JP6398787B2 - Binder resin for ink and printing ink - Google Patents

Description

  The present invention relates to a binder resin for ink excellent in heat resistance and stain resistance, a printing ink containing the same, and a method for producing a decorated resin molded article using the ink.

  Conventionally, a film with decorative printing on the surface is attached to the mold, and the molten resin is injected into the mold to the film printing surface, and the film with decorative printing on the resin surface is integrated. 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. This method can be applied, for example, to various meter panels and sunroofs of automobiles, edges of window glass, mobile phone housings, AV product housings, display parts of portable terminal devices / copiers, etc., and injection molded products such as miscellaneous goods. Applied.

  The printing ink for the decoratively printed film is mainly composed of a solvent, a coloring matter (dye and / or pigment) and a binder resin (binder resin). The printing ink is printed on a film and dried to remove the solvent and fix the pigment to the binder resin. At the same time, the film and the binder resin are brought into close contact with each other to obtain a decorative printed film. 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.

Since the heat resistance depends on the heat resistance of the binder resin, a heat-resistant printing ink using a special polycarbonate resin having excellent heat resistance and good solvent solubility as a binder resin has been developed (Patent Document 1, Patent Document) 2). These binder resins have good heat resistance, are well soluble in various solvents, and are suitable as binder resins for heat-resistant printing inks. However, these heat-resistant printing inks are susceptible to cracking due to fingerprints and hand cream contamination and adhesion at injection molding sites and storage sites, and there is room for improvement.
On the other hand, it has been disclosed that a polycarbonate resin using bis (4-hydroxybiphenyl) ether as a raw material is used as a polycarbonate resin solution for cast film formation (Patent Document 3). However, a specific ink use is not described, and it has not been examined whether it can be applied to a heat-resistant ink use.

Japanese Patent Laid-Open No. 2001-19885 JP 2008-63501 A JP-A-4-268365

  The object of the present invention is excellent in heat resistance, even if fingerprints or hand cream adheres to the printed surface before insert molding, the adhering part is in contact with the hot melt resin, and the appearance that ink flow does not occur is a good decoration An object of the present invention is to provide a binder resin for ink excellent in stain resistance from which a molded product can be obtained, and a printing ink using the binder resin.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that printing ink using a polycarbonate resin having a specific structural unit as a binder resin has good printability and the printed surface has a fingerprint or hand. It has been found that it has heat resistance and stain resistance that do not cause ink flow even when it is contaminated with cream or in contact with a hot-melt resin after printing, and the present invention has been completed. That is, this invention relates to the manufacturing method of the binder resin for inks shown below, the printing ink using this binder resin, and also the decorative resin molding using this ink.

<1> A binder resin for ink comprising a polycarbonate resin having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), the following general formula (1) Is a binder resin for ink, wherein the content of the structural unit represented by is 20 mol% or more and 70 mol% or less with respect to all the structural units constituting the polycarbonate resin.
(In the formula, R _{1 to} R ₄ each independently represent hydrogen, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 1 to 1 carbon atoms, each of which may have a substituent. 5 represents an alkoxy group having 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms.)
(In the formula, R ₅ and R ₆ each independently represent hydrogen, an alkyl group having 1 to 16 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, each of which may have a substituent (provided that , _{R 5} and _{R 6} are not the same), or, _{R 5} and _{R 6} are bonded, .R ₇ to R ₁₀ to form a heterocyclic ring of carbon ring or element number 5 to 12 5 to 20 carbon atoms Are each independently hydrogen, an optionally substituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 6 carbon atoms. Represents an -12 aryl group.)
<2> The binder resin for ink according to <1>, wherein R _{1 to} R ₄ in the general formula (1) are hydrogen.
<3> In the general formula (2), R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 16 carbon atoms, or each having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. The binder resin for ink according to the above <1> or <2>, which represents an alkenyl group (however, R ₅ and R ₆ are not the same).
<4> In the general formula (2), R ₅ and R ₆ represent hydrogen or an alkyl group having 1 to 16 carbon atoms (provided that R ₅ and R ₆ are not the same), described in the above <3> This is a binder resin for ink.
<5> The binder resin for ink according to any one of <1> to <4>, wherein R _{7 to} R ₁₀ in the general formula (2) are hydrogen.
<6> The structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1- Bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) The binder for ink according to <1> or <2> above, derived from butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, or 1,1-bis (4-hydroxyphenyl) cyclododecane Resin.
<7> The structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, Or it is binder resin for inks in any one of said <1> to <6> derived | led-out from 1, 1-bis (4-hydroxyphenyl) -2-ethylhexane.
<8> The binder resin for ink according to any one of <1> to <7>, wherein the polycarbonate resin has an intrinsic viscosity of 0.4 to 2.0 dl / g.
<9> A printing ink containing the binder resin for ink according to any one of <1> to <8>.
<10> The printing ink according to <9>, further including one or more pigments selected from dyes and pigments.
<11> The printing ink according to <9> or <10>, further including a non-halogen organic solvent as an ink adjusting solvent.
<12> A decoration wherein the film printed with the ink according to any one of <9> to <11> is inserted into a mold, and then a heat-melted resin is injected into the mold. It is a manufacturing method of a resin molded product.

