TWI490280B - An active energy ray hardening type inkjet ink composition and a - Google Patents

Description

Active energy ray-curable inkjet ink composition and thermoplastic resin sheet with pattern

The present invention relates to an active energy ray-curable inkjet ink composition, and a patterned thermoplastic resin sheet suitable for thermoforming.

Conventionally, a thermoplastic resin sheet with a pattern attached thereto is produced by pattern printing using a plate on a film or sheet-like plastic substrate by, for example, gravure printing or screen printing. However, as described in Patent Document 1, there is a problem in that, even in the case of large-scale production, the proportion of the plate cost per molded article is extremely small, as in the case of small batch production such as production of a molded article. At the time of the introduction, the cost of each molded product will become large, and as an initial investment for official production (large batch), the cost burden of the manufacturer will become excessive.

On the other hand, a method of printing a pattern is known as an ink jet method, and a solvent-based or water-based ink composition is also proposed. However, as a printing substrate, it is usually limited to a substrate which can only absorb a certain degree of solvent or water. For example, when a thermoplastic resin sheet which can be molded such as an acrylic resin sheet or a polycarbonate resin sheet is used as a printing substrate, a step of providing a receiving layer or the like is required.

The active energy ray-curable ink composition which can be adhered to some extent to the thermoplastic resin sheet which can be formed is described in Patent Document 2 to Patent Document 4, but is bent or pulled during thermoforming processing after hardening. Stretching and other steps cause problems such as cracking or whitening of the formed pattern.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-247694

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-56232

Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-7687

Patent Document 4: Japanese Patent Laid-Open Publication No. 2008-19408

An object of the present invention is to provide an active energy ray-curable inkjet ink composition which can be directly printed and excellent in adhesion even in the case of a non-treated layer. Further, an object of the present invention is to provide a thermoplastic resin sheet having a pattern in which a pattern is printed on a thermoplastic resin sheet and cured, and the sheet is subjected to curing. Thermoforming does not cause cracking or whitening, and it does not detract from the appearance of the pattern.

The active energy ray-curable inkjet ink composition of the present invention contains at least: from vinyl caprolactam, benzyl (meth) acrylate, and (meth) acrylate One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of a bisphenol A alkylene oxide modified substance represented by the following formula (1); One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate More than one monomer (C); and an active energy ray polymerization initiator (D).

[Chemical 1]

(Wherein, R1 represents hydrogen or a methyl group, R2 represents hydrogen, methyl or ethyl, R3 represents -CH ₂ - or -C (CH _{3) 2} - group, in addition, m + n represents an integer of 6 to 30)

Preferably, the monofunctional monomer (A) is vinyl caprolactam, benzyl (meth)acrylate, and (meth)acrylic acid The mixed monomer of the ester, the active energy ray-curable inkjet ink composition of the present invention contains the mixed monomer in an amount of 50% by mass to 90% by mass in the ink composition, and is 0.5% by mass to 10% by mass. The ratio contains a di(meth)acrylate body (B), and the monomer (C) is contained in a ratio of 0.5% by mass to 30% by mass, and the active energy ray polymerization initiator is contained in a proportion of 5% by mass to 15% by mass. D).

The active energy ray-curable inkjet ink composition of the present invention preferably further contains a colored material.

The patterned thermoplastic resin sheet of the present invention is obtained by printing an active energy ray-curable inkjet ink composition on a thermoplastic resin sheet and performing active energy ray hardening to form a pattern; the active energy ray The hardened inkjet ink composition contains at least: from vinyl caprolactam, benzyl (meth)acrylate, and (meth)acrylic acid One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of the bisphenol A alkylene oxide modified substance represented by the above formula (1); One or two selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate The above monomer (C); active energy ray polymerization initiator (D); and colored materials.

The preferred tensile fracture point strain of the patterned thermoplastic resin sheet of the present invention when extended at a strain rate of 50 mm/min in an environment of 150 ° C is 150% or more.

The thermoplastic resin sheet is preferably selected from the group consisting of an acrylic resin sheet, a polycarbonate resin sheet, a polyvinyl chloride resin sheet, an ABS resin sheet, and a polystyrene resin sheet.

Further, in the present invention, in the case of (meth) acrylate, it means methacrylate or acrylate.

