JPS63146846A - Novel compound and use thereof - Google Patents

Abstract

NEW MATERIAL:A bis(phenoxymethyl or naphthoxymethyl)benzene derivative shown by formula I (A is group shown by formula II or formula III; R is 1-4C alkyl, phenyl or benzyl; X is H or halogen). EXAMPLE:1,3-Bis(p-carbobenzyloxy-phenoxymethyl)benzene. USE:An addition capable of improving fading fading and void phenomena of recording image after coloring of heat-sensitive recording paper having coloring properties, high-speed recording characteristics and stability of ground. PREPARATION:An alkali salt of a compound shown by the formula A-OH and a compound shown by formula IV (Y is halogen) are subjected to dehydrohalogenating reaction to give a compound shown by formula I. In producing the heat-sensitive recording paper, (A) leuco dye, (B) a developer and (C) the compound shown by formula I in a preferably blending ratio of the compound A:B=1:1-10 and B:C=100-1:200 are added to the heat-sensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bis(phenoxymethyl or naphthoxymethyl)benzene derivative and a thermal recording paper using the same.

In general, thermal recording paper is prepared by coating a support with a colorless or light coloring dye such as a leuco dye as a coloring agent, a phenolic compound as a color developer to make the dye color when heated, and further binders, fillers, and excipients. , lubricants, and other auxiliary agents, and are widely used in practical applications.

Thermal recording paper produces colored images through an instantaneous chemical reaction between a color forming agent and a color developer when heated, and is used for copying books, documents, etc., as well as thermal pen type recorders for various measuring instruments, and thermal recording paper. It is widely used in printers, thermal ticket vending machines, facsimile machines, etc. In particular, in information-related equipment such as facsimile machines, the speed of the recording device itself is required to be faster.
The heat-sensitive recording paper used is also required to have the ability to quickly produce a dense recorded image.

Among the phenolic compounds used as color developers, parahydroxybenzoic acid esters, especially parahydroxybenzoic acid benzyl ester, are known as those suitable for high-speed thermal recording (Japanese Patent Application Laid-open No. 140485/1983).
(See Publications No. 56-144193, No. 57-82089, and No. 57-107885). Thermal recording paper containing these color developers has good coloring performance, high density and clear recorded images, and has properties suitable for high-speed thermal recording, such as low background fog. However, the stability of the recorded image after color development is not sufficient (it is known that fading and whitening phenomena occur in the recorded image.The reason for this is not necessarily clear, but the relationship between the color former and rose hydroxybenzoate ester is known to occur). This is thought to be due to detachment and crystallization of hydroxybenzoic acid ester, which may be a charge transfer complex.Methods of adding certain compounds are known to prevent this crystallization, but the results are not always satisfactory. is not obtained.

In view of the above-mentioned points in research on thermal recording paper, the present inventors have made extensive studies and have discovered a novel compound capable of inhibiting discoloration or whitening, thereby completing the present invention.

The present invention shows a general formula, in which R may be the same or different, and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a benzyl group, and X represents a hydrogen atom or a rogene atom) It is a bis(phenoxymethyl or naphthoxymethyl)benzene derivative represented by

Furthermore, the present invention is a heat-sensitive recording paper characterized in that the heat-sensitive layer contains a leuco dye, a color developer, and a compound of formula I.

The compound of formula I is, for example, an alkali salt of an aromatic hydroxycarboxylic acid ester represented by the general formula A -OHIf (in which the humans have the above-mentioned meanings) and a compound of the general formula (wherein Y represents a halogen atom). It can be produced by a dehydrohalogenation reaction with the represented quinolyl dihalogenoid.

As the alkali salt of the compound of formula I, for example, sodium salt, potassium salt, etc. are used.

This reaction is preferably carried out in the presence of a solvent.

Solvents include polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide,
Dimethyl sulfoxide and the like are preferred. The reaction temperature is 5
The temperature is 0 to 150°C, and the reaction is completed in 1 to 8 hours.

After the reaction is completed, water is added to the reaction solution, the precipitate is collected and recrystallized to obtain a purified product of the compound of formula I.

