WO2003101751A1 - Recording material and recording sheet - Google Patents

Abstract

The invention provides a recording material which does not cause fog and is excellent in color-developing sensitivity and shelf stability of non-image areas and images, and recording sheets obtained by making a recording layer from the recording material on a supporting sheet. The recording material contains a color-forming dye and is characterized by containing at least one compound represented by the general formula (1): (1) [wherein R1 and R2 are each hydrogen or C1-6 alkyl; a1 is an integer of 1 to 6; n1 is an integer of 0, 1 or 2; m1 and m2 are each an integer of 0 to 3 with the proviso that both of m1 and m2 are not 0; R3 and R4 are each nitro, carboxyl, halogeno, C1-6 alkyl, or the like; m3 and m4 are each an integer of 0,1 or 2; and Y1 is CO or NR5CO] and at least one compound selected from among phthalic acid derivatives, hydroxybenzoic acid derivatives, anilide derivatives, biphenyl derivatives, benzotriazole derivatives, amorphous silica, 4-benzyloxy-4’-(2-methylglycidyloxy)- diphenyl sulfone and compounds represented by the general formula (2): (2)

Description

 Description Recording material and sheet Technical field:

 The present invention relates to a recording material having excellent coloring sensitivity and excellent storage stability of background and images, and a recording sheet having a recording material layer formed from the recording material on a base sheet. Background art:

 A recording material that utilizes color development by the reaction between a color-forming dye and a developer can be recorded in a relatively simple apparatus in a short time without performing complicated processing such as development and fixing. Widely used as heat-sensitive recording materials or pressure-sensitive copying materials for output recording.

 It is demanded that these recording materials rapidly develop color, maintain the whiteness of uncolored portions (hereinafter referred to as "background"), and have high rigidity of developed images and background. In particular, in recent years, the demand for high-speed recording has increased, and the development of high-sensitivity recording materials that can sufficiently cope with high-speed recording has been desired. In general, when the sensitivity is increased, the skin coloration phenomenon (so-called “skin capri”) occurs, and the storage stability of the skin is deteriorated. Recording material excellent in the above has not been found yet.

 In addition, the POS (Point of sales) label system has been used in various manufacturing processes, and there is no background capri even in places where the environmental temperature is 100, and the preservation of recorded images is also good. There is a growing demand for thermal recording paper that can read barcode readers in the infrared region.

Further, the compound represented by the formula (1) of the present invention is described in WO 01/25193, a compound represented by the formula (10), and a compound represented by the formula (11). The compound and / or the composition of the compound represented by the formula (12) is disclosed in WO 02/82129, but the recording material using these can always satisfy the coloring sensitivity. Not something In addition, there is a need for a technique for improving this sensitivity to provide a recording material having excellent coloring sensitivity and excellent preservability of the background and image.

 The present invention has been made in view of the above circumstances, has no background capri, is excellent in coloring sensitivity, and has excellent background and image storability, and a recording material on a base sheet. It is an object to provide a recording sheet having a recording material layer formed. Disclosure of the invention:

 The present invention

 1. For a recording material containing a chromogenic dye, the formula (1)

[In the formula, Shaku ¹ and! 1 ² each independently represent a hydrogen atom or a C 1 through C 6 alkyl group, a ¹ represents an integer of. 1 to 6, n ¹ represents 0, 1 or 2 integer, m ¹ And m ² each independently represent 0 or an integer of 1 to 3. However, m ¹ and m ² are not simultaneously 0.

R ³ and R ⁴ are each independently a nitro group, a carbonyl group, a halogen atom C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkyl force Ruponiru group or C. 1 to C 6 alkoxy force Lupo two group, 1 [1 ³ and 111 ⁴ are each independently 0, 1 or 2 of an integer, 111 ³ and 111 ⁴ are respectively When 2, R ³ and R ⁴ may be different from each other, and Y ¹ is CO or NR ⁵ CO (wherein, R ⁵ has a hydrogen atom, a C 1 -C 6 alkyl group, A phenyl group or a benzyl group which may have a substituent.). Phthalic acid derivative, hydroxybenzoic acid derivative, anilide derivative, biphenyl derivative, benzotriazole derivative, amorphous silica, 4-benzyloxy-4 ′ -(2-Methyldaricidyloxy) Diphenyl sulfone and formula (2)

 (2)

[In the formula, X ¹ and X ² are each independently a straight-chain or branched hydrocarbon which may have 1 to 12 carbon atoms which may have a saturated, unsaturated or ether bond. Group, or formula (3) or formula (4)

 (3) (4)

(Wherein, R ^{1 2} represents a methylene group or an ethylene group, R ^{1 3} is. Representing a hydrogen atom or an alkyl group C. 1 to C 4) represents a group represented by ⁶ ~! ^ ^{1 1} are each independent, a halogen atom, a C 1 ~ C 6 alkyl group or C. 2 to C 6 alkenyl group and table, ms m ^1. Each independently represents 0 or an integer of 1 to 4, and when it is an integer of 2 or more, R e R ¹¹ may be the same or different, and b is 0 or 1 to 10 Represents an integer. ] A recording material comprising at least one compound selected from the compounds represented by the formula: However, when the compound represented by the formula (2) is contained, at least two or more kinds of the compound represented by the formula (1) are contained.

2. In a recording material containing a chromogenic dye, the formula (1)

[Wherein R ¹ , RRR nmmmm ⁴ and Y ¹ represent the same meaning as described above. At least one compound selected from the group consisting of phthalic acid derivatives, hydroxybenzoic acid derivatives, anilide derivatives and biphenyl derivatives. 3. A recording material containing a chromogenic dye, wherein the formula (1)

[In the formula, R ¹ R ² , R ³ , R ⁴ , ¹ , nm ¹ , m ² , m ³ , m ⁴ and Y ¹ represent the same meaning as described above. ] A recording material comprising at least one compound represented by the formula: and a benzotriazole derivative.

4. In a recording material containing a chromogenic dye, the formula (1)

[Wherein, R ¹ , RRR anmmmm ⁴ and Y ¹ represent the same meaning as described above. ] A recording material characterized by containing at least one compound represented by the formula (1) and containing amorphous silicon.

5. In a recording material containing a chromogenic dye, the formula (1)

^{Wherein, R 1 R 2 R 3 R} 4 a 1, 1 1 m 1, m 2 m 3 m 4及Pi Y ¹ are as defined above. ] A recording material comprising at least one compound represented by the formula: and 4-1 benzyloxy-4 '-(2-methylglycidyloxy) diphenylsulfone.

 6. In a recording material containing a chromogenic dye, the formula (1)

[Wherein, RRRR anmmmm ⁴ and Y ¹ represent the same meaning as described above. And at least two compounds represented by the formula (2)

 (2)

[Wherein, X ¹ and X ² are each independently a straight-chain or branched hydrocarbon which may have a saturated or unsaturated C 1 C 12 or an ether bond. Group, or formula (3) or formula (4)

 (3) (4)

(Wherein, R ^{1 2} represents a methylene group or an ethylene group, R ^{1 3} is. Representing a hydrogen atom or an alkyl group C 1 through C 4) represents a group represented by ⁶ ~! ^ ^{1 1} are each independent, halogen atom, and display the C. 1 to C 6 alkyl group or C. 2 to C 6 alkenyl group, ms m ¹ ° are each independently 0 or 1-4 Represents an integer, and when it is an integer of 2 or more, Re R ¹¹ may be the same or different, and b represents 0 or an integer of 1 to 10. ] A recording material comprising at least one compound represented by the formula:

 7. The phthalic acid derivative has the formula (5)

[Wherein, R ¹⁴ and R ¹⁵ each independently represent a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, an aryl group which may have a substituent or a substituent. And R ¹⁶ represents a hydroxyl group, a halogen atom, a C 1 -C 6 alkyl group or a C 2 -C 6 alkenyl group, and m ¹¹ represents 0 or 1 to 4 When m ¹¹ is an integer of 2 or more, R ¹⁶ may be different. The recording material according to 1. or 2., characterized by being represented by:

 8. The recording material according to 7, wherein the phthalic acid derivative is dimethyl terephthalate.

9. The hydroxybenzoic acid derivative has the formula (6)

[Wherein, R ¹⁷ is a hydroxyl group, a halogen atom, 〇1 to. 6 represents an alkyl group or 〇 2-6 alkenyl group, m ¹² represents an integer of 0 or 1 to 4, and when m ¹² is an integer of 2 or more, R ¹⁷ may be different; ¹⁸ represents a C1-C6 alkyl group, a C2-C6 alkenyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent. ] The recording material described in 1. or 2., characterized by the following.

 10. The recording material according to 9, wherein the hydroxybenzoic acid derivative is 4-benzyloxybenzoate. '

 1 1. The anilide derivative has the formula (7)

(7)

Wherein R ¹⁹ is a C 1 -C 18 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylene group, Represents an aryl group or an aralkyl group which may have a substituent; R ^{2 Q} is a hydrogen atom; a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, Represents an aryl group or an aralkyl group which may have a substituent, and R 21 represents a halogen atom, a C ¹ -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkoxy groups, C. 1 to C 6 alkylcarbonyl group, optionally § Li Ichiru group or may have a substituent represents an even better Ararukiru group substituted, m ^{1 3} is 0 or 1 represents an integer of 1-5, when m ^{1 3} are each an integer of 2 or more, R ^{2 1} may be different. ] The recording material as described in 1. or 2. above, characterized in that:

1 2. It is characterized in that the anilide derivative is a single acetate toluidide. The recording material described.

 1 3. The biphenyl derivative has the formula (8)

Wherein, R ^{2 2} and R ^{2 3} are each independently a hydroxyl group, a force Rupokishiru group, C 1 ~ C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C 1 To C 6 alkyl carbonyl group, C 1 to C 6 alkyl carbonyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent, m ¹⁴ and m ¹⁵ They are each independently an integer of 0 or from 1 to 5 when m ^{1 4} and m ^{1 5} is an integer of 2 or more, respectively, R ^{2 2} and R ^{2 3} may be different from each other. The recording material according to 1. or 2., characterized by being represented by:

 1 4. The recording material according to 1 3., wherein the biphenyl derivative is 4-acetyl phenyl biphenyl.

 1 5. The benzotriazole derivative has the formula (9)

24, _m1

Wherein, R ^{2 4} and R ^{2 5} each independently represents a hydroxyl group, a halogen atom, C l to C 8 alkyl group, a C. 2 to C 6 alkenyl or C 1 through C 8 alkoxy group, m ^{1 6} represents an integer of 0 or 1-4, when m ^{1 6} is an integer of 2 or more, R ^{2 4} is different connexion may, m ^{1 7} represents an integer of 0 or from 1 to 5, m ^{When 17} is an integer of 2 or more, R ²⁵ may be different. ] The recording material according to 1. or 3., characterized in that:

1 6. The recording material according to 1 5., wherein the benzotriazole derivative is 2- (2-benzotriazolyl) -p-cresol. 1 7. The recording material according to 1 5., wherein the benzotriazole derivative is 2-((2′-hydroxy-3 ′, 5′-z-t-butylphenyl) benzotriazole).

 1 8. The recording material according to any one of 1 to 1 to 7, characterized in that it contains at least two kinds of compounds represented by the formula (1).

 1 9. At least two kinds of compounds represented by the formula (1) are represented by the formula (10)

Wherein, R ^{2 6} and R ^{2 7} independently represent a hydrogen atom or a C 1 through C 6 alkyl le group, a ² represents an integer of. 1 to 6, n ² is 0, M ¹⁸ represents 0 or an integer of 1 to 3;

R ^{2 8} and R ^{2 9} are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C 1 through C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C 1 represents ~ C 6 alkyl group or a C. 1 to C 6 alkoxycarbonyl two Le group, m ^{1 9} and m ² ° each independently represent 0, 1 or 2 integer, m ^{1 9} and m ² . When each is 2, R ²⁸ and R ²⁹ may be different from each other, and Y ² is CO or NR ³ ° CO (where R ³ ° is a hydrogen atom, a C1-C6 alkyl group, A phenyl group which may have a substituent or a benzyl group which may have a substituent.). And at least one compound represented by the formula (11):

Wherein, R ^{3 1} and R ^{3 2} are each independently, represent a hydrogen atom or a C. 1 to C 6 alkyl le group, a ³ represents an integer of. 1 to 6, n ³ is 0, Represents an integer of 1 or 2, m ^{2 1} represents an integer of 0 or 1-3.

R ^{3 3} and R ³⁴ are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C. 1 to C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C. 1 to represents C 6 alkyl force Ruponiru group or C. 1 to C 6 alkoxy force Lupo two Le group, m ^{2 2} and m ^{2 3} are each independently 0, 1 or 2 of an integer, m ^{2 2}及Pi when m ^{2 3} are each 2, R ^{3 3}及Pi R ³⁴ may be different from each other, Y ³ is, CO or NR ^{3 5} C_〇 (wherein, R ^{3 5} is a hydrogen atom, C. 1 to C 6 represents an alkyl group, a phenyl group which may have a substituent or a benzyl group which may have a substituent.) At least one compound represented by the formula: and Z or the formula (12)

(12)

Wherein, R ^{3 6} and R ^{3 7} each independently represent a hydrogen atom or a C. 1 to C 6 alkyl le group, a ⁴ represents an integer of. 1 to 6, n ⁴ is 0, 1 or an integer 2, m ^{2 4} represents an integer of 0 or 1-3.

