JPH08198791A - New terpene diphenol compound - Google Patents

Abstract

PURPOSE: To obtain a new terpene diphenol compound, capable of imparting excellent heat and solder crack resistances, color developing properties of a developer, shelf life of colored images, tacky adhesion of a tacky adhesive, strength of a cured resin, low hygroscopicity, etc., and useful as a raw material for a tacky adhesive, the developer, a medicine, an agrochemical, a curing agent, etc. CONSTITUTION: This compound of the formula (R1 to R4 are each H or methyl), e.g. 1,3-bis(4-hydroxybenzene)-p-menthane. The compound of the formula is obtained by reacting (A) 1mol cyclic terpene compound (e.g. limonene, dipentene, α-pinene, β-pinene, terpinolene or terpinene) with (B) 0.5-20mol, especially 2-12mol phenols (e.g. phenol, cresol or xylenol) in the presence of (C) an acidic catalyst [e.g. hydrochloric acid, sulfuric acid or (poly)phosphoric acid or boron trifluoride] at 40-160 deg.C temperature for 1-10hr.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel terpene diphenol compound. More specifically, as a polymer material having a terpene skeleton in the molecule and adding a phenol compound at the 1-position and 3-position of the terpene skeleton, polyester resin such as unsaturated polyester or aromatic polyester, polycarbonate, As a polymer raw material for phenol resin, polysulfone, polyimide, polyamideimide, polyetherimide, polybismaleimide, polyarylate, liquid crystal polymer, polyacetal, polyketone, etc., and natural rubber, SBR, SIS, SBS, SE
Thermoplastic rubber such as BS, EVA, LDPE, LLD
As a raw material for adhesives such as polyolefins such as PE, acrylics such as 2ethylhexyl acrylate, butyl acrylate, etc., and developers, antioxidants, UV absorbers, surfactants, insecticides, bactericides, pesticides, The present invention relates to a novel phenolic compound capable of improving performance such as heat resistance and stability when used as a raw material for dyes, pharmaceuticals, rubber chemicals, plasticizers, curing agents and the like.

[0002]

2. Description of the Related Art Conventionally, unsaturated polyester, polycarbonate, phenol resin, plastic polyester, polysulfone, polyimide, polyamideimide, polyetherimide, polybismaleimide, polyarylate, liquid crystal polymer, polyacetal, antioxidant and developer. Phenolic compounds such as bisphenol dioxoethyl ether and bisphenol A are used as raw materials for insecticides.

Specifically, bisphenol dioxoethyl ether in the case of unsaturated polyester, bisphenol A in the case of polycarbonate, a color developer for pressure-sensitive copying paper, heat transfer of dye, heat-sensitive recording material, phenol resin, Antioxidant, insecticide, polysulfone, polyimide,
In the case of polyamide imide, polyether imide, polybismaleimide, polyarylate, liquid crystal polymer, polyacetal and the like, phenolic compounds such as bisphenol A are mainly used.

However, in the case of unsaturated polyester or polycarbonate, heat resistance is obtained, and in the case of a developer for pressure-sensitive copying paper, dye thermal transfer, dry heat recording material, etc., color-forming ability and storability of color-developed image, phenol resin. In the case of, heat resistance and electric insulation, antioxidant, insecticide, polysulfone, polyimide, polyamideimide, polyetherimide, polybismaleimide, polyarylate, liquid crystal polymer, polyacetal, etc., heat resistance is sufficient. It does not satisfy practical performance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made against the background of the problems of the prior arts described above, and includes polyester resin such as unsaturated polyester and aromatic polyester, polycarbonate, phenol resin, polysulfone, polyimide, polyamideimide, As a polymer raw material such as polyether imide, poly bismaleimide, polyarylate, liquid crystal polymer, polyacetal, polyketone, etc., and also natural rubber type, thermoplastic rubber type such as SBR, SIS, SBS, SEBS, polyolefin such as EVA, LDPE, LLDPE. As a raw material for tacky adhesives such as acrylics such as 2-ethylhexyl acrylate, butyl acrylate, etc., and also as developers, antioxidants, UV absorbers, surfactants, insecticides, bactericides, agricultural chemicals, dyes, pharmaceuticals, Rubber chemicals, plasticizers, hard By using as a raw material for such agents, and to provide a novel phenolic compound which can be reduced heat resistance, the improvement of performance such as stability.