Compounds of formula I include:

1.2-11,3- or 1,4-bis(0-carbalkoxy-phenoxymethyl)benzene, 1.2-11,
3- or 1,4-bis(m-carbalkoxy-phenoxymethyl)benzene, 1,2-11,3- or 1,4
-bis(p-carbalkoxy-phenoxymethyl)benzene, 1.2-11,3- or 1,4-bis(2-carbalkoxy-1-naphthoxymethyl)benzene, 1
．． 2-11,3- or 1,4-bis(4-carbalkoxy-1-naphthoxymethyl)benzene, 1.2-11
,6- or 1,4-bis(1-carbalkoxy-2-
naphthoxymethyl)benzene, 1.2-11.3- or 1,4-bis(3-carbalkoxy-2-naphthoxymethyl)benzene, 1.2-11,3- or 1,4-bis(6 -carpoalkoxy-2-naphthoxymethyl)benzene, 1.2-11.3- or 1.4-bis(2-halogeno-4-carbalkoxy-phenoxymethyl)benzene, 1.2-11,3- or 1,4-bis(6-halogeno-
4-Carbalkoxy-phenoxymethyl)benzene, 1.2-11.3- or 1,4-bis(3-)-cogeno2-carbalkoxy-phenoxymethyl)benzene, 1.2-11.3- or 1 ,4-bis(4-halogeno-
2-carbalkoxy-phenoxymethyl)benzene, 1.2-11.3- or 1,4-bis(2-halogeno-
3-carbalkoxy-phenoxymethyl)benzene, 1,2-11,3- or 1,4-bis(2-halogeno-
4-carbalkoxy-1-naphthoxymethyl)benzene, 1,2-11,3- or 1,4-bis(4-halogeno-
2-carbalkoxy-1-naphthoxymethyl)benzene, 1.2-11.3- or 1.4-bis(6-halogeno-
2-carbalkoxy-1-naphthoxymethyl)benzene, 1,2-11,3- or 1,4-bis(8-halogeno-
4-carbalkoxy-1-su7toxymethyl)benzene, 1,2-11,3- or 1,4-bis(8-halogeno-
6-carbalkoxy-1-naphthoxymethyl)benzene, 1,2-11,3- or 1,4-bis(1-halogeno-
4-carbalkoxy-2-naphthoxymethyl)benzene, 1,2-11,3- or 1,4-bis(4-halogen-
1-carbalkoxy-2-naphthoxymethyl)benzene, 1,2-11,3- or 1,4-bis(6-halogeno-
8-carbalkoxy-2-naphthoxymethyl)benzene, 1,2-11,6- or 1,4-bis(8-halogeno-
6-carbalkoxy-2-naphthoxymethyl)benzene, 1,2-11,3- or 1,4-bis(4-halogeno-
6-carpalkoxy-2-naphthoxymethyl) dye, 1,2-11,3- or 1,4-bis(1-halogeno-
8-carbalkoxy-2-naphthoxymethyl)benzene, etc., and compounds having a carbophenoxy group or a carbobenzyloxy group in place of the carbalkoxy group of these compounds.

In the compound of formula 1, examples of the carbalkoxy group include carbomethoxy group, -ethoxy group, -propoxy group, and -butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

When producing the thermal recording paper of the present invention, a leuco dye, a color developer, and a compound of formula (2) are mixed. The mixing ratio is 100 to 1 part by weight of color developer to 100 parts by weight of leuco dye.
000 parts by weight is preferred. Compounds of formula I can also be used as developer 1
It is preferable to mix 1 to 200 parts by weight per 00 parts by weight.

Examples of the leuco dyes used in the present invention include triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, and spiropyran-based dyes. These dyes may be used alone or in combination of two or more. Specific examples of such leuco dyes include the following.

