JP4310357B2 - Method for producing ultraviolet curable ink, and ink, printed matter and molded product based on the method - Google Patents

Description

  The present invention is an ultraviolet curable ink (hereinafter abbreviated as “UV ink”) that can be cured by irradiation with ultraviolet rays after being printed by a predetermined method such as an inkjet printing method, a screen printing method, a gravure printing method, or an offset printing method. In addition to two or three or more polyfunctional radical polymerizable oligomers, one or more types of polyfunctional radical polymerizable monomers are added as a photopolymerization reactive composition. Manufacturing method based on blending cyclodextrin or a derivative thereof according to the method, UV ink based on the method, decorative printed matter obtained by printing or applying with the ink, and insert manufactured using the decorative printed matter It relates to moldings.

  The UV curable ink usually contains a photoreaction initiator and a photopolymerization reactive composition as essential components, and a pigment, a dispersant, and other additives are blended as necessary. In the invention, on the premise of such a blend, the ink is cured by irradiation with ultraviolet rays after being printed on the substrate sheet by the above-described methods (in this respect, the conventional technology It is no different from the case.)

Since the UV ink is required to have sufficient fluidity suitable for each printing method, a monofunctional radical polymerizable monomer is adopted as an indispensable component as a photopolymerization reactive composition. With only a monofunctional radically polymerizable monomer, the curing speed and the crosslinking density are low, so that there are many cases where tack remains in the cured film, and the durability against external force such as friction resistance is inferior, and the adhesiveness is also insufficient. Since it is often in a state, usually a polyfunctional radical polymerizable oligomer or a polyfunctional radical polymerizable monomer is also blended.
However, this is because there is an emphasis on sufficient fluidity in the printing stage as described above, and in general, as the compounding ratio of the polyfunctional monomer increases, the adhesion to a substrate such as plastic becomes poor. Until now, it has not been studied to mix a polyfunctional radical polymerizable monomer instead of a monofunctional radical polymerizable monomer as a photopolymerization reactive composition.

  On the other hand, blending cyclodextrin or a derivative thereof as an ink production method already corresponds to a technical matter well known in the ink production industry as shown in Patent Documents 1 to 5.

  However, especially in the field of manufacturing UV ink that cures ink by ultraviolet irradiation, what kind of photopolymerization reactive composition is examined in terms of adhesion and tackiness by blending with cyclodextrin or its derivatives. Until now, there has been little technical consideration.

  Actually, Patent Document 6 discloses a method for producing a UV ink, but does not assume any combination with cyclodextrin or a derivative thereof.

This also applies to the case of Japanese Patent Application No. 2006-116810 (hereinafter referred to as “prior application invention”), which is the applicant's own prior application.
JP-A-5-132642 JP-A-9-31390 Japanese Patent Laid-Open No. 11-106694 Japanese Patent Laid-Open No. 11-263065 JP 2006-316225 A Japanese Patent Application No. 2007-131754

  In view of the state of the prior art as described above, the present invention contains two or three or more polyfunctional radical polymerizable monomers as a photopolymerization reactive composition, and cyclodextrin or a derivative thereof as necessary. It is an object of the present invention to obtain a UV ink having good characteristics by blending and clarifying an appropriate selection regarding the composition to be blended and an appropriate weight ratio between them.

