JPH02723A - Novel o-substituted 1,4-naphthohydroquinone derivative and heat-sensitive recording medium - Google Patents

Abstract

NEW MATERIAL:An O-substituted 1,4-naphthohydroquinone derivative expressed by the formula (RA is R1-OH, R1-OA, R1-X or glycidyl; RB is R2-OB, R2-X2 or 1-10C alkyl; R1 and R2 are 1-6C alkylene; A and B are phenyl, benzyl, naphthyl or 1-12C alkyl; X1 and X2 are halogen). EXAMPLE:1-(2-Hydroxyethoxy)-4-ethoxynapthalene. USE:Useful as a sensitizer for heat sensitive paper, excellent in image density, etc., and good in performances with great industrial effects and hardly any sublimableness. PREPARATION:1,4-Napthoquinine is hydrogenated in the presence of a hydrogenation catalyst or reduced with a reducing agent, such as sodium dithionite, and the resultant 1,4-naphthohydroquinone is subjected to a method for condensation through dehydration with an alcohol or phenol corresponding to R4 or R5 in the presence of, e.g., an etherification catalyst, to afford the compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to novel 0-substituted 1,4-naphthohydroquinone derivatives, specifically 1,4-naphthohydroquinone obtained by reducing 1,4-naphthoquinone. Novel 〇-substituted 1 advantageously derived from (or α-naphthohydroquinone)
．． The present invention relates to 4-naphthohydroquinone derivatives and thermal recording materials such as thermal paper containing these derivatives as sensitizers.

BACKGROUND ART Conventionally, heat-sensitive recording materials such as heat-sensitive recording paper containing a leuco compound and an organic acid are already known, for example, from Japanese Patent Publication No. 14039/1983. Such thermosensitive recording paper is based on the principle of applying thermal energy to the thermosensitive recording layer to soften or melt the leuco compound, organic acid, and binder, thereby bringing the two coloring components into contact and developing color. Yes, and has recently been used in fields such as various printers and facsimile IJs.

By the way, the characteristics of such recording papers are their uses:
Therefore, it is a matter of course that this type of technology has become more sophisticated, and in recent years, more advanced technology has been required in this type of technical field. Therefore, for example, to increase the recording speed: Second, of course, the recording device should be improved, but at the same time or incidentally, the color development of the recording paper used should also be improved! We request that you promote this.

Therefore, as a method for promoting this color development, a method of incorporating a low melting point substance into the heat-sensitive recording layer is usually carried out.To be more specific, a low melting point substance, that is, a color development accelerator or a sensitizer is used. As, in Special Publication No. 43-4160, urea,
Phthalic anhydride and acetanilide; also disclosed in JP-A-48-1
In No. 9231, paraffin, carnauba wax, beeswax, wood base, higher fatty acids, and higher fatty acid esters; In addition, in Japanese Patent Publication No. 17748/1974, salicylic acid, anisic acid, phthalic acid monophenylestenohepthalate monobenzyl ester; and more recently Practically speaking, it is widely practiced to use fatty acid amides as color accelerators.

Furthermore, Japanese Patent Publication No. 51-27599 discloses the sensitizing effect of fatty acid amide by a combination of paraffin or microwax and fatty acid amide; The sensitizing effect of: or JP-A-58-8709
No. 4 has a sensitizing effect such as 2-benzyloxynaphthalene; JP-A-60-127189, JP-A-60-1780.
No. 86, JP-A-61-29583, JP-A-61-51
No. 383, JP-A-62-170384, JP-A-62-
1.92333 and JP-A-62-192340.
．． The sensitizing effect of naphthalene-1,4-substituted compounds such as 4-diacryloyloxynaphthalene is described.

Problems to be Solved by the Invention The present inventors confirmed the sensitizing effect of conventionally known compounds and conducted intensive research to find a compound with even better properties.As a result, 1,4-jethoxynaphthalene discovered 〇-substituted 1,4-naphthohydroquinone derivatives, and filed a patent application earlier.

(JP-A-60-127189) These O-substituted l,4-naphthohydroquinone derivatives have the advantage of being easy to synthesize and having better dynamic sensitivity than conventional compounds.

However, for multi-purpose use in the field of thermal recording paper, it is currently necessary to improve color development at higher temperatures and sublimation while maintaining dynamic sensitivity.

Means and Effects for Solving the Problems The present inventors have found that these 0-substituted 1,4-naphthohydroquinone derivatives have a good color development rate, similar color development properties in a high temperature range, and, in particular, 1. From 4-jetoxynaphthalene,
As a result of intensive study to obtain a compound with low sublimation,
Novel O-substituted 1, advantageously produced from 1,4-naphthohydroquinone obtained by reducing 1゜4-naphthoquinone
, 4-naphthohydroquinone derivatives, and further arrived at the present invention as a heat-sensitive recording material.

That is, the present invention:'! First of all, it relates to a novel 〇-purchased 1,4-naphthohydroquinone derivative represented by the following general formula [wherein RA is R, -OH, R1-0A, R, -''X , or a glycidyl group, and Re ftR20B, R2X2 or an alkyl group having 1 to 10 carbon atoms. In addition, R1 and R2 are alkylene groups having 1 to 6 carbon atoms, and A and B are phenyl, benzyl, naphthyl or a carbon number 1
~12, preferably 1 to 6 alkyl groups (all of these substituents may be substituted) and xl and X2 represent halogen. ] The 0-substituted 1,4-naphthohydroquinone derivative of the present invention is more specifically represented by the following general formula.

Compound-■ and ■ Compound-■ Compound-■ [However,
R and R2 have the same meaning as the alkylene group in the above general formula, B has the same meaning as the definition in the above general formula, and R3 represents an alkyl group having 1 to 10 carbon atoms] These alkylene groups may be linear or branched, and may be the same or different, as well as OH (
The substitution position of the hydroxyl group may be the 2-position or the terminal, and is not particularly limited.