3.3-bis(p-dimethylaminophenyl)-phthalide, 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone), L3 bis(p-dimethylaminophenyl) )-6-diethylaminophenyl, 513-bis(p-dimethylaminophenyl)-6-
Chlorphthalide, 3.3-bis(p-dibutylaminophenyl)phthalide, 6-cyclobexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3-ethylamino-7-chloro Fluorane, 3-diethylamine-7-methylfluorane, 6-diethylamino-7,8-benzfluorane, 3-′)ethylamino-6-methyl-7-chlorofluorane, 3-(N-p-tolyl -N-ditylamino)-6
-Methyl-7-anilinofluorane, 3-pyrrolidino-
6-Methyl-7-anilinofluorane, 2-(N-(3'-1)fluoromethylphenyl)amino)-6-dinithylaminofluorane, 2-(3,6
-bis(diethylamino)-9-(0-chloroanilino)xantylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)fluoran, 3-diethylamine-
7-(0-chloroanilino)fluoran, 3-dibutylamino-7-(O-chloroanilino)fluoran, 5-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6
-Methyl-7-anilinofluora/, s-(N,N-diethylamino)-5-methyl-7-
(NlN-dibenzylamino)fluoran, benzoylleucomethylene blue, 6'-chloroda-methoxy-benzoindolino-pyrylospirane, 6'-bromo3'-methoxy-benzoindolino-pyrylospirane, 3-(2'-hydroxy-4 '-dimethylaminophenyl)-5-(2'-methoxy-5'-chlorophenyl)
Phthalide, 6-(2'-hydroxy-4'-dimethylaminophenyl)-5-(gumethoxy-5'-nitrophenyl)phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-( 2'-methoxy-5'-methylphenyl)
Phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-5-(2'-hydroxy-4'-chloro-5'-methylphenyl)phthalide, 3-morpholino-7-(N-propyl- trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 6-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluorane, 5-hyo! j C/-7-(C-p-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7 -(α-phenylethylamino)fluoran, 6-diethylamino-7-(o-methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-mef7-(α-phenylethylamino)fluoran, 3-diethylamino- 7-piperidinofluorane, 2-rioo-5(N-methyltoluidino)-7-(p-
n-butylanilino)fluorane, 3-(N-benzyl-N-cyclohexylamino')-5,6-penzo7-α-naphthylamino-4'-bromofluorane, 3-diethylamino-6-methyl-7-mesitisino 4
',5'-benzofluorane etc.

Examples of color developers include parahydroxybenzoic acid esters such as methyl parahydroxybenzoate, -ethyl, -propyl, -isopropyl, -butyl, -isobutyl, -hexyl, -benzyl, -phenethyl, -phenyl, -naphthyl, and the like. It will be done.

These materials are atomized using water as a medium using a grinder such as a ball mill, attritor, or sand grinder, or a suitable emulsifying device, and various additive materials are added depending on the purpose to form a coating liquid.

Additive materials include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starches, binders such as styrene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, styrene-butadiene copolymer, and kaolin. , fillers such as diatomaceous earth, talc, titanium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, excipients such as fatty acid metal salts, zinc stearate, aluminum stearate, calcium stearate, zinc oleate, waxes, Examples include lubricants such as paraffin wax, cowna wax, and polyethylene wax, benzophenone-based and triazole-based ultraviolet absorbers, water-resistant agents such as glyoxal, dispersions, antifoaming agents, and the like.

The heat-sensitive recording paper of the present invention can be obtained by applying a coating solution containing these additive materials to a support such as paper or film.

The heat-sensitive recording paper of the present invention has good color development, high-speed recording performance, and background stability, and furthermore, fading and whitening of recorded images are improved and stability is excellent.

Example 1 Synthesis of 1.6-bis(p-carbobenzyloxy-phenoxymethyl)benzene Parahydroxybenzoic acid benzyl ester 45,6F
(0.2 mol) and sodium carbonate 10.69 (0
, 1 mol) of N,N-dimethylformamide 200 mA
! was added and stirred at room temperature for 10 minutes. Next (・N, N-
17.4 g (0.1 mol) of m-xylylene dichloride dissolved in 100 g of dimethylformamide was added dropwise over 10 minutes with stirring, and the mixture was further heated at 113° C. for 4 hours. After the reaction, the mixture was cooled and blown into water, and the precipitate was taken from house to house.

The obtained precipitate was washed with water, further suspended in methanol, stirred at 60° C. for 6 minutes, and then cooled. Next, the precipitate is separated and dried to a melting point of 92.5-93.8°C.
15.8 g (yield 26.9%) of 1,3-bis(p-benzyloxy-phenoxymethyl)benzene was obtained as white crystals.