[0006]

The present invention provides a novel terpene diphenol compound represented by the following general formula (I).

[0007]

Embedded image

[In the general formula (I), R ₁ , R ₂ , R ₃ and R
₄ are the same or different and represent a hydrogen atom or a methyl group. The novel terpene diphenol compound of the present invention comprises 1 mol of a cyclic terpene compound and 0.5 to 20 mol of phenols,
Preferably, it can be produced by reacting 2 to 12 mol at a temperature of 40 to 160 ° C. for 1 to 10 hours in the presence of an acidic catalyst.

The cyclic terpene compound may be a monocyclic terpene compound or a bicyclic terpene compound, and examples thereof include limonene, dipentene, α-pinene and β.
-Pinene, terpinolene, terpinene and the like can be used.

As for the phenols, whichever kind of phenols is used, it is considered that the phenol skeleton is directly bonded to the 1 and 3 positions of the terpene skeleton. Therefore, depending on the target terpene diphenol compound. Then, phenol, cresol, xylenol, etc. are used.

Acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid,
Examples thereof include polyphosphoric acid, boron trifluoride or its complex, activated clay, and cation exchange resin. At this time, the reaction solvent does not necessarily have to be used, but usually aromatic hydrocarbons, alcohols, ethers and the like are used as the reaction solvent.

When the novel terpene diphenol compound of the present invention is produced by the above-mentioned production method, a compound of the following general formula (II) is produced as a main by-product. This by-product is characterized by its heat resistance and other properties.
Although inferior to the novel terpene diphenol compound of the present invention,
It can also be used as a raw material for polyesters, polycarbonates, color developers, phenol resins, and the like.

[0013]

Embedded image

[In the general formula (II), R ₁ , R ₂ , R ₃ and R
₄ are the same or different and represent a hydrogen atom or a methyl group. At this time, as a method of separating the novel terpene diphenol compound of the present invention from the by-product of the general formula (II),
Examples thereof include a recrystallization method using a solvent, column chromatography, liquid chromatography, and centrifugal partition chromatography.

The structure of the novel terpene diphenol compound of the present invention can be analyzed by NMR (nuclear magnetic resonance), MS (mass spectrometry), IR (infrared spectroscopy) and the like. Specifically, in NMR, the number and type of hydrogen atoms can be confirmed by ¹ H-NMR spectrum, and the number and type of carbon atoms can be confirmed by ¹³ C-NMR spectrum. Further, in GC-MS (gas chromatography mass spectrometry), the molecular weight and atomic group can be confirmed. Furthermore, in IR, the type of functional group and the type of bond between atoms can be confirmed.

The novel terpene diphenol compound of the present invention can be used as a raw material for unsaturated polyester. The unsaturated polyester is usually obtained by subjecting a dibasic acid such as maleic anhydride or fumaric acid to a condensation reaction of a dihydric alcohol such as ethylene glycol or bisphenol, and the novel terpene diphenol compound of the present invention is It is used as a substitute for the dihydric alcohol. At this time, the novel terpene diphenol compound may replace the total amount of the dihydric alcohol or may be used in combination with the dihydric alcohol depending on the required practical level.
Preferably, the amount of the novel terpene diphenol compound used is 30% by weight or more. Thus, by using the novel terpene diphenol compound as a raw material, the heat resistance of the unsaturated polyester can be improved.

The novel terpene diphenol compound of the present invention can be used as a raw material for polycarbonate. Polycarbonate is usually obtained by mixing bisphenol A and diphenyl carbonate, heating and melting, and performing polycondensation by transesterification under high temperature and reduced pressure, or by reacting Na salt of bisphenol A and phosgene. The novel terpene diphenol compound of the invention is used as a substitute for this bisphenol A. At this time, the novel terpene diphenol compound may replace the entire amount of bisphenol A or may be used in combination with bisphenol A depending on the required practical level, but the amount of the novel terpene diphenol compound used is preferably 20 Weight% or more is preferable. Thus, by using the novel terpene diphenol compound as a raw material, the heat resistance of polycarbonate can be improved.