Examples of compound-I include and others 1-(2-hydroxyethoxy)-4-
Ethoxynaphthalene, l-(2-hydroxypropoxy)-4-n-octyloxynaphthalene, l-(2-hydroxypropoxy')-4-n-propoxynaphthalene, 1-(2-hydroxypropoxy)-4-i- Propoxynaphthalene, 1-(2-hydroxyethoxy)
-4-methoxynaphthalene, 1-(2-hydroxyethoxy)-4-n-butoxynaphthalene, 1-(2-hydroxyethoxy)-4-n-propoxynaphthalene, 1
-(2-hydroxyethoxy)-4-n-octyloxynaphthalene, 1-(2-hydroxybutoxy)-4-
Methoxynaphthalene, l-(2-hydroxybutoxy)
-4-n-butoxynaphthalene, 1-(2-hydroxybutoxy)-4-n-propoxynaphthalene, '1-(
For example, OH and others 1-(2-hydroxyethoxy)-4-
(2-phenoxyethoxy)naphthalene, 1-(2-hydroxybutoxy)-4-(2-phenoxyethoxy)
Naphthalene, 1-(2-hydroxyethoxy)-4-
(2-ethoxyethoxy)naphthalene, 1-(2-hydroxypropoxy)-4-(2-ethoxyethoxy)naphthalene, 1-(2-hydroxypropoxy')-4-
(2-methoxyethoxy)naphthalene is mentioned.

Compound-■ [However, in the formula, R,, R2, A and B are as defined in the above general formula] Even if R1 and R2 and A and B are the same,
May be different.

Compound -■, for example, Compound -81 OCHzC)I20Ph OCH2C1 (20CH2Ph and others 1-(2-phenoxyethoxy)-4-
(2-p-)lyloxyethoxy)naphthalene, 1-(
2-phenoxyethoxy)-4-(2-methoxymethoxy)naphthalene, 1-(2-phenoxyethoxy)-4
-(2-methoxyethoxy)naphthalene.

0-R2-X2 [However, R,, R2, X, and X2 are as defined in the above general formula. ] R1 and R2, X, and X2 may be the same or different, and the halogen generally includes chlorine or bromine.

Compounds -■ include, for example, 0CH2CH2C1 and others 1,4-di(2-bromoethoxy)naphthalene, l-(2-chloroethoxy)-4-(2-bromoethoxy)naphthalene, 1,4-di( 3-chloropropoxy)naphthalene, 1゜4-di(4-chloro-
(n-butoxy)naphthalene.

Compound -■ C)-4-methoxynaphthalene, 1-(2,3-epoxypropoxy)-4-n-butoxynaphthalene, I-
(2,3-epoxypropoxy)-4-n-propoxynaphthalene is mentioned.

Compound - ■ ORH.

[However, R1 represents an alkyl group having 1 to 10 carbon atoms.] As the compound -■, for example, -R3 [However, RI, R3 and A are as defined in the above general formula] As for the compound -■ , for example, 0CR2CH3 and others 1-(2,3-epoxybropoki0C1
12[:R3 and others 1-(2-phenoxyethoxy)-4-
Methoxynaphthalene, 1- (2-ethyne ethoxy)
-4-methoxynaphthalene, 1-(2-ethoxyethoxy)-4-ethoxynaphthalene, 1-(2-methoxyethoxy)-4-methoxynaphthalene, 1-(2-methoxyethoxy)-4-ethoxynaphthalene. .

These novel 〇-substituted 1,4-naphthohydroquinone derivatives of the present invention have lower sublimability than conventional 0-M-substituted 1,4-naphthohydroquinone derivatives such as 1,4-jethoxynaphthalene, and are color-forming. The promoting effect is also almost comparable.

A second aspect of the present invention is a thermal recording paper containing a leuco compound and an organic acid that develops a color by reacting with the leuco compound as a color development accelerator.
Recording layer made of 4-naphthohydroquinone derivative! A heat-sensitive recording material characterized by containing two components.

General formula [In the formula, R is R1-○H, R+0ASR+ L or a glycidyl group, and RB is R2-0BSR2-X2 or carbon number 1-10
represents an alkyl group. Note that R1 and R2 are alkylene groups having 1 to 6 carbon atoms, and A and B are alkyl groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms.
The alkyl group, phenyl, benzyl, naphthyl group (all of these substituents may be substituted), and Xl and X2 represent halogen. ] Particularly, 〇-anonymized 1,4-naphthohydroquinone derivatives are used in thermal recording materials using compounds of the following general formula as sensitizers.

General formula [wherein Ra is R, -OA and Ra is an alkyl group having 1 to 10 carbon atoms, R3 is an alkylene group having 1 to 6 carbon atoms, A
is an alkyl, phenyl, benzyl or naphthyl group having 1 to 12 carbon atoms (any of these groups may be substituted), or Ra and RB are each Rr
Xl and R2X2, R3 and R2 are the same as in the above (■), and X and X2 represent halogen. ] The 0-substituted 1,4-naphthohydroquinone derivatives of the present invention typically include the same compounds as the compounds described above.

Production method The 0-substituted 1,4-naphthohydroquinone derivative of the present invention can be produced, for example, by the following method.

1,4-Naphthohydroquinone can be obtained industrially advantageously by hydrogenating 1,4-naphthoquinone in the presence of a hydrogenation catalyst or reducing it with a reducing agent such as sodium dithionite. In the presence of an etherification catalyst, the alcohol or phenol corresponding to RA or R8 in the general formula; It can be produced by a method of reacting hydroquinone with the corresponding halides of RA and RB in the presence of a basic substance.

The manufacturing method of these compounds is 1. Although it can be prepared directly from 4-naphthohydroquinone, first the corresponding 0
It is also possible to adopt a method in which the -monosubstituted product is synthesized and then further 0-alkylated or 0-phenylated.

These 0-211.4-naphthohydroquinone derivatives have a melting point in the range of 60 to 180°C, and r in the general formula
By preparing a mutual combination of -oR,J and "-oR5", that is, ether groups, the melting point can be adjusted to 60 to 120°C, more preferably 80 to 120°C.

