KR100522001B1 - Compound for color developer of thermally sensitive recording paper and synthesis thereof - Google Patents

Abstract

The present invention relates to a compound containing a thionyl urea group and an amide group represented by the following formula (1), which is useful as a developer for thermal recording paper, and when used in thermal recording paper, it has good color sensitivity, good heat resistance, good oil resistance, water resistance, and fire resistance. Thermal recording paper can be obtained.

Where

R ₁ represents a hydrogen atom or at least one C _{1 to} C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom,

R ₂ is a hydrogen atom or at least one C _{1 to} C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom.

Description

Compound useful as a developer for thermal recording paper and a method for producing the same {Compound for color developer of thermally sensitive recording paper and synthesis}

The present invention relates to a compound useful as a developer for thermal recording paper, and more particularly, having a thionylurea group and an amide group in a molecular structure, having good color sensitivity, good heat resistance, good oil resistance and fire resistance, and a compound useful as a developer for thermal recording paper. It is about.

In the 1970's, a phenolic developer that reacted with a colorless thermal dye with a lactone ring was developed.

In order to record on a thermal recording paper coated with a thermal dye and a developer, a thermal printer with a thermal head is used. This thermal recording method is more effective than other conventional recording methods. There is no noise, no need to settle, it is free to maintain, the device is relatively inexpensive and small in size, and the color obtained is very clear. Therefore, with the development of the information industry, thermal recording methods are widely used in the field of fax, computer, various measuring instruments and labels. However, as these recording apparatuses are diversified and improved in performance, the quality of thermal recording papers is required to be higher. ought.

Currently, as a main developer, developers of various structures having a phenolic structure are used. Among them, diphenyl sulfone compounds have been proved to be excellent as a developer, and their development has been actively conducted since the 80s. International Patent Publication WO84 / 02882, International Patent Publication WO91 / 11433, Japanese Patent Publication 2001-261633, Korean Publication Various technologies have been published in patent 2002-0005619 and the like.

However, none of these phenolic developers have defects such as deterioration of the heat-resistant background color or powdering as time goes by, and a decrease in color concentration when recorded after long-term storage of undeveloped parts. It was difficult to say that the quality was sufficient because it was not sufficiently complemented. In order to meet these demands, a method of increasing the color development sensitivity by using a novel developer having high color developing ability has been devised, but no obvious developer has been developed yet.

In other words, phenolic colorants have been used as a thermal agent for thermal papers until now, but the phenolic colorant is removed in a short time by wiping with alcohol, etc., and when it is put into a notebook or purse made of PVC, it becomes thin due to leached plasticizers or automobiles. There is a problem of deterioration even under a high temperature environment, such as a receipt, which requires long-term storage, and has many problems in use.

Therefore, there is a need for the development of a new developer that surpasses the existing developer in terms of heat resistance, water resistance, plasticizer, alkali resistance, and factor preservation of a fluorescent pen.

The patent of Japanese Patent Application Laid-Open No. 11-263769, filed recently by Hodogaya Chemical Co., Ltd., in Japan, synthesizes a urea urethane compound having a color development mechanism different from that of an acidic developer using conventional bisphenol S. The color developer which improved the was disclosed. This urea urethane compound is more heat resistant than conventional phenolic developer, bisphenol A, 4-hydroxy-4'-isopropoxydiphenylsulfone, 3, 3'-diaryl-4, and 4'-dihydroxydiphenylsulfone. It has a better effect on water resistance, oil resistance and fire resistance.

As disclosed in the aforementioned Japanese Patent Application Laid-Open No. 11-263769, a urea urethane compound having a color development mechanism different from that of a conventional acidic developer using bisphenol S can be synthesized to improve heat resistance and factor preservation. Is more heat resistant, water-resistant, oil-resistant, than bisphenol A, 4-hydroxy-4'-isopropoxydiphenylsulfone, 3,3'-diaryl-4,4'-dihydroxydiphenylsulfone, I was showing a better effect on fire extinguishing.

Therefore, the present inventors have studied why the urea urethane compound shows better results than the conventional developer, and as a result, the urea urethane compound has a resonance structure showing better electron acceptability than the conventional phenolic developer. The urethane compound structure was found to exhibit better heat resistance and factor preservation.

Therefore, the present inventors developed a colorant having a thionylurea group and an amide group while developing a material having a better resonance structure, and the compound was superior to conventional phenolic colorants in oil resistance, heat resistance, and factor preservation. In addition to showing the results, it was found that the results are almost similar to the urea urethane developer.

Accordingly, an object of the present invention is to provide a novel compound useful as a color developing agent for thermal recording paper having good color sensitivity, good heat resistance, and excellent oil resistance and fire resistance.

