JP4815684B2 - Heat resistant printing ink - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a printing ink for insert film that has excellent heat resistance and excellent flex resistance in a printed portion after printing.
[0002]
[Prior art]
Conventionally, a film with decorative printing on the surface is attached to the mold, and molten resin is injected into the mold toward the film printing surface to integrate the film with decorative printing on the resin surface. A method of obtaining various printed injection molded products having curved surfaces, irregularities, or flat surfaces by injection molding (hereinafter referred to as insert molding) is used. For example, it is applied to injection moldings such as various meter panels and sunroofs of automobiles, edges of window glass, mobile phone housings, AV product housings, display parts of portable terminal devices and copying machines, and miscellaneous goods.
[0003]
The printing ink for the decoratively printed film is mainly composed of a solvent, a dye / pigment, and a binder resin. The printing ink removes the solvent by printing on the film and then drying to fix the dye / pigment to the binder resin, and at the same time the film and the binder resin are in close contact with each other, whereby a decorative printed film is obtained. The decoratively printed film is required to have heat resistance that does not cause bleeding or blurring on the printed surface even when it is in contact with the molten resin or held in a heated mold during insert molding.
[0004]
Since the heat resistance depends on the heat resistance of the binder resin, a special polycarbonate resin having excellent heat resistance and good solvent solubility is used as the binder resin in JP-A-8-3502 and JP-A-2000-109492. Heat resistant printing inks have been developed. These binder resins have good heat resistance and good solubility in various solvents, and were suitable as binder resins for heat-resistant printing inks. However, the binder resins are hard and brittle, and bend and injection-molded films. There was room for improvement because cracks could occur due to impacts such as time.
[0005]
[Problems to be solved by the invention]
The subject of this invention is providing the heat resistant printing ink which was excellent in the heat resistance of the printing part after printing, and was excellent in the bending resistance of the printing part, and reduced the crack generation of the printing surface.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the conventional problems, the present inventors have found that a printing ink using a copolymer polycarbonate resin derived from a specific bisphenol as a binder resin has good printability and is The present invention has been completed by finding that the printed surface is excellent in bending resistance and can be used as a heat-resistant printing ink suitable for a decorative film for insert molding.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
That is, a polycarbonate obtained by reacting a compound represented by the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the general formula (C) with a carbonate-forming compound. The general formula (B) is 20 to 60 wt% with respect to all monomer components [general formula (A) + general formula (B) + general formula (C)], and the intrinsic viscosity [η] is It is another object of the present invention to provide a heat-resistant printing ink characterized by using a polycarbonate resin of 0.1 to 1.0 [dl / g] as a binder resin.
[Chemical formula 5]
Wherein R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number (It can also have 1 to 5 alkoxy groups.)
[Chemical 6]
Wherein R _{5 to} R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number R _{9 to} R ₁₂ may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or carbon. An alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms A group having an alkoxy group having 1 to 5 carbon atoms. That .R ₁₃ is either an aliphatic group having 1 to 6 carbon atoms, the .X simply represents a _{bond, -SiO (R 14) (R} 15) - and / or _{-SiO (R 16) (R 17} ) - represents a homopolymer or random copolymer, the polymerization degree is 0 to 200, R ₁₄ to R ₁₇ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, carbon atoms 6-12 An aryl group, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, (It can also have a 1-5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group.)
[Chemical 7]
(In the formula, R _{18 to} R ₁₉ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 alkoxy groups or aralkyl groups having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon It may also have an alkoxy group of 1 to 5. Y is
[Chemical 8]
Wherein R _{20 to} R ₂₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 carbon atoms. Represents an aryl group having ˜12 or a group in which R ₂₀ and R ₂₁ are bonded together to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms, and when these groups have a carbon atom, As a substituent, it can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group. a represents an integer of 0 to 20. )
[0008]
Specific examples of the compound of the general formula (A) for deriving the polycarbonate resin of the present invention include 9,9-bis (4-hydroxy-2-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3). -Methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methoxy-4-) Hydroxyphenyl) fluorene, 9,9-bis (3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9 Bis (3-methyl-4-hydroxyphenyl) fluorene and 3,6-diphenyl-9,9-bis (4-hydroxyphenyl) fluorene, and the like. Among these, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene are particularly preferable. preferable. Two or more of these compounds can be used in combination.