Moreover, when used as a sensitizer for thermal paper, 1.4-
It has a lower sublimation property than jetoxynaphthalene, and has a superior color development promotion effect compared to conventionally used fatty acid amides.

Furthermore, the 1,4-naphthohydroquinone derivative of the present invention has much better properties as a color former than the naphthalene-substituted product at the same substitution position, and has an advantageous manufacturing method.

Regarding the above-mentioned naphthalene-1,4-substituted product, the following compounds are the most preferable group combinations from these points of view.

That is, it is a compound represented by the following general formula.

[However, in the formula (1) RA is R, -OH, glycidyl group, and R, -0
, to and Ri are alkyl groups having 1 to 10 carbon atoms, R, is an alkylene group having 1 to 6 carbon atoms, and A is an alkylene group having 1 to 6 carbon atoms.
12 alkyl group, phenyl, benzylmodi or naphthyl group (any of these groups may be substituted), or @RA is R, -OH and R3 is R20B, R1
and R2 is an alkylene group having 1 to 6 carbon atoms, B is an alkyl group having 1 to 12 carbon atoms, pheninopebenzyl, or naphthyl group (any of these groups may be substituted with C)
shows. ] Particularly suitable combinations of substituents are combinations of different groups, such as a group in which one suppresses sublimation (RA above) and a group that contributes to color development (Rs above). .

Specific examples of these are shown as the above-mentioned compound = (2), compound - (2), compound - (2), compound - (2), and compound - (2).

This has a lower one-stone sublimation property than conventional O-substituted naphthohydroquinone derivatives such as 1,4-jethoxynaphthalene, and is almost comparable in its excellent color development promotion effect.

In the present invention, the intended purpose of the present invention can be achieved by setting the amount of the 〇-substituted naphthohydroquinone derivative to be 1 to 50% by weight, preferably 10 to 40% by weight of the total solid content of the heat-sensitive recording layer. can be achieved within the day.

Leuco Compound The leuco compound used in the present invention can be any colorless or light-colored substance that reacts with an organic acid.

Examples include various derivatives such as triphenylmethane type, triphenylmethanephthalide type, fluoran type, leucoolamine type, diphenylmethane type, phenothiazine type, phenoxazine type, spiropyran type, indoline type, and indigo type.

More specifically, for example, the following can be suitably used (the color in parentheses is the color after coloring).

Crystal violet lactone (blue), 3-diethylamino-6-methyl-7-anilinofluorane (black), 3-dibutylamino-6-methyl-7-anilinofluorane (black), 3-N.

N-ethylisoamylamino-6-methyl-7-anilinofluorane (black), 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluorane (black)
, 3-diethylamino-6-methyl-7-(ortho, para-dimethylanilino)fluoran (black) 3-pyrrolidino-6-methyl-7-7anilinofluorane (black), 3-piperidino-6-methyl -7-anilinofluorane (black), 3- (N-cyclohexyl-N-
methylamine)-6-methyl-7-anilinofluorane (black), 3-diethylamino-7-(ortho-chloroanilino)fluorane (black), 3-diethylamino-
7-(Meta-trifluoromethylanilino)fluorane (black), 3-diethylamino-6-methyl-chlorofluorane (red), 3-diethylamino-6-methyl-
Fluorane (red), 3-cyclohexylamino-6-
Chlorofluorane (orange), 3-(N-isoamyl-N-ethylamino)-6-methyl-7-anilinofluorane (black).

Organic acid (or ester thereof) The organic acid used in the present invention is a substance that is solid at room temperature, melts when heated, and becomes a color developer when it comes into contact with a leuco compound. Specifically: various phenolic substances, fatty acids, aromatic carboxylic acids, etc.

In the present invention, various objects of the present invention can be achieved by setting the amount of the organic acid used in a proportion of 1 to 40% by weight of the total solid content of the heat-sensitive recording layer.

More specifically, the following are used.

Gallic acid, salicylic acid, 1-hydroxy-2-naphthoic acid, 0-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-p-)ruylic acid, 3,5-xylenol, zymonope p-tert-butylphenol,
4-hydroxyphenoxide, methyl-4-hydroxybenzony), 4-hydroxyacetophenone, α-naphthol, β-naphthol, catechol, resorcinol,
4-tert-octylcatechol, 4. 4'-5
ea-butylidenephenol, 2.2'-dihydroxydiphenyl, 2. 2'-methylenebis(4-methyl-
5-tert-butylphenol), 2,2'-bis(4-hydroxyphenyl)furopane (also known as bisphenol A), 4,4'-isopropylidene-bis(
2-tcrt-butylphenol), bilogalonoheflologlycin, phloroglucin carboxylic acid.

p-Methylphenol, p-tert-butylphenol, p-phenylphenol, 4,4'-cyclohexylidene diphenol, 4.4'-(1-methyl-n-hexylidene) diphenol, 4°4'-( Impropylidene) dicateconobe 4゜4'-Benzylidene diphenope 4,4'-isopropylidene bis(2-chlorophel), 3-phenylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 1-oxy-2 - Naphthoic acid, gallic acid, estenopesalicylic acid, estenope 4-hydroxyphthalic acid ester.

Binder In the present invention, a known binder is used. Note that it is desirable to use a water-soluble one.

The binder has the function of separating and fixing the color forming agent dispersed in fine particles from each other. Specifically, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyacrylic acid, casein, gelatin, starch, and derivatives thereof are used.

In the present invention, various objects of the present invention can be achieved by using the binder in an amount of 1 to 35% by weight, preferably 10 to 30% by weight of the total solid content of the heat-sensitive recording layer. .

Other Additives The heat-sensitive recording material of the present invention may further contain other additives commonly used in heat-sensitive recording layers, such as clay, silica, calcium carbonate, aluminum hydroxide, talc,
Inorganic or organic materials such as titanium oxide and zinc oxide, wax neck, antioxidants for storage stability, ultraviolet absorbers, various fatty acid metal salts to prevent stickiness, water resistant agents to improve water resistance, phenol Resins, surfactants, etc. may be added.