  The decorative printing film using the printing ink of the present invention has excellent heat resistance as compared with those using conventional printing ink, and is resistant to contamination by fingerprints and hand cream in the working environment, and is decorated. Even if the contaminated surface of the film is insert-molded, ink flow and cracks hardly occur at the contaminated portion.

  The decorative printing film using the printing ink of the present invention is suitable for insert molding by injection molding, and the printing ink of the present invention is particularly suitable for various meter panels such as automobiles, housings of portable terminal devices including mobile phones, It is suitable as a heat-resistant printing ink for decorative printing films used for input keys, AV equipment, housings and operation panels of small game machines and home appliances, insert injection molded products such as toys and miscellaneous designs.

  The polycarbonate resin which is a binder resin for ink of the present invention (hereinafter sometimes referred to as a binder resin) is a biphenol derived from the structural unit represented by the general formula (1), which is represented by the general formula (2). It can be produced by reacting bisphenols that derive the structural unit represented and a carbonic acid ester forming compound. Known methods used in the production of polycarbonate derived from bisphenol A, such as direct reaction of bisphenols with phosgene (phosgene method), or transesterification of bisphenols with bisaryl carbonate (transesterification method) ) And the like.

  The structural unit represented by the general formula (1) is derived from bisphenols represented by the following general formula (3).

In General Formula (3), R _{1 to} R ₄ are each independently hydrogen, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, or carbon, each of which may have a substituent. An alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms is represented. Examples of the substituent that the alkyl group having 1 to 9 carbon atoms optionally include an aryl group having 6 to 12 carbon atoms, and examples of the substituent that the aryl group having 6 to 12 carbon atoms optionally include: , An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and the like. As the substituent that the alkoxy group having 1 to 5 carbon atoms optionally has, for example, an alkyl group having 1 to 8 carbon atoms , An aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and the like. The substituent that the alkenyl group having 2 to 5 carbon atoms optionally has, for example, an aryl group having 6 to 12 carbon atoms Examples of the substituent that the aralkyl group having 7 to 17 carbon atoms optionally has include an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. Etc. Preferably, in the general formula (3), R _{1 to} R ₄ are hydrogen.
The explanation about the general formula (3) also applies to the structural unit represented by the general formula (1).

  Specific examples of the bisphenols represented by the general formula (3) include bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, and bis (4-hydroxy-3,5- Dimethylphenyl) ether, bis (4-hydroxy-3-t-butylphenyl) ether, bis (4-hydroxy-3-phenylphenyl) ether, bis (4-hydroxy-3-allylphenyl) ether, bis (4- Examples thereof include hydroxy-3-ethylphenyl) ether, bis (4-hydroxy-3-sec-butylphenyl) ether, and bis (4-hydroxy-3-cumylphenyl) ether. These can be used in combination of two or more. Among these, bis (4-hydroxyphenyl) ether is particularly preferable.