[0009]
Specific examples of the compound of the general formula (B) for deriving the polycarbonate resin of the present invention include the following.
[0010]
[Chemical 9]
[0011]
These can be used in combination of two or more. X preferably includes 1 to 100 dimethylsiloxanes or 1 to 100 diphenylsiloxanes, and random copolymers thereof. Among these, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymer siloxane and α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane are particularly preferable.
[0012]
Specific examples of the compound represented by formula (C) in the present invention include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl). ) Sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4 -Hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) ) Cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3-methylphenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP; BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl) ) Propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-2-methyl-5-t-butylphenyl) butane The These can be used in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.
[0013]
Examples of the carbonate ester-forming compound in the present invention include phosgene, bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Is mentioned. Two or more of these compounds can be used in combination.
[0014]
The polycarbonate resin used for the binder resin of the heat-resistant printing ink of the present invention is the compound represented by the general formula (A) and the general formula (B), or the general formula (A), the general formula (B), and the general formula (C). Can be produced by reacting with a carbonate ester-forming compound, which is a known method used in producing a polycarbonate derived from bisphenol A, such as a direct reaction between bisphenols and phosgene. A method such as a reaction (phosgene method) or a transesterification reaction (transesterification method) between a bisphenol and a bisaryl carbonate can be employed.
[0015]
The polycarbonate resin of the present invention needs to maintain the necessary solvent solubility and strength as a binder resin for heat-resistant printing ink in a well-balanced manner. If the intrinsic viscosity of the binder resin is too low, the strength is insufficient and the intrinsic viscosity is low. Is too high, the solvent solubility decreases and the ink viscosity increases, and the printability decreases. As a desirable intrinsic viscosity range, the intrinsic viscosity is preferably in the range of 0.1 to 1.0 dl / g, and more preferably in the range of 0.15 to 0.5 dl / g.
[0016]
The amount of the general formula (B) used is 20 to 60 with respect to the total amount of the general formula (A), the general formula (B), and the general formula (C) in consideration of the strength and heat resistance of the binder resin. % By weight is preferred. When the general formula (B) is less than 20% by weight, the bending resistance is lowered, and when it exceeds 60% by weight, the heat resistance is insufficient.
[0017]
The use of the general formula (C) can be used for improvement of various performances, compatibility with dyes / pigments, etc., but is used within a range not impairing the performance of the binder resin for heat-resistant printing ink of the present invention. The amount of the general formula (C) used is preferably less than 50% by weight based on the total amount of the general formula (A) and the general formula (C).
[0018]
The heat-resistant printing ink of the present invention is produced by dissolving the binder resin and dye / pigment in a desired solvent. Examples of the dye / pigment used in the printing ink of the present invention include, for example, anthraquinone-based and naphthoquinone-based dyes, inorganic pigments such as titanium oxide, carbon black, calcium carbonate, and metal particles, and organic pigments such as azo pigments and phthalocyanine pigments. And pigments. These dyes / pigments are present together with the binder resin in a dissolved or dispersed state in the ink.
[0019]
As the solvent for ink preparation, non-halogen organic solvents are preferable, for example, aromatic hydrocarbons such as toluene and xylene, cyclic ketones such as cyclohexanone and cyclopentanone, cyclic ethers such as tetrahydrofuran and dioxane, dimethyl Examples include formamide and dimethyl sulfoxide. Among them, dioxane, tetrahydrofuran, toluene, xylene, and cyclohexanone are preferable. Moreover, a solvent may be used independently or may be used with 2 or more types of mixed solvents. Furthermore, for the purpose of improving dye / pigment dispersibility, coatability and drying properties, alcohols such as methanol and ethanol, acyclic ketones such as methyl ethyl ketone and acetone, esters such as ethyl acetate and methyl acetate, cyclohexane, n- Solvents or poor solvents such as aliphatic hydrocarbons such as heptane, alkylene glycols and derivatives thereof, and oils such as silicone oil and soybean oil can be used in combination.