It is also an object of the present invention to provide a method for producing a novel compound useful as a developer for thermal recording paper.

Another object of the present invention is to provide a thermal recording paper containing a novel compound as a developer.

The compound useful as a developer for the thermal recording paper of the present invention for achieving the above object is characterized in that the compound represented by the following formula (1).

Formula 1

Wherein R ₁ represents a hydrogen atom, or one or more C _{1 to} C ₈ alkyl, alkenyl or alkynyl, nitro, sulfonated, amine, hydroxy or halogen atoms, and R ₂ represents a hydrogen atom, or At least one C ₁ -C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom.

The compound represented by Chemical Formula 1 is characterized in that it is prepared by reacting an isocyanate compound represented by Chemical Formula 2 with a thionyl urea compound represented by Chemical Formula 3.

Formula 2

Wherein R ₁ is as defined above.

Formula 3

Wherein R ₂ is as defined above.

The present invention will be described in more detail as follows.

Compound represented by the formula (1) has a structure that can form a resonance structure as a whole, because it is easy to receive electrons from a colorless thermal dye, not only good color sensitivity, but also exist with thionylurea group and an amide group coexisting benzene ring It is made of a structure that can significantly improve oil resistance and fire resistance.

The compound represented by the formula (1) is obtained by reacting the isocyanate compound (1) represented by the formula (2) and the thionyl urea compound (2) represented by the formula (3) as shown in the following scheme.

(Chemical Scheme 1)

Wherein R ₁ and R ₂ are the same as defined in Chemical Formula 1.

Isocyanate compound (1) represented by the formula (2) which can be used for the reaction includes 1-isocyanate-2-p-tolueneethene, 1-isocyanate-2-o-tolueneethene, 1-isocyanate-2- (2,4 -Dimethylbenzene) ethene, 1-isocyanate-2- (4-fluorobenzene) ethene, 1-isocyanate-2- (4-chlorobenzene) ethene, 1-isocyanate-2- (4-bromobenzene) ethene, 1-isocyanate-2- (3,4-diethylbenzene) ethene, 1-isocyanate-2- (2,4-diethylbenzene) ethene, 1-isocyanate-2- (4-nitrobenzene) ethene and the like Can be.

As the thionyl urea compound (2) represented by the formula (3), p-toluene thionyl urea, o-toluene thionyl urea, m-toluene thionyl urea, o-bromobenzene thionyl urea, m-bromobenzene Thionylurea, p-bromobenzenethionylurea, o-chlorobenzenethionylurea, m-chlorobenzenethionylurea, p-chlorobenzenethionylurea, o-fluorobenzenethionylurea, m-fluoro Benzenethionilurea, p-fluorobenzenethionylurea, 2,3-dimethylbenzenethionylurea, 2,4-dimethylbenzenethionylurea, 2,5-dimethylbenzenethionylurea, 2-ethylbenzenethionyl Urea, 3-ethylbenzenethionylurea, 4-ethylbenzenethionylurea, 2,4-diethylbenzenethionylurea, 2,4-dichlorobenzenethionylurea, 3,5-dichlorobenzenethionylurea, etc. Can be used.

It is most effective to make the isocyanate compound (1) and the thionyl urea compound (2) used in the reaction react in a 1: 1 equivalent ratio.

Solvents usable during the reaction include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, propanol, isopropanol, butanol and hexanol, and N, N-dimethylformamide, dimethyl sulfoxide and dichloromethane. Of these, methanol can be used most effectively.

It is preferable that reaction temperature is -10-40 degreeC, and 30-40 degreeC is the most effective among these.

In a specific manufacturing method, methanol is added to a reactor, a thionyl urea compound represented by the formula (3) and an isocyanate compound represented by the formula (2) are added and stirred while the temperature is raised. As the reaction proceeds, the compound represented by Chemical Formula 1 is precipitated in the reaction solution as a solid compound because it is not dissolved in methanol. After stirring for 1 to 5 hours, the compound represented by the formula (1) is filtered and washed with methanol. It is then dried and pulverized to prepare a mixed solution for thermal recording paper.

The developer represented by Chemical Formula 1 is used for the thermal recording paper, which is obtained by preparing a dispersion of a dye, a developer, a filler, and a binder and then applying the same on a support.

At this time, the amount of the developer and dye, the type and amount of the other various components are determined according to the required performance and recordability, and are not particularly limited, but the basic fluorane-based leuco dye 0.1 to 2 usually Parts and 0.5 to 4 parts of a filler are used, and the binder is preferably 5 to 25% of the total solids.