The active energy ray-curable inkjet recording ink composition of the present invention can be directly printed on a thermoplastic resin sheet such as an acrylic resin sheet or a polycarbonate resin sheet, particularly in the case of a non-treated layer. The patterned thermoplastic resin sheet of the present invention does not impair the appearance of the pattern due to whitening caused by thermoforming. Therefore, even if the patterned thermoplastic resin sheet of the present invention is produced in a small batch as in the case of a molded article, the production of the pattern substantially does not require a plate fee, and the burden of the initial investment is reduced.

The active energy ray-curable inkjet recording ink composition of the present invention (hereinafter also referred to as an ink composition) contains the following components as an essential component: a vinyl caprolactam as a compound having an ethylenically unsaturated double bond Benzyl (meth) acrylate, (meth) acrylate One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of the bisphenol A alkylene oxide modified product represented by the above formula (1); One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate More than one monomer (C).

The monofunctional monomer (A) is derived from vinyl caprolactam, benzyl (meth)acrylate, or (meth)acrylic acid. One or two or more kinds of the esters are selected, and the purpose thereof is to improve the printability and adhesion to the thermoplastic resin sheet. Specific examples of the resin constituting the thermoplastic resin sheet suitable for thermoforming are polymethyl methacrylate (PMMA), polycarbonate (PC), acrylonitrile-butadiene-styrene resin (ABS resin), and poly Vinyl chloride resin. The sheet containing any of the resins is excellent in printability and adhesion. In order to obtain a widely used ink composition, a suitable combination of vinyl caprolactam, benzyl (meth)acrylate, and (meth)acrylic acid Three monofunctional monomers of esters. When three kinds of monofunctional monomers are used in combination, it is preferred to contain vinyl caprolactone in a ratio of 10% by mass to 40% by mass in the ink composition, and to contain 0.5% by mass to 30% by mass. Benzyl (meth)acrylate containing (meth)acrylic acid in a proportion of 10% by mass to 60% by mass The ester, the preferred total content of the three monofunctional monomers is from 50% by mass to 90% by mass based on the ink composition. If the total content is less than 50% by mass, there is a possibility that the printing property and the adhesion of the ink composition are lowered, and the wide-use property is lost, and the thermoplastic resin sheet with the pattern formed by the ink composition is patterned. The tensile strain at the tensile point of the material becomes low, and the workability causes problems. For the thermoplastic resin sheet with a pattern attached, the thermal extensibility is important, and the patterned thermoplastic resin sheet is stretched at a strain rate of 50 mm/min in an environment of 150 ° C. The preferred elongation at break (hereinafter referred to as tensile strain) is from 150% to 400%. If the tensile strain is too low, the workability of the thermoplastic resin sheet with the pattern is deteriorated.

Next, the bis(meth)acrylate body (B) of the bisphenol A alkylene oxide modified product represented by the above formula (1) (hereinafter referred to as di(meth)acrylate body (B)) can be used as By imparting strength to the coating film with cross-linking components of various monomers, and improving the printability and adhesion of the ink composition to various substrates, the pattern can be formed without impairing the pattern formed by the ink composition. The tensile strain is increased in the case of the appearance of the thermoplastic resin sheet after stretching. The specific bis(meth) acrylate body (B) is preferably contained in the ink composition in an amount of from 0.5 to 15% by mass, more preferably from 1 to 10% by mass. When the content of the di(meth)acrylate body (B) is too large, there is a possibility that the printing property and the adhesion of the ink composition are lowered, and the wide-use property is lost, and the pattern is formed by the ink composition. The tensile fracture point strain of the thermoplastic resin sheet with a pattern is lowered, and the workability is problematic. When the EO addition amount of the di(meth)acrylate body (B) is less than 6 mol, the printability and adhesion of the ink composition are lowered. A di(meth)acrylate such as a bifunctional urethane acrylate can be used as a di(meth)acrylate body (B) in combination with the formula (1). If the di(meth)acrylate body is not a bisphenol A alkylene oxide modification, but an alkylene oxide modification of neopentyl glycol, the pattern-attached thermoplasticity formed by the ink composition can be improved. The tensile strain of the resin sheet, but the thermoplastic resin sheet with the pattern is whitened after stretching. The patterned thermoplastic resin sheet formed by the ink composition must have excellent thermoformability without causing whitening after stretching.