R ^{3 8} and R ^{3 9} are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C. 1 to C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C 1 represents ~ C 6 alkyl force Ruponiru group or C. 1 to C 6 alkoxy force Lupo two Le group, m ^{2 5} and m ^{2 6} each independently represent 0, 1 or 2 integer, m ^{2 5} and when m ^{2 6} are each 2, R ^{3 8} and R ^{3 9} may be different from each other, Y ⁴ is, CO or NR ^{3 5} C_〇 (wherein, R ^{3 5} is a hydrogen atom, C. 1 to C 6 represents an alkyl group, a phenyl group which may have a substituent or a benzyl group which may have a substituent.) 18. The recording material according to item 8, wherein the recording material is at least one compound represented by the formula:

20. A recording sheet having a base material sheet and a recording material layer formed on the base material sheet from the recording material described in any one of 1. to 19. The recording material layer formed from the recording material of the present invention is excellent in color development sensitivity and excellent in background and preservation of images. Further, the recording material of the present invention does not cause background capri.

 The present invention relates to a recording material containing a chromogenic dye, comprising at least one compound represented by the formula (1), and further comprising a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, and biphenic acid. Derivatives, benzotriazole derivatives, amorphous silica, 4-benzyloxy 4 '-(2-methyldaricyloxy) diphenyl sulfone, and a small number of compounds selected from the compounds represented by the formula (2). It is characterized by containing at least one.

 Although the content of the phthalic acid derivative is arbitrary, it is usually 10 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). Parts by weight, more preferably in the range of 30 to 70 parts by weight.

 The content of the hydroxybenzoic acid derivative is arbitrary, but is usually 1 to 100 parts by weight, preferably 10 to 3 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). It is in the range of 100 parts by weight, more preferably 20 to 100 parts by weight.

 Although the content of the anilide derivative is optional, it is usually 10 to 100 parts by weight, preferably 20 to 20 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably 30 to 100 parts by weight.

 The content of the biphenyl derivative is optional, but is usually 10 to 100 parts by weight; preferably 100 to 100 parts by weight, preferably 20 to 30 parts by weight, per 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably in the range of 30 to 200 parts by weight.

 The content of the benzotriazole derivative is arbitrary, but is usually from 10 to 200 parts by weight, preferably from 20 to 10 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably 30 to 70 parts by weight.

 Although the content of the amorphous silica is arbitrary, it is usually 50 to 100 parts by weight, preferably 75 to 70 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably 100 to 500 parts by weight.

The content of the 4-benzyloxy-4 ′-(2-methyldalicydyloxy) diphenylsulfone is arbitrary, but is not limited to 100 parts by weight of the compound represented by the formula (1). On the other hand, it is usually in the range of 10 to 200 parts by weight, preferably 20 to 170 parts by weight, more preferably 30 to 150 parts by weight.

 Although the content of the compound represented by the formula (2) is arbitrary, it is usually 1 Q to 500 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). It is in the range of 10 to 300 parts by weight, more preferably 10 to 100 parts by weight.

 The compound of the present invention represented by the formula (10), and the compound represented by the formula (11) and / or the compound represented by the formula (12) are used as a developer mixture. You. The mixing method includes mixing with each powder, melt mixing, addition and mixing during crystallization of the compound represented by the above formula (10), and o-hydroxylazine as the raw material hydroxylazine. There is a method in which a reaction is performed using a mixture of phosphorus, m-hydroxydirin, p-hydroxydirin and the like, and two or three or more compounds are simultaneously synthesized and contained.

In the formula (1), R ¹ and R ² are each independently a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group, etc. Represents a C1-C6 alkyl group. a ¹ represents an integer of. 1 to 6, n ¹ represents 0, 1 or 2. m ¹ and m ² each independently represent 0 or an integer of 1 to 3, provided that 111 ¹ and 111 ² are not simultaneously 0.

R ³ and R ⁴ are each independently a nitro group; a propyloxyl group; a halogen atom such as fluorine, chlorine, bromine or iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n C 1 -C 6 alkyl groups such as pentyl and n-hexyl groups; C 2 -C 6 alkenyl groups such as probenyl, isopropenyl and butenyl groups; methoxy, ethoxy, n-propoxy, isopropoxy, C1-C6 alkoxy groups such as n-butoxy, sec-butoxy and t-butoxy groups; methylcarbonyl, ethylcarbonyl, n-propyl-lponyl, isopropyl-lponyl, n-butylpropyl, t-butylpropyl and the like C1-C6 alkyl carbonyl group; methoxycarbonyl, X-toxoxycarbonyl, n-propoxyl-propanol, isopropoxyl Poniru represents n- butoxide deer Lupo cycloalkenyl, t one butoxide deer Lupo sulfonyl C 1 through C 6 alkoxy force Lupo two Le groups such as ...

m ³ and m ⁴ each independently represent 0, 1 or 2, and Y ¹ represents CO or NR Represents ^{5 Co.}

R ⁵ is a hydrogen atom; a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, etc .; A phenyl group which may be substituted; a benzyl group which may have a substituent; As a substituent of a phenyl group which may have a substituent and a benzyl group which may have a substituent, a nitro group; a carboxyl group; a halogen atom such as a fluorine, chlorine, bromine or iodine atom; C 1 -C 6 alkyl groups such as, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl; C such as probenyl, isoprobenyl and butenyl 2-C 6 alkenyl group; C 1 -C 6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group; methyl carbonyl, C1-C6 alkyl propylonyl groups such as ethyl carbonyl, n-propyl propylonyl, isopropyl propylonyl, n-butyl propylonyl, t-butyl carbonyl, etc .; C1-C6 alkoxycarbonyl groups such as ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl and t-butoxycarbonyl.

Wherein (1 0), R ^{2 6} and R ^{2 7} are each independently a hydrogen atom; hexyl methyl, E chill, n- propyl, isopropyl, n- butyl, t-butyl, n- pentyl, n- Represents a C1-C6 alkyl group such as a group. a ² represents an integer of. 1 to 6, n ² represents 0, 1 or 2. m ¹⁸ represents 0 or an integer of 1 to 3.

R ^{2 8} and R ^{2 9} are each independently, a nitro group; force Rupokishiru group; fluorine, chlorine, bromine, halogen atom such as an iodine atom; methyl, Echiru, n- propyl, I an isopropyl, n- butyl, t —C 1 -C 6 alkyl group such as butyl, n-pentyl, n-hexyl group; C 2 -C 6 alkenyl group such as propenyl, isoprobenyl, butenyl group; methoxy, ethoxy, n— C1-C6 alkoxy groups such as propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy; methylcarbonyl, ethylcarbonyl, n-propylcapillonyl, isopropylcarbonyl, n-butylcarbonyl, t —C 1 -C 6 alkylcarbonyl group such as butylcarbonyl group; methoxycarbonyl, ethoxycarbonyl, n-propoxyl Represents a C 1 -C 6 alkoxyl group such as luponyl, isopropoxyl-ponyl, n-butoxycarbonyl, and t-butoxyl-carbonyl.

m ¹⁹ and m ² . Each independently represents 0, 1 or 2, and Y ² represents CO or NR ³⁰ C 0.

R ³ Q is a hydrogen atom; a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group; A phenyl group which may have a benzyl group which may have a substituent; As a substituent of the phenyl group which may have a substituent and the benzyl group which may have a substituent, a nitro group; a carbonyl group; a halogen atom such as a fluorine, chlorine, bromine, iodine atom; C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl; propyl, isopropyl, butenyl, etc. C2-C6 alkenyl group; C1-C6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group; methyl carbonyl C :! to C6 alkyl propylonyl groups, such as ethoxypropyl, n-propyl propylonyl, isopropyl propylonyl, n-butyl propylonyl, t-butyl carbonyl, etc .; methoxycarbonyl And C-C6 alkoxycarbonyl groups such as X-ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl and t-butoxycarbonyl.

Wherein ⁽¹ 1), R ³ 1 and R ^{3 2} are each independently a hydrogen atom; methyl, E chill, n- propyl, isopropyl, n- butyl, t - butyl, n- pentyl, n- Represents a C1-C6 alkyl group such as a xyl group. a ³ represents an integer of. 1 to 6, n ³ represents 0, 1 or 2. m ^{2 1} represents an integer of 0 or 1-3.

R ^{3 3} and R ^{3 4} are each independently, a nitro group; force Rupokishiru group; fluorine, chlorine, bromine, halogen atom such as an iodine atom; methyl, Echiru, n- propyl, I an isopropyl, n- heptyl, t C 1 -C 6 alkyl groups such as -butyl, n-pentyl and n-hexyl groups; C 2 -C 6 alkenyl groups such as probenyl, isopropenyl and butenyl groups; methoxy, ethoxy, n-propoxy C 1 -C 6 alkoxy groups such as, isopropoxy, n-butoxy, sec-butoxy, t-butoxy; C1-C6 alkylcarbonyl groups such as rucarbonyl, ethylcarbonyl, n-propylcapillon, isopropylcarbonyl, n-butylcarbonyl, t-butylcarbonyl, etc .; methoxycarbonyl, ethoxycarponyl, n-propoxyproponyl, isopropanol Represents a C 1 -C 6 alkoxycarbonyl group such as a propoxyl-ponyl, n-butoxyl-carbonyl, t-butoxyl-carbonyl group, etc.

m ^{2 2} and m ^{2 3} each independently represent 0, 1 or 2, Y ³ represents CO or NR ^{3 5} C 0.

R ^{3 5} is a hydrogen atom; -; the location substituent methyl, Echiru, n- propyl, isopropyl, n- butyl Le, t-butyl, n- pentyl, C. 1 to C 6 alkyl group such as hexyl group n- A phenyl group which may have a benzyl group which may have a substituent; As a substituent of a phenyl group which may have a substituent and a benzyl group which may have a substituent, a nitro group; a carbonyl group; a halogen atom such as a fluorine, chlorine, bromine or iodine atom; C1-C6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group; C such as propyl, isopropyl, butenyl group 2-C6 alkenyl group; C1-C6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group; methylcarbonyl, ethylcarbonyl A C 1 -C 6 alkyl radical such as n-propyl radical, isopropyl radical, n-butylcarbonyl, t-butylcarbonyl, etc .; Tokishikaruponiru, n- propoxy force Ruponiru, isoproterenol epoxy force Ruponiru, n- Bed Bok Kishikaruponiru, the C. 1 to C 6 alkoxy Cal Poni Le group such as t-Bed Bok Kishikaruponiru group.

Wherein (1 2), R ^{3 6} and R ^{3 7} are each independently a hydrogen atom; hexyl methyl, E chill, n- propyl, isopropyl, n- butyl, t-butyl, n- pentyl, n- Represents a C1-C6 alkyl group such as a group. a ⁴ is an integer of. 1 to 6, n ⁴ represents 0, 1 or 2. m ^{2 4} represents an integer of 0 or 1-3.

R ^{3 8} and R ^{3 9} are each independently, a nitro group; force Rupokishiru group; fluorine, chlorine, bromine, halogen atom such as an iodine atom; methyl, Echiru, n- propyl, I an isopropyl, n- heptyl, t 1-butyl, n-pentyl, n-hexyl, etc. To C 6 alkyl group; C 2 to C 6 alkenyl groups such as propenyl, isopropenyl and butenyl groups; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t — A C 1 -C 6 alkoxy group such as a butoxy group; a C 1 -C 6 alkylcarbonyl group such as a methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, t-butylcarbonyl group; Represents a C 1 -C 6 alkoxycarbonyl group such as carbonyl, X toxiccarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and t-butoxycarbonyl.

111 ²⁵ and 11 ²⁶ each independently represent 0, 1 or 2, and Y ⁴ represents CO or NR ⁴ ° C.

R ⁴⁰ is a hydrogen atom; a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, etc .; A phenyl group which may be substituted; a benzyl group which may have a substituent; As a substituent of the phenyl group which may have a substituent and the benzyl group which may have a substituent, a nitro group; a carbonyl group; a halogen atom such as a fluorine, chlorine, bromine, iodine atom; C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl groups; probenyl, isoprobenyl, butenyl groups, etc. C2-C6 alkenyl group; C1-C6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group; methyl carbonyl, ethyl C1 to C6 alkyl propylonyl groups such as rucarponyl, n-propyl propylonyl, isopropyl propylonyl, n-butyl propylonyl, t-butylcarbonyl group, etc .; C1 to C6 alkoxycarbonyl groups such as ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and t-butoxycarbonyl group.

Among these, in the present invention, in the formula (1), a compound in which Y ¹ is NR ⁵ C〇 is preferable, and a compound in which Y ¹ is NHC 0 is more preferable.