In order to achieve the above object, the basic configuration of the present invention is:
(1) In the method for producing an ultraviolet curable ink, as a photopolymerization reactive composition, among 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate 2 are selected and blended, and cyclodextrin or a derivative thereof is blended as necessary, and a state in which peeling of the coating film formed at the stage of curing by ultraviolet rays after printing on the substrate does not occur is good Adhesive, while peeling does not occur, but the state where some peeling occurs in the periphery is a state where the adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) by touching it is a good tackiness, A state in which there is a slight stickiness when touching a finger, but no trace of the finger touch is left as a state where the tackiness is not defective. Ede, tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, UV-curable ink that allows printing as other is not bad In the production method , 1,6-hexanediol diacrylate and 1,6-hexanediol diglycidyl ether diacrylate are used as two polyfunctional radical polymerizable monomers in a weight ratio of 1: 0.5 to 2.0. Or by selecting 1,6-hexanediol diacrylate and ethoxylated trimethylolpropane triacrylate at a weight ratio of 1: 0.5 to 2.0. the weight ratio between the number of multi-functional radical polymerizable monomer and cyclodextrin or its derivative 1: 0.05 to 0.2 and to particular groups Dzu The method of manufacturing the ultraviolet curable ink,
(2) In the method for producing an ultraviolet curable ink, among the photopolymerization reactive compositions, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, ethoxylated trimethylolpropane triacrylate 2 are selected and blended, and cyclodextrin or a derivative thereof is blended as necessary, and a state in which peeling of the coating film formed at the stage of curing by ultraviolet rays after printing on the substrate does not occur is good Adhesive, while peeling does not occur, but the state where some peeling occurs in the periphery is a state where the adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) by touching it is a good tackiness, A state in which there is a slight stickiness when touching a finger, but no trace of the finger touch is left as a state where the tackiness is not defective. Ede, tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, UV-curable ink that allows printing as other is not bad In this production method , 1,6-hexanediol diglycidyl ether diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 1: 0.5 to 2.0 are used as two polyfunctional radical polymerizable monomers. And then producing a UV curable ink based on the weight ratio of the two polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof being 1: 0 to 0.2. Method,
(3) In the method for producing an ultraviolet curable ink, among the photopolymerization reactive compositions, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, ethoxylated trimethylolpropane triacrylate Select and mix three , and add cyclodextrin or its derivatives as necessary, and in a state where peeling of the coating film formed in the stage cured by ultraviolet rays after printing on the substrate does not occur Adhesive, while peeling does not occur, but the state where some peeling occurs in the periphery is a state where the adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) by touching it is a good tackiness, A state in which there is a slight stickiness when touching a finger, but no trace of the finger touch is left as a state where the tackiness is not defective. Ede, tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, UV-curable ink that allows printing as other is not bad In this production method , 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate were used as three polyfunctional radical polymerizable monomers at 1: 0. After selection by combining at a weight ratio of 1 to 0.5: 1 to 2, the weight ratio of the three polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof is set to 1: 0 to 0. .3, a method for producing an ultraviolet curable ink based on
(4) In the method for producing an ultraviolet curable ink, among the photopolymerization reactive composition, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, ethoxylated trimethylolpropane triacrylate Select and mix three , and add cyclodextrin or its derivatives as necessary, and in a state where peeling of the coating film formed in the stage cured by ultraviolet rays after printing on the substrate does not occur Adhesive, while peeling does not occur, but the state where some peeling occurs in the periphery is a state where the adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) by touching it is a good tackiness, A state in which there is a slight stickiness when touching a finger, but no trace of the finger touch is left as a state where the tackiness is not defective. Ede, tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, UV-curable ink that allows printing as other is not bad In the production method , 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate are used as three polyfunctional radical polymerizable monomers: 1: 1 to 2: Combined at a weight ratio of 0.1 to 0.5, and the weight ratio of the three polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof is set to 1: 0.05 to 0.3. UV curable ink manufacturing method based on
Consists of.

  As is apparent from the basic structure, in the present invention, 1,6-hexanediol diacrylate, 1,6-hexanediol is used as a photopolymerization reactive composition without blending a polyfunctional radical polymerizable oligomer. The ink can be formed by only two or three of diglycidyl ether diacrylate and ethoxylated trimethylolpropane triacrylate, and the manufacturing process can be simplified.

  Moreover, if this production method is employed, a high-performance UV ink can be produced without blending cyclodextrin or a derivative thereof, depending on the combination of the two or three polyfunctional radical polymerizable monomers. It becomes possible.

  Each embodiment based on the basic configuration will be described below.

The UV ink of the present invention is premised on UV ink that can be used not only for the inkjet printing method but also for other printing methods such as a screen printing method, a gravure printing method, and an offset printing method. Furthermore, in the embodiment, in the normal case where the thickness of the printed ink is set to 30 μm or less and the irradiation amount of ultraviolet rays is set to 100 to 400 mJ (millijoule) per 1 cm ² , the adhesive property and tackiness of UV ink The performance related to the performance is generally appropriate regardless of the type of various printing methods such as the inkjet method, screen printing method, gravure printing method, offset printing method, etc. Will be adopted as representative data.

  Embodiment (1) is characterized in that two polyfunctional radically polymerizable monomers are selected.