The novel terpene diphenol compound of the present invention can be used as a raw material of a color developer used as a material for pressure-sensitive recording paper or a material for heat-sensitive recording paper. The color developer is usually produced from a phenolic compound such as bisphenol A or benzyl ester of parahydroxybenzoic acid as a raw material, and the novel terpene diphenol compound of the present invention is used as a substitute for this phenolic compound. . At this time, the novel terpene diphenol compound may be replaced with the entire amount of the phenolic compound or may be used in combination with the phenolic compound according to a required practical level, but preferably the novel terpene diphenol compound is used. The amount is preferably 5% by weight or more. Thus, by using the novel terpene diphenol compound as a raw material, the color developing ability of the color developer and the storage stability of the color image can be improved.

The novel terpene diphenol compound of the present invention can be used as a raw material for a phenol resin.
Phenolic resins are used for electrical materials and varnishes after forming novolacs and resoles by reacting with formaldehyde, and also for paints, rubber additives, printing inks and the like. This phenolic resin is usually produced from a phenolic compound as a raw material, but the novel terpene diphenol compound of the present invention is used as a substitute for this phenolic compound. At this time, the novel terpene diphenol compound may be replaced with the entire amount of the phenolic compound or may be used in combination with the phenolic compound according to a required practical level, but preferably the novel terpene diphenol compound is used. The amount is preferably 20% by weight or more. Thus, by using a new terpene diphenol compound as a raw material,
The heat resistance and electric insulation of the phenol resin can be improved.

Further, the novel terpene diphenol compound of the present invention is a polyester resin such as aromatic polyester, polysulfone, polyimide, polyamideimide, polyetherimide, polybismaleimide, polyarylate, liquid crystal polymer, polyacetal, polyketone. Polymer such as natural rubber, SBR, SIS, S
Thermoplastic rubber such as BS, SEBS, EVA, LDP
E, LLDPE and other polyolefin-based, 2-ethylhexyl acrylate, butyl acrylate and other acrylic-based adhesives, antioxidants, UV absorbers, surfactants, insecticides, bactericides, agricultural chemicals, dyes, pharmaceuticals, rubber It can be used as a raw material for chemicals, plasticizers, curing agents and the like.

These are usually produced from a phenolic compound as a raw material, but the novel terpene diphenol compound of the present invention is used as a substitute for this phenolic compound. At this time, the novel terpene diphenol compound may replace the entire amount of the phenolic compound, or may be used in combination with the phenolic compound in accordance with the required practical level, but the novel terpene diphenol compound is preferably used. The amount used is preferably 20% by weight or more. Thus, by using the novel terpene diphenol compound of the present invention, its heat resistance and stability can be improved.

As described above, the novel terpene diphenol compound of the present invention is a very useful compound which can be used in a wide variety of applications and can be expected to improve their performance.

[0023]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. Example 1 This example relates to a method for producing 1,3-bis (4-hydroxy-benzene) -p-menthane of the present invention represented by the following structural formula (I).

[0024]

[Chemical 4]

A 4-liter flask having an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube was charged with 564 g of phenol (equivalent to about 6 mol) and 34 g of a strong acid cation exchange resin, and then 80 While maintaining the temperature at 0 ° C., 136 g (corresponding to about 1 mol) of limonene was added dropwise over 4 hours, and then the mixture was reacted by stirring for 2 hours.

Then, the cation exchange resin was removed from the mixed solution by filtration, and the resulting reaction solution was washed twice with distilled water, and then at 30 ° C. at 250 ° C. under a reduced pressure of 5 mmHg.
After being kept for a minute, residual phenol and by-products were distilled off to obtain a pale yellow resinous material. This light yellow resinous material,
Crystallization was performed by a recrystallization method using toluene, and purification was performed to obtain 98 g of a white powder.

As a result of analyzing this white powder by gas chromatography, the terpene diphenol compound corresponding to the general formula (I) and the by-product corresponding to the general formula (II) were 68% by weight and 32% by weight, respectively. It was found to be included.

Further, the above-mentioned two kinds of compounds contained in the obtained white powder were subjected to structural analysis by NMR and MS. As a result, the compound represented by the general formula (I) and the compound represented by the general formula (II) have the same structure as 1,3-bis (4-hydroxy-benzene) -p-menthane represented by the structural formula (I): It was identified as 2,8-bis (4-hydroxy-benzene) -p-menthane of (II). ¹ H and ¹³ C nuclear magnetic resonance spectra, ¹³ C NMR-DE
Charts of PT spectrum and mass spectrum are shown in Figs.
Table 1 shows chemical shifts in ¹ H and ¹³ C nuclear magnetic resonance spectra.