  The structural unit represented by the general formula (2) is derived from bisphenols represented by the following general formula (4).

In General Formula (4), R ₅ and R ₆ each independently represent hydrogen, an alkyl group having 1 to 16 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, each of which may have a substituent. R ₅ and R ₆ are not the same, or R ₅ and R ₆ are combined to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements. Examples of the optional substituent include an aryl group having 6 to 12 carbon atoms.
Preferably, in the general formula (4), R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 16 carbon atoms, or each having a substituent, or 2 to 12 carbon atoms. Represents an alkenyl group (wherein R ₅ and R ₆ are not the same), and more preferably, in general formula (4), R ₅ and R ₆ represent hydrogen or an alkyl group having 1 to 16 carbon atoms ( However, R ₅ and R ₆ are not the same).
Here, it is defined that R ₅ and R ₆ are not the same because when one of R ₅ and R ₆ is long and the other is short, it is excellent in terms of ink binding properties.
In general formula (4), R _{7 to} R ₁₀ are each independently hydrogen, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or carbon, each of which may have a substituent. An alkenyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms is represented. Examples of the optional substituent include an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. Preferably, in the general formula (4), R _{7 to} R ₁₀ are hydrogen.
The description regarding the general formula (4) also applies to the structural unit represented by the general formula (2).

  Specifically, the bisphenols represented by the general formula (4) are 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1 -Bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis ( 4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) dodecane, 2,2-bis (4-hydroxyphenyl) tridecane, 2,2-bis (4-hydroxyphenyl) pentadecane, 4,4 ′ -(1,5,9,13-tetramethyltetradecylidene) bisphenol, 1,1-bis (4-hydroxyphenyl) pentane, 1,1-bis (4 Hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis ( Examples include 4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, and the like. . These can be used in combination of two or more. Among these, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) butane, 1,1-bis (4-hydroxy) Phenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) cyclododecane are preferred, in particular 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) ) -2-methylpropane and 1,1-bis (4-hydroxyphenyl) -2-ethylhexane are preferred.

The biphenol represented by the general formula (3) needs to be used in an amount of 20 mol% to 70 mol% with respect to the total amount of bisphenols used. Thereby, content of the structural unit represented by General formula (1) will be 20 mol% or more and 70 mol% or less with respect to all the structural units which comprise polycarbonate resin. Outside the above range, the stain resistance is poor. Preferably, the biphenol represented by the general formula (3) is used in an amount of 25 mol% to 65 mol% with respect to the total of the bisphenols used.
The biphenol represented by the general formula (4) is preferably used in an amount of 30 mol% to 80 mol%, more preferably 35 mol to 75 mol%, based on the total amount of bisphenols used. Thereby, the content of the structural unit represented by the general formula (2) is preferably 30 mol% or more and 80 mol% or less, more preferably 35 mol or more and 75 mol% with respect to all the structural units constituting the polycarbonate resin. It becomes as follows.

  Examples of the carbonic acid ester forming compound include phosgene, bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Two or more of these compounds can be used in combination.

  In the phosgene method, the biphenols represented by the general formula (3) and the bisphenols represented by the general formula (4) are reacted with phosgene in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. Furthermore, it is preferable to add a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt in order to promote the condensation polymerization reaction. In order to adjust the polymerization degree, it is preferable to add a monofunctional compound such as phenol, pt-butylphenol, p-cumylphenol, or a long-chain alkyl-substituted phenol as a molecular weight regulator. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually in the range of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

  On the other hand, in the transesterification method, the biphenol represented by the general formula (3), the bisphenol represented by the general formula (4) and the bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably at most 133 Pa or less, and the phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding a molecular weight regulator, antioxidant, and a branching agent as needed.

  The polycarbonate resin in the present invention needs to maintain the necessary solvent solubility and strength as a binder resin for 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 high. If it is too high, there will be a decrease in solvent solubility and an increase in ink viscosity, resulting in a decrease in printability. The intrinsic viscosity is preferably in the range of 0.4 to 2.0 dl / g, more preferably in the range of 0.45 to 1.5 dl / g.