Examples of the compound represented by the formula (1) include N— (2′-hydroxyphenylthio) acetyl-2-hydroxydiline and N— (3′-hydroxyphenyl). Enylthio) acetyl-2-hydroxyaline, N-(4'-hydroxyphenylthio) acetyl-2-hydroxyaniline, N-(2 '-hydroxyphenyl) acetyl-4-hydroxyaniline, N-(3' —Hydroxyphenylthio) acetyl-4—Hydroxyphenyl, N— (4′-hydroxyphenyl) acetyl-4—Hydroxyphenyl, N- (2′-hydroxyphenylthio) acetyl-3-hydroxy Diphosphorus, N— (3′-hydroxyphenylthio) a-cetyl-3-hydroxyhydrin, N— (4′-hydroxyphenylthio) acetyl-3-hydroxycarbinyl and the like.

 Preferred examples of the compound represented by the formula (10) and a mixture of the compounds represented by the formulas (11) and / or (12) include the following (a) to (c). One. .

 (a) N- (4'-hydroxyphenylthio) acetyl-2-hydroxyaniline and N- (4-hydroxyphenylthio) acetyl-4-hydroxyaniline

 (b) N- (4-hydroxyphenylthio) acetyl-2-hydroxyaniline and N- (4-hydroxyphenylthio) acetyl-3-hydroxyaniline

(c) N- (4—hydroxyphenylthio) acetyl-2-hydroxyaniline, N— (4'hydroxyphenylthio) acetyl-4-hydroxyhydrinyl and N— (4'hydroxyphenylthio) Acetyl-3-hydroxylineline In the above formula (2), X ¹ and X ² each independently represent a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group. Group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, methylmethylene group, dimethylmethylene group, ethylmethylene group, methylethylene group, ethylethylene group, 1,2-dimethylethylene group, 1- Methyltrimethylene, 1-methyltetramethylene, 1,3-dimethyl Methylene group, 1-ethyl-4-methyltetramethylene group, vinylene group, propenylene group, 2-butenylene group, ethynylene group, 2-butynylene group, 1 vinylethylene group, ethyleneoxyethylene group, Traramethyleneoxy Tetramethylene group, ethyleneoxyethyleneoxyethylene group, ethyleneoxymethyleneoxyethylene group, 1,3-dioxane-1,5,5-bismethylene group, 1,2-xylyl group, 1,3-xylyl group, 1,4 -Hydroxylyl group, 2-hydroxytrimethylene group, 2-hydroxy-12-methyltrimethylene group, 2-hydroxy-12-ethyltrimethylene group, 2-hydroxy-2-propyltrimethylene group, 2-hydroxy-2- An isopropyl trimethylene group and a 2-hydroxy-2-butyl trimethylene group are exemplified.

R e R ¹¹ is each independently a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group C 1 -C 6 groups such as t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl Alkyl group; pinyl group, aryl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanenyl group, 2-methyl-2-propenyl group, C1-C6 alkenyl groups such as 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1_hexenyl group, 2-hexenyl group, 3-hexenyl group, etc. Is mentioned.

As an example of the compound represented by the formula (2), for example, 4- [4— (4-hydroxyphenylsulfonyl) phenoxy-1-4-butyloxy] -4′-1 [4— (4-hydroxyphenylsulfonyl) ) 1-phenoxy-3-propyloxy] diphenyl sulfone, 4, 4 '-bis [4-(4-hydroxyphenylsulfonyl) phenoxy-2-ethyloxy] diphenyl sulfone, 4, 4' 1bis [4- (4-Hydroxyphenylsulfonyl) phenoxy-1- (3-propyloxy) diphenylsulfone, 4,4'-bis [4- (4-Hydroxyphenylsulfonyl) phenoxy 4-butyloxy] diphenylsulfone, 4,4'-one Bis [4- (4-hydroxyphenylsulfonyl) phenoxy-1-5-pentyloxy] diphenylsulfone, 4,4'-bis [4-(4-hydroxyphenyl) Rusulfonyl) phenoxy — 6-hexyloxy] diphenylsulfone, 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-4-butyloxy] 1-4'-1 [4-(4-hydrogen) Xyphenylsulfonyl) phenoxy-1 2 —ethyloxy] diphenylsulfone, 4-1 [4— (4-hydroxyphenylsulfonyl) phenoxy— 3 _propyloxy] 1 4 ′ — [4-1- (4-hydroxyphenylsulfonyl) ) Phenyloxy 2-ethyloxy] diphenylsulfone, 4, 4 'monobis [4-1 [4-(2-Hydroxyphenylsulfonyl) phenoxy] butyloxy] diphenylsulfone, 4, 4'-bis [4-1 [2- (4-Hydroxyphenylsulfonyl) phenoxy] butyloxy] diphenylsulfone, 1,1-bis [4— (4-hydroxyphenylsulfonyl) phenoxy] methane, 1,2-bis [4— (4-Hydroxyphenylsulfonyl) phenoxy] ethane, 1,3-bis [4 -— (4-Hydroxyphenylsulfonyl) phenoxy] propane, 1, 4-bis [4 -— (4-hydroxyphenylsulfonyl) phenoxy] butane, 1,5-bis [4 -— (4-hydroxyphenylsulfonyl) phenoxy] pentane, 1,6-bis [4— ( 4-hydroxyphenylsulfonyl) phenoxy] hexane;

1,2-bis [4- (4-hydroxyphenylsulfonyl) phenoxy] ethylene, 4,4, —bis [4- [4- (4-hydroxyphenylsulfonyl) phenoxy] 1-2-tributyl Lansbutenyloxy] diphenylsulfone, 4- [4- [4-(4-hydroxyphenylsulfonyl) phenoxy] —2-trans-butenyloxy] 1-4 '-[4- (4-hydroxyphenyl) Enylsulfonyl) phenoxy-1 4-butyloxy] diphenylsulfone, 4- [4- (4-hydroxyphenylsulfonyl) phenoxy-1 2—trans-butenyloxy] —4 '-[4— (4-hydroxyphenylsulfonyl) phenoxy-1 3- [propyloxy] diphenyl sulfone, 4- [4-[4- (4-hydroxyphenylsulfonyl) phenoxy]]-2-trans-butenyloxy]-4 '-[4- (4- (Droxyphenylsulfonyl) phenoxy-l- 2-ethyloxy] diphenylsulfone, 1, 4-bis [4-1 [4-1 [4-1 (4-hydroxydroxyphenylsulfonyl) phenoxy] 2-1 trans-butenyloxy] Enylsulfonyl] phenoxy] cis-1-2-butene, 1,4-bis [4- [4-1- [4- (4-hydroxyphenylsulfonyl) phenoxy-12-trans-butenyloxy] phenylsulfonyl] phenoxy] — trans One—butene: 4,4'-Bis [4— (4-hydroxyphenylsulfonyl) phenoxy] dibutylether, 2,2'-Bis [4-1 (4-hydroxyphenylsulfonyl) phenoxy] getyl ether, 4, 4'-Bis [4 -— (4-hydroxyphenylsulfonyl) phenoxy-1-2-ethyleneoxhetoxy] diphenylsulfone, 2,2'—Bis [4— [4— [4- (4-hydroxyf Enylsulfonyl) phenoxy-1-ethyleneoxyethoxy] phenylsulfonyl] phenoxy] ethyl ether, 2,4'-bis [2— (4-hydroxyphenylsulfonyl) phenoxy-2—ethyleneoxyethoxy] diph Enylsulfone, 2,4'-bis [4-(2-hydroxyphenylsulfonyl) phenoxy-1-2-ethyleneoxyethoxy] diphenylsulfone, 4,4'-bis [ 3,5-Dimethyl-41- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenoxy-1 2—ethyleneoxyethoxy] diphenylsulfone, 4,4'-bis [3-aryl-1-4— (3-aryl-1 4-Hydroxyphenylsulfonyl) phenoxy-1- [2-ethyleneoxy] diphenylsulfone;

 a, a '— bis [4 — (4-hydroxyphenylsulfonyl) phenoxy]-P-xylene,,'-bis [4-(4-hydroxyphenylsulfonyl) phenoxy] 1 m-xylene, ' a 'Bis [4-(4-hydroxyphenylsulfonyl) phenoxy] 1 o-xylene,,'-Bis [4-1 [4-[4-(4-Hydroxyphenylsulfonyl) phenyl 1, 4-phenylenebismethyleneoxy] phenylsulfonyl] phenoxy] 1-p-xylene, a, '-bis [4- [4- [4-(4-hydroxyphenylsulfonyl) phenyl] 1, 4-phenyl Lenbismethyleneoxy] phenylsulfonyl] phenoxy] 1-m-xylene, a, a'-bis [4— [4— [4 -— (4-hydroxyphenylsulfonyl) phenyl 1,4 Lenbismethyleneoxy] phenylsulfo Nil] phenoxy ”o-xylene;

4,4'-bis [4— (4-hydroxyphenylsulfonyl) phenyl 1,4-phenylenemethyleneoxy] diphenylsulfone, 4,4'-bis [4-1- (4- Droxyphenylsulfonyl) phenyl 1,3-phenylenebismethylenoxy] diphenylsulfone, 4,4, —bis [4- (4-hydroxydroxyf) Phenylsulfonyl) phenyl 1,2-phenylenedismethyleneoxy] diphenylsulfone, 4,4'-bis [3,5-dimethyl-41- (3,5-dimethyl-4-hydroxyphenylsulfonyl) phenyl 1,4-Phenylenebismethylenoxy] diphenylsulfone, 4,4'-bis [3,5-dimethyl-4- (3-, 5-dimethyl-4-hydroxyphenylsulfonyl) phenyl-1,3-phenyl 2,4-Diphenylsulfone, 4,4'-bis [3,5-dimethyl-2- (3,5_dimethyl-4-hydroxyphenylsulfonyl) phenyl] -1,2-phenylenedismethylene 4-Diphenylsulfone, 4, 4'-pis [3-arylu 4- (3-hydroxyphenylsulfonyl)-1,4-phenylenebismethyleneoxy] diphenyl Lefon, 4,4'-bis [3-arylyl4- (3-arylyl-4-hydroxydroxyphenylsulfonyl)-1,3'-phenylenebismethyleneoxy] diphenylsulfone, 4,4'-one Bis [3-aryl-4 (3-aryl-1-4-hydroxyphenylsulfonyl) -1-1,2-phenylenebismethyleneoxy] diphenylsulfone;

4,4'-bis [4- (4-hydroxyphenylsulfonyl) phenoxy-1-hydroxypropyloxy] diphenylsulfone, 1,3-bis [4 -— [4-—4- (4- Hydroxyphenylsulfonyl) phenoxy-1 2 -hydroxypropyoxy] phenylsulfonyl] phenoxy] _ 2 -hydroxypropane can be mentioned, and these may be used alone or in combination of two or more. Can also. Among these compounds, a compound in which ¹ and / or ² in the formula (2) is one CH ₂ CH ₂ —0_CH ₂ CH ₂ — or —CH ₂ CH = CH CH ₂ — is preferable.

 The compound represented by the formula (2) can be produced, for example, according to a known method such as the method described in WO97 / 16420.

In the formula (5), R ¹⁴ and R ¹⁵ are each independently a methyl, ethyl, n-butyl pill, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group, etc. A C 1 -C 6 alkyl group; a C 2 -C 6 alkenyl group such as propenyl, isopropyl, butenyl group; an aryl group such as phenyl, naphthyl, and pyridyl group; an aralkyl group such as benzyl and phenethyl group. Represents the aryl and aralkyl groups. The benzene ring, naphthalene ring and pyridine ring may further have a substituent. Examples of such a substituent include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; methyl, ethyl, n-propyl, C 1 -C 6 alkyl groups such as isopropyl, n-butyl, t-butyl, n-pentyl and n-hexyl; C 2 -C 6 alkenyl such as propenyl, isopropyl and butenyl; No.

R ¹⁶ is a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine or iodine atom; C 1 to C- such as methylethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl and n-hexyl group. C 6 alkyl group; represents a C 2 to C 6 alkenyl group such as probenyl, isopropylidene, butenyl group, and m ¹¹ represents 0 or an integer of 1 to 4. Examples of the phthalic acid derivative include dimethyl isophthalate, dimethyl terephthalate, getyl isophthalate, diphenyl isophthalate, dibenzyl terephthalate, etc., and these may be used alone or in combination of two or more. You can also. Among these, dimethyl terephthalate is preferred.

In the formula (6), R ¹⁷ is a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine or iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n— A C 1 -C 6 alkyl group such as a hexyl group; a C 2 -C 6 alkenyl group such as a propenyl, isopropenyl or butenyl group; m ¹² represents 0 or an integer of 1-4;

R ¹⁸ is a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl; propenyl, isoprobenyl A C 2 -C 6 alkenyl group such as a butenyl group; an aryl group such as a phenyl, naphthyl, or pyridyl group; an aralkyl group such as a benzyl group or a phenyl group; a benzene ring, a naphthalene ring, and a pyridine ring of an aryl group and an aralkyl group; It may further have a substituent. Examples of such a substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and n. —C 1 to C 6 alkyl groups such as pentyl and n—hexyl groups; and C 2 to C 6 alkenyl groups such as propenyl, isopropenyl and butenyl groups. That.

Hydroxybenzoic acid derivatives include 4-hydroxymethyl benzoate and 3-hydroxymethylbenzoate. Ethyl hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, and the like. One type or a mixture of two or more types can be used. Among these, benzyl 4-hydroxybenzoate is preferred.