The basic fluorane-based leuco dyes that can be used here are 3-diethylamino-6-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl- 7-chlorofluorane, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-methylfluoran etc. are mentioned.

As the filler, inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide and aluminum hydroxide can be used.

As the binder, a fully saponified polyvinyl alcohol having a degree of polymerization of 200 to 1900, a partially saponified polyvinyl alcohol, a carboxy modified polyvinyl alcohol, an amide modified polyvinyl alcohol, a sulfonic acid modified polyvinyl alcohol, and a butyral modified polyvinyl alcohol can be used.

The target thermal recording paper can be obtained by applying a dispersion liquid obtained by mixing the above materials in the composition ratio to any support such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, nonwoven fabric, and gold foil.

In general thermal recording paper, the coating amount of the dispersion is preferably about 6 g / m ² based on the coating amount after drying.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1: Preparation of 4-methylphenylethenyl-4-methylphenylthionylurea amide compound

100 mL of methanol was added to a 4-neck 250 mL round bottom flask reactor, 10.0 g (0.06 mol) of p-toluene thionyl urea and 9.6 g (0.06 mol) of 1-isocyanate-2-p-toluene ethene were added and the temperature was raised to 30 ° C. or higher. Stirring with stirring. As the reaction proceeded, 4-methylphenylethenyl-4-methylphenyl thionylurea amide precipitated in the reaction solution as a solid compound. After stirring for 4 hours, 4-methylphenylethenyl-4-methylphenyl thionylurea amide was filtered, washed with methanol, and dried to obtain 15.6 g (80%).

¹ H-NMR (DMSO, 400 MHz) δ: 2.3 (s, CH ₃ , 6H), 2.6 (s, NH, 1H), 4.2 (s, NH, 1H), 6.1 (d, = CH, 1H), 6.4 7.2 (m, ArH, 8H), 7.5 (s, NH, 1H), 7.7 (d, = CH, 1H)

Example 2: Preparation of 4-Chlorophenylethenyl-4-methylphenylthionylurea amide compound

Put 100 mL of methanol in a 4-neck 250 mL round bottom flask reactor, add 10.0 g (0.06 mole) of p-toluene thionylurea and 10.8 g (0.06 mole) of 1-isocyanate-2- (4-chlorobenzene) ethene. It stirred, heating up. As the reaction proceeded, 4-chlorophenylethenyl-4-methylphenyl thionylurea amide precipitated in the reaction solution as a solid compound. After stirring for 2 hours, 4-chlorophenylethenyl-4-methylphenyl thionylurea amide was filtered, washed with methanol, and dried to obtain 15.7 g (76%).

¹ H-NMR (DMSO, 400 MHz) δ: 2.3 (s, CH ₃ , 3H), 2.5 (s, NH, 1H), 3.9 (s, NH, 1H), 6.0 (d, = CH, 1H), 6.4 7.2 (m, ArH, 8H), 7.7 (s, NH, 1H), 8.0 (d, = CH, 1H)

Example 3: Preparation of 2, 4-dimethylphenylethenyl-4-ethylphenylthionylurea amide compound

100 mL of methanol was added to a 4-neck 250 mL round bottom flask reactor and 10.0 g (0.055 mole) of 4-ethylbenzenethionylurea and 9.6 g (0.055 mole) of 1-isocyanate-2- (2,4-dimethylbenzene) ethene were added. It stirred, heating up at 30 degreeC or more. As the reaction proceeded, 2,4-dimethylphenylethenyl-4-ethylphenyl thionylurea amide precipitated in the reaction solution as a solid compound. After stirring for 5 hours, 2, 4-dimethylphenylethenyl-4-ethylphenylthionylurea amide was filtered, washed with methanol and dried to obtain 13.0 g (69%).

¹ H-NMR (DMSO, 400 MHz) δ: 1.3 (t, CH ₃ , 3H), 2.4 (d, CH ₃ , 6H), 2.5 (s, NH, 1H), 2.6 (q, CH ₂ , 2H), 3.9 (s, NH, 1H), 6.3 (d, = CH, 1H), 6.4 to 7.1 (m, ArH, 7H), 7.5 (d, = CH, 1H), 8.2 (s, NH, 1H)

Example 4: Preparation of 4-ethylphenylethenyl-2-methylphenyl thionylurea amide compound

Put 100 mL of methanol in a 4-neck 250 mL round bottom flask reactor, add 10.0 g (0.06 mole) of 2-methylthionylurea and 10.4 g (0.06 mole) of 1-isocyanate-2- (4-ethylbenzene) ethene. It stirred, heating up. As the reaction proceeded, 4-ethylphenylethenyl-2-methylphenyl thionylurea amide precipitated in the reaction solution as a solid compound. After stirring for 5 hours, 4-ethylphenylethenyl-4-methylphenylthionylurea amide was filtered, washed with methanol, and dried to obtain 17.3 g (85%).