  The printing ink of the present invention is produced by dissolving the binder resin and the coloring matter (dye and / or pigment) in a desired solvent. Examples of the dye / pigment used in the printing ink of the present invention include, for example, dyes such as anthraquinone and naphthoquinone, inorganic pigments such as titanium oxide, carbon black, calcium carbonate, and metal particles, 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.

  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, cyclopentanone and isophorone, and cyclic ethers such as tetrahydrofuran and dioxane. , Dimethylformamide, dimethyl sulfoxide and the like. Among them, dioxane, tetrahydrofuran, toluene, xylene, cyclohexanone and isophorone are preferable, and isophorone is particularly 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, coating properties, drying properties, etc., alcohols such as methanol and ethanol, acyclic ketones such as methyl ethyl ketone and acetone, esters such as ethyl acetate, methyl acetate and methoxypropyl acetate, Solvents or poor solvents such as aliphatic hydrocarbons such as cyclohexane and n-heptane, alkylene glycols and derivatives thereof, and oils such as silicone oil and soybean oil can be used in combination.

  For the printing ink, in addition to binder resin and pigment (dye and / or pigment), if necessary, organic and inorganic fine particles, release agent, antioxidant, plasticizer, dispersant, infrared absorber, antistatic Agents, ultraviolet absorbers, antifoaming agents, leveling agents and the like may be added. The blending amount of the binder resin in the ink depends on the intrinsic viscosity and the solvent solubility, but is preferably 1 to 70% by weight, more preferably 5 to 40% by weight. 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. On the other hand, the blending amount of the coloring matter (dye and / or pigment) is preferably from 0.1 to 60% by weight, more preferably from 1 to 50% by weight, based on the binder resin. When the concentration of the coloring matter (dye and / or pigment) is within such a range, the coloring effect of the coloring matter can be sufficiently exhibited while maintaining the strength of the binder resin.

  The viscosity of the printing ink of the present invention can be arbitrarily set, but is preferably in the range of 500 to 100,000 mPa · s, more preferably 1,000 to 50,000 mPa · s. If it is this range, there is little ink dripping, and it is easy to apply | coat and the printing with a favorable external appearance is obtained.

  In the present invention, the printing ink is applied to a substrate film and used for insert molding decoration. Examples of the resin film used for the base film include a thermoplastic resin film. Specifically, a polycarbonate resin film, a polyester resin film, a polyamide resin film, a heat-resistant polyolefin resin film, a polycarbonate / polyester blend film, and a polycarbonate / ABS blend. In particular, a polycarbonate resin film and a polycarbonate / polyester blend film are preferably used because of their excellent transparency, heat resistance, mechanical strength, and the like. These resin films usually have a thickness of 0.01 to 2 mm, preferably 0.1 to 0.5 mm.

  Examples of the method for applying the printing ink of the present invention to the substrate film include screen printing, gravure printing, flexographic printing, etc., but the film thickness range of the applied ink layer is wide, and the ink layer can be thickened. Therefore, screen printing is particularly preferable. 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. In addition, in order to remove the high-boiling solvent, the printing ink of the present invention has heat resistance that does not melt and flow out even when it is dried at, for example, 100 ° C. or higher for a long time. Therefore, the binder resin in the present invention preferably has a glass transition point of 100 ° C. or higher.

  The printing ink of the present invention has heat resistance capable of holding the printed surface even when it comes into contact with a molten resin as an ink for a decorative printing film in insert molding for the purpose of decorating a thermoplastic resin. Examples of the resin molded by insert molding include polystyrene, polyester, polycarbonate, polyarylate, polysulfone, and nylon. Among them, the decorative printing film using the printing ink of the present invention is caused by insufficient heat resistance during insert molding when decorating a polycarbonate resin or polycarbonate / polyester blend resin molded at a high temperature, particularly 300 ° C or higher. No blur or blur of the printed part pattern is observed, and the adhesiveness of the printed part is maintained. Furthermore, because it is resistant to deterioration and solvent cracks due to contamination and adhesion of fingerprints and hand cream on the printed part, even in the printed part contaminated with them, cracks and omissions in the printed part pattern due to heat and impact during insert molding can be seen. It maintains a good printed appearance.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