[0020]
In addition to the binder resin and dye / pigment, the printing ink includes organic and inorganic fine particles, a release agent, an antioxidant, a plasticizer, a dispersant, an infrared absorber, an antistatic agent, an ultraviolet absorber, as necessary. You may add an antifoamer, a leveling agent, etc.
[0021]
Moreover, although the compounding quantity of binder resin in ink is influenced by intrinsic viscosity or solvent solubility, 1 to 70 weight% is preferable and 5 to 50 weight% is more preferable. When the concentration of the binder resin is within this range, the solvent solubility and the ink application property are well balanced, and the workability is improved.
[0022]
In the present invention, the heat-resistant printing ink is applied to a base film and used for insert molding decoration. The resin film used for the base film is a thermoplastic resin film, specifically, a polycarbonate resin film, a polyester resin film, a polyamide resin film, a heat-resistant polyolefin resin film, and the like. It is excellent in heat resistance and mechanical strength and is preferably used. These resin films are usually 0.1 to 2 mm thick, and preferably 0.1 to 0.5 mm thick.
[0023]
Examples of the method for applying the heat-resistant printing ink of the present invention to the base film include screen printing, gravure printing, flexographic printing, etc., but the ink layer to be applied has a wide film thickness range, and the ink layer can be thickened. Screen printing is particularly preferable because it can be performed. The coated ink is dried by natural standing, cold / hot air blowing, infrared irradiation, heat baking, ultraviolet irradiation or the like to obtain a dried printed surface.
[0024]
The heat-resistant printing ink of the present invention can be suitably used as an ink for a decorative printing film in insert molding for the purpose of decorating a thermoplastic resin. In particular, the decorative print film using the heat-resistant printing ink of the present invention is also suitable for decorating a polycarbonate resin or a polycarbonate / ABS blend resin that is molded at a relatively high temperature. No blur or blur is seen, and the adhesiveness of the printed part is excellent.
[0025]
In addition, the decorative printing film using the heat-resistant printing ink of the present invention is superior in bending resistance of the decorative printing film printing surface as compared with the conventional printing ink, so that the normal transportation, storage, Even if it is exposed to bending or impact applied during the molding operation or the like, the decorative surface is less likely to be damaged, and the appearance defect after insert molding is reduced, and at the same time, the workability is improved.
[0026]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0027]
[Bending resistance test of printed film]
One side of a 0.2 mm thick polycarbonate film was subjected to a solid coating screen printing using the printing ink of the example or the comparative example and dried at 100 ° C. for 2 hours to obtain a printed film test piece. The obtained film test piece was cut into a strip of 70 mm length × 50 mm width, fixed on the test stand, and after bending test for 40 minutes in the vertical direction with a shaker at 180 times / min for 5 minutes and 1 hour. The presence or absence of cracks on the printed surface of the film test piece was visually determined. When the crack was confirmed visually, it was indicated by x, and when the crack was not confirmed, it was indicated by ○.
[0028]
[Appearance of molded product after bending resistance test of printed film]
Using the printed film after the 5-minute bending test, the printed part of the molded product after the insert molding was visually determined, and a case where color loss or unevenness was confirmed was indicated as x, and a case where no color was confirmed was indicated as ◯.
[0029]
[Measurement method of intrinsic viscosity]
A 0.5 w / v% solution of polycarbonate resin in dichloromethane was determined using an Ubbelohde viscosity tube at 20 ° C. and a Huggins constant of 0.45.
[0030]
Example 1
A normal interfacial polycondensation reaction is performed between 50 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as BCFL), 50 parts by weight of the following polysiloxane compound (hereinafter abbreviated as Si1) and phosgene. Thus, a polycarbonate resin (intrinsic viscosity 0.38 dl / g) was obtained.