接着試験 ○：塗膜の剥離が生じない状態を示す。
△：基本的に塗膜の剥離は生じないが、周辺において若干剥離が生ずる状
態を示す。
×：塗膜の剥離が目立つ状態を示す。
タック試験 ○：指触によって全くベタツキ（タック）を感じない状態を示す。
△：指触に際し、多少ベタツキを感じるが、指触の痕跡が残らない状態を
示す。
×：硬化状態が完成せずに、指触した場合に痕跡が残る状態を示す。
尚、前記各○、△、×の評価基準は、以下の表においても同様であり、「△又は×」の「又は」の用語によって示される変化は、紫外線の照射量に基づく変化を示しているが、この点もまた以下の表においても同様である。 About 10% by weight of a photopolymerization initiator (specifically, 2-hydroxy 2-methyl-1-phenyl-propan-1-one or 2,4,6, trimethylbenzoyldiphenylphosphine oxide) In addition, the selection by each combination supporting the specific example realizing the embodiment (1), the tackiness corresponding to the weight ratio accompanying the selection, and the adhesiveness situation when the polycarbonate is used as the base material are As shown in Table 1-1 and 1-2 below.

Adhesion test (circle): The state in which peeling of a coating film does not arise is shown.
Δ: Basically, no peeling of the coating film occurs, but a slight peeling occurs in the periphery
Show the state.
X: The state where peeling of a coating film is conspicuous is shown.
Tack test (circle): It shows the state which does not feel stickiness (tack) by finger touch at all.
△: Feels somewhat sticky when touching, but no trace of touch remains
Show.
X: The state where a trace remains when touched with a finger without completing the cured state.
In addition, the evaluation criteria for each of the above ○, Δ, and × are the same in the following tables, and the change indicated by the term “or” in “Δ or ×” indicates a change based on the irradiation amount of ultraviolet rays. This is also true for the following table.

As is clear from Table 1-1, 1,6-hexanediol diglycidyl ether diacrylate or ethoxylated trimethylolpropane, which is another polyfunctional radical polymerizable monomer, with respect to 1,6-hexanediol diacrylate When triacrylate is blended 1/2 to 2 times and cyclodextrin or a derivative thereof is blended, a weight ratio of 0.05 to 0.2 with respect to the weight of two polyfunctional radical polymerizable monomers It is found that good performance can be exhibited with respect to at least one of tackiness and adhesiveness when a polycarbonate is used as a base material. It turns out that cannot be demonstrated.

As apparent from Table 1-2 above, when 1,6-hexanediol diglycidyl ether diacrylate was selected as a ratio of 1: 0.5 to 2 as two polyfunctional radical polymerizable monomers. In the case where the two polyfunctional radical polymerizable monomers are blended with cyclodextrin or a derivative thereof in a weight ratio of 0 to 0.2, the tackiness which is not good or bad , and the case where a polycarbonate is used as a base material it can be obtained in the adhesive.

  Embodiment (2) is characterized in that three polyfunctional radically polymerizable monomers are selected.

In the same manner as in the embodiment (1), after blending a photopolymerization initiator, selection by each combination realizing the embodiment (2), tackiness corresponding to the weight ratio associated with the selection , and polycarbonate The adhesive situation when the substrate is used is as shown in Tables 2-1 and 2-2.

As is apparent from Table 2-1, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate were 1: 0.1 to 0.00. When combined at a weight ratio of 5: 1 to 2, the weight ratio of the three polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof is appropriately adjusted to 1: 0 to 0.2. It turns out to obtain a UV ink with performance.

  As is apparent from Table 2-2, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate were mixed in a ratio of 1: 1 to 2: 0.1. After selection by combining at a weight ratio of ˜0.5, the weight ratio of the three polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof is 1: 0.05 to 0.3. It becomes clear that the UV ink which can exhibit suitable performance is obtained by the blending.

In the ink production method according to the present invention, in particular, the ink production method according to the embodiments (1) and (2), and further, in these methods, pigments, polymer dispersants, additives and the like are added as necessary. The ink according to the above inevitably exhibits good characteristics with respect to at least one of tackiness and adhesiveness when polycarbonate is used as a base material .

Therefore, a single or a plurality of coating layers are formed on the base material based on the ink jet injection or printing on the base material, and a decorative laminate is formed on the basis of a curing process by irradiation of ultraviolet rays on the coating layer. In an insert molding molded product obtained by integrating a molding resin by injection from an injection molding machine with respect to the decorative printed matter, the coating printed in the process leading to the lamination, It is possible to obtain a product in a state where almost no peeling occurs.
In addition, as said base material, sheets and films of polycarbonate, (treated) polyester, (treated) polypropylene, (treated) polyethylene, acrylic, etc. can be used, but screen printing, offset printing, What provided the printing layer or the coating layer by gravure printing, roll coating, spray coating etc. can also be used as a base material.