The di(meth)acrylate body (B) is a bisphenol A alkylene oxide modified product represented by the above formula (1), and the molar number (m+n) of the alkylene oxide is 6 to 30. Good for 10 to 30 moles. Specific examples of the di(meth)acrylate body (B) are an alkylene oxide (EO) 10 molar addition of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd.), and an EO20 molar addition of bisphenol A. Qualitative (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EO30 bis-addition of bisphenol A (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate The above monomers (C) can improve the printing and adhesion of the ink composition to various plastic substrates, and impart moderate ductility and flexibility. The monomer (C) is preferably contained in the ink composition in an amount of from 1 to 30% by mass, more preferably from 1 to 25% by mass. When the content is too large, the tensile strain amount of the thermoplastic resin sheet with a pattern formed by the ink composition is lowered, and the printability and adhesion of the ink composition to various plastic substrates are lowered.

The ink composition of the present invention may contain an inorganic pigment or an organic pigment which is usually used in a conventional oil-based ink composition as a colored material (pigment). Specific examples of pigments are carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, chrome green, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, diketopyrrolopyrrole, anthracene Anthracene, benzimidazolone, pyrimidine, azo pigment, indigo pigment, quinacridone pigment, isoindolinone pigment, two A pigment, an indanthrene pigment, an anthraquinone pigment, a piperidone pigment, a thioindigo pigment, a quinophthalone pigment, or a metal complex pigment.

The preferred volume average particle diameter of the pigment primary particles is 50 to 200 nm as measured by laser scattering. When the average particle diameter of the pigment is less than 50 nm, the light resistance is lowered due to the smaller particle diameter. On the other hand, when it exceeds 200 nm, it is difficult to maintain the stability of dispersion, and it is easy to cause precipitation of a pigment. The pigment is added as needed, and the content of the ink composition is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

The ink composition of the present invention may contain a polymer dispersant as a dispersing agent. The main chain of the polymer dispersant includes polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the polymer dispersant has an amine group, a carboxyl group, a thiol group, a hydroxyl group, etc. The polar group acts as a side chain. A preferred polymer dispersant is a polyester-based dispersant, and specific examples thereof are "SOLSPERSE 33000", "SOLSPERSE 32000", and "SOLSPERSE 24000" manufactured by Lubrizol Corporation of Japan; "DisperBYK168" manufactured by BYK Chemie Co., Ltd.; and manufactured by Ajinomoto Fine-Techno Co., Ltd. "Ajisper PB821". The polymer dispersant is added in a ratio of preferably 0.03 parts by mass to 5 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, per part by mass of the pigment. The polymer dispersant is preferably contained in the ink composition in an amount of 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass.

Next, the photopolymerization initiator contained in the active energy ray-curable inkjet recording ink composition of the present invention will be described. The active energy ray in the present invention is an energy ray in which a radical, a cation, an anion or the like such as an electron beam, an ultraviolet ray, or an infrared ray can cause a polymerization reaction. Specific examples of the photopolymerization initiator are bis(2,4,6-trimethylbenzylidene)-phenyl-phosphine oxide (Irgacure 819, manufactured by Ciba Japan Co., Ltd.) which belongs to fluorenylphosphine oxide, and double (2) ,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (Darocur TPO: manufactured by Ciba Japan Co., Ltd.; Lucirin TPO: manufactured by BASF Corporation).

A specific example of the α-hydroxyketone used as a photopolymerization initiator is 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl} 2-methyl-propan-1-one (Irgacure 127, manufactured by Ciba Japan Co., Ltd.), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (Irgacure 2959, manufactured by Ciba Japan Co., Ltd.).

A specific example of the α-aminoalkylphenone used as a photopolymerization initiator is 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 ( Irgacure 369, manufactured by Ciba Japan Co., Ltd.).

A specific example of the phenylketone used as the photopolymerization initiator is 1-cyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.).

The active energy ray-curable inkjet recording ink composition of the present invention may contain a surface conditioner. A specific example of the surface conditioning agent is a polyether modified dimethyl polyoxyalkylene terminal acrylate (TegoRao 2300, manufactured by Degussa Co., Ltd.). The content ratio of the surface conditioner to the ink composition is preferably 0.1 to 0.3% by mass.