Nagiyama value: δ 5.11 (4H, s), 5.35 (4H1B), 6.9
1-8.07 (22H, m) Mass value: m/z=558 CM+) Elemental analysis value: HO Calculated value (匈 77.4 5,4 17.2 Actual value (
Ring 76.8 5.5 17.7 Example 2 Synthesis of 1.4-bis(p-carbobenzyloxy-phenoxymethyl)benzene Rose hydroxybenzoic acid benzyl ester 68, 49
(o, 5 mol) and sodium carbonate 15.9jI (o
, 1 s mol) of N,N-dimethylformamide 274
g was added thereto, and the mixture was heated to 100°C. Then p-xylylene dichloride 26.2, i? (0.15 mol) was added over 10 minutes with stirring and further heated at 100° C. for 1 hour. Water was added to the resulting reaction mixture, and the deposited precipitate was collected from house to house.

The obtained precipitate was added to N,N-dimethylformamide, heated to 90°C to dissolve, and then cooled.

The precipitate is separated from each other and dried to a melting point of 154~
1,4-bis(p-carbobenzyloxy-phenoxymethyl)benzene 27.8 as white crystals at 157°C
g (yield 33.0%) was obtained.

NMR value: δ 5.11 (4H, s), 5.33 (4HSs), 6.
92-8.07 (22H, m) Mass value: m/z = 558 (M”) Elemental analysis value: CHO Calculated value (%l 77.4 5.4 17.2 Actual value (%) 76.8 5 .5 17.7 Example 3 1. Synthesis of 3-bis(6-carpomethoxy-2-naphthoxymethyl)benzene Sodium salt of 2-hydroxynaphthalene-6-carboxylic acid methyl ester 44.89 to N,N-dimethylformamide 200 ml was added and stirred at room temperature. Next, m-xylylene dichloride 1Z51 (o, 1 mol) dissolved in N,N-dimethylformamide was added dropwise over 10 minutes with stirring, and the mixture was further heated at 105°C for 4 hours. After the reaction, the precipitate was cooled and separated from each other.The precipitate was washed with N,N-dimethylformamide, further stirred and washed with 80°C warm water for 30 minutes, and then stirred and washed with 60°C methanol for 30 minutes. Thereafter, the product was cooled and dried separately to obtain 59.7 g of 1,3-bis(6-carpomethoxy-2-naphthoxymethyl)benzene (yield 77.8) as white crystals with a melting point of 177.6-178.0°C. %) was obtained.

NMR value: δ 5.95 (6H, S), 5.21 (4H, s), 120
~8.52 (16H, m) Mass value: m/z=506 (M”) Elemental analysis value: CHO Calculated value (%) 75.8 5.1 19.1 Actual value (%) 75.7 5. 2 19.1 Example 4 1. Synthesis of 3-bis(m-carbomethoxy-phenoxymethyl)benzene Metahydroxybenzoic acid methyl ester 30°4,!9
(o, 2 moles)! After adding 150 ml of X/-l and then adding sodium methane (0.2 mol), the mixture was stirred at 100°C for 1 hour, cooled, and concentrated to dryness. To this, N,N-dimethylformamide 15
Add 0ml, m-xylylene dichloride 17.5
After adding g (o, 1 mol), the mixture was stirred at 110°C for 2 hours. After cooling, the precipitate was separated, and after blowing liquid F into water-methanol (1:1), the precipitate was separated.

The obtained precipitate was washed with methanol and then dried.
1,3- as white crystals with a melting point of 57.8-58.5°C.
28.5 g (yield: 697%) of bis(m-lupomethoxyphenoquinemethyl)benzene was obtained.

Example 5 Synthesis of 1.4-bis(0-lupomethoxyphenoxymethyl)benzene Salicylic acid methyl ester 45.6, li+ (0,
5 mol) and sodium carbonate 18.0,! i' (0
, 17 mol) total N. N-dimethylformamide 1som
In addition to this, 29.89 (0.17 mol) of p-xylyle/dichloride was added to the mixture while stirring and heating to 100°C, followed by heating at 144°C for 8 hours. After the reaction, the mixture was cooled and blown into water, and then the precipitate was collected. The obtained precipitate was washed with methanol heated to 80°C and then dried to form white crystals with a melting point of 115-120°C.
8.3 g (yield 14%) of -bis(0-carbomethoxy-phenoxymethyl)benzene was obtained.