Example 1
To 1100 ml of a 5 w / w% aqueous sodium hydroxide solution, 40.4 g (0.20 mol) of bis (4-hydroxyphenyl) ether represented by the following structural formula (hereinafter abbreviated as “DHPE”: manufactured by Tokyo Chemical Industry Co., Ltd.) ), 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter abbreviated as “BPZ”: Taoka Chemical Industries, Ltd.) represented by the following structural formula, and hydrosulfite 0.1 g was dissolved. To this, 500 ml of methylene chloride was added and stirred, while maintaining at 15 ° C., 60 g of phosgene was blown in over 60 minutes.
After completion of the phosgene blowing, 2.3 g of pt-butylphenol (hereinafter abbreviated as “PTBP”: DIC Corporation) was added as a molecular weight regulator and stirred vigorously to emulsify the reaction solution. Triethylamine was added, and the mixture was stirred at 20 to 25 ° C. for about 1 hour for polymerization.

After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the washing solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 110 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.50 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, it is polycarbonate resin having a carbonate bond Was confirmed.

The resulting polycarbonate resin was mixed with 20 parts by weight as a binder resin, 10 parts by weight of anthraquinone Plast Red 8370 (Arimoto Chemical Co., Ltd.) and 80 parts by weight of isophorone as a solvent, and printing ink (2 Pa · s) was mixed. Was prepared. Next, the printing ink is applied to one side of a commercially available polycarbonate film (Mitsubishi Gas Chemical Co., Ltd .; Iupilon FE-2000) having a thickness of 0.2 mm × 150 mm × 70 mm as a base film. -MINI), screen-printed at 100 ° C. for 3 hours, 2 × 2 cm square shape on the surface of the printed film, JISK2246 compliant artificial fingerprint liquid (manufactured by Isekyu Corporation), and commercially available hand cream (Johnson & Johnson Co., Ltd .; Neutrogena Hand Cream) was applied and left to stand for 4 hours. The surface was wiped with a waste cloth and mounted on a 2 mm thick mold of the same size as the base film. Polycarbonate melted at 300 ° C. (Mitsubishi Gas Chemical Co., Ltd .; Iupilon S-20 0) was insert molding. The resulting insert-molded product was visually evaluated for the absence of the printing ink in the artificial fingerprint liquid and the hand cream application part as follows. The evaluation results are shown in Table 1 below.
A: The insert-molded product was visually observed directly under a fluorescent lamp, and there was no ink unevenness (light and shade), and no ink loss (no ink was transmitted and almost no light was transmitted).
○: The insert molded product was visually observed directly under the fluorescent lamp, and the density of some ink was confirmed, but no ink omission was confirmed.
X: The insert molded product was visually observed directly under the fluorescent lamp, and ink omission was clearly confirmed.