Furthermore, in combination with the color development promoter according to the invention, color development promoters already known in this type of technical field may be added.

Substrate Various types of paper, including wood-free paper, medium-quality paper, and coated paper, are usually used as the substrate for use in the present invention. In the present invention, other materials such as glass fiber sheets, plastic sheets, film laminates, etc. can also be used as the substrate. Hereinafter, the structure and effects of the present invention will be explained in more detail with reference to synthesis examples and examples. However, the technical scope of the present invention is not limited to these examples.

"Example" Example 1 (1) Molecular formula C+ s H+ a 03 (2) Name 1-(2-hydroxypropoxy)4-ethoxynaphthalene (3) Identification data IR (KBr) 3300.2975, 1590, 1
450,1380°1280.1240.111+,
1091), 7g0゜760(Cm-') 'HN~・r R(CDCl2.270λIH2)δ1
．． 36 (d, 3H), 1.53 (t, 3)
1) 2, 30 (S, 1) 1) , 3.93 (d
d, LH).

4,06 (dd, IH), 4.17 (q,
2H).

4, 3 (m, LH), 6.68 (S, 2)
1) 7.45~7,55 (m, 2)1) , 8
．． 1-8.3 (m, 2H)m, p, 103℃ CHcalcd, C73,Pr% H7,37%f
ound C72,92% H7,20% (4) Manufacturing method 1-Hydroxy-4-ethoxynaphthalene 18.8g (
0.10 mol), propylene oxide 23g (0.4 mol)
Methanol 5Qrd! To the solution was added 30 mj2 of an aqueous solution containing 0.5 g of IJium hydroxide under a nitrogen atmosphere. After heating at 50°C for 1.5 hours, the reaction solution was cooled and diluted with water for 20 hours.
Added. The precipitated crystals were filtered, thoroughly washed with water, and then dried to obtain 19.0 g (0,077 mol) of white powder. This product was recrystallized from methanol 50i, 15.
4 g<0.063 mol) of colorless crystals were obtained. Yield 6
It was 3 mol%. The melting point of this substance is 103℃,
IR and NMR1 elemental analysis confirmed that it was 1-(2-hydroxypropoxy)-4-ethoxynaphthalene.

Example 2 [Compound-I] (1) Molecular formula Cl4H1603 (2) Name 1-(2-hydroxyethoxy)-4
-Ethoxynaphthalene (3) Identification data IR (KBr) 3300, 2975.2925, 2
875,1600°1460,1380.1280.1
240.1160°1100, 1090.1080.1
030.910°770,750 (Cm-') NMR (CDCl2.60 MHz) δ1.4 (t, 3H), 2.6 (br, IH).

3, 8-4.1 (m, 4H), 4.13 (Q, 2
H) H 6,6 (S, 2H); 7.3 to 7.7 (m, 2)
1).

8,1~8.4 (m, 2H) m, p, 96℃ CH'calcd, C72,39% H6,94%
Found C72,49% H6,80% (4)
Production method 1. A mixture of 16.0 g (0.10 mol) of 4-naphthohydroquinone, 50 ml of ethylene glycol, and 0.3 g of sulfuric acid was heated at 90° C. for 1.5 hours under a nitrogen cloud.

The reaction solution was cooled, and 16.0 g of diethyl sulfate (0,1
04 mol) was added, and then 43 mf of an aqueous solution containing 4.3 g of sodium hydroxide was added dropwise. The solution generated heat and the internal temperature rose to 40°C. After stirring for 1.5 hours, the precipitated crystals were filtered, thoroughly washed with water, and then dried. 15.
4 g of pale mauve powder was obtained. This stuff is ethanol/
Recondensed from a mixed solvent of water (50rn, 1150ml),
2.2 g of white crystals were obtained. The yield was 53 mol%. The melting point of the product was 96°C, and it was confirmed by IRSNMR and elemental analysis that it was 1-(2-hydroxyethoxy)4-ethoxynaphthalene.

Example 3 [Compound-■] (1) Molecular formula CI 48, s 03 (2) Name
1-(2-hydroxypropoxy)-4-methoxynaphthalene (3) Identification data IR (KBr) 3325.2925.1630.1600. 1460
゜1390.1280,1240,1160. 110
0°1080, 1026.810.770 (c+rr'
) HNMR (CDC13,60!, 1) IZ) δ1.2
(6,3H), 2.4 (s, 1tl).

3, 9 (S, 3H), 4.0 (d, 2H),
4.05-4.5 (m, 1), 6.7 (S,
2)1), ? , 3-7.7 (m, 2H),
8.1 ~ 8.4 (m, 2) 1) 101't: calcd, C72, 39% 86.94% fou
nd C72,25% 86.80%m, p.

M (4) Production method ■-Hydroxy-4-methoxynaphthalene 17.4g (
0.10 mol), propylene oxide 23.4 g (0.40 mol), propylene oxide 23.4 g (0.40 mol)
An aqueous solution 35 containing 0.5 g of IJ hydroxide was added dropwise to a solution of 54 mf of methanol under a nitrogen atmosphere.

After heating the mixture at 55° C. for 1.5)1 r, 50 ml of water was added to the reaction solution and cooled. Filter the precipitated crystals,
After thorough washing with water, it was dried to obtain 20.6 g of pale flesh-colored powder. This is ethanol/water (50-/30d)
was recrystallized from a mixed solvent to obtain 10.2 g of white crystals. The yield was 44 mol%. The melting point of the product is 101
It was confirmed to be 1(2-hydroxypropoxy)-4-butoxynaphthalene by IR, NMR, and elemental analysis at °C.
I endured it.

Example 4 [Compound-■] (1) Molecular formula C1s H1s O5 (2) Name 1-(2-hydroxybutoxy)4-methoxynaphthalene (3) Identification data IR (KBr) 3300, 2960.2940.2700.1630゜1600, 1460.1395.12g0.1240
゜1126, 1100゜10fl14.810.764
(c++r')' HN MR (CDCl2.60MHz) δ1.0
(t, 3H), 1.56 (q, 2H).