The active energy ray-curable inkjet ink composition of the present invention may further contain various additives such as a plasticizer, an ultraviolet inhibitor, a light stabilizer, and an antioxidant.

The active energy ray-curable inkjet ink composition of the present invention is produced by dispersing a pigment together with a monomer or a pigment dispersant by a usual disperser such as a sand mill. A concentrate having a high concentration of the pigment is prepared in advance, and the concentrate is diluted with a monomer. The ink which is excellent in stability can be prepared by performing a sufficient dispersion by a usual dispersing machine. The ink is filtered using a filter having a pore diameter of preferably 3 μm or less, more preferably 1 μ or less.

The preferred energy ray-curable inkjet ink composition of the present invention has a viscosity at 40 ° C of 5 to 20 mPa ‧ s. When the viscosity is too low, the follow-up of the spit of the high-frequency nozzle is lowered. On the other hand, in the case where the viscosity is too high, even if a mechanism for lowering the viscosity by heating is incorporated in the head, the discharge is lowered, the stability of the discharge is deteriorated, and the ink composition cannot be completely discharged.

The active energy ray-curable inkjet ink composition of the present invention is supplied to a printing head of a printer for inkjet recording, discharged from the printing head onto a substrate, and then irradiated with active energy rays such as ultraviolet rays and electron beams. To make it harden on the print media.

Specific examples of the light source of the ultraviolet rays of the active energy ray are a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, and sunlight. When the electron beam is an active energy ray, an electron beam of an energy of 300 eV or less is usually irradiated, but the active energy ray-curable inkjet ink composition of the present invention can be instantaneously hardened by an irradiation amount of 1 to 5 Mrad.

A preferred printing substrate formed by the active energy ray-curable inkjet ink composition of the present invention is an acrylic resin, a polycarbonate resin, a polystyrene resin, or a polyvinyl chloride resin. A printing substrate for an absorbent resin. These printed substrates were found to have excellent adhesion by the adhesion test described later.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not particularly limited to the examples. Further, the "parts" in the examples mean "parts by mass".

[Examples] [Example 1] [Preparation of dispersion]

A polymer dispersant (SOLSPERSE 33000, manufactured by Lubrizol Co., Ltd.) in the following table was dissolved in benzyl acrylate (Viscoat #160, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and then a yellow pigment in the ratio of the following table was added. (E4GN-GT, manufactured by Lanxess Co., Ltd.) was dispersed by a paint shaker to have a pigment particle diameter (median diameter) of 200 nm or less to obtain a dispersion. The particle size was measured by "LB-550" manufactured by HOLIBA Co., Ltd.

The raw materials shown in Tables 1 and 2 were mixed in order except for the dispersion, and the mixture was stirred while heating to 50 ° C for 1 hour, and it was confirmed that there was no dissolution remaining. After returning to room temperature, the dispersion was added and stirred. Thereafter, the ink of Example 1 was produced by filtration using a membrane filter.

[Examples 2 to 5, Comparative Examples 1 to 4]

In the examples 2 to 5 and the comparative examples 2 to 4, the pigments and the dispersing agents shown in Tables 1 and 2 were used, and the dispersion was produced in the same manner as in Example 1, except that the same procedure as in Example 1 was carried out. The ink is produced in the same manner. Further, the ink of Comparative Example 1 was produced in the same manner as in Example 1 except that phenoxyethyl acrylate was used in place of the benzyl acrylate of Example 1 in the dispersion system of Comparative Example 1.

Each of the obtained inks was developed on each substrate by means of a bar coater #8 so as to have an average film thickness of 18 μm. Thereafter, a high-pressure mercury lamp (HAL250NL) was used to accumulate light amount: 112.63 mJ/cm ² (UV-351), peak illuminance: 134.43 mW/cm ² (UV-351), output: 80 W/cm, and conveying speed: 10 The condition of m/min hardens it. The results were judged according to the following evaluation methods.

(1) Viscosity

The viscosity of the ink was measured at 40 ° C using a B-type viscometer based on JIS K7117-1.

(2) Adhesion

Adhesive tape is adhered to the hardened film at a spacing of 1 mm and cut into 100 parts as specified in ASTM D3359. After sufficient adhesion, the cellophane tape is peeled off at 90 degrees. The degree of closeness is determined to determine the adhesion. The judgment criteria are as follows.

5B: No peeling.