[0029]

Embedded image

[0030]

[Table 1]

Example 2 This example relates to a process for producing 1,3-bis (3-methane-4-hydroxy-benzene) -p-menthane of the present invention having the following structural formula (III).

[0032]

[Chemical 6]

In a 4-neck flask having an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel and a condenser, o-
After charging 648 g of cresol (equivalent to about 6 mol) and 34 g of activated clay (Galeoearth H made by Mizusawa Chemical Co., Ltd.), 80 ° C
While maintaining the temperature at 1, 136 g (corresponding to about 1 mol) of α-pinene was added dropwise over 4 hours, and then stirred for 2 hours to cause a reaction.

Then, the activated clay was removed from the mixed solution by filtration, the obtained reaction solution was washed twice with distilled water, and then the mixture was kept at 250 ° C. for 30 minutes under a reduced pressure of 5 mmHg to retain the remaining o-cresol. And a by-product were distilled off by distillation to obtain 245 g of a pale yellow resinous material.

The pale yellow resinous material was analyzed by gas chromatography, and as a result, the terpene diphenol compound corresponding to the general formula (I) and the by-product corresponding to the general formula (II) were respectively contained in a weight ratio of 61. %, 24% was found to be included.

Further, the above-mentioned two kinds of compounds contained in the obtained single yellow resinous substance were analyzed by NMR and MS to carry out a structural analysis. As a result, the general formula (I)
And the compound corresponding to the general formula (II) are 1,3-bis (3-methyl-4-hydroxy-benzene) -p-menthane of the structural formula (III) and the following structural formula (III), respectively. IV) identified as 2,8-bis (3-methyl-4-hydroxy-benzene) -p-menthane. Charts of ¹ H nuclear magnetic resonance spectrum and mass spectrum are shown in FIGS.

[0037]

[Chemical 7]

Example 3 In this example, 1,3-bis (3,5-dimethyl-4-hydroxy-benzene) -p of the present invention represented by the following structural formula (V) was used.
-Regarding the manufacturing method of Mentan.

[0039]

Embedded image

A 4-liter flask with an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube was charged with 2.
After charging 732 g of 6-xylenol (equivalent to about 6 mol) and 34 g of activated clay (Galeoearth H manufactured by Mizusawa Chemical Co., Ltd.),
136 g of limonene (about 1
(Corresponding to mol) was added dropwise over 4 hours, and then stirred for 2 hours for reaction.

Next, the activated clay was removed from the mixed solution by filtration, and the obtained reaction solution was washed with distilled water three times, and then kept at 250 ° C. for 30 minutes under a reduced pressure of 5 mmHg to leave 2,6 -Xylenol and by-products were distilled off to obtain 310 g of a pale yellow resinous material.

The pale yellow resinous material was analyzed by gas chromatography, and as a result, the terpene diphenol compound corresponding to the general formula (I) and the by-product corresponding to the general formula (II) were each added in a weight ratio of 63. %, 21% was found to be included.

Further, the above-mentioned two kinds of compounds contained in the obtained single yellow resinous material were subjected to structural analysis by NMR and MS. As a result, the compound corresponding to the above general formula (I) and the compound corresponding to the above general formula (II) were respectively formed into 1,3-bis (3,5-dimethyl-) of the structural formula (V).
It was identified as 4-hydroxy-benzene) -p-menthane and 2,8-bis (3,5-dimethyl-4-hydroxy-benzene) -p-menthane of the following structural formula (VI). ¹
14 to 16 show charts of nuclear magnetic resonance spectrum and mass spectrum of H.

[0044]

[Chemical 9]

Test Example 1 The white powder obtained in Example 1 was further separated into a compound of structural formula (I) and a compound of structural formula (II) by a recrystallization method using toluene. In a 1 liter separable flask having a stirrer, a thermometer, a nitrogen inlet, an exhaust port and a vacuum port, 224 g of diphenyl carbonate
(1.05 mol), the compound 324 of the structural formula (I)
g (1 mol) was charged, and at 30 ° C. under a nitrogen stream, 30
After the reaction for a minute, the pressure was switched to a reduced pressure, the degree of vacuum was gradually increased from normal pressure to 30 minutes, and the reaction was performed at 1 mmHg for 1 hour to obtain a colorless and transparent aromatic polycarbonate. Table 2 shows the results. The weight average molecular weight (Mw) and freezing point temperature (° C.) of the obtained aromatic polycarbonate were measured. The molecular weight is G by Waters
The glass transition temperature is a GPC polystyrene-equivalent molecular weight of a PC device, and the glass transition temperature was measured using an SSC / 560S differential scanning calorimeter manufactured by Daini Seikosha Co., Ltd.