In the formula (7), R ¹⁹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n— Nonyl, n-tesinole, n-indesi, n-doors, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heppudecyl, n -C18 alkyl group; C2-C6 alkenyl group such as probenyl, isoprobenyl, butenyl group; methylcarbonylmethylene, ethylcarbonylmethylene, n-propylcapillonylmethylene, isopropylcarbonylmethylene, methylcarbonyl C 1 -C 6 alkyl C 1 -C 6 alkylene groups such as ethylene, methylcarbonylpropylene, and ethylcarbonylethylene; phenyl Aralkyl groups such as benzyl, phenethyl and the like; R ^{2 ()} represents a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl , N-C 1 -C 6 alkyl group such as hexyl group; C 2 -C 6 alkenyl group such as probenyl, isopropenyl, butenyl group; aryl group such as phenyl, naphthyl, pyridyl group; represents a Ararukiru group such Enechiru group, R ^{2 1} is fluorine, chlorine, bromine, halogen atom such as iodine atom; methyl, Echiru, n - propyl, isopropyl, n - butyl, t - heptyl, n - pentyl, n —C 1 -C 6 alkyl group such as hexyl group; C 2 -C 6 alkenyl group such as probenyl, isopropenyl, butenyl group; methoxy, ethoxy, n C 1 -C 6 alkoxy groups such as propoxy, isopropoxy, n-butoxy, t-butoxy groups; methylcarbonyl, ethylcarbonyl, n-propylcapillonyl, isopropylcaprolponyl, n-butylcarbonyl, t-butylcarbonyl, etc. An aryl group such as a C1-C6 alkylcarbonyl group, phenyl, naphthyl, and pyridyl group; an aralkyl group such as a benzyl group and a phenethyl group; Also, R

^{1 9,} R ^{2 D,} or a substituent represented by R ^{2 1,} Ariru group or Ararukiru group location The substituent may be substituted because the benzene ring, naphthalene ring or pyridine ring of the aryl group or the aralkyl group may further have a substituent, such as fluorine, Halogen atoms such as chlorine, bromine and iodine atoms; C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, and n-hexyl groups; And C 2 -C 6 alkenyl groups such as benzyl, isopropenyl and butenyl groups. m ¹³ represents 0 or an integer of 1 to 5.

 Examples of anilide derivatives include acetoacetate anilide, p—acetotoluidide, o—acetotoluidide, m—acetotoluidide, o—acetoanisidide, m—acetoanisidide, p—acetoanisidide, and N—acetoacetide. Triluidine, N-acetoacetyl-m-Truidin, N-acetoacetyl-p-toluidine, N-methylacetoanilide, 0-acetoacetanilidide, m-acetoacetinide , P-acetoacenicidide, stearic acid anilide and the like, and these can be used alone or in combination of two or more. Among these, p-acetotoluzide is preferred.

Wherein (8), R ^{2 2} and R ^{2 3} are each independently a hydroxyl group, a force Rupokishiru group; methyl, Echiru, n - propyl, isopropyl, n- butyl, t one heptyl, n- pentyl, n - C 1 -C 6 alkyl group such as hexyl group; C 2 -C 6 alkenyl group such as propenyl, isoprobenyl, butenyl group; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , T — C 1 -C 6 alkoxy group such as butoxy group; methyl C -C 6, such as methyl carbonyl, ethyl carbonyl, n-propylcarbonyl, isopropyl carbonyl, n-butyl carbonyl, t-butyl carbonyl Alkyl carboxy group; methyl carboxy, n-propyl oxy, n-propyl oxy, isopropyl oxy, n-butyl carbonyl C 1 -C 6 alkyl groups such as ethoxy, t-butylcarbonyloxy groups, etc .; roponyoxy groups; optionally substituted aryl groups (such as phenyl, naphthyl, pyridyl groups); 7 represents an aralkyl group (such as a benzyl or phenethyl group), and the aryl group or the aralkyl group may have a substituent, for example, a benzene ring, a naphthalene ring, or a pyryl group of the aryl group or the aralkyl group. The gin ring may further have a substituent. As such a substituent, a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc .; And C 2 -C 6 alkenyl groups such as benzyl, isopropenyl and butenyl groups. m ¹⁴ and m ¹⁵ each independently represent 0 or an integer of 1 to 5;

 Examples of the biphenyl derivatives include biphenyl, 2,2′-biphenyl, 4,4′-biphenyl, 4,4′-diacetoxybiphenyl, 4-acetoxybiphenyl, 4-acetylbiphenyl, 4-methoxybiphenyl, 4,4'-Diacetyl biphenyl, 4,4'-Dimethyl biphenyl, 4-benzylbiphenyl, m-Ethyl phenyl, etc. These may be used alone or in combination of two or more. Can also be used. Among these, 4-acetylbiphenyl is preferred.

Wherein (9), R ^{2 4} and R ^{2 5} are each independently a hydroxyl group; fluorine, chlorine, a bromine, a halogen atom such as an iodine atom; methyl, Edjiru, n- propyl, isopropyl, n - butyl, C 1 -C 8 alkyl groups such as t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl; propyl and isopropyl C 2 -C 6 alkenyl groups such as enyl and butenyl groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec—butoxy, t-butoxy, pentoxy, hexoxy, heptoxy, octoxy groups represents C. 1 to C 8 alkoxy group such as, m ^{1 6} is an integer of 0 or from 1 to 4, m ^{1 7} represents an integer of 0 or 1-5.

Benzotriazole derivatives include 2- (2, -hydroxy-5'-methylphenyl) benzotriazole, 2- (2, -hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'- Hydroxy—3 ', 5'-di-1: monobutylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-clobenzobenzotriazole, 2-((2'-hydroxy-3 ', 5'-di-t-butylphenyl) -15-chlorobenzotriazole, 2- (2'-hydroxy-13', 5'-d-amylphenyl) benzotriazo 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-1,3- (3 ", 4", 5 ", 6, '- Tetrahydrophthalimidome Tyl) 1 5'-methylphenyl] benzotriazole, 2,2'-methylenebis [4-1 (1,1,3,3-tetramethylbutyl) 16- (2H-benzotriazole-1-2-yl)] Phenol, 2 (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2-benzotriazolyl) —: — cresol, 2- (5—chloro-2—benzotriazoli 1) 6-t-butyl-p-cresol, 1- [3,5-di (2H-1,2,3-benzotriazole-2-yl) 1,2,4-dihydroxyphenyl] ethane- 1-one, 2- (2H-benzotriazole-l-yl) -1 6-dodecyl- 4-methylphenol, 2- (2H-benzotriazole-1-2-yl) 1-4, 6- Bis (1-methyl-1-1-phenylethyl) phenol, 2,2'-methylenebis [6 — (Benzotriazol-2-yl)-4-t-octylphenol], 4-butoxybenzoic acid 2 —benzotriazole-2-yl-phenyl ester, 4-methyl-benzoic acid 2— Benzotriazole-2-yl 4-methyl-phenyl ester, furan-2-carbonic acid 2-benzotriazo-l-yl 2-yl-4-methyl-phenyl ester, 2,4-dichloro-benzoic acid 2-benzotriazole-2-yl- 4-Methyl-phenyl ester 2- (2H-benzotriazole-2-yl) -1-4-methyl-6- (2-probenyl) -phenol, toluene-4-sulfonic acid 2-benzotriazo- 2- 2-yl 4-methyl monophenyl ester, 2- (2'-methacryloxy- 1 5'-methylphenyl) benzotriazole, 3-phenylcarbamoyl-benzenes 2-Henic acid 2-benzotriazole-2-yl-4-methyl-phenyl ester. 2- [2, -hydroxy-1- 3 ', 5'-bis (a, α-dimethylpentyl) phenyl -] 2-benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-pandecyl-5,1-methylphenyl) Benzotriazole, 2 — (2'-hydroxy-1 3'-tridecyl-5'-methylphenyl) benzotriazol, 2- (2'-hydroxy-3'-tetradecyl-5'-methylphenyl) benzotriazole, 2 — (2'-hydroxy-3'-pentadecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-hexadecyl-5'-methylphenyl) benzotriazole 2- [2 '- Non-Dorokishi 4' single (2 '' - E Tylhexyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-1 -'- (2 ''-ethylheptyl) oxyphenyl] benzotriazole, 2-[2'-hydroxy 4 '-(2''—Ethyloctyl) oxyphenyl] benzotriazole, 2 — [2'-hydroxy-4'-(2 ''-propyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(2 "-propyl Butyl) oxyphenyl] benzotriazole, 2-1 [2'-hydroxy- 4 '-(2''-propylhexyl) oxyphenyl] benzotriazole, 2 — [2'-hydroxy-4'- (1 "-ethylhexyl) oxyphenyl] benzotriazole, 2- [2, -hydroxy-1 4 '-(1'"-ethylheptyl) oxyphenyl] benzotriazole, 2 — [2 ' —Hydroxy 4 ′-(1′—ethyloctyl) oxyphenyl) benzotriazole, 2— [2 * -Hydroxy-1 4 ′-(1 ′ ′ — propyloxy) oxyphenyl] benzotriazole, 2- [2′- Hydroxy-4 '-(1 "-propylheptyl) oxyphenyl] benzotriazole, 2- [2'-Hydroxy-1 4'-(1" -propylhexyl) oxyphenyl] benzotriazole, etc. These can be used alone or in combination of two or more.

Among them, the compound represented by the formula (9) is preferable. As the compound represented by the formula (9), 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- ( 2'-Hydroxy- 5'-t-Butylphenyl) benzotriazole, 2- (2'-Hydroxy-3,, 5'-T-butylbutyl) benzotriazole, 2- (2, —Hydroxy-1 3 ′ —t—Butyl_5, —Methylphenyl) -1 5 Monobenzobenzotriazole, 2— (2′—Hydroxy 3 ′, 5 ′) — T—Butylphenyl) 1-5—Black Benzotriazole, 2 — (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-4, —octoxyphenyl) benzotriazole, 2 — (2'-hydroxy-1 5'-t-octylph Nyl) benzotriazole, 2-((2-benzotriazolyl) -r-ρ-cresol, 2- (5-chloro-2-benzotriazolyl) -6-t-petit-ru-p-cresol, 2- ( 2 H—Venzotriazo-1-yl) —4-Methyl—6— (2-Propenyl) —Phenol, 2— (2-Benzotria Zolyl) -p-cresol or 2- (2'-hydroxy-3 ', 5'-di_t-butylphenyl) benzotriazole is more preferred.

 The present invention contains at least one kind of the coloring dye and at least one kind of the compound represented by the formula (1), and further comprises a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, and a biphenyl derivative. Derivatives, benzotriazole derivatives, amorphous silicic acid, at least one compound selected from the group consisting of 4-benzyloxy-4 '-(2-methyldaricyloxy) diphenylsulfone and the compound represented by the formula (2). Any kind of recording material containing one kind can be used for any purpose. For example, it can be used as a heat-sensitive recording material or a pressure-sensitive copying material.

 The color-forming dye used in the recording material of the present invention is not particularly limited as long as it is a color-forming dye that forms a color when it comes into contact with a developer which is an acidic substance. Specific examples thereof include leuco dyes such as fluoran, phthalide, lactam, 1, phenylmethane, phenothiazine and spiropyran.

Examples of the fluoran-based color-forming dyes include, for example, 3- (ethylethylamino 6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, and 3- (N-ethyl-1-N-isobutylamino) 6—Methyl—7—A Nilinofluoran, 3— (N—Methyl-N—Propylamino) 1 6—Methyl-1 7-Anilinofluoran, 3 -— (N—Ethylu N—Isopentylamino) — 6—Me Cyl-1 7-anilinofluorane, 3-Jetylamino-1 7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-(N-ethyl-p-toluidino 1) 6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) 1-6-methyl-1 7-anilinofluoran, 3-pyrroli 1-6-methyl-1 7-anilinofluoran, 3—piperidino-1 6-methyl-7-anilinofluoran, 3 —dimethylamino-7— (m-trifluoromethylanilino) fluoran, 3 —Dipentylamino 6 —Methyl-1 7—anilynofluoran, 3- (N—ethoxypropyl-1-N—ethylamino) -1-6-methyl-7—anilynofluoran, 3 —Dibutylamino-1 7— (o—fluoroanilino) fluoran, 3 —Jetylaminobenzo [a] fluoran, 3-dimethylamino-6—methyl_7—black fluoran, 3-methylethylamino-5-methyl Cyl-1 7-dibenzylamino fluoran, 3-Jethylamino 7-dibenzylamino fluoran, 3-Jetylamino 5-cloth fluoran, 3-Jetylamino 6- (N, Ν'-dibenzylamino) fluoran, 3,, 6-Dimethoxyfluoran, 2,4-dimethyl-6- (4-dimethylaminophenyl) aminofluoran and the like.

 Examples of phthalide-based coloring dyes include 3- {4- [4- (4-anilino) -anilino] anilino} —6-methyl-7-chloro fluoran and 3,3-bis [2-1- (4-dimethylaminophenyl) _2 -— (4-methoxyphenyl) vinyl] 1,4,5,6,7-tetrachlorophthalide, 3,6,6 'tris (dimethylamino ) Spiro (fluorene-9,3'-phthalide), 3,3-bis (4'-getylaminophenol) -16-getylaminophthalide.