2, 5 (br, IH), 3.9 (s, 3H),
4.0 (br, m, 2H), il 1-4.
3 (L 1) 1).

6.7 (S, 2H), 7.4~7.8 (+y
+, 2H).

8, 1-8.5 (m, 2H) m, p, 64℃ CHcalcd, C73, 15% H7, 37%f
ound C73,40% H7,31% (4) Manufacturing method 1-Hydroxy-4-methoxynaphthalene 17.4g (
30 ml of an aqueous solution containing 0.4 g of sodium hydroxide was added to a solution of 0.10 mol), 21.6 g (0.30 mol) of butylene oxide, and 60 Inl of methanol under a nitrogen cloud;
I put in two drops. The mixture was heated at 50° C. for 1.5 hours, the reaction solution was allowed to cool, and 100 mj of methanol was added. , water 100r
d was added, the precipitated crystals were filtered and dried, and 16.2 g
A bluish-white powder was obtained. This product was reconsolidated from a mixed solvent of ethanol/water, and 13. White crystals of Og were obtained.

The yield was 53 mol%. Melting point is 64℃, IR, NM
R, 1-(2-hydroxybutoxy)-4 from elemental analysis
- It was confirmed that it was methoxynaphthalene.

Example 5 [Compound-■] (1) Molecular formula CI 782203 (2) Name 1-(2-hydroxypropoxy)-4
-n-Butoxynaphthalene (3) Identification data I R (KBr) 3250.2960.2875.
1590. 1460°13g0.1280.1240
．． 1160, 1100°760 (Cm″″1) ' HN M R (CDCl2.270 MHz) 61
．． 00(t, 3H), 1.36(d, 3H).

1,52-1.67 (m, 2)1), 1.8.
2-1.95 (m, 2H), 2.22 (s, L
H), 3.95 (dd.

IH), 4.06 (dd, LH>, 4.11
(t, 2H).

4, 28-4.40 (m, IH), 6.66 (S,
2)1).

7.44~7.55 (m, 2ft), 8.15~8,
29 (m, 2H) m, p, 89℃ CHcalcd, C74,42% H8,08%f
Made of ound C74, 40% 88.21% (4)
Method 1-Hydroxy-4-n-butoxynaphthalene 21.6
18 rnl of an aqueous solution containing 0.25 g of sodium hydroxide was added dropwise to a solution of 23 g (0.10 mol) of propylene oxide, 23 g (0.4 mol) of propylene oxide, and 54 ml of methanol under a nitrogen atmosphere.

The mixture was heated at 50° C. for 5 hours. Add 2 parts of water to the reaction solution
The precipitated crystals were filtered, washed with water, and dried to obtain 22.1 g of a grayish white powder.
．． 1 g of white crystals was obtained. The yield was 66 mol%. The melting point of the product was 89 DEG C., and it was determined by IR, NMR, and elemental analysis that it was 1-(2-hydroxypropoxy)-4-n-butoxynaphthalene.

Example 6 [Compound-■] (1) Molecular formula CI 782204 (2) Name 1-(2-ethoxyethoxy)-4-(
2-Hydroxypropoxy)naphthalene (3) Identification data IR (KBr) 3310, 2980, 2925, 2
870.1600゜1450.13g4.1280,1
244.1160°1100, 940.860.790
．． 770.750° (cm-')' HN MR (CDCl2.60 MHz)61.
2 (t, 3) 1), 1.3 (d, 3H) 2, 60 (
br, IH), 3.6 (q, 2H).

3, 7-4.0 <m, 4H), 4.1-4.4
(m, 2) 1), 4.4-4.5 (m, 1) I)
.

6, 7 (s, 2H), 7.3~? , 7 (m,
2)1).

8, 0-8. , 5 (m, 2H) m, p, 74℃ CHcalcd, C70, 32% H7, 64% fou
nd C70,51% 87.50% (4) Manufacturing method 1.4-naphthohydroquinone 20.0 g (0,125
mol), 2-ethoxyethanol 22.5 g (0,25
A mixture of 1.0 g of mol) oyohimethanesulfonic acid was heated at 115° C. for 20 minutes under a nitrogen cloud. 100 ml of water was added to the reaction solution and heated, and the excess amount of 2-ethoxyethanol was distilled off. Next, extraction was carried out using 50 ml of chloroform, and the chloroform layer was preheated under reduced pressure to a-condense to obtain 21.3 g of brown oil. Add 22g of methanol to this and dissolve it, and 40g of propylene oxide (0,
68 mol) was added thereto, and then under a nitrogen atmosphere, an aqueous solution of 20-2 containing 0.4 g (0.01 mol) of sodium hydroxide was added, and after stirring at room temperature for 48 hours, methanol 100-
100ml of water! The precipitated crystals were filtered, thoroughly washed with water, and then dried to obtain 16.0 g of flesh-colored powder. Add activated carbon to 50ml of acetone and
After IHr treatment at 0°C, water was added, concentrated, and recrystallized to obtain 11.8 g of white crystals. The yield was 41 mol%. The melting point of this product is 74°C, and IR, NMR
, elemental analysis revealed that 1-(2-ethoxyethoxy')
It was confirmed that it was -4-(2-hydroxypropoxy)naphthalene.

Example 7 [Compound-■] (1) Molecular formula C28H2404 (2) Name 1.4-di(2-phenoxyethoxy)
Naphthalene (3) identification data IR (KBr) 3070,2930.1600.
1500, 1460° 1370.1280, 1240.
1180. 1100°940.810,760,75
0 (cm-')' HN MR (CDC1a, 6
0? , IHz) δ4.6 (br, s, 8H), 7.
1 (s, 2H).

7, 2~7.7 (m, 10) 1), 7.7~8
．． 0 (m, 2H), 8.6-8.9 (m, 2
H) 118℃ calcd, C77, 98% 86.04%fou
nd C77, 76% 86.10% m, p.