4B: There is a peel of less than 5%.

3B: There are more than 5% and less than 15% of the divestiture.

2B: There are more than 15% and less than 35% of the divestiture.

1B: There are more than 35% and less than 65% of the stripping.

0B: There are more than 65% of the stripping.

(3) Tensile strain

Each of the ink compositions was applied to a PMMA substrate (thickness: 2 mm, Acrylite EX, manufactured by Mitsubishi Rayon Co., Ltd.) by a bar coater #8 to have an average film thickness of 18 μm, and the heat of the pattern was prepared. Plastic resin sheet. The thermoplastic resin sheet with the pattern was pressed into a strip shape together with a substrate by a press machine (manufactured by Dumbbell Co., Ltd.), and the obtained test piece was heated to the obtained test piece by Tensilon (UCT-IT; manufactured by ORIENTEC Co., Ltd.) in accordance with JIS K7113. Tensile tests were carried out together with the substrate at a strain rate of 50 mm/min at 150 °C. The break point of the coating film was measured by visually confirming that the elongation at the time of cracking of the surface of the coating film was a percentage (%).

(4) Appearance after extension

The extended appearance of the thermoplastic resin sheet with the pattern attached was evaluated by visual observation and according to the following criteria.

A: No whitening

B: slightly whitened

C: Obvious whitening

1) to 28) in Tables 1 to 4 are as follows.

1): E4GN-GT (manufactured by Lanxess)

2): CINQUASIA MAGENTA RT-355D (manufactured by Ciba Japan)

3): LIONOL BLUE FG7400G (manufactured by Toyo Ink Manufacturing Co., Ltd.)

4): CARBON BLACK #MA-14 (Mitsubishi Chemical Co., Ltd.)

5): CFR6121EC (made by Daisei Seiki Co., Ltd.)

6): V-CAP/RC (made by ISP Japan)

7): Viscoat # 160 (made by Osaka Organic Chemical Industry Co., Ltd.)

8): Light Acrylate IBXA (manufactured by Kyoeisha Chemical Co., Ltd.)

9): NK Ester 702A (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

10): Laromer TBCH (manufactured by BASF Corporation)

11): Light Acrylate PO-A (manufactured by Kyoeisha Chemical Co., Ltd.)

12): Light Acrylate BP-10EA (manufactured by Kyoeisha Chemical Co., Ltd.)

13): NK Ester A-BPE-20 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

14): NK Ester A-BPE-30 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

15): Light Acrylate BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.)

16): SR9045 (manufactured by SARTOMER)

17): CN996 (manufactured by SARTOMER)

18): Irgacure 184 (1-cyclohexyl phenyl ketone, manufactured by Ciba Japan Co., Ltd.)

19): Lucirin TPO (diphenyl-(2,4,6-trimethylbenzylidene) phosphine oxide, manufactured by BASF)

20): Irgacure 369 (2-benzyl-2dimethylamino-1-(4-morpholinylphenyl)butanone-1, manufactured by Ciba Japan Co., Ltd.)

21): DisperBYK168 (made by BYK Chemie)

22): SOLSPERSE33000 (made by Lubrizol, Japan)

23): TegoRad 2300 (made by Degussa)

24): Acrylite EX (manufactured by Mitsubishi Rayon Co., Ltd., film thickness 2.0 mm)

25): polycarbonate plate (manufactured by Takiron, film thickness 2.0 mm)

26): Carbo Glass Twin Carbo 9034-30 (manufactured by AGC Asahi Glass Co., Ltd., film thickness 4.0 mm)

27): ABS board Natural (manufactured by Takiron, film thickness 2.0 mm)

28): S640 (manufactured by Takiron, film thickness 2.0 mm)

The unit of the numerical values in Tables 1 and 2 is % by mass, and the addition ratio of the surface conditioner is relative to the addition ratio of the ink composition.

[Industrial availability]

The active energy ray-curable inkjet ink composition of the present invention is excellent in printability and adhesion to various formable thermoplastic resin sheets, and the active energy ray-curable inkjet ink composition of the present invention is widely used. The ink composition. The thermoplastic resin sheet with a pattern of the present invention can be molded without deteriorating the appearance of the pattern even if it is thermoformed.