Example 2
Polymerization was conducted in the same manner as in Example 1 except that 56.6 g (0.28 mol) of DHPE, 32.2 g (0.12 mol) of BPZ, and 1.2 g of PTBP were changed, and a polycarbonate resin (with an intrinsic viscosity of 0. 71 dl / g) was obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Example 3
Instead of BPZ, 48.4 g (0.20 mol) of 2,2-bis (4-hydroxyphenyl) butane represented by the following structural formula (hereinafter abbreviated as “BPB”: manufactured by Honshu Chemical Industry Co., Ltd.) Except for the use, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.54 dl / g). The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Example 4
Polymerization was carried out in the same manner as in Example 1 except that DHPE was changed to 16.2 g (0.08 mol) and BPB 77.4 g (0.32 mol) was used instead of BPZ, and polycarbonate resin (intrinsic viscosity 0.56 dl / g) was obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Example 5
DHPE was changed to 32.3 g (0.16 mol), and 1,1-bis (4-hydroxyphenyl) cyclododecane (hereinafter abbreviated as “HPCD”) represented by the following structural formula instead of BPZ: Taoka Chemical Industries Except that 84.5 g (0.24 mol) was used and PTBP was changed to 0.9 g, polymerization was performed in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity 0.74 dl / g). . The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Example 6
DHPE was changed to 44.4 g (0.22 mol) and 2,2-bis (4-hydroxyphenyl) -4-methylpentane (hereinafter abbreviated as “MIBK”) represented by the following structural formula instead of BPZ; Honshu Chemical Co., Ltd.) 48.6 g (0.18 mol) was used, and polymerization was performed in the same manner as in Example 1 except that PTBP was changed to 0.8 g. Polycarbonate resin (intrinsic viscosity 0.94 dl / g) Got. Printing, molding, and evaluation were performed in the same manner as in Example 1 except that the obtained polycarbonate resin was changed to 10 parts by weight as an ink binder resin. The evaluation results are shown in Table 1 below.

Example 7
In place of BPZ, 48.6 g (0) of 1,1-bis (4-hydroxyphenyl) -2-methylpropane (hereinafter abbreviated as “IBTD”: Wako Pure Chemical Industries, Ltd.) represented by the following structural formula Polymerization was carried out in the same manner as in Example 1 except that 20 mol) was used to obtain a polycarbonate resin (intrinsic viscosity 0.53 dl / g). The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Example 8
DHPE was changed to 36.4 g (0.18 mol), and 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) butane (hereinafter referred to as the following structural formula) was used instead of BPZ. Polycarbonate resin (intrinsic viscosity) was polymerized in the same manner as in Example 1 except that 84.3 g (0.22 mol) abbreviated as “AO-40” (manufactured by ADEKA Corporation) was used and PTBP was changed to 2.2 g. 0.51 dl / g) was obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Example 9
DHPE was changed to 48.5 g (0.24 mol), and 1,1-bis (4-hydroxyphenyl) -2-ethylhexane (hereinafter abbreviated as “IOTD”) represented by the following structural formula instead of BPZ: Polycarbonate resin (intrinsic viscosity 1.17 dl / g) was polymerized in the same manner as in Example 1 except that 53.6 g (0.16 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used and PTBP was changed to 0.8 g. Got. Printing, molding, and evaluation were performed in the same manner as in Example 1 except that the obtained polycarbonate resin was changed to 10 parts by weight as an ink binder resin.

Example 10
Printing was performed in the same manner as in Example 1, except that 20 parts by weight of a cobalt blue pigment (manufactured by Bayer Corporation; Lightfast Blue 100) was used instead of the dye, and isophorone was changed to 60 parts by weight of cyclohexanone and 20 parts by weight of toluene. Molding and evaluation were performed. The evaluation results are shown in Table 1 below.

Comparative Example 1
Polymerization was carried out in the same manner as in Example 1 except that 107.2 g (0.40 mol) of BPZ was used without using DHPE, and PTBP was changed to 1.5 g, and a polycarbonate resin (intrinsic viscosity 0.50 dl / g) was obtained. Obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Comparative Example 2
Polymerization was conducted in the same manner as in Example 1 except that DHPE was changed to 8.1 g (0.04 mol), BPZ was changed to 96.5 g (0.36 mol), and PTBP was changed to 1.9 g. 0.51 dl / g) was obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Comparative Example 3
Polymerization was carried out in the same manner as in Example 1 except that DHPE was changed to 64.6 g (0.32 mol) and BPZ was changed to 21.4 g (0.08 mol), but a solvent-insoluble polycarbonate was produced to prepare an ink. I couldn't do it.

Comparative Example 4
Without using DHPE, 91.2 g (0.40 mol) of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) manufactured by Mitsui Chemicals Co., Ltd. represented by the following structural formula instead of BPZ ) And polymerization was performed in the same manner as in Example 1 except that PTBP was changed to 2.0 g to obtain a polycarbonate resin (intrinsic viscosity 0.50 dl / g). The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1, but it was not dissolved in isophorone and an ink could not be prepared.