H (4) Production method 1. 32.0 g (0.20 mol) of 4-naphthohydroquinone, 72.0 g (0.52 mol) of 2-phenoxyethanol
A mixture of 10 g of methanesulfonic acid and 10 g of methanesulfonic acid was heated at 110° C. for 2 hours under a nitrogen cloud. The reaction solution was allowed to cool, and an ethanol/water (%) solution of 160 mj! added. The precipitated crystals were filtered, thoroughly washed with water, and then dried. 44
．． 4 g of off-white powder was obtained. This was heated and dissolved in 100ml of chloroform, and 100ml of 9/-ml was added.
was added to precipitate crystals.

After filtration and drying, white crystals of 3', Og were obtained.

The yield was 46 mol%. The melting point of the product is 118°C
From lR5NNlR1 elemental analysis, 1.4-di(2
- phenoxyethoxy) naphthalene.

Example 8 [Compound-■] (1) Molecular formula Ct = Hl 40□Cl2 (2) Name 1.4-di(2-chloroethoxy)naphthalene (3) Identification data IR (KBr) 3050, 2925.2g75. 1600.1460°1380, 1280.1240.880.790.76
0゜740.670 (cm-') ' HNMR (CDCl2.60!JHz) δ4.1
(t, 4H), 4.6 (t, 4H).

7.0 (s, 2H), 7.8-8.2 (m.

2H), 8.6-3.9 (m, 2H) 1'11. I], 127°C CH, calcd, C58, 97% 84.95χ
Found C58,40% 84.90% (4
) Production method (1) A mixture of 48.0 g (0.30 mol) of 4-naphthohydroquinone, 80.0 g (1.02 mol) of ethylene chlorohydrin, and 10 g of oyohimethanesulfonic acid was heated to 119°C under a nitrogen atmosphere. ) Heated for 1r. The reaction solution was allowed to cool, and 200 mj2 of methanol was added. The precipitated crystals were filtered, thoroughly washed with methanol, and then dried.

53.9 g of pale pink powder was obtained. Yield is 46 mol%
Met. This product was recrystallized from chloroform/methanol, and the resulting white crystals were analyzed. The melting point of the product is 127°C, and 1.4-
It was confirmed that it was di(2-chloroethoxy)naphthalene.

In addition, 1,4-di(2-furomoethoxy)
Naphthalene (CI48140□Br2) was synthesized. Its melting point is 128°C, IR.

Confirmed by NMR and elemental analysis. Identification data is as follows.

IR(KBr) 3050.2930.2870,1
635,1595°1455,1380.1280.1
240.1220°1100, 870,790,770
,740 (cm-')' HN MR (CDC13
,60n,IHz)63,8(t,4)1),
4.5(t, 4)1).

6.8 (s, 2) 1), 7.5-7.8 (m,
2)1) , 8.2~8.5 (m, 21()m,
I), 128℃ CHcalcd, C44,95%) (3,77χ
Found C45,05% H3, flG% Example 9 [Compound-V] (1) Molecular formula C+ s H+ e O5 (2) Name 5-(2,3-epoxypropoxy)-4-ethoxynaphthalene (3) Identification Data I R (KBr) 2g9Q, 1600.1470.
1390, 1280° 1240, 1180.1100
．． 1095.1020°850.800,770.75
0 (cm-') HXMR (CDC13,270M)
Iz) δ1.53 (t, 3H), 2.84rdd,
LH).

2, 96 (dd, IH), 3.43-3.50
(m.

1B), 4.10(dd, 1tl), 4.14(
q, 2H).

4, 34 (dd, LH), 6.68 (s, 2H
).

7, 46~7.55 (m, 2H), 8.19~
8.28 (m, 2H) m, p, 77℃ CHcalcd C73,75% H6,60χf
ound C73.94% 86.40% (4) Manufacturing method 1-Hydroxy-4-ethoxynaphthalene 18.8g (
0.1 Q mol), 13.4 g of epichlorohydrin (0.1 Q mol),
15 mol>, an aqueous solution containing 4.0 g of sodium hydroxide in a solution of 40 methanol 40 rITI! was dropped under a nitrogen cloud.

The mixture was stirred at room temperature for 4) 1r. The precipitated crystals in the reaction solution were filtered, thoroughly washed with water, and dried to yield 22.9 g.
A pale blue powder was obtained. This product was recrystallized from acetone/water to obtain 14.7 g of white crystals, yield of 60 mol%.
Met.

The melting point of the product was 77°C, and it was confirmed by lR1NXlR1 elemental analysis that it was l-(2,3-epoxypropoxy)-4-ethoxynaphthalene.

Example 10 [Compound-■] (1) Molecular formula C2oH2005 (2) Name 1-(2-phenoxyethoxy)-4-
Ethoxynaphthalene (3) Identification data IR (KBr) 2960, 1592.1490.1455.1385°1280, 1160.1100.1090.935°7
70.75 et al., 698 (cm-')'HNMR (C
DCl2.60MH2) δ1.5 (t, 3H), 4.
3 (Q, 2H).

4.6(s, 4t(), 7.1(s, 2H), 7.2
~7,8 (m, 5H), 7.8~8.2 (f
n, 2H).

8, 6-9.0 (m, 2H) m, p.

99℃ CHcalcd, C77, 90% 86.54%fo
und C78,00% H6,60% (4) Production method 1. 4-naphthohydroquinone 16.0 g (0.10 mol), 2-phenoxyethanol 41.4 g (0.3 mol) and methanesulfonic acid 1. The Og mixture was heated at 115° C. for 0.5)1 r under a nitrogen atmosphere. The reaction solution was allowed to cool, 40 cm of methanol was added, and insoluble materials were filtered off.

To the resulting solution was added 12.3 g of diethyl sulfate (0.08
mol) and then hydroxide) IJium 3.2g (0
, 08 mol) was added. 1) 1r
After stirring, the precipitated crystals were suction filtered, thoroughly washed with methanol on a funnel, and dried to obtain 19.0 g of crude crystals. Chloroform/n-hexane? / (60m
j! /100ml) and recrystallized with a mixed solvent of 16.2
g white crystals were obtained. The yield was 63 mol%. The melting point of the product was 99°C, and IRSNMR and elemental analysis confirmed that it was 1-(2-phenoxyethoxy)-4-ethoxynaphthalene.