  In the molding of the insert molding molded product, a binder layer is printed or painted on the decorative layer in order to enhance the adhesion between the molding resin and the decorative printed material or the decorative laminate of the decorative sheet molded product. By providing in this way, it is possible to create a higher quality insert molding product.

  Examples of inks and paints for forming the binder layer include thermoplastic resins such as acrylic resins and vinyl chloride vinyl acetate copolymer resins such as IMB-003 binder and IMB-009 binder manufactured by Teikoku Ink Manufacturing Co., Ltd. A binder ink using a resin can be mentioned.

  Examples of the molding resin include ABS (acryl butadiene styrene) resin, PC (polycarbonate) resin, PP (polypropylene) resin, PA (polyamide) resin, and the like.

As described above, an embodiment using a polyfunctional radical polymerizable monomer or a combination thereof is shown. However, in the present invention, the addition of a polyfunctional radical polymerizable oligomer and / or a monofunctional radical polymerizable monomer is completely excluded. However, with respect to tackiness and adhesiveness when polycarbonate is used as a base material, it is naturally possible to add such an amount that does not impair the function of the present invention and further enhance the function. The blending state corresponds to the use form of the present invention.

Hereinafter, it demonstrates according to an Example.
In the examples, the data using the UV ink for the ink jet method is also used. However, in the case of adopting the normal film thickness of 30 μm or less in the other printing methods, the same data is used for each performance. As described above, is obtained.

  Based on the comparison between the above Table 4-1 and 4-2, the rationality of the selection range of the polyfunctional radical polymerizable monomer of the embodiment (1) and the weight ratio with the cyclodextrin or a derivative thereof is confirmed. be able to.

  Example 1 shows the specific example and comparative example regarding Table 1-1 and Table 1-2 among Embodiment (1).

As a color pigment, 3.0% by weight of carbon black, 10.0% by weight of 2,4,6, trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator, 2-hydroxy 2-methyl-1-phenyl-propane- 3.0% by weight of 1-one, 1.0% by weight of a silicone-based antifoaming agent, and 12.0% by weight of a urethane-based polymer are prepared. Similarly to the case of the embodiment, the irradiation amount of ultraviolet rays is 1 cm ^2. The result when a film thickness of 20 to 25 μm is formed after selecting a combination of two polyfunctional radical polymerizable monomers and a weight ratio with a methylated cyclodextrin after setting 100 to 400 mJ per unit, It is as shown in the following Table 3-1.

About a coloring agent, a photoreaction initiator, and a silicon leveling agent without blending a urethane-based polymer, the polyfunctional radical polymerizable monomer is blended in substantially the same ratio as in Example 1 shown in Table 3-1 above. When 1,6-hexanediol diglycidyl ether diacrylate or ethoxylated trimethylolpropane triacrylate is selected, good properties are obtained in the case of selection and weight ratio as shown in Table 3-2 below. Could not get.

Each ink according to Table 3-1 was irradiated with ultraviolet rays under the same conditions as in Example 1, and cured on a polycarbonate resin substrate sheet, and an ABS resin was laminated by an injection molding machine, And when molding an insert molding product by integrating, it shows roughly good moldability, tackiness, and adhesion when polycarbonate is used as the base material , and also has good adhesion to the polycarbonate base material. As a result, it was possible to obtain a solid insert molding product.

  Example 2 shows a specific example and a comparative example regarding the embodiment (2).

For the urethane polymer, color pigment, photopolymerization initiator, and silicon-based antifoaming agent, the same formulation as in Table 4-1 was performed, the same formulation as in Example 1 was performed, and three multifunctional products were used. The result of forming a film thickness of 10 μm after selecting the combination of radical polymerizable monomers and the weight ratio with methylated cyclodextrin is as shown in Table 4-1 below.

※紫外線の照射量を１ｃｍ^２当たり１００〜４００ｍＪとした場合には○であるが、紫外線の照射量を１ｃｍ^２当たり１００ｍＪとした場合には×であり、その中間領域である紫外線の照射量を１ｃｍ^２当たり２００〜３００ｍＪとした場合には△である。 On the other hand, in the case of the combination of three polyfunctional radically polymerizable monomers in the lower column of Table 4-1, when trimethylated cyclodextrin is not blended, as shown in Table 4-2 below, Good characteristics could not be obtained.