Comparative Example 5
Polycarbonate resin (intrinsic viscosity 0.50 dl / g) was polymerized in the same manner as in Example 1, except that DHPE was not used and 96.3 g (0.40 mol) of BPB used in Example 3 was used instead of BPZ. Got. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Comparative Example 6
Polymerization was conducted in the same manner as in Example 1 except that DHPE was not used, 140.1 g (0.40 mol) of HPCD used in Example 5 was used instead of BPZ, and PTBP was changed to 0.9 g. Intrinsic viscosity 0.71 dl / g) was obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

Comparative Example 7
Polymerization was carried out in the same manner as in Example 1 except that 108 g (0.40 mol) of MIBK used in Example 6 was used instead of BPZ, and PTBP was changed to 0.8 g instead of BPZ. 0.93 dl / g) was obtained. The obtained polycarbonate resin was used as an ink binder resin in the same manner as in Example 1 to perform printing, molding, and evaluation. The evaluation results are shown in Table 1 below.

  As an application example of the present invention, it can be used as a printing ink for a decorative printing film, and the decorative printing film can be applied to an injection molded product in which insert molding is performed at a high temperature. The present invention particularly relates to various types of meter panels for automobiles, housings and input keys for portable terminal devices including mobile phones, AV devices, housings and operation panels for small game machines and household electrical appliances, insert injections such as toys and sundries designs. It is suitable as a heat-resistant printing ink for a decorative printing film used for a molded product.

Claims (11)

A printing ink containing a binder resin for ink comprising a polycarbonate resin having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), The said printing ink whose content of the structural unit represented by 1) is 20 mol% or more and 70 mol% or less with respect to all the structural units which comprise the said polycarbonate resin.
(In the formula, R _{1 to} R ₄ each independently represent hydrogen, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 1 to 1 carbon atoms, each of which may have a substituent. 5 represents an alkoxy group having 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms.)
(In the formula, R ₅ and R ₆ each independently represent hydrogen, an alkyl group having 1 to 16 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, each of which may have a substituent (provided that , _{R 5} and _{R 6} are not the same), or, _{R 5} and _{R 6} are bonded, .R ₇ to R ₁₀ to form a heterocyclic ring of carbon ring or element number 5 to 12 5 to 20 carbon atoms Are each independently hydrogen, an optionally substituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 6 carbon atoms. Represents an -12 aryl group.) In the general formula _(1), R 1 to R ₄ are hydrogen, printing ink according to claim 1. In General Formula (2), R ₅ and R ₆ each independently represent hydrogen, an alkyl group having 1 to 16 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, each of which may have a substituent. The printing ink according to claim 1 or 2, wherein R ₅ and R ₆ are not the same. In the general formula (2), _{R 5} and _{R 6} are hydrogen, or an alkyl group having 1 to 16 carbon atoms (provided that, _{R 5} and _{R 6} are not the same), the printing ink according to claim 3. Printing ink in any one of Claims 1-4 whose R < ₇ > -R < ₁₀ > is hydrogen in General formula (2). The structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) butane, Printing ink according to claim 1 or 2, derived from 1,1-bis (4-hydroxyphenyl) cyclohexane or 1,1-bis (4-hydroxyphenyl) cyclododecane. The structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, or 1, Printing ink according to any of claims 1 to 6, derived from 1-bis (4-hydroxyphenyl) -2-ethylhexane. The printing ink according to any one of claims 1 to 7, wherein the intrinsic viscosity of the polycarbonate resin is 0.4 to 2.0 dl / g. Furthermore, the printing ink in any one of Claim 1 to 8 containing the 1 or more types of pigment | dye selected from dye and a pigment. Furthermore, the printing ink in any one of Claim 1 to 9 which contains a non-halogen-type organic solvent as a solvent for ink adjustment. A method for producing a decorative resin molded product, comprising: inserting a film printed with the ink according to any one of claims 1 to 10 into a mold, and then injecting a heat-melted resin into the mold. .