[0031]
[Chemical Formula 10]
[0032]
The obtained polycarbonate resin was mixed with 30 parts by weight as a binder resin, 10 parts by weight of anthraquinone Plast Red 8370 (Arimoto Chemical Industry) as a dye, 100 parts by weight of cyclohexanone and 30 parts by weight of dioxane as a solvent, and printing ink. Adjusted. Next, the printing ink was screen-printed on one side of a commercially available polycarbonate film (Mitsubishi Gas Chemical; Iupilon FE-2000) having a thickness of 0.2 mm × 150 mm × 70 mm as a base film, dried at 100 ° C. for 2 hours, The printed film was subjected to a flexibility test for 5 minutes and 1 hour, and the printed surface was visually evaluated. Further, the printed film after the bending test for 5 minutes was mounted on a mold, and polycarbonate (Mitsubishi Gas Chemical Co., Ltd .; Iupilon S-2000) melted at 300 ° C. was insert-molded with a vertical injection molding machine. The appearance of the obtained insert-molded product was visually evaluated. The results are shown in Table 1.
[0033]
Example 2
Instead of Si1, the following polysiloxane compound (hereinafter abbreviated as Si2) was changed to 40 parts by weight, and the polycarbonate resin (extreme viscosity 0.28 dl / g) obtained by changing BCFL to 60 parts by weight was used as the binder resin. In the same manner as in Example 1, printing, molding, and evaluation were performed. The results are shown in Table 1.
[0034]
Embedded image
[0035]
Example 3
Instead of Si1, the following polysiloxane compound (hereinafter abbreviated as Si3) was changed to 40 parts by weight, and the polycarbonate resin (extreme viscosity 0.25 dl / g) obtained by changing BCFL to 60 parts by weight was used as the binder resin. In the same manner as in Example 1, printing, molding, and evaluation were performed. The results are shown in Table 1.
[0036]
Embedded image
[0037]
Example 4
Polycarbonate resin obtained by changing BCFL to 50 parts by weight, Si1 to 40 parts by weight, and using 10 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BPA) (intrinsic viscosity 0.35 dl / Printing, molding, and evaluation were performed in the same manner as in Example 1 except that g) was used as the binder resin. The results are shown in Table 1.
[0038]
Example 5
Printing, molding, and evaluation were performed in the same manner as in Example 1 except that 20 parts by weight of a cobalt blue pigment (manufactured by Bayer; Lightfast Blue 100) was used instead of the dye. The results are shown in Table 1.
[0039]
Example 6
Printing, molding, and evaluation were performed in the same manner as in Example 1 except that 100 parts by weight of cyclohexanone was changed to 80 parts by weight of cyclopentanone and 30 parts by weight of dioxane was changed to 20 parts by weight of tetrahydrofuran. The results are shown in Table 1.
[0040]
Example 7
Printing, molding, and evaluation were performed in the same manner as in Example 1 except that 30 parts by weight of dioxane was changed to 30 parts by weight of toluene and the dye was changed to 15% by weight. The results are shown in Table 1.
[0041]
Comparative Example 1
Instead of the polycarbonate resin of Example 1, a commercially available polycarbonate resin derived from 1,1-bis (4-hydroxyphenyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd .; Iupilon Z200, intrinsic viscosity 0.49 dl / g) was used as the binder resin. Printing, molding, and evaluation were performed in the same manner as in Example 1 except that it was used. The results are shown in Table 1.
[0042]
Comparative Example 2
Instead of the polycarbonate resin of Example 1, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane and phosgene were used to carry out a normal interfacial polycondensation reaction to produce a homopolycarbonate resin (intrinsic viscosity). Printing, molding, and evaluation were performed in the same manner as in Example 1 except that 0.35 dl / g) was used as the binder resin. The results are shown in Table 1.
