were stirred at room temperature for 25 hours. The ethyl ether layer was separated, washed with water, 2N ammonia (aq) and 2N NaOH (aq), dried over 30 dl, filtered and concentrated in vacuo to give 9.0 g of 4- [1-ethyl-1- (4-methoxyphenyl) ) propyl] phenol (77% yield, mp 124-126 ° C)

102598 27

Example 28 Synthesis of 4- [1- (4-Methoxy-phenyl) -1-methyl-propyl] -phenol] CH (-VCH) -?

\ | \ '^ // NaOH (aq) \ _ / I \ _ /' - 'CHZ' - 'Et20 CH2

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Dimethyl sulfate (14 mL, 0.15 mol) was dissolved in ethyl ether (350 mL). NaOH (12.0 g, 0.3 mol) was dissolved in water (350 mL). 4- [1- (4-Hydroxyphenyl) -1-methylpropyl] -phenol (24.2 g, 0.1 mol) was dissolved in NaOH-1. The two solutions were then stirred at room temperature for 24 hours. The ethyl ether layer was separated. The aqueous layer was washed with ethyl ether. The combined ethyl ether layers were washed with water and 2N ammonia (aq) and again with water, and then dried with drierate, filtered and concentrated in vacuo. This gave a white solid which was recrystallized from hot ethyl ether to give 12.6 g of 4- [1- (4-methoxyphenyl) -1-methylpropyl] -phenol (49% yield, mp 112-113 ° C).

Example 29 Synthesis of 4- (1-M-methoxyphenyl) -cyclohexyl] -phenol 25 ° C (c) (c).

. fl H

I H

Sp. 115-117 ° C

Dimethyl sulfate (7 mL, 0.075 mol) was dissolved in ethyl ether (350 mL). NaOH (6.0 g, 0.15 mol) was dissolved in water (350 mL). To the NaOH solution was added 1,1-bis (4- 102598 28 hydroxyphenyl) cyclohexane (13.4 g, 0.05 mol). 1,1-bis (4-hydroxyphenyl) cyclohexane was not completely dissolved in aqueous NaOH. The two mixtures were then stirred at room temperature for 18.5 hours. The ethyl ether layer 5 was separated. The aqueous layer was washed with ethyl ether. The combined ethyl ether layers were washed with water, 2N ammonia (aq), and again with water. The ethyl ether layer was then dried over drier, filtered and concentrated under reduced pressure to give 9.3 g of 4- [1- (4-methoxyphenyl) cyclo-10-hexyl] -phenol (65% yield, mp 115-117 ° C).

EXAMPLE 30 Synthesis of 4- [4- (4-methoxyphenyl) -3-methylbutyl] phenol 15'-° - (oY ™ / oV 51 - '- (o) -R (o) - °' - '- CH.' 'CHjC 12' 7 Cilj -

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Dimethyl sulfate (1.0 mL, 0.011 mol) was dissolved ... CH2Cl2 (50 mL). NaOH (0.99 g, 0.025 mol) was dissolved in water (50 ml). Then, 4- [1- (4-hydroxyphenyl) -3-methylbutyl] phenol (1.2 g, 4.7 moles) was dissolved in aqueous NaOH. The two solutions were stirred together for 22 hours. The organic layer was separated. The aqueous layer was extracted with CH 2 Cl 2. The combined organic layers were evaporated under reduced pressure. The residue was mixed with water. The mixture was extracted with diethyl ether. The ether extract was washed with 2N ammonia (aq) and 2N NaOH (aq). It was then dried over drier, filtered and concentrated under reduced pressure to give 0.6 g of a viscous liquid. This slowly turned to a white solid identified as 4- [1- (4-methoxyphenyl) -3-methylbutyl] -phenol (47% yield, mp 79-102598 2980 ° C).

Example 31 4- [1- (3,5-Dibromo-4-methoxyphenyl) -1-methyl-butyl] - 2.6-5 dibromo-phenol CH,

Dr CHj Dr MCjSOj Drv J J Dr HO —— C— (7) —— OH KaOK (aq) IIP— <^ Q ^) -C - OCiij

Dr. Cllj Dr 2 3r ^ t) r 10 3

Dimethyl sulfate (1.2 mL, 0.013 mol) was dissolved in diethyl ether (30 mL). NaOH (1.2 g, 0.03 mol) was dissolved in water (30 ml). Then 15 tetrabromobisphenol A (5.4 g, 0.01 mol) was dissolved in NaOH solution. The two solutions were stirred at room temperature for 23 hours. A small amount of precipitate formed which was removed by filtration. The ethyl ether layer was then separated. The aqueous layer was washed with ethyl ether. The combined ether layers were washed with water, 2N ammonia (aq), and again with water. The ether layer was dried over drier, filtered and evaporated in vacuo to give 1.4 g of a white solid (mp 126-140 ° C). GC analysis indicated this as a mixture of compounds. Some precipitate formed in the water wash.

This was collected by filtration to give 1.08 g of 4- [1- (3,5-dibromo-4-methoxyphenyl) -1-methyl-ethyl] -2,6-dibromophenol (19% yield, mp 133- 134 ° C). 1 ·

Claims (10)

A recording material comprising a substrate and a color-developing material, characterized in that the color-developing material contains a substituted phenol of formula (Λ ') 4 (Π2), high ~ Sy ~ {- (j ^) ~ ° r3 wherein both R 1 and R 2 are independently hydrogen, C 1 -C 6 alkyl, or halogen; R3 is allyl, benzyl or C1-C6 alkyl; and either bed R 4 and R 3 are independently hydrogen or C 1 -C 8 alkyl, or R 4 and R 5 together form an alkyl ring of 5 or 6 members, provided that R 4 and R 5 are both methyl and R 1 and R 2 are both hydrogen, so R3 is not benzyl. 2. Record material comprising a substrate and a color-developing material, characterized in that the color-developing material contains an alkoxyphenylalkylphenol of formula (R ') 4 (R 1) wherein both R 1 and R halo; R 3 is C 1 -C 6 alkyl; and either R 4 and R 5 are independently hydrogen or C 1 -C 6 alkyl, or R 4 and R 5 together form an alkyl ring of 5 or 6 members. Recording material according to claim 2, characterized in that in the formula for the alkoxyphenylalkylphenols R1 and R2 are hydrogen. Recording material according to claim 3, characterized in that the developing material comprises a compound: 10 ch3 --- K ° A®) in 2 ° C CH 3 I CH 2 H Recording material according to claim 3, characterized in that the developing material comprises a compound: ch3 20 I CH, 25 6. Recording material according to claim 3, characterized in that the developing material comprises a compound: m Recording material according to claim 3, characterized in that the developing material comprises a compound: - (ο XX q XX) - or H Recording material according to claim 3, characterized in that the developing material comprises a compound: - H - H0 = - (OV ° r3 V - - / CH, - - 'ch3 I ch3 H 9. Recording material according to claim 2, characterized in that the developing material comprises a compound: Dr ch. Dr 25 ho - (O / * - <: ~ ^ 0) - ° Ri / I \ 30 Dr CH3 Dr ♦ Record material according to any of claims 3-9, characterized in that R 3 is methyl.