Claims (9)

An active energy ray-curable inkjet ink composition comprising at least: from vinyl caprolactam, benzyl (meth) acrylate, and (meth) acrylate One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of a bisphenol A alkylene oxide modified substance represented by the following formula (1); One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate The above monomer (C); and the active energy ray polymerization initiator (D); the content of the above monomer (C) is 0.5 to 25% by mass; In the formula, R1 represents hydrogen or a methyl group, R2 represents hydrogen, a methyl group or an ethyl group, R3 represents a -CH ₂ - or -C(CH ₃ ) ₂ - group, and m+n represents an integer of 6 to 30. An active energy ray-curable inkjet ink composition comprising at least: from vinyl caprolactam, benzyl (meth) acrylate, and (meth) acrylate One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of a bisphenol A alkylene oxide modified substance represented by the following formula (1); One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate More than one monomer (C); and active energy ray polymerization initiator (D); the content of the above monomer (C) is 0.5 to 25% by mass, and does not contain N-propylene oxiranyl ethyl hexahydroortylene Dimethyl imine; In the formula, R1 represents hydrogen or a methyl group, R2 represents hydrogen, a methyl group or an ethyl group, R3 represents a -CH ₂ - or -C(CH ₃ ) ₂ - group, and m+n represents an integer of 6 to 30. The active energy ray-curable inkjet ink composition according to claim 1 or 2, wherein the monofunctional monomer (A) is vinyl caprolactam, benzyl (meth)acrylate, and (methyl) Acrylic The mixed monomer of the ester contains the mixed monomer in an amount of 50% by mass to 90% by mass in the ink composition, and contains the di(meth)acrylate body (B) in a ratio of 0.5% by mass to 10% by mass. The monomer (C) is contained in a proportion of 0.5% by mass to 30% by mass, and the active energy ray polymerization initiator (D) is contained in a proportion of 5% by mass to 15% by mass. The active energy ray-curable inkjet ink composition according to claim 1 or 2, further comprising a colored material. An active energy ray-curable inkjet ink composition according to claim 3, which further comprises a colored material. A thermoplastic resin sheet with a pattern in which an active energy ray-curable inkjet ink composition is printed on a thermoplastic resin sheet and subjected to active energy ray hardening to form a pattern; the active energy ray The hardened inkjet ink composition contains at least: from vinyl caprolactam, benzyl (meth)acrylate, and (meth)acrylic acid One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of a bisphenol A alkylene oxide modified substance represented by the following formula (1); One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate More than one monomer (C); active energy ray polymerization initiator (D); and colored material; the content of the above monomer (C) is 0.5 to 25% by mass; In the formula, R1 represents hydrogen or a methyl group, R2 represents hydrogen, a methyl group or an ethyl group, R3 represents a -CH ₂ - or -C(CH ₃ ) ₂ - group, and m+n represents an integer of 6 to 30. A thermoplastic resin sheet with a pattern in which an active energy ray-curable inkjet ink composition is printed on a thermoplastic resin sheet and subjected to active energy ray hardening to form a pattern; the active energy ray The hardened inkjet ink composition contains at least: from vinyl caprolactam, benzyl (meth)acrylate, and (meth)acrylic acid One or two or more kinds of monofunctional monomers (A) selected from the group consisting of: a bis(meth)acrylate body (B) of a bisphenol A alkylene oxide modified substance represented by the following formula (1); One or two selected from 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and phenoxyethyl (meth)acrylate More than one monomer (C); active energy ray polymerization initiator (D); and colored material; the content of the above monomer (C) is 0.5 to 25% by mass, and does not contain N-propylene oxiranyl ethyl six Hydrogen o-phthalimide; In the formula, R1 represents hydrogen or a methyl group, R2 represents hydrogen, a methyl group or an ethyl group, R3 represents a -CH ₂ - or -C(CH ₃ ) ₂ - group, and m+n represents an integer of 6 to 30. The thermoplastic resin sheet with a pattern as disclosed in claim 6 or 7 has a tensile breaking point strain of 150% or more when stretched at a strain rate of 50 mm/min in an environment of 150 °C. The thermoplastic resin sheet with a pattern attached to the sixth or seventh aspect of the patent application, wherein the thermoplastic resin sheet is from an acrylic resin sheet, a polycarbonate resin sheet, a polyvinyl chloride resin sheet, or ABS. Selected from resin sheets and polystyrene resin sheets.