Comparative Test Example 1 Instead of the terpene diphenol compound used in Test Example 1, 324 g of the compound of the above structural formula (II) was used.
(1 mol) The same procedure as in Test Example 1 except that
A colorless transparent aromatic polycarbonate was obtained. Table 2 shows the results
Shown in

Comparative Test Example 2 Instead of the terpene diphenol compound used in Test Example 1, 228 g (1 mo) of bisphenol A was used.
l) A colorless and transparent aromatic polycarbonate was obtained in the same manner as in Test Example 1 except that it was used. Table 2 shows the results.

[0048]

[Table 2]

According to Table 2, the aromatic polycarbonate of Test Example 1 has a higher glass transition temperature than the aromatic polycarbonates of Comparative Test Examples 1 and 2. Therefore,
Aromatic polycarbonate using a novel terpene diphenol compound as a raw material has improved heat resistance as compared with conventional aromatic polycarbonates. Further, the terpene diphenol compound of the present invention is superior to the by-product of structural formula (II) (Comparative Example Test Example 2) in improving the heat resistance.

Test Example 2 The white powder obtained in Example 1 was further separated into the compound of structural formula (I) and the compound of structural formula (II) by a recrystallization method using toluene. A mixture having the following composition was pulverized and dispersed using a sand grinder so that the average particle diameter was 2 μm or less, to prepare solutions A and B, respectively.

Solution A 3-diethylamino-6-methyl-7-anilinofluorane; 25 parts by weight 10% by weight PVA aqueous solution; 50 parts by weight water; 25 parts by weight Solution B terpene diphenol compound of structural formula (I); 5 parts by weight Kaolin; 8 parts by weight 50% by weight calcium carbonate dispersion; 10 parts by weight 10% by weight PVA aqueous solution; 52 parts by weight water; 25 parts by weight

Further, the weight ratio of liquid A and liquid B is 6:94.
To prepare a thermosensitive color developing layer coating solution, and weigh 50
It was coated on a fine paper of g / m ^{2 so} as to have a dry weight of about 12 g / m ^2, and dried to obtain a heat-sensitive recording material. The following quality performance test was conducted on this heat-sensitive recording material.

Coloring Density The surface of the thermosensitive recording sheet on which the coloring layer was coated was pressed against a hot plate heated to 110 ° C. for 5 seconds at a pressure of 10 g / cm ² to develop a color, and then a Macbeth densitometer (using a visible filter,
The same shall apply hereinafter), and this was used as the color density. Heat resistance The color layer coating surface of the heat-sensitive recording sheet is pressed against a hot plate heated to 110 ° C for 5 seconds at a pressure of 10 g / cm ² to develop color, and left in a constant temperature layer at 60 ° C for 24 hours, and then measured with a Macbeth densitometer. It is the residual rate (%) of the measured color image area. Moisture resistance The surface of the thermosensitive recording sheet to which the color-developing layer is applied is pressed against a hot plate heated to 110 ° C for 5 seconds at a pressure of 10 g / cm ² to develop color, and left in a constant-humidity bath at 40 ° C and 90% relative humidity for 24 hours. Later, it is the residual rate (%) of the color image portion measured by a Macbeth densitometer.

Water resistance The surface of the thermosensitive recording sheet to which the color-developing layer was applied was pressed against a hot plate heated to 110 ° C. for 5 seconds at a pressure of 10 g / cm ² to develop color, and immersed in tap water at room temperature for 24 hours, and then a Macbeth densitometer. It is the residual rate (%) of the color image portion measured in (1). Plasticizer resistance The coloring layer coated surface of the thermosensitive recording sheet is pressed against a hot plate heated to 110 ° C for 5 seconds at a pressure of 10 g / cm ² to develop a color, and a PVC wrap film is superposed on both sides to 100 g / c.
It is the residual ratio (%) of the color image portion measured by a Macbeth densitometer after left for 15 hours at room temperature under a load of m ² . The results are shown in Table 3.