Example 6 Synthesis of 1.3-bis(2-10-4-carbobenzyloxy-phenoxymethyl)benzene 2-chloro-4-
Hydroxybenzoic acid hensyl ester 26.39 (0
, 1 mol) and 5.59 (0.05 mol) of sodium carbonate were added 100++ l of N,N-dimethylformamide and stirred at room temperature for 10 minutes. Then, 8,8! 9 (0.05 mol) while stirring
The mixture was added dropwise over 0 minutes and further heated at 120°C for 2 hours.

After the reaction, the mixture was cooled and blown into water, and the precipitate was taken from house to house. The obtained precipitate was washed with water, further suspended in methanol, stirred at 60° C. for 60 minutes, and then cooled. Next, the precipitate is separated and dried to a melting point of 95.8 to 97.0.
1,3-bis(2-chloro-4-
Carbobenzyloxy-phenoxymethyl)benzene 2
5.2 g (yield: 80%) was obtained.

Example 7 Solution A (dye dispersion) 3-(N-cyclohexyl-N-methylamine)-6-methyl-74.0 parts -anilinofluorane 10% polyvinyl alcohol aqueous solution 92 parts water
5.0
Part B Solution (Developer dispersion) 10% polyvinyl alcohol aqueous solution 30.0 parts Each solution having the above composition was pulverized and mixed in a ball mill.

Next, 1.0 parts of liquid A and 4.0 parts of liquid B were mixed to prepare a coating liquid, and this coating liquid was applied to high-quality paper using a wire bar to coat thermal recording paper (coating amount: 6 #/m" ) was obtained.

Example 8 The same procedure as Example 7 was used except that 1,4-bis(p-carbobenzyloxy-phenoxymethyl)benzene was used instead of 1,3-bis(p-carbobenzyloxy-phenoxymethyl)benzene. A thermosensitive recording paper was obtained in the same manner.

Example 9 1,6-bis(6-carpomethoxy-2-naphthoxymethyl)benzene was used instead of 1,5-bis(p-carbobenzyloxy-phenoxymethyl)benzene, and the other conditions were the same as in Example 7. A thermosensitive recording paper was obtained.

Example 10 1.3-bis(2-chloro-4-carbobenzyloxy-phenoxymethyl)benzene was used instead of 1.3-bis(p-carbobenzyloxy-phenoxymethyl)benzene, and the rest was as in Example A thermosensitive recording paper was obtained in the same manner as in Example 7.

Comparative Example 1. A thermosensitive recording paper was obtained in the same manner as in Example 7 except that 6-bis(p-carbobenzyloxy-phenoxymethyl)benzene was not used.

Test Example 1 The background density and the image density at the time of color development at 120° C. were measured for five types of heat-sensitive recording papers of Examples 7 to 10 and Comparative Example.

Next, heat-sensitive recording paper after color development is heated at 40°C and humidity 90% or 6
Each sample was left at 0° C. for 24 hours, and changes in background density and image density were measured. The results are shown in Table 1. From this, it is known that the thermal recording paper of the present invention exhibits less change in image density over time and has excellent storage stability compared to the thermal recording paper of the comparative example.

Example 2 Regarding two types of thermal recording paper of Example 7 and Comparative Example 120
After color development at .degree. C., the image was left to stand for 24 hours under harsh conditions of 60.degree. C. and 90% humidity, and changes in image density were measured. The results are shown in Table 2.

Table 2 ○ means almost no change, X means crystal is white (precipitated or discolored in spots).

Applicant: Ueno Pharmaceutical Application Research Institute Co., Ltd. Agent: Patent attorney: Tadashi Kobayashi, Yugai (1 person)

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ I (In the formula, A is a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ where R may be the same or different, and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a benzyl group, and X represents a hydrogen atom or a halogen atom. Bis(phenoxymethyl or naphthoxymethyl)benzene derivatives represented by 2. Leuco dye, color developer and general formula ▲mathematical formula in the heat-sensitive layer
There are chemical formulas, tables, etc. ▼ I (In the formula, A is a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ where R may be the same or different, and each represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a benzyl group, and X represents a hydrogen atom or a halogen atom. A thermosensitive recording paper characterized by containing a bis(phenoxymethyl or naphthoxymethyl)benzene derivative represented by