¹ H-NMR (DMSO, 400 MHz) δ: 1.2 (t, CH ₃ , 3H), 2.4 (s, CH ₃ , 6H), 2.5 (s, NH, 1H), 2.6 (q, CH ₂ , 2H), 3.9 (s, NH, 1H), 6.0 (d, = CH, 1H), 6.7 to 7.1 (m, ArH, 8H), 7.8 (d, = CH, 1H), 8.6 (s, NH, 1H)

Example 5 Preparation of Thermal Recording Paper

Each material of the dye, the developer, the filler, and the binder was previously prepared in the form of a dispersion liquid, and wet grinding was performed until the average particle size was 1 micron using a sand mill.

① Dye Dispersion

2-aniline-3-methyl-6-dibutylaminofluorane ------------- 8 parts

10% polyvinyl alcohol solution ---------------------------- 40 parts

Water ------------------------------------------------- Part 28

② Colorant Dispersion

4-methylphenylethenyl-4-methylphenylthionylurea amide ------- 4 parts

10% polyvinyl alcohol solution ------------------------------ 10 parts

Water ------------------------------------------------- Part 59

③ Dispersion of filler (30% aluminum hydroxide)

④ Binder (10% polyvinyl alcohol) dispersion

Each of the above compositions is mixed in the following ratio to prepare a thermal layer coating solution.

① Dye Dispersion Solution -------------------------------------- Part 4

② Colorant dispersion ------------------------------------ 16 parts

③ Filler (30% Aluminum Hydroxide) dispersion ----------------- 10 parts

④ Binder (10% polyvinyl alcohol) dispersion -------------------- 8 parts

This coating solution was applied to a good weight paper having a basis weight of 50 g / m 2 so that the coating amount after drying was 7 g / m 2, and placed in a hot air dryer to dry, thereby obtaining a thermal recording paper.

Example 6 Preparation of Thermal Recording Paper

Instead of the 4-methylphenylethenyl-4-methylphenylthionylurea amide of Example 5, 4-chlorophenylethenyl-4-methylphenylthionylurea amide was used to prepare a heat-sensitive layer coating solution. The thermal recording paper was obtained using this thermal layer coating liquid.

Example 7 Preparation of Thermal Recording Paper

Instead of the 4-methylphenylethenyl-4-methylphenylthionylurea amide of Example 5, 4-ethylphenylethenyl-2-methylphenyl thionylurea amide was used to prepare a thermal layer coating solution. The thermal recording paper was obtained using this thermal layer coating liquid.

Comparative Example 1 Preparation of Thermal Recording Paper

Instead of the 4-methylphenylethenyl-4-methylphenylthionylurea amide of Example 5, 4, 4'-bis (p-toluenesulfonylureidocarbonylamine) diphenylmethane was used to prepare a thermal layer coating solution. It was. The thermal recording paper was obtained using this thermal layer coating liquid.

Comparative Example 2: Preparation of Thermal Recording Paper

Instead of 4-methylphenylethenyl-4-methylphenylthionylurea amide of Example 5, bisphenol A was used to prepare a thermal layer coating solution. The thermal recording paper was obtained using this thermal layer coating liquid.

Comparative Example 3: Preparation of Thermal Recording Paper

Instead of the 4-methylphenylethenyl-4-methylphenylthionylurea amide of Example 5, 4-hydroxy-4'-isopropoxydiphenylsulfone was used to prepare a thermal layer coating solution. The thermal recording paper was obtained using this thermal layer coating liquid.

The following evaluation items were evaluated using the thermal recording papers made in Examples 5, 6, and 7 and Comparative Examples 1, 2 and 3.

(1) color development

Using TH-PMD manufactured by Okura Electric Co., Ltd., applied energy of 8 to 30 mj / mm 2 was applied to the thermal recording paper produced above. The image density of the printing part was measured with a Mechves concentration meter (using Invar filter). The larger the value, the higher the color development.

(2) heat resistance

After leaving for 24 hours in an environment of 60 ° C. using a hot air dryer, the result was measured with a Mechves concentration meter. The larger the value, the better the heat resistance.

(3) water resistance

Using tap water, it was soaked for 24 hours at room temperature and measured with a Mechves densitometer. The larger the value, the better the water resistance.

(4) oil resistance

After applying the diesel oil to a thickness of 1 ㎛ and left for 3 hours at 50 ℃ using a hot air dryer, it was measured by a mechvez concentration meter. The larger the value, the better the oil resistance.