Among these, 3-ethylamino-1-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7_anilinofluoran, and 31- (methylethyl-1-isobutylamino) 16-methyl-17-anili No-fluoran, 3- (Ν-methyl-Ν-propylamino) 1- 6-methyl-1-7-anilino-fluoran, 3 -— (Ν-ethyl-Ν-isopentylamino)-6-methyl-7-anilino-fluoran, 3-—ethylamino — 7 — (ο-chloroaniline) fluoran, 3-dibutylamino — 7— (ο-chloroaniline) fluoran, three-one (Ν-ethyl-1 ρ-tolyzino) 1-6 —methyl-7 —Anilinofluoran, 3 — (cyclohexyl-1-methylamino) -1-6-methyl-7 —anilinofluoran, 3-pyrrolidino-16 Methyl-7-anilinofluoran, 3—piperidino-1-6-methyl-7-anilinofluoran, 3-dimethylamino-7- (m-trifluoromethylanilino) fluoran, 3-dibenflamino-1-6-methyl- 7-anilinofluorane, 3- (N-ethoxypropyl-N-ethylamino) 1-6-methyl-1 7-anilinofluoran, 3-dibutylamino 7- (o-fluoroanilino) fluoran, 3-diethylamino Novenzo [a] fluoran, 3-dimethylamino 6-methyl-7-methyl fluoran, 3-getylamino-5-methyl-7-dibenzylamino fluoran, 3—getylamino 7-dibenzylamino fluoran, 3 —Jechirami No 5—Black mouth fluoran, 3—Jetylamino 6— (N, N'—Jibe Fluorane-based coloring dyes such as fluoran, fluoran, 3,6-dimethoxyfluoran, and 2,4-dimethyl-6- (4-dimethylaminophenyl) aminofluorane are preferable, and 3-getylamino-6-methyl-7 —Anilinofluoran, 3 —dibutylamino— 6 —methyl-7 —anilinofluoran, 3— (N—ethyl-N—isobutylamino) -1-6-methyl-7-anilinofluoran, 3- (N—methyl-1-N—propylamino) 1 6 —methyl-7 —anilinofluorane, 3— (N—ethyl-1 N—isopentylamino) 1—6—methyl-1 7 —anilinofluoran, 3 — (N—cyclohexyl-1 N—methylamino) — 6—methyl 7-Anilinofluorane is more preferred.

 Of course, these coloring dyes can be used alone to obtain a recording material of the coloring color, but two or more of them can be used in combination. For example, a recording material that develops a true black color can be manufactured by using a mixture of three primary color developing dyes of red, blue, and green or a black dye.

 The recording material of the present invention includes a coloring dye, a compound represented by the above formula (1), a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, a biphenyl derivative, a benzotriazole derivative, and an amorphous compound. Silica, 4-Benzyloxy-4 '-(2-methyldaricyloxy) diphenylsulfone and the compound represented by the formula (2), as well as known head colorants, image stabilizers, and sensitizers One, two or more kinds of fillers, dispersants, antioxidants, desensitizers, anti-adhesives, defoamers, light stabilizers, optical brighteners and the like can be contained as necessary.

 These chemicals may be contained in the color-forming layer. However, in the case of a multilayer structure, they may be contained in any layer such as a protective layer. In particular, when an overcoat layer or an undercoat layer is provided above and / or below the coloring layer, these layers may contain an antioxidant, a light stabilizer and the like. Further, an antioxidant and a light stabilizer can be contained in these layers in a form encapsulated in microcapsules as necessary.

Other developers include those for heat-sensitive recording materials and those for pressure-sensitive recording materials. The former includes, for example, bisphenol A, 4, 4'-sec-butylidene bisphenol, 4, 4 '—cyclohexylidenebisphenol, 2,2 1-dimethyl-3,3-bis (4-hydroxyphenyl) butane, 2,2'-dihydroxydiphenyl, pentamethylene-bis (4-hydroxybenzoate), 2 _: 2 mono-dimethyl-3,3-di Bisphenol compounds such as (4-hydroxyphenyl) pentane, 2,2-di (4-hydroxyphenyl) hexane; 4,4'-dihydroxy-opened xidiphenylthioether, 1,7-di (4-hydroxy Phenylthio) ―3,5-dioxaheptane, 2,2'-bis (4-hydroxyphenylthio) diethyl ether, 4,4'dihydroxy-3,3'-dimethyldiphenylthioether Bisphenol compound;

 Metal salts of benzoic acid such as zinc benzoate, zinc 4-benzotobenzoate, etc. Salicylic acids such as 4- [2- (4-methoxyphenyloxy) ethyloxy] salicylic acid; zinc salicylate, bis [4-1] (Octyloxycarponylamino) I 2 -hydroxybenzoic acid] Metal salt of salicylic acid such as zinc;

4,4'-dihydroxydiphenylsulfone, 2,4'dihydroxydiphenylsulfone, 4-hydroxy-1 4'-methyldiphenylsulfone, 4-hydroxy-1 4'-isopropoxydiphenylsulfone, 4-hydroxy- 4 ', 1-butoxydiphenyl sulfone, 4,4'-dihydroxy-1,3,3'-diaryldiphenyl sulfone, 3,4-dihydroxy-1 4'-methyldiphenyl sulfone, 4,4'-dihydroxy-1 3 Hydroxysulfones such as 3,3 ', 5,5'-tetrabromodiphenylsulfone; 4-Hydroxy such as dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate, and diphenylhexyl 4-hydroxyphthalate. 2-hydroxyphthalic acid diesters; 2-hydroxy-6-esters of hydroxynaphthoic acid such as carboxynaphthalene Trihalomethyl sulfones such as tribromomethylphenylsulfone; sulfonyl pereas such as 4,4, -bis (-toluenesulfonylaminocarbonylamino) diphenylmethane; hydroxyacetophenone, p-phenylphenol, Examples include benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroxyquinone-monobenzyl ether, 2,4-dihydroxy-12'-methoxybenzanilide, tetracyanoquinodimethane and the like. Further, as a developer for the pressure-sensitive recording material, for example, acid clay, activated clay, avatargite, bentonite, colloidal silica, aluminum silicate, magnesium silicate Inorganic acidic substances such as nesidum, zinc silicate, tin silicate, calcined kaolin, and talc; aliphatic sulfonic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, and stearic acid; benzoic acid, P—t —Butyl benzoic acid, phthalic acid, gallic acid, salicylic acid,

3-Isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5 .-Di-t-butylsalicylic acid, 3 _methyl-5-benzylsalicylic acid, 3 -phenyl- 5— (2,2 —Dimethylpentyl) salicylic acid, 3,5-di- (2-methylbenzyl) salicylic acid, 2-hydroxy-11-benzyl-1-aromatic carboxylic acid such as naphthoic acid; zinc of these aromatic carboxylic acids, Metal salts such as magnesium, aluminum, and titanium; phenolic resin-based developers such as p-phenylphenol-formalin resin and p-butylphenol-acetylene resin; these phenolic resin-based developers and the above fragrances And mixtures thereof with a metal salt of an aromatic carboxylic acid.

 Other image storage stabilizers include, for example, epoxy group-containing diphenylsulfones such as 4,4′-diglycidyloxydiphenylsulfone; 1,4-diglycidyloxybenzene, and 4- [a- (hydroxymethyl) benzyloxy ] — 4 '—Hydroxydiphenyl sulfone, 2-propanol derivative, salicylic acid derivative, oxynaphthoic acid derivative metal salt (especially zinc salt), 2,2,2-methylenebis (4,6-t-butylphenyl) phosphate And other water-insoluble zinc compounds.

 Other sensitizers include, for example, higher fatty acid amides such as stearate amide; benzamide, thioacetamide; dibenzyl oxalate, dioxalate (4-methylpentyl), dioxalate (4 —Cross-opening benzyl), bis (t-butylphenol) s; diphenylsulfone and its derivatives; 4,4′dimethoxydiphenylsulfone, 4,4′diethoxydiphenylsulfone, 4,4 ′ — Dipropoxydiphenylsulfone, 4,4'diisopropoxydiphenylsulfone, 4,4'-dibutoxydiphenylsulfone, 4,4'diisobutoxydiphenylsulfone,

4,4'-dihydroxydiphenylsulfone, such as 4,4'-dipentyloxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, etc .; 2,4, dimethoxydiphenylsulfone, 2 , .4 'One Jet Nyl sulfone, 2, 4 'dipropoxy diphenyl sulfone, 2, 4' diisopropoxy diphenyl sulfone, 2, 4 'dibutoxy diphenyl sulfone, 2, 4' diisobutoxy diphenyl sulfone, 2, 4 'Diethers of 2,4'-dihydroxydiphenylsulfone such as dipentyloxydiphenylsulfone, 2,4,1-dihexyloxydiphenylsulfone;

 1,2-bis (phenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,2-bis (3-methylphenoxy) ethane, 2-naphthylbenzyl ether, diphenylamine, carbazole, 2,3- Di-m-tributylbutane, di] 3-naphthylphenylenediamine, 1-hydroxy-naphthenyl phenyl phenate, 21-naphthylbenzyl ether, 4—methylphenylloop phenyl ether, 2,

2-bis (3,4-dimethylphenyl) ethane; 2,3,5,6-tetramethyl-14'-methyldiphenylmethane; diphenyl carbonate;

 Other fillers include, for example, silica, clay, kaolin, sintering power, talc, satin white, aluminum hydroxide, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium silicate, aluminum silicate, Plastic pigments and the like. Among them, preferred are salts of alkaline earth metals, and more preferred are carbonates such as calcium carbonate and magnesium carbonate.

 Examples of the dispersing agent include sulfosuccinates such as dioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfate, and fatty acid salt.

 Antioxidants include, for example, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2, -methylenebis (4-ethyl-6-t-butylphenol), 4,4′-propylmethylene Bis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-t-butyl-5-methyl) 1,1,3—tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,

3-tris (2-methyl-1-hydroxy-5-cyclohexylphenyl) butane, 4- {4-[1,1-bis (4-hydroxyphenyl) ethyl] —a, a- Dimethylpenyl} phenol.

 Examples of the desensitizer include aliphatic higher alcohols, polyethylene glycol, guanidine derivatives and the like.

 Examples of the antiadhesive include stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax, ester wax and the like. · As light stabilizers, besides benzotriazole derivatives, salicylic acid UV absorbers such as phenylsalicylate, Pt-butylphenylsalicylate, and p-octylphenylsalicylate; 2,4-dihydroxybenzophenone , 2-hydroxy 1-4-methoxybenzophenone, 2-hydroxy 4-benzyloxybenzophenone, 2-hydroxy 4-octyloxybenzophenone, 2-hydroxy 4-dodecyloxy Benzophenone, 2, 2'-dihydroxy-1-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-14-methoxy-1 5-sulfobenzo Benzophenone ultraviolet rays such as phenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane Absorbent; cyanoacrylate ultraviolet absorbers such as 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-1,3,3-diphenylacrylate; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, monobis (2,2,6,6-tetramethyl-4_piperidyl) succinate, 2- (3,5-di-t-butyl) ester ) Hindered amine UV absorbers such as monobis (1,2,2,6,6—pentamethyl-1-piperidyl) malonate; 1,8-dihydroxy-2-acetyl-3-methyl-6-methoxynaphthalene Can be mentioned.

Examples of optical brighteners include 4,4'-bis [2-anilino-4-1 (2-hydroxyshethyl) amino-1,3,5-triaziruyl-6-amino] stilbene 1-2,2'- Disulfonic acid = disodium salt, 4, 4'-bis [2-anilino-14-bis (hydroxyethyl) amino-1,3,5-triazinyl-1 6-amino] stilbene -1,2,2'-disulfonic acid = 2 Sodium salt, 4, 4'-bis [2-Methoxy 4- (2-hydroxyshethyl) amino-1,3,5-triazirule 6-amino] stilbene 1,2,2'-disulfonate = disodium salt, 4,4'-bis [2-methoxy-14- (2-hydroxypropyl) amino-1,3,5-triazinyl 6-amino] stilbene-1,2,2'-disulfonic acid = ninatriamium salt, 4,4'-bis [2-m-sulfoarilino-1,4-bis (hydroxyxethyl) amino-1,3-, 5- Triazinyl-1-6-amino] stilbene-2,2, -disulfonic acid = disodium salt, 4- [2—p-sulfoarilino-14-bis (hydroxyxethyl) amino-1,3,5—triazinyl-6 —Amino] 1 4 '1 [2-m-Sulfoa 2 lino 14 1 bis (hydroxyethyl) amino-1,3,5—triazidinu 6-amino] stilbene 2, 2' -Disulfonic acid = 4 Sodium salt, 4, 4'-bis [2—p-sulfoarilino-4 Bis (hydroxymethyl E chill) amino - 1, 3, 5 - triazinyl one 6-Amino] stilbene one 2, 2, One disulfo phosphate = tetrasodium salt,

 4,4'-Bis [2— (2,5—disulfoalumino) -1-4-phenoxyamino—1,3,5-triadinyl-6—amino] stilbene-1 2,2'—Disulfonic acid = Hexasodium salt, 4,4'-bis [2— (2,5-disulfoalinelino) _4-1 (p-methoxycarbonylphenoxy) amino-1,3,5—triazinyl-6-amino] stilbene 1,2'-disulfonic acid = hexasodium salt, 4,4'-bis [2- (p-sulfophenoxy) -14-bis (hydroxyxethyl) amino-1,3,5-triazirone 6-amino Stilbene 1, 2'-disulfonic acid = tetrasodium salt, 4,4'-bis [2— (2,5-disulfoarinino) 1-4 1formalinylamino-1,3,5—triaziniru 6 —Amino] stilbene-1,2'-disulfonic acid = hexasodium salt, 4, 4 ' Bis [2- (2,5-di-sulfoarilino) -14-bis (hydroxyxethyl) amino-1,3,5-triazinyl-6-amino] stilbene-2,2'-disulfonic acid = hexasodium salt No.