Comparative Test Example 3 A thermosensitive recording sheet was obtained in the same manner as in Test Example 2 except that the compound of the above structural formula (II) was used instead of the terpene diphenol compound used in Test Example 2. It was Table 2 shows the results.

Comparative Test Example 4 The same procedure as in Test Example 2 was repeated except that 2,2 '-(p-hydroxyphenyl) propane was used instead of the terpene diphenol compound used in Test Example 2, and the heat sensitivity was increased. A recording sheet was obtained. The results are shown in Table 3.

[0057]

[Table 3]

According to Table 3, a heat-sensitive recording sheet using the novel terpene diphenol compound of the present invention (Test Example 2)
Has a high color density and is improved in heat resistance, moisture resistance, water resistance, and plasticizer resistance as compared with the conventional thermal recording sheet (Comparative Test Example 4).
The plasticizer resistance is remarkably improved. In addition, the terpene diphenol compound of the present invention (Test Example 2) is superior to the by-product of structural formula (II) (Comparative Test Example 3) in improving the performance.

[0059]

The novel terpene diphenol compound of the present invention is a polyester resin such as unsaturated polyester or aromatic polyester, polycarbonate, phenol resin, polysulfone, polyimide, polyamideimide, polyetherimide, polybismaleimide, polyarylate, Liquid crystal polymers, polymers such as polyacetal, polyketone, natural rubber, SBR, SIS, SBS,
Thermoplastic rubber such as SEBS, EVA, LDPE, L
Polyolefin-based adhesive such as LDPE and acrylic-based adhesive such as 2-ethylhexylbutyl, developer, antioxidant, UV absorber, surfactant, insecticide, bactericide, pesticide, dye, pharmaceutical, rubber By using it as a raw material for chemicals, plasticizers, hardeners, etc., its heat resistance and stability are improved, and in the case of a color developer, the coloring ability and the preservation of colored images are improved, making it a phenol resin In that case, electrical insulation is improved, in the case of adhesives, the adhesive strength is improved, in the case of curing agents, the strength of the resin is improved, moisture absorption is suppressed, and solder crack resistance is improved. Also has the effect of being excellent.

[Brief description of drawings]

FIG. 1 is a chart of ¹ H nuclear magnetic resonance spectrum of the white powder of Example 1.

FIG. 2 is a chart of ¹³ C nuclear magnetic resonance spectrum of the white powder of Example 1 (No. 1).

FIG. 3 is a chart of ¹³ C nuclear magnetic resonance spectrum of the white powder of Example 1 (No. 2).

FIG. 4 ¹³ C NMR-DEPT of the white powder of Example 1.
It is a chart of a spectrum.

FIG. 5: By-product 1 of the general formula (II) in Example ¹
It is a chart of the nuclear magnetic resonance spectrum of H.

FIG. 6 is a by-product ¹³ of the general formula (II) in Example 1.
It is a chart of the nuclear magnetic resonance spectrum of C.

FIG. 7: By-product ¹³ of the general formula (II) in Example 1
It is a chart of the nuclear magnetic resonance spectrum of C.

FIG. 8: By-product ¹³ of the general formula (II) in Example 1
It is a chart of NMR-DEPT spectrum of C.

FIG. 9 is a mass spectrum chart of the compound of the present invention in Example 1.

FIG. 10 is a mass spectrum chart of a by-product of the general formula (II) in Example 1.

FIG. 11 is a chart of ¹ H nuclear magnetic resonance spectrum of the pale yellow resinous material of Example 2.

12 is a chart of a mass spectrum of the compound of the present invention in Example 2. FIG.

FIG. 13 is a mass spectrum chart of a by-product of the general formula (II) in Example 2.

FIG. 14 is a chart of ¹ H nuclear magnetic resonance spectrum of the pale yellow resinous material of Example 3.

15 is a chart of a mass spectrum of the compound of the present invention in Example 3. FIG.

16 is a chart of a mass spectrum of a by-product of general formula (II) in Example 3. FIG.

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[Procedure amendment]

[Submission date] June 15, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

Comparative Test Example 3 A thermosensitive recording sheet was obtained in the same manner as in Test Example 2 except that the compound of the above structural formula (II) was used instead of the terpene diphenol compound used in Test Example 2. It was The results are shown in Table 3.

Claims (1)

[Claims] 1. A novel terpene diphenol compound represented by the following general formula (I). Embedded image [In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each represents a hydrogen atom or a methyl group. ]