(5) plasticizer

The vinyl chloride wrap was wound around the paper tube in a single layer, and a load of 20 g / cm 2 was applied thereto, and the resultant was left to stand at 50 ° C. for 3 hours using a hot air dryer, and then measured by using a Mechves concentration meter. The larger the value, the better the flame resistance.

Table 1 shows the results of the above inspection items according to the Examples and Comparative Examples.

Color Heat resistance Water resistance Oil resistance Fire retardant Example 5 1.35 97 90 98 98 Example 6 1.33 97 89 97 97 Example 7 1.36 98 89 100 97 Comparative Example 1 1.33 97 83 100 97 Comparative Example 2 1.31 85 16 98 74 Comparative Example 3 1.24 96 27 102 96

As shown in the results of Table 1, in the case of including a new developer represented by the formula (1) as in Example 5, 6, 7, than when using the conventional phenolic developer as in Comparative Examples 2, 3 It has excellent water resistance and overall color development sensitivity is better. In addition, it showed better water resistance than the urea urethane-based developer used in Comparative Example 1, and the other items generally showed more than equivalent results.

Therefore, the present invention has been completed by the invention of a novel developer which shows a better effect than the existing phenolic developer, and exhibits an effect equal to or higher than that of the urea urethane developer.

As described in detail above, in the case of developing a developer having a thionyl urea group and an amide group in a molecular structure according to the present invention and using it in a thermal recording paper, the thermal recording paper has good color sensitivity and good heat resistance, and has good oil resistance, water resistance, and fire resistance. Can be obtained.

Claims (7)

(Correction) A compound containing a thionyl urea group and an amide group represented by the following formula (1), which is useful as a developer for thermal recording paper . Formula 1 Where R ₁ represents a hydrogen atom or at least one C _{1 to} C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom, R ₂ is a hydrogen atom or at least one C _{1 to} C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom. (Correction) A method for preparing a compound containing a thionyl urea group and an amide group represented by the following Chemical Formula 1 which is useful as a developer for thermal recording paper by reacting an isocyanate compound represented by the following Chemical Formula 2 with a thionyl urea compound represented by the following Chemical Formula 3 . Formula 1 Where R ₁ represents a hydrogen atom or at least one C _{1 to} C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom, R ₂ is a hydrogen atom or at least one C _{1 to} C ₈ alkyl group, alkenyl group or alkynyl group, nitro group, sulfonated group, amine group, hydroxy group or halogen atom. Formula 2 Wherein R ₁ is as defined above. Formula 3 Wherein R ₂ is as defined above. (Correction) The method of claim 2, wherein the isocyanate compound represented by the formula (2) is 1-isocyanate-2-p-tolueneethene, 1-isocyanate-2-o-tolueneethene, 1-isocyanate-2- (2 , 4-dimethylbenzene) ethene, 1-isocyanate-2- (4-fluorobenzene) ethene, 1-isocyanate-2- (4-chlorobenzene) ethene, 1-isocyanate-2- (4-bromobenzene) In ethene, 1-isocyanate-2- (3,4-diethylbenzene) ethene, 1-isocyanate-2- (2,4-diethylbenzene) ethene and 1-isocyanate-2- (4-nitrobenzene) ethene A production method characterized by using at least one kind . (Correction) The method according to claim 2, wherein the thionyl urea compound represented by the formula (3) is p-toluenthionyl urea, o-toluenthionyl urea, m-toluene thionyl urea, o-bromobenzenethionyl urea, m-bromobenzene thionyl urea, p-bromobenzene thionyl urea, o-chlorobenzene thionyl urea, m-chlorobenzene thionyl urea, p-chlorobenzene thionyl urea, o-fluorobenzene thionyl urea , m-fluorobenzenethionylurea, p-fluorobenzenethionylurea, 2,3-dimethylbenzenethionylurea, 2,4-dimethylbenzenethionylurea, 2,5-dimethylbenzenethionylurea, 2 -Ethylbenzenethionylurea, 3-ethylbenzenethionylurea, 4-ethylbenzenethionylurea, 2,4-diethylbenzenethionylurea, 2,4-dichlorobenzenethionylurea and 3,5-dichlorobenzene A process for producing at least one compound selected from thionylurea. (Correction) The process according to claim 1, wherein the isocyanate compound represented by the formula (2) and the thionyl urea compound represented by the formula (3) are reacted in a 1: 1 equivalent ratio . (Correction) The process according to claim 1, wherein the reaction is carried out at -10 to 40 캜 . A thermal recording paper comprising the compound represented by the formula (1) of claim 1 as a developer.