Each of the above-mentioned color developers, image stabilizers, sensitizers, fillers, dispersants, antioxidants, desensitizers, anti-adhesives, defoamers, light stabilizers, fluorescent brighteners, etc., is used alone. Alternatively, two or more kinds can be used in combination. The amount of each is usually 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of the chromogenic dye. You.

 The recording sheet of the present invention has a recording material layer formed by using the recording material of the present invention on a base sheet. Examples of the base sheet include a paper base sheet, a synthetic resin film or a synthetic resin sheet. Paper base sheets include, for example, thin paper, craft paper, titanium paper, phosphor paper, paperboard, woodfree paper, coated paper, art paper, parchment paper, dalasin paper, parchment paper, paraffin paper, Recycled paper and the like. Examples of the synthetic resin film or sheet include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene monoacetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, and polyethylene na. Examples include films or sheets of phthalate, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, and polycarbonate. Among these, the use of a paper base sheet is preferred. The thickness of the base sheet is not particularly limited. 5500 m.

The recording material layer can be formed, for example, by applying a solution or dispersion of the recording material on a base sheet by a known coating method. The amount of coating depends on the concentration of the solution or dispersion of the recording material, but is usually 0.1 OO g Zm ² after drying, preferably; It is in the range of ~ ² 0 g / m 2.

 Examples of the method of applying the solution or dispersion of the recording material of the present invention on a substrate sheet include a roll coating method, a curtain flow coating method, a myaba coating method, a reverse coating method, a gravure coating method, and a gravure reverse coating method. Air-knife coat method, kiss coat method, blade coat method, smooth coat method, roll knife coat method and the like.

Further, the recording material layer may be formed directly on the base material sheet, may be formed by interposing another layer such as an anchor coat layer, or a protective layer may be further provided on the recording material layer. It can also be formed. Such an anchor coat layer and a protective layer can be formed from a solution or a dispersion containing one or more of known synthetic resins, and include the above-mentioned other developers, other image stabilizers, and other photosensitive materials. Agents, other fillers, dispersants, antioxidants, desensitizers, anti-adhesives, defoamers, light stabilizers, optical brighteners, etc. Can be.

 Among these, the recording sheet of the present invention is preferably a thermosensitive recording paper / a pressure-sensitive copying paper. The thermosensitive recording paper is prepared, for example, by dispersing fine particles of a color-forming dye and fine particles of a recording material in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose, and preparing a dispersion. It can be manufactured by coating on a material sheet and drying.

 For the pressure-sensitive copying paper, for example, a chromogenic dye microencapsulated by a known method is dispersed with an appropriate dispersant to prepare a chromogenic dye dispersion, and the dispersion is placed on the first paper base sheet. To form a color developing dye sheet, while a developer dispersion is applied to a second paper base sheet to form a color developer sheet, and the obtained sheets are combined. To produce pressure-sensitive copying paper. At that time, the recording material of the present invention is dispersed in one or both of the color dye dispersion and the developer dispersion.

 The pressure-sensitive copying paper is composed of an upper paper having a microphone opening capsule containing an organic solvent solution of a color-forming dye applied and carried on the lower surface, and a lower paper having a developer (acidic substance) applied and carried on the upper surface. Or a so-called self-content paper in which microcapsules containing an organic solvent solution of a chromogenic dye and a developer are applied on the same paper surface. There may be. Examples of the developer include those similar to those listed as usable as the developer for the pressure-sensitive recording material. Brief invention of drawings:

 FIG. 1 is a graph showing the results of a comparative test of dynamic color sensitivity (Test Example 1). FIG. 2 is a graph showing the results of a comparative test in the near infrared absorption region (Test Example 4). FIG. 3 is a graph showing the results of a comparative test of dynamic color sensitivity (Test Example 5). FIG. 4 is a graph showing the results of a dynamic color sensitivity comparison test (Test Example 10). BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to examples. It is not limited. Unless otherwise specified, “parts” means “parts by weight”. The image density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD_514, filter used: # 106, manufactured by Macbeth). Example 1 (Preparation of thermal recording paper)

 First, dispersions (A to D liquids) containing the following components were prepared. However, each component used was sufficiently crushed with a sand grinder.

 • Dye dispersion (Solution A) ''

 3—Di-n-butylamino-6-methyl-7-anilinofluoran 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts

• Developer dispersion (Solution B)

 Mixture of 8 parts of N- (4'-hydroxyphenythio) acetyl-2-hydroxyhydroxylinine and 8 parts of N- (4'-hydroxyphenythio) acetyl-14-hydroxyaniline (W 00 2/8 1 It was synthesized according to the method of Synthesis Example 4 described in JP-A-229-209.)

 Polyvinyl alcohol 10% aqueous solution 8 4 parts

• Auxiliary dispersion (liquid C)

 Dimethyl terephthalate 16 parts Polypinyl alcohol 10% aqueous solution 8 4 parts

• Filler dispersion liquid (D liquid)

 Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 7 1 part These dispersions were mixed with 1 part by weight of liquid A, 2 parts by weight of liquid B, 1 part by weight of liquid C, and 4 parts of liquid D. The mixture was mixed in parts by weight to prepare a coating solution of a recording material for thermal recording paper.

 Next, the coating liquid for the recording material was applied to a wire rod (trade name: wire bar, No.

1 2, Webster Co., Ltd.) (applied amount == about 5.

After drying at 5 g / m ² ), the sheet was calendered to produce a thermal recording paper. As a result of visually observing the obtained thermal recording paper, no background capri was observed. Comparative Example 1

 A recording material was prepared in the same manner as in Example 1 except that di (4-methylbenzyl) oxalate was used in place of the dimethyl terephthalate in the auxiliary dispersion (liquid C) of Example 1. Then, a thermal recording paper was made. Test example 1 (dynamic color sensitivity)

試験例 2 (画像耐光性試験） A part of the heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was cut out and used as each test paper. For each test paper, use a thermal paper coloring tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) at 0.38 and 0.50 mJ per dot. Heat was applied to develop a saturated checkerboard pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 1 and FIG. Table 1 (Measurement results of dynamic color sensitivity)

Test Example 2 (Image light fastness test)

試験例 3 (地肌耐熱性試験） A part of the heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was cut out, and saturated coloring was performed in the same manner as in Test Example 1. Next, the saturated color image was subjected to a light fastness tester (trade name: Ultraviolet Long Life Fed Dome Ichiyo FAL-5, manufactured by Suga Test Machine Co., Ltd.) to obtain a wavelength of 380. The image density (Macbeth value) of each test paper was measured 24 hours and 72 hours after irradiation with ultraviolet light of nm. Table 2 shows the measurement results and the residual ratio (= image density (after the test) and image density (before the test) XI 00). Table 2 (Results of image light resistance test measurement)

Test Example 3 (Skin heat resistance test)

 A part of the thermal recording paper prepared in Example 1 and Comparative Example 1 was cut out, and each test paper was subjected to a constant temperature incubator (trade name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 0 ° C., 100 ° C. and 110 for 24 hours.

試験例 4 (近赤外線吸収測定試験） The skin density (Macbeth value) was measured after holding for 24 hours in a constant temperature incubator. Table 3 shows the measurement results. Table 3 (Surface heat resistance test measurement results)

Test example 4 (Near infrared absorption measurement test)

実施例 2 A part of the heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was cut out, and saturated coloring was performed in the same manner as in Test Example 1. Then, the saturated color image was measured with a self-recording altimeter (U-340, manufactured by Hitachi, Ltd.). Table 4 shows the results. FIG. 2 shows an example of the measurement chart (500 nm to 800 nm). Table 4 (Near infrared absorption measurement results)

Example 2

Instead of dimethyl terephthalate in the auxiliary agent dispersion liquid (liquid C) of Example 1, 4-hid A recording material was prepared in the same manner as in Example 1 except that benzyl roxybenzoate was used, and a thermal recording paper was prepared. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed. Test example 5 (dynamic color sensitivity)

試験例 6 (画像耐光性試験） A part of the heat-sensitive recording paper prepared in Example 2 and Comparative Example 1 was cut out and used as each test paper. For each test strip, use a thermal paper color tester (trade name: TH-PMD type, manufactured by Oshoku Denki Co., Ltd.), and apply 0.38 and 0.50 mJ per dot. Then, heat was applied to cause saturated color development of the checkerboard pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-5514, manufactured by Macbeth). The results are shown in Table 5 and FIG. Table 5 (Results of measurement of dynamic color sensitivity)

Test Example 6 (Image light fastness test)

 A part of the heat-sensitive recording paper prepared in Example 2 and Comparative Example 1 was cut out, and saturated color development was performed in the same manner as in Test Example 5. Next, the saturated color image was subjected to a light fastness tester (trade name: UV long life feeder FAL-5, manufactured by Suga Test Instruments Co., Ltd.) to obtain a wavelength of 38. The image density (Macbeth value) of each test paper 24 hours and 72 hours after irradiation with 0 nm ultraviolet light was measured. Table 6 shows the measurement results and the residual ratios (= image density (after the test) and image density (before the test) XI 00). Table 6 (Results of image light resistance test measurement)

24 hours after irradiation 7 hours after irradiation Original Macbeth value Residual rate (%) Macbeth value Residual rate (%) Example 2 1.30 1.25 96 1.19 89 Comparative example 1 1.28 1.18 92 1.06 83 Example 3

 A recording material was prepared in the same manner as in Example 1 except that p-acetotoluid was used instead of dimethyl terephthalate in the auxiliary agent dispersion liquid (liquid C) of Example 1. Thermal recording paper was made. As a result of visual observation of the obtained heat-sensitive recording paper, no background blur was observed. Test Example 7 (Dynamic color sensitivity)

試験例 8 (地肌耐熱性試験） A part of the heat-sensitive recording paper prepared in Example 3 and Comparative Example 1 was cut out and used as each test paper. For each test paper, use a thermal paper coloring tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) at 0.38 and 0.50 mJ per dot. Heat was applied to develop a saturated checkerboard pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 7. Table 7 (Measurement results of dynamic color sensitivity)

Test Example 8 (Skin heat resistance test)

 A portion of the thermosensitive recording paper prepared in Example 3 and Comparative Example 1 was cut out, and each test paper was heated at a constant temperature and constant temperature (trade name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 90 and at 100 ° C. for 24 hours.

試験例 9 (画像耐光性試験） The skin density (Macbeth value) was measured after holding for 24 hours in a constant temperature incubator. Table 8 shows the measurement results. Table 8 (Surface heat resistance test measurement results)

Test Example 9 (Image light fastness test)

実施例 4 A part of the thermosensitive recording paper prepared in Example 3 and Comparative Example 1 was cut out, and saturated color development was performed in the same manner as in Test Example 7. Then, using the light resistance tester (trade name: UV long life feed meter FAL-5, manufactured by Suga Test Instruments Co., Ltd.) for the saturated color-developed image, an ultraviolet ray having a wavelength of 380 nm was used. The image density (Macbeth value) of each test paper was measured 24 hours and 72 hours after irradiation. Table 9 shows the measurement results and the residual ratio (= image density (after test) / image density (before test) X100). Table 9 (Results of image light resistance test measurement)

Example 4

 A recording material was prepared in the same manner as in Example 1 except that 4-acetyl phenyl biphenyl was used instead of dimethyl terephthalate in the auxiliary agent dispersion liquid (solution C) of Example 1, and a thermosensitive recording was performed. Created paper. As a result of visual observation of the obtained thermosensitive recording paper, no background capri was observed. Test example 10 (Dynamic color sensitivity)

試験例 1 1 (地肌耐熱性試験） A part of the heat-sensitive recording paper prepared in Example 4 and Comparative Example 1 was cut out and used as each test paper. For each test paper, use a thermal paper coloring tester (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.) and heat at 0.32 and 0.44 mJ per dot. To make the checkered pattern saturated, and the print density (Macbeth value) The measurement was performed with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 10 and FIG. Table 10 (Measurement results of dynamic color sensitivity)

Test Example 1 1 (Surface heat resistance test)

 A portion of the thermosensitive recording paper prepared in Example 4 and Comparative Example 1 was cut out, and each test paper was heated at a constant temperature and constant temperature (product name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 90 ° C and 100 for 24 hours.