[0043]
Comparative Example 3
Example 1 except that a homopolycarbonate resin derived from commercially available BPA (manufactured by Mitsubishi Gas Chemicals; Iupilon H-4000, intrinsic viscosity 0.35 dl / g) was used as the binder resin instead of the polycarbonate resin of Example 1. However, the binder resin could not be dissolved in the solvent, and printing ink could not be prepared.
[0044]
[Table 1]
[0045]
【Effect of the invention】
The decorative printing film using the heat-resistant printing ink of the present invention is characterized by maintaining the heat resistance and adhesion as well as the bending resistance of the printing surface of the decorative printing film, compared to those using the conventional printing ink. Have Therefore, it is less likely to damage the decorative surface even if it is exposed to bending or impact applied during normal transportation, storage, molding operations, etc., and the workability is improved while reducing appearance defects after insert molding. , Contribute to quality and yield improvement. Especially for various meter panels and sunroofs of automobiles with large thin areas and printing areas, window glass edges, mobile phone housings, AV product housings, display parts of portable terminal devices / copiers, etc. It is suitable as a printing ink for the decorative printing film used.

Claims (9)

A polycarbonate obtained by reacting a compound represented by the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the general formula (C) with a carbonate-forming compound. The general formula (B) is 20 to 60 wt% with respect to all monomer components [general formula (A) + general formula (B) + general formula (C)], and the intrinsic viscosity [η] is 0 A heat-resistant printing ink comprising a polycarbonate resin having a viscosity of 0.1 to 1.0 [dl / g] as a binder resin.
Wherein R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number (It can also have 1 to 5 alkoxy groups.)
_(Wherein, R 5 to R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, 1 to 5 carbon atoms Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number R _{9 to} R ₁₂ may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. An alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms Group having an alkoxy group having 1 to 5 carbon atoms Whether it _{.R 13} represents an aliphatic group having 1 to 6 carbon atoms, .X represents a single bond to the benzene ring and Si are directly _{bonded, -SiO (R 14) (R} 15) - and / or - This represents a homopolymer or random copolymer of SiO (R ₁₆ ) (R ₁₇ ) —, the degree of polymerization is 1 to 200, and R _{14 to} R ₁₇ are each independently a hydrogen atom, 1 to 5 carbon atoms. An alkyl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and these groups have a carbon atom. In some cases, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.)
(Wherein R _{18 to} R ₁₉ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 alkoxy groups or aralkyl groups having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon It may also have an alkoxy group of 1 to 5. Y is
Wherein R _{20 to} R ₂₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 carbon atoms. Represents an aryl group having ˜12, or R ₂₀ and R ₂₁ are bonded together to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms, and when these groups have a carbon atom, As a substituent, it can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group. a represents an integer of 0 to 20. ) The general formula (A) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2- The heat-resistant printing ink according to claim 1, which is at least one selected from the group of (methylphenyl) fluorene. The heat-resistant printing ink according to claim 1, wherein the carbonate forming compound is phosgene. The heat-resistant printing ink according to claim 1, wherein R _{9 to} R _{12 in} the general formula (B) are at least one selected from a methyl group and a phenyl group. Random copolymer of dimethylsiloxane and diphenylsiloxane having a 3- (o-hydroxyphenyl) propyl group at the α, ω position, and α, ω-bis [3- (o-hydroxyphenyl) propyl The heat-resistant printing ink according to claim 1, which is at least one derived from the group of polydimethylsiloxanes. The heat-resistant printing ink according to claim 1, wherein the general formula (C) is 2,2-bis (4-hydroxyphenyl) propane. The heat-resistant printing ink according to claim 1, wherein the ratio of the general formula (C) is, by weight ratio, the general formula (C) / [general formula (A) + general formula (C)] <0.5. The heat-resistant printing ink according to claim 1, wherein a non-halogen organic solvent is used as the ink adjusting solvent. A method for producing a decorative resin molded product, comprising: using a film on which the ink according to claim 1 is printed; inserting the film into a mold; and injecting a heat-melted resin into the mold. .