Example 11 [Compound-■] Synthesis of 1-(2-phenoxyethoxy)-4-methoxynaphthalene and 1-(2-phenoxyethoxy)-4-propoxynaphthalene 1. As an alkylating agent,
l-(2-phenoxyethoxy) was prepared in the same manner as in Example 10 except that dimethyl sulfate or propyl bromide was used.
-4-methoxynaphthalene and 1-(2-phenoxyethoxy)-4-propoxynaphthalene were synthesized.

Its identification data is as follows.

2.1-(2-phenoxyethoxy)-4-methoxynaphthalene (1) Molecule 2 C+ s H+ s O3 [2] Identification data IR (KBr) 3060.2950, 1600.1
500, 1460° 1395, 1280.1240.1
160.1100゜1090, 940.905.81)
5.780.760°7L5.700 (cm-')' HN M R (CDCl2.6O-(H2)64.
6 (s, 3H), 4.43 (s, 4H).

6,8 (s, 2H), 6.9~7.5 (+n,
5H).

7, 5-7.7 (m, 2H), 8.2-8.
5(m, 2)1) m, p, 92℃ CHcalcd, C77,53% 86.16%f
ound C77, 41% H6, 02% 1-12
-phenoxyethoxy)-4-propoxynaphthalene (1) Molecular formula C2□H2203 (2) Identification data IR (KBr) 3060, 2975, 2940.1
600,1500°1460,1380,1280,1
240.1160°1100, 1090.930,8
00,770,760°695,745,700 (cm
-') (CDC1:l, 60Mth) 61.1 (t, 3N), 1.9 (tQ 2H).

'HNMR 3°4,07 (t, 2H), 4.4 (S, 4H
), 6.75 (S, 2H), 6.9-7.4 (m
, 5H), 7.4-7.7([11,2H), 8
．． 2-8.5 (m, '2H) m, p, 86°C CHcalcd.

ound C78,23% H6,fil! % C78,30% H6,80% Example 12 [Compound-■] [1] Molecular formula C2, H2□04 (2) Name 1-(2-phenoxyethoxy)-4-
(2-Hydroxypropoxy) Naphthalene (3) Identification data I R (KBr) 3550.3450,3050.
2980.2920°2870, 1600.1500.
1455.1400°1380, 1280.1240.
1100.930°780, 750.690 (cm-
')'HNMR (CDCl2.60!, (H2)61,
33 (d, 3H), 2.5 (tlr, IH).

4,0(d, 2H), 4.0~4.2(m, LH
).

4, 4 (S, 4H), 6.7 (S, 2H)
.

6.8 ~ 7.4 (lTl, 5H), 7.5 ~ 7
．． 7 (m, 2H), 8.1 ~ L 4 (m,
2H) m, p, 77℃ CHcalcd, C70, 53% 86.56%fou
nd C74.44% 86.60% (4) Manufacturing method ■, 4-naphthohydroquinone 32.0 g (0.20 mol), 2-phenoxyethanol 55.0 g (0.40 mol)
A mixture of 1.6 g of methanesulfonic acid (mol) and 1.6 g of methanesulfonic acid was heated at 110° C. for 0.5 Hr under a nitrogen atmosphere. This reaction solution was allowed to cool, 8 (lrnl) of methanol was added, and insoluble matter was filtered off.

To the resulting solution was added 32.4 g of propylene oxide (0.60 g
mol) and then added 4.0 g'(0 mol) of sodium hydroxide.
, 10 mol) was added and heated by IH at 50°C.
After heating, the mixture was allowed to cool, and the precipitated crystals were suction filtered, thoroughly washed with methanol, and dried to obtain 35.0 g of crude crystals.

This product was recrystallized with a mixed solvent of chloroform/methanol (60mf/200mf), and
, 0 g of white crystals were obtained.

The melting point of this product is 77°C, and IRIN MR1 elemental analysis shows that 1-(2-phenoxyethoxy)-4-(
It was confirmed that it was 2-hydroxypropoxy)naphthalene.

Experimental Example The sublimability of the 〇-substituted 1,4-naphthohydroquinone derivative of the present invention and 1,4-jethoxynaphthalene was measured using a thermogravimetric measuring device (differential scanning calorimeter, Rigaku Ther).
The weight loss due to heat was measured using a Moflex TG-DSC (standard type) and compared.

The results are shown in Table 1.

Each given sample was heated to 200°C at a heating rate of 10°C/min.
and the temperature was raised to 250°C. 〇-substitution 1 of the claimed invention,
For 4-naphthohydroquinone derivatives, 1,4-
All of them were able to lower the sublimation property compared to jetoxynaphthalene.

Z-poor Examples 13 to 20 and Comparative Examples 1 to 2 (1) Production of thermosensitive recording paper Liquid OA and liquid B having the following compositions were separately ground and dispersed in a ball mill for 72 hours.

Solution A: Aluminum hydroxide zinc stearate 0g 5g Solution B: Hysulfinol A Calcium carbonate Zinc stearate 5g 0g 5g Water 2g Next 1. 125g of liquid B, 125g of liquid B and polyvinyl alcohol 105 (n@9 manufactured by Rare) 12% liquid 50
Add 40 g of water and mix and stir to prepare the coating liquid.
Using a wire bar, apply on the surface of 0g/m' high-quality paper so that the coating amount after drying is 8g/m+, and dry.
A thermosensitive recording paper was obtained.