実施例 5 The skin density (Macbeth value) was measured after holding for 24 hours in a constant temperature incubator. Table 11 shows the measurement results. Table (Surface heat resistance test measurement results)

Example 5

 In the same manner as in Example 1, except that dimethyl terephthalate was replaced with 2- (2-benzotriazolyl) -p-cresol in the auxiliary dispersion (liquid C) in Example 1 Then, a recording material was prepared to prepare a thermal recording paper. As a result of visually observing the obtained heat-sensitive recording paper, no background strength was observed. Example 6

In Example 1, 2— (2′-hydroxy 3 ′, 5′-di-t-butylphenyl) benzotriazole was used in the auxiliary dispersion (solution C) instead of dimethyl terephthalate. Other than the above, a recording material was prepared in the same manner as in the method described in Example 1 to prepare a thermal recording paper. As a result of visual observation of the obtained heat-sensitive recording paper, no ground capri was observed. Comparative Example 2

 A recording material was prepared in the same manner as in Example 1 except that the auxiliary dispersion liquid (liquid C) of Example 1 was not used, and a thermosensitive recording paper was prepared. Test example 1 2 (Dynamic color sensitivity)

 A part of the heat-sensitive recording paper prepared in Examples 5 and 6 and Comparative Example 2 was cut out and used as test papers. For each test paper, use a thermal paper coloring tester (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.) and heat at 0.38 and 0.50 mJ per dot. Was added to form a checkered pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-5514, manufactured by Macbeth). The results are shown in Table 12. Table 12 (Measurement results of dynamic color sensitivity)

試験例 1 3 (画像耐光性試験）

Test Example 1 3 (Image light fastness test)

A part of the heat-sensitive recording paper prepared in Examples 5 and 6 and Comparative Example 2 was cut out, and saturated coloring was performed in the same manner as in Test Example 12. Then, using the light-fastness tester (trade name: UV Long Life Fedometer FAL-5, manufactured by Suga Test Instruments Co., Ltd.) for the saturated color-developed image, ultraviolet light having a wavelength of 380 nm was used. The image density (Macbeth value) of each test paper was measured 24 hours and 48 hours after irradiation. Table 13 shows the measurement results and the residual ratio (= image density (after test) image density (before test) X 100). Was. As a result of visual observation of the obtained thermosensitive recording paper, no background capri was observed. Table 13 (Results of image light resistance test measurement)

試験例 1 4 (地肌耐光性試験）

Test example 1 4 (background light resistance test)

 A part of the thermal recording paper prepared in Examples 5 and 6 and Comparative Example 2 was cut out, and a light resistance tester (trade name: UV Long Life Fade Meter-1 FAL-5 type, manufactured by Suga Test Machine Co., Ltd.) was used. The surface density (Macbeth value) of each test paper was measured at 2 hours, 6 hours, 12 hours, and 24 hours after irradiation with ultraviolet light having a wavelength of 380 nm. The measurement results are shown in Table 14. Table 14 (Surface light resistance test measurement results)

 (In the table, B is the Macbeth filter per ratten # 10 6 Y is the

Represents Vesfilter Wratten # 47. Example 7 (Preparation of thermal recording paper) First, dispersions (Α ′ to Ε ′) containing the following components were prepared. However, each component used was sufficiently crushed with a sand grinder.

 • Dye dispersion (Α 'solution)

 3-di-η-butylamino-6-methyl-17-anilino fluoran 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts

• Developer dispersion (Β 'solution)

 Mixture of 8 parts of 4- (4'-hydroxyphenylthio) acetyl-2-hydroxyaniline and 8 parts of Ν- (4'-hydroxyphenylthio) acetyl-4-hydroxyaniline (WO 02/8 The compound was synthesized according to the method of Synthesis Example 4 described in JP-A-229-129.)

 Polyvinyl alcohol 10% aqueous solution 8 4 parts

-Sensitizer dispersion liquid (C 'liquid)

 Di (oxalic acid) oxalate 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts

-Image stabilizer dispersion liquid (D 'liquid)

 4 1-Benzyloxy—4 '-(2-methyldaricidyloxy) diphenyl sulfone 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts

• Filler dispersion (E 'liquid)

 Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 71 1 part These dispersions were mixed with 1 part by weight of liquid A ', 2 parts by weight of liquid B', 1 part by weight of liquid C ', The D 'solution was mixed in a ratio of 0.5 part by weight and the E' solution in a ratio of 4 parts by weight to prepare a coating solution for a recording material for thermosensitive recording paper.

Next, the coating liquid for the recording material was applied to white paper using a wire rod (trade name: Wire Par, No. 12, manufactured by Webster) (applied amount of about 5.5 by dry weight). g / m ² ), dried and calendered to prepare a thermal recording paper. As a result of visually observing the obtained thermal recording paper, no background capri was observed. Example 8 (Preparation of thermal recording paper)

 A recording material was prepared in the same manner as in Example 7, except that the composition of the D 'solution of the coating solution of Example 7 was changed to 1 part by weight, to prepare a thermosensitive recording paper. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed. Example 9 (Preparation of thermal recording paper)

 A recording material was prepared in the same manner as in Example 7, except that the composition of the D 'solution of the coating solution in Example 7 was changed to 2 parts by weight, to prepare a thermosensitive recording paper. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed. Comparative Example 3

 A recording material was prepared in the same manner as in Example 7 except that the image stabilizer dispersion liquid (D 'liquid) of Example 7 was not used, and a thermosensitive recording paper was prepared. Test Example 15 (Image plasticizer resistance test)

 A part of the thermal recording paper prepared in Examples 7 to 9 and Comparative Example 3 was cut out and used as each test paper. For each test paper, use a thermal paper color tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) under the conditions of 0.08 to 0.72 mJ per dot. Heat was applied to make the checkered pattern saturated. Next, a vinyl chloride wrap film was adhered to the color-developing surface and the back surface of each of the test papers, and the state was maintained at 40 at 32 hours. Measure the optical density of the image immediately after saturation and after holding at 40 ° C for 32 hours with a Macbeth reflection densitometer (trade name: RD-514, filter used: # 106, manufactured by Macbeth) did. The results are shown in Table 15. Table 15 (Image plasticizer resistance test results)

 Colored image (before test) Colored image (after test) Image remaining rate (%) Example 7 1.2 4 0.5 4 4 4

 Example 8 1.1 9 0.6 7 5 6

 Example 9 1.1.5 '0.7.

Comparative Example 3 1.2 6 0.3 0.3 5 2 8 Test Example 16 (Image oil resistance test)

 Each test paper that had been saturated and colored in the same manner as in Test Example 15 was immersed in salad oil and kept at room temperature for 24 hours. The optical densities of the images were measured with a Macbeth reflection densitometer immediately after saturation coloring and after 24 hours at room temperature. The results are shown in Table 16. Table 16 (Image oil resistance test results)

実施例 1 0 (感熱記録紙の作成）

Example 10 (Preparation of thermal recording paper)

 First, a dispersion (Α''C "liquid) containing the following components was prepared.

 • Dye dispersion (Α '' liquid)

 3 —Gee η-Butylamino-6-methyl 7 —Anylinofluorane 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts • Developer dispersion (Β '' liquid)

 Mixture of 8 parts of Ν- (4'-hydroxyphenylthio) acetyl-2-hydroxyaniline and 8 parts of Ν- (4'-hydroxyphenylthio) acetyl-4-hydroxyaniline (WO 02/81 2 12 The compound was synthesized according to the method of Synthesis Example 4 described in Japanese Patent Publication No. 29).

 Polyvinyl alcohol 10% aqueous solution 8 4 parts • Inorganic pigment dispersion (C '' liquid)

 Amorphous silica (P-603, manufactured by Mizusawa Chemical Industry Co., Ltd.) 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 7 1 part Parts by weight, 2 parts by weight of the liquid B '', and 4 parts by weight of the liquid C were mixed to prepare a coating liquid for a recording material for thermosensitive recording paper.

Next, the coating liquid for the recording material was applied to a wire rod (trade name: Wire Par, No. 1 2, applied using the Webster Inc.) white paper (coating weight - about dry weight 5. 5 g / m ^2), and dried and then treated one seat calender, a heat-sensitive recording paper did. As a result of visually observing the obtained thermal recording paper, no background capri was observed. Example 1 1

 The amorphous silica (P—527, P—527, P—603, manufactured by Mizusawa Kagaku Kogyo Co., Ltd.) of the inorganic pigment dispersion liquid (C ″ liquid) of Example 10 was used. A recording material was prepared in the same manner as in Example 10 except for changing to Mizusawa Chemical Industry Co., Ltd.), and a thermosensitive recording paper was prepared. As a result of visual observation of the obtained heat-sensitive recording paper, no ground capri was observed. Comparative Example 4

 The amorphous pigment (P-603, manufactured by Mizusawa Kagaku Kogyo Co., Ltd.) of the inorganic pigment dispersion liquid (C "liquid) of Example 10 was replaced with calcium carbonate (Unibur-70, Shiraishi Kogyo Co., Ltd.). A recording material was prepared and a thermosensitive recording paper was prepared in the same manner as described in Example 10 except that the method was changed to).

A part of the thermosensitive recording paper prepared in Examples 10 and 11 and Comparative Example 4 was cut out and used as each test paper. Using a thermal paper color tester (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.) for each test paper, the conditions were 0.38 and 0.50 mJ per dot. Heat was applied to make the checkered pattern develop a saturated color, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 17. Table 17 (Results of measurement of dynamic color sensitivity)

試験例 1 8 (地肌耐光性試験）

Test Example 1 8 (Background light resistance test)

 A part of the heat-sensitive recording paper prepared in Examples 10 and 11 and Comparative Example 4 was cut off, and a light resistance tester (trade name: UV long life fedometer FAL-5, manufactured by Suga Test Instruments Co., Ltd.) The surface density (Macbeth value) of each test paper was measured at 2 hours, 6 hours, 12 hours, and 24 hours after irradiation with ultraviolet light having a wavelength of 380 nm. The measurement results are shown in Table 18. Table 18 (Surface light resistance test measurement results)

 (In the table, B is the Macbeth filter per ratten # 10 6 Y is the Macbeth filter

 Represents Sfilter Wratten # 47. Example 1 2 (Preparation of thermal recording paper)

First, dispersions (Α ′ ″ to Α ″ ′ ′) containing the following components were prepared. However, each component used was sufficiently crushed with a sand grinder. Dye dispersion (Α "'liquid)

 3-Gee η-Butylamino-6-methyl 7-anilinofluoran 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts Developer dispersion (Β '' 'liquid)

 Mixture of 8 parts of Ν— (4′-hydroxyphenylthio) acetyl-2 and hydroxyphenylinine and 8 parts of Ν— (4′-hydroxyphenylthio) acetyl-4 and hydroxyaniline (WO 02/81 22 9 The compound was synthesized according to the method of Synthesis Example 4 described in Japanese Patent Publication No.

 Polyvinyl alcohol 10% aqueous solution 8 4 parts Sensitizer dispersion (C "'solution)

 Di (oxalic acid) oxalate 16 parts Polyvinyl alcohol 10% aqueous solution 8 4 parts Image stabilizer dispersion (D "'solution)

4,4 '-[Oxybis (ethylene-ρ-phenylenesulfonyl)] diphenol (containing 40% or more) and a compound represented by the formula (13)

[In the formula, c represents an integer of 2 to 10. 1 6 parts Polypinyl alcohol 10% aqueous solution 8 4 parts-Filler dispersion (Ε '' 'liquid)

 Calcium carbonate 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 Parts water 7 1 part These dispersions were mixed with A '' 'liquid 1 part by weight, B' '' liquid 1.5 parts by weight C ' One part by weight of the liquid, 0.5 parts by weight of the liquid D '' ', and 4 parts by weight of the liquid E' '' were mixed to prepare a coating solution for a recording material for thermosensitive recording paper.

Next, the coating liquid for the recording material was applied to white paper using a wire rod (trade name: wire bar, No. 12, manufactured by Webster) (applied amount-about 5% by dry weight). After drying at 5 g / m ² ), the sheet was calendered to produce a thermal recording paper. As a result of visually observing the obtained thermal recording paper, no background capri was observed. Example 13 (Preparation of thermal recording paper)

 Recording was performed in the same manner as in Example 12 except that dimethyl terephthalate was changed to di (4-methylpendyl) oxalate in the sensitizer dispersion liquid (C '' 'liquid) of Example 12. The materials were prepared and thermal recording paper was made. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed. Comparative Example 5

 Example 12 The procedure was the same as that described in Example 2 except that the image stabilizer dispersion liquid (D 'liquid) was not used and the composition of the C' '' liquid of the coating liquid was 1 part by weight. The recording material was prepared in this manner, and a thermal recording paper was prepared. Test Example 1 9 (Image plasticizer resistance test)

A part of the heat-sensitive recording paper prepared in Examples 12, 13 and Comparative Example 5 was cut out and used as each test paper. For each test paper, use a thermal paper coloring tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) under the conditions of 0.08 to 0.72 mJ per dot. Heat was applied to make the checkered pattern saturated. Next, a vinyl chloride wrap film was adhered to the coloring surface and the back surface of each of the test papers, and kept in this state at 40 ° C. for 24 hours. The optical density of the image immediately after saturation and after holding at 40 at 24 hours was measured with a Macbeth reflection densitometer (trade name: RD-514, filter used: # 106, manufactured by Macbeth). did. The results are shown in Table 19. Table 19 (Image plasticizer resistance test results)

産業上の利用可能性 ： Test Example 20 (Image oil resistance test) Each test paper saturated with the same method as in Test Example 19 was immersed in salad oil and kept at room temperature for 24 hours. The optical densities of the images were measured with a Macbeth reflection densitometer immediately after saturation coloring and after 24 hours at room temperature. The results are shown in Table 20. Table 20 (Image oil resistance test results)

Industrial applicability:

 As described above, according to the present invention, there is provided a recording material and a recording sheet which are free from background capri, have excellent color development sensitivity, and have excellent background and image storage stability.

 Also,

 (1) The recording material containing the phthalic acid derivative of the present invention is particularly excellent in the heat resistance of the background and the light resistance of the image, and is capable of reading barcodes in the near infrared region.

 (2) The recording material containing the hydroxybenzoic acid derivative of the present invention can significantly improve the color sensitivity particularly, and is excellent in light fastness of an image.

 (3) The recording material containing the anilide derivative of the present invention is particularly excellent in heat resistance of the background and light resistance of images.

 記録 The recording material containing the biphenyl derivative of the present invention is particularly excellent in heat resistance of the background,

記録 The recording material containing the benzotriazole derivative of the present invention is particularly excellent in light resistance of the background.

 (4) The recording material containing the amorphous silica of the present invention can greatly improve the coloring sensitivity, in particular, and is excellent in the light resistance of the background.

 記録 The recording material containing 4'-benzyloxy 4 '-(2-methyldalicydyloxy) diphenyl sulfone of the present invention is particularly excellent in the plasticizer resistance and oil resistance of images,

化合物 The compound of the present invention represented by the above formula (2) is particularly excellent in plasticizer resistance and oil resistance of an image.

Claims

 The scope of the claims  In a recording material containing a chromogenic dye, the formula (1)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a CI to C 6 alkyl group, a ¹ represents an integer of 1 to 6, and n ¹ represents 0, 1 or 2 And m ¹ and m ² each independently represent 0 or an integer of 1 to 3. However, m ¹ and m ² are not simultaneously 0. R ³ and R ⁴ are each independently a nitro group, a propyloxyl group, a halogen atom. A C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkoxy group, a C 1 -C 6 represents an alkyl force Ruponiru group or C. 1 to C 6 alkoxy force Lupo two Le group, m ³ and m ⁴ are each independently 0, 1 or 2 of an integer, m ³ and m ⁴ are each 2 In the formula, R ³ and R ⁴ may be different from each other, and Y ¹ is CO or NR ⁵ CO (where R ⁵ is a hydrogen atom, a C 1 -C 6 alkyl group, A phenyl group or a benzyl group which may have a substituent.). And a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, a biphenyl derivative, a benzotriazole derivative, amorphous silica, 4-benzyloxy-1 4 ′-( 2-Methyldaricidyloxy) diphenyl sulfone and a compound of the formula (2)

 (2) [Wherein, X ¹ and X ² each independently may have a straight-chain or branched A C 1 to C 12 hydrocarbon group which may have a saturated, unsaturated or ether bond, or formula (3) or (4)

 (3) (4) (Wherein, R ¹² represents a methylene group or an ethylene group, and R ¹³ represents a hydrogen atom or a C 1 -C 4 alkyl group.) ^ ⁶ ~! ^ ^{1 1} are each independent, and display the halogen atom, C. 1 to C 6 alkyl group or C. 2 to C 6 alkenyl group, m ⁵ ~m ^{1 ()} are independently 0 or 1 Represents an integer of 4 to 4, and when it is an integer of 2 or more, R e R ¹¹ may be the same or different, and b represents 0 or an integer of 1 to 10. ] A recording material comprising at least one compound selected from the compounds represented by the formula: However, when the compound represented by the formula (2) is contained, at least two or more kinds of the compound represented by the formula (1) are contained. 2. In a recording material containing a chromogenic dye, the formula (1)

[Wherein R ¹ , R ² , RR anmmmm ⁴ and Y ¹ represent the same meaning as described above. And at least one compound selected from the group consisting of phthalic acid derivatives, hydroxybenzoic acid derivatives, anilide derivatives and biphenyl derivatives. Recording material, 3. In a recording material containing a chromogenic dye, the formula (1)

[Wherein, R ¹ , R ² , RR anmmmm and Y ¹ represent the same meaning as described above. ] A recording material comprising at least one compound represented by the formula: and a benzotriazole derivative.  4. In a recording material containing a chromogenic dye, the formula (1)

[Wherein, RRRR anmmmm ⁴ and Y ¹ represent the same meaning as described above. ] A recording material comprising at least one compound represented by the formula: and amorphous silica.  5. In a recording material containing a chromogenic dye, the formula (1)

[Wherein, RR ² , RR anmmmm ⁴ and Y ¹ represent the same meaning as described above. ] A recording material comprising at least one compound represented by the formula: and 4-1 benzyloxy-4 '-(2-methyldaricidyloxy) diphenylsulfone. 6. In a recording material containing a chromogenic dye, the formula (1)

[Wherein R ¹ R ² , R ³ , R ⁴ , a ¹ > n ¹ , mm ² > m ³ , m ⁴ and Y ¹ represent the same meaning as described above. And at least two compounds represented by the formula (2)

 (2) [Wherein X ¹ and X ² each independently represent a linear or branched C 1 -C 12 saturated, unsaturated or carbonized carbon which may have an ether bond. A hydrogen group, or formula (3) or formula (4)

 (3) (4) (Wherein, R ¹² represents a methylene group or an ethylene group, and R ¹³ represents a hydrogen atom or a C 1 -C 4 alkyl group.) R s R ¹¹ They are each independent, and display the halogen atom, C. 1 to C 6 alkyl group or a C 2 ~ C 6 alkenyl group, m ⁵ ~m ^{1 Q} each independently represents an integer of 0 or 4 When R is an integer of 2 or more, R e R ¹¹ may be the same or different, and b represents 0 or an integer of 1 to 10. ] A recording material comprising at least one compound represented by the formula: 7. The phthalic acid derivative has the formula (5)

[Wherein, R ¹⁴ and R ¹⁵ each independently represent a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, an aryl group which may have a substituent or a substituent. And R ¹⁶ represents a hydroxyl group, a halogen atom, a C 1 -C 6 alkyl group or a C 2 -C 6 alkenyl group, and m ¹¹ represents 0 or 1 to 4 And when m ¹¹ is an integer of 2 or more, R ¹⁶ may be different. The recording material according to claim 1, wherein the recording material is represented by:  8. The recording material according to claim 7, wherein the phthalic acid derivative is dimethyl terephthalate.  9. The hydroxybenzoic acid derivative has the formula (6)

Wherein R ¹⁷ represents a hydroxyl group, a halogen atom, a C 1 -C 6 alkyl group or a C 2 -C 6 alkenyl group, m ¹² represents 0 or an integer of 1-4, and m ¹² When is an integer of 2 or more, R ¹⁷ may be different, and R ¹⁸ is a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, or an aryl group which may have a substituent. Or an aralkyl group which may have a substituent. 3. The recording material according to claim 1, wherein the recording material is represented by the following formula:  10. The recording material according to claim 9, wherein the hydroxybenzoic acid derivative is benzyl 4-hydroxybenzoate. 1 1. The anilide derivative has the formula (7)

Wherein R ¹⁹ is a C 1 -C 18 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylene group, Represents an aryl group or an aralkyl group which may have a substituent; R ^{2 Q} is a hydrogen atom; a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, Represents an aryl group or an aralkyl group which may have a substituent, and R 21 represents a halogen atom, a C ¹ -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 Represents an alkoxy group, a C 1 to C 6 alkyl carbonyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent, and m ¹³ represents 0 or 1 to represents 5 an integer, when m ^{1 3} are each an integer of 2 or more, R ^{2 1} may be different. 3. The recording material according to claim 1, wherein:  12. The recording material according to claim 11, wherein the anilide derivative is p-acetotoluid.  1 3. The biphenyl derivative has the formula (8)

Wherein, R ^{2 2} and R ^{2 3} are each independently a hydroxyl group, a force Rupokishiru group, C 1 -C 6 alkyl group, C. 2 to C 6 alkenyl group, C. 1 to C 6 alkoxy group, C l To C 6 alkyl carbonyl group, C 1 to C 6 alkyl carbonyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent, m ¹⁴ and m ¹⁵ They are each independently an integer of 0 or from 1 to 5 when m ^{1 4} and m ^{1 5} is an integer of 2 or more, respectively, R ^{2 2} and R ^{2 3} may be different from each other. The recording material according to claim 1, wherein the recording material is represented by: 14. The recording material according to claim 13, wherein the biphenyl derivative is 4-acetylbiphenyl.  1 5. The benzotriazole derivative has the formula (9)

Wherein, R ^{2 4} and R ^{2 5} each independently represents a hydroxyl group, a halogen atom, C l to C 8 alkyl group, a C 2 to C 6 alkenyl or C 1 through C 8 alkoxy group, m ^{1 6} represents 0 or 1-4 because integer, when m ^{1 6} is an integer of 2 or more, R ^{2 4} is different connexion may, IE ^{1 7} represents an integer of 0 or from 1 to 5, m ^{When 17} is an integer of 2 or more, R ²⁵ may be different. The recording material according to claim 1, wherein the recording material is represented by:  16. The recording material according to claim 15, wherein the benzotriazole derivative is 2- (2-benzotriazolyl) -1-p-cresol.  17. The recording material according to claim 15, wherein the benzotriazole derivative is 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole.  1 8. The recording material according to any one of claims 1 to 17, wherein the recording material contains at least two kinds of compounds represented by the formula (1).  1 9. At least two kinds of compounds represented by the formula (1) are represented by the formula (10) (Ten)

Wherein, R ^{2 6} and R ^{2 7} independently represent a hydrogen atom or a C. 1 to C 6 alkyl le group, a ² represents an integer of. 1 to 6, n ² is 0, Represents an integer of 1 or 2, m ¹⁸ represents 0 or an integer of 1 to 3. R ^{2 8} and R ^{2 9} are each independently two Bok port group, the force Rupokishiru group, a halogen atom, C 1 through C 6 alkyl group, C 2 to C 6 alkenyl group, C. 1 to C 6 alkoxy group, represents C. 1 to C 6 alkyl force Ruponiru group or C 1 through C 6 alkoxy force Lupo two Le group, m ^{1 9} and m ² ° each independently represent 0, 1 or 2 integer, m ^{1 9} and m ² . When each is 2, R ²⁸ and R ²⁹ may be different from each other, and Y ² is CO or NR ³ ° CO (where R ³ ° is a hydrogen atom, a C1-C6 alkyl group, A phenyl group which may have a substituent or a benzyl group which may have a substituent.). And at least one compound represented by the formula (11):

Wherein, R ^{3 1} and R ^{3 2} are each independently, represent a hydrogen atom or a C. 1 to C 6 alkyl le group, a ³ represents an integer of. 1 to 6, n ³ is 0, 1 or an integer 2, m ^{2 1} is 0 or;! Represents an integer of 3 R ^{3 3} and R ^{3 4} are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C 1 through C 6 alkyl group, C. 2 to C 6 alkenyl group, C. 1 to C 6 alkoxy group, C 1 represents ~ C 6 alkyl force Ruponiru group or C. 1 to C 6 alkoxycarbonyl two Le group, m ^{2 2} and m ^{2 3} each independently represents 0, 1 or 2 integer, m ^{2 2} and m ² when ³ is respectively 2, R ^{3 3} and R ^{3 4} may be different from each other, Y ³ is, CO or NR ^{3 5} C_〇 (wherein, R ^{3 5} is a hydrogen atom, C. 1 to C 6 An alkyl group, a phenyl group which may have a substituent or a benzyl group which may have a substituent). And at least one compound represented by the formula or (12)

Wherein, R ^{3 6} and R ^{3 7} each independently represent a hydrogen atom or a C. 1 to C 6 alkyl le group, a ⁴ represents an integer of. 1 to 6, n ⁴ is 0, 1 or an integer 2, m ²⁴ represents an integer of 0 or 1-3. R ^{3 8} and R ^{3 9} are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C 1 through C 6 alkyl group, C. 2 to C 6 alkenyl group, C. 1 to C 6 alkoxy group, C 1 Represents a C 6 alkyl group or a C 1 -C 6 alkoxy group, m ²⁵ and m ²⁶ each independently represent an integer of 0, 1 or 2; m ²⁵ and when m ^{2 6} are each 2, R ^{3 8} and R ^{3 9} may be different from each other, Y ⁴ is, CO or NR ^{3 5} CO (wherein, R ^{3 5} is a hydrogen atom, C. 1 to C 6 represents an alkyl group, a phenyl group which may have a substituent or a benzyl group which may have a substituent.) 19. The recording material according to claim 18, wherein the recording material is at least one kind of the compound represented by the formula:  20. A recording sheet having a base material sheet and a recording material layer formed on the base material sheet from the recording material according to any one of claims 1 to 19.