-Substituted 1,4-naphthohydroquinone derivative compound used as sensitizer ■1-(2-hydroxypropoxy)-4-methoxynaphthalene (HPMN) (Example ■1-(2-hydroxypropoxy)-4-ethoxy Naphthalene (HPEN) (
Example ■1- (2-hydroxypropoxy)-4n-
Butoxynaphthalene (HPBN) (Example 15) ■1-(2-hydroxypropoxy)-4-(2-phenoxyethoxy)-naphthalene (HPPBN) (Example 16) ■1.4-di(2-phenoxyethoxy) Naphthalene (DPEN) (Example 17) ■1,4-di(2-chloroethoxy)naphthalene (CIEN) (Example 18) ■1-(2,3-epoxypropoxy)-4-ethoxynaphthalene (GEN) ( Example ■1- (2-phenoxyethoxy)-4-ethoxynaphthalene (PEEN) (
Example 20) Comparative Example Material ■ Stearic acid amide (STAM) (Comparative Example 1) ■ Jetoxynaphthalene (DEN) (Comparative Example 2) (2) Test of thermal recording paper Thermal sensitivity obtained in the above examples and comparative examples The recording paper was surface-treated with a super-chillender so that the recording surface had a Bekk smoothness of 500 seconds.

Next, each of the obtained thermal recording papers was subjected to the following tests, and the results are shown in Table 2.

(2) Color development start temperature This is the temperature at which the color density becomes 0.2 in a static color development test.

■Image density Commercially available thin film thermal head KFT-216-8NIPD
! (manufactured by Kyocera@) Printing power: 0.70W/dat, Printing pulse time: 0.4ms, Printing pulse cycle: 5.0ms
Solid printing was performed under these conditions, and the color density at that time was measured.

(2) Color development ability test The obtained thermal recording paper was stored in a dry cloud environment at 40° C. for one week, and after storage, recording was performed under the conditions (2), and the rate of decrease in image density was measured.

0 - 10% or less × - 10% or more The sample obtained by dusting ■ was stored at 40° C. in a dry cloud atmosphere for one week, and the dusting condition of the printed area was visually judged.

◎　・・・－・・・・・・Not accepted at all.

○－...I'm indebted to you.

△　・　・--No practical problem, but somewhat common.

No. z "Effect of the invention" First, the compound of the present invention is new.

(2) This new 0-substituted 1,4-naphthohydroquinone derivative is an extremely important compound as a sensitizer for thermal paper.

■ 〇-substitution 1, 4- in claim paragraph (2) containing these
Naphthohydroquinone derivatives have excellent image density etc. compared to stearamide, which has been conventionally used industrially, and have lower sublimation properties than 1,4-jethoxynaphthalene, etc., and have excellent performance! It is comparable to other products, and its industrial effects are remarkable.

(2) The compounds in claim (3) are a specific group of novel compounds.

(2) The compounds of claim (4) are a more typical group of compounds of claim (2).

(2) When the above 〇-substituted 1,4-naphthohydroquinone derivative is used as a thermal paper sensitizer, the preferable melting point range is 60 to 180°C, more preferably 60 to 120°C, and still more preferably 80 to 120°C.

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, in the formula, R_A is R_1-OH, R_1-OA, R_1-X_
1 or a glycidyl group, and R_B represents R_2-OB, R_2-X_2 or an alkyl group having 1 to 10 carbon atoms. Note that R_1 and R_2 are alkylene groups having 1 to 6 carbon atoms, and A
and B is phenyl, benzyl, naphthyl, or an alkyl group having 1 to 12 carbon atoms (any of these substituents may be substituted), and X_1 and X_2 are halogen] A novel O- Substituted 1,4-naphthohydroquinone derivatives. (2) In a thermosensitive recording material mainly composed of a leuco compound and an organic acid that develops a color by reacting with the leuco compound, an O-substituted 1,4-naphthohydroquinone derivative of the following general formula is used as a color development accelerator in the recording layer. Thermal recording material general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R_A is R_1-OH, R_1-OA, R_1-X_
1 or a glycidyl group, and R_B represents R_2-OB, R_2-X_2 or an alkyl group having 1 to 10 carbon atoms. In addition, R_1 and R_2 are alkylene groups having 1 to 6 carbon atoms, A and B are phenyl, benzyl, naphthyl, or alkyl groups having 1 to 12 carbon atoms (all of these substituents may be substituted), and X_1 and X_2
indicates halogen]. (3) The O-substituted 1,4-naphthohydroquinone derivative is a compound of the following general formula.The general formula of the heat-sensitive recording material described in claim (2)▲There are numerical formulas, chemical formulas, tables, etc.▼ [However, In the formula (1) R_A is R_1-OA and R_B is R_2-
OB, R_1 and R_2 are alkylene groups having 1 to 6 carbon atoms, and A and B are alkyl, phenyl, benzyl, or naphthyl groups having 1 to 12 carbon atoms (all of these groups may be substituted). ), or (2) R_A represents R_1-OH, where R_1 is the same as in (1) above, and R_B has 1 to 1 carbon atoms.
0 alkyl group or the same R_2-O as in (1) above
B, or (3) R_A and R_B are R_1-X_1 and R_2-X_2, respectively, R_1 and R_2 are the same as in (1) above, and X_1 and X_2 represent halogen, or (4) R_A is a glycidyl group, and R_B has 1 to 10 carbon atoms.
or (5) R_A represents the same R_A as in (1) above, and R_A represents the same alkyl group as in (1) above;
B represents an alkyl group having 1 to 10 carbon atoms. ] (4) The heat-sensitive recording material general formula according to claim (2), wherein the O-substituted 1,4-naphthohydroquinone derivative is a compound having the following general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [However, R_A in the formula is R_1-OA, R_B is an alkyl group having 1 to 10 carbon atoms, R_1 is an alkylene group having 1 to 6 carbon atoms, and A is an alkyl, phenyl, benzyl or naphthyl group (all of these groups are substituted). ), or R_A and R_B are R_1-X_1, respectively.
and R_2-X_2, R_1 and R_2 are the same as in (1) above, and X_1 and X_2 represent halogen. (5) The O-substituted 1,4-naphthohydroquinone derivative has a melting point of 60 to 180°C (
2) The thermosensitive recording medium described above. (6) The thermosensitive recording material according to claim (2), wherein the O-substituted 1,4-naphthohydroquinone derivative has a melting point of 60 to 120°C. (7) The heat-sensitive recording material according to claim (2), wherein the O-substituted 1,4-naphthohydroquinone derivative has a melting point of 80 to 120°C.