※ Although the case where the irradiation amount of ultraviolet rays and 1 cm ² per 100~400mJ is ○, when the irradiation amount of ultraviolet rays was 1 cm ² per 100mJ is ×, the irradiation amount of ultraviolet rays is an intermediate region in the case of a 1cm ² per 200~300mJ it is △.

Based on the comparisons in Tables 4-1 and 4-2, the rationality of the selection range of the monofunctional radical polymerizable monomer of the embodiment (2) and the weight ratio with the cyclodextrin or its derivative should be confirmed. Can do.
For the inks based on the specific examples in Table 4-1, an insert molding molded product was molded under the same conditions as in Example 1. Similarly, substantially good moldability, tackiness, and polycarbonate were used as the base material. In other words, it was possible to obtain a firm insert molding molded article with good adhesion to the polycarbonate substrate.

  The present invention can be used in the field of UV inks by blending single and plural polyfunctional radical polymerizable monomers, and further decorative molded articles based on the inks.

Claims (8)

The method of manufacturing a UV-curable ink, 1,6-hexanediol diacrylate as the photopolymerizable reactive composition, 1,6-hexanediol diglycidyl ether diacrylate, two of the ethoxylated trimethylolpropane triacrylate Select and mix, and if necessary, mix cyclodextrin or its derivative and print it on the substrate, and after it is cured by ultraviolet rays, the state where peeling of the formed film does not occur is considered good adhesiveness The state in which peeling does not occur but slight peeling occurs in the periphery is considered to be a state in which adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) due to finger touch is considered to be good tackiness. Although it feels somewhat sticky, the state in which no traces of finger touch remain is not bad for tackiness Tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, the method of manufacturing the ultraviolet-curable ink that allows printing as other is not bad In the above , 1,6-hexanediol diacrylate and 1,6-hexanediol diglycidyl ether diacrylate are combined at a weight ratio of 1: 0.5 to 2.0 as two polyfunctional radical polymerizable monomers. Or after selection by combining 1,6-hexanediol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 1: 0.5 to 2.0, the weight ratio of the monofunctional radically polymerizable monomer and cyclodextrin or its derivative 1: ultraviolet, which is based on a 0.05 to 0.2 Method for producing a curable ink. The method of manufacturing a UV-curable ink, 1,6-hexanediol diacrylate as the photopolymerizable reactive composition, 1,6-hexanediol diglycidyl ether diacrylate, two of the ethoxylated trimethylolpropane triacrylate Select and mix, and if necessary, mix cyclodextrin or its derivative and print it on the substrate, and after it is cured by ultraviolet rays, the state where peeling of the formed film does not occur is considered good adhesiveness The state in which peeling does not occur but slight peeling occurs in the periphery is considered to be a state in which adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) due to finger touch is considered to be good tackiness. Although it feels somewhat sticky, the state in which no traces of finger touch remain is not bad for tackiness Tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, the method of manufacturing the ultraviolet-curable ink that allows printing as other is not bad In the above, as two polyfunctional radical polymerizable monomers, 1,6-hexanediol diglycidyl ether diacrylate and ethoxylated trimethylolpropane triacrylate are combined in a weight ratio of 1: 0.5 to 2.0. And a method for producing an ultraviolet curable ink based on the weight ratio of the two polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof being 1: 0 to 0.2. In the method for producing an ultraviolet curable ink, three of 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate are used as a photopolymerization reactive composition. Select and mix, and if necessary, mix cyclodextrin or its derivative and print it on the substrate, and after it is cured by ultraviolet rays, the state where peeling of the formed film does not occur is considered good adhesiveness The state in which peeling does not occur but slight peeling occurs in the periphery is considered to be a state in which adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) due to finger touch is considered to be good tackiness. Although it feels somewhat sticky, the state in which no traces of finger touch remain is not bad for tackiness Tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, the method of manufacturing the ultraviolet-curable ink that allows printing as other is not bad In the above, as three polyfunctional radical polymerizable monomers, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate were 1: 0.1-0. .5: After selection by combining at a weight ratio of 1 to 2, the weight ratio of the three polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof is 1: 0 to 0.3. A method for producing an ultraviolet curable ink based on In the method for producing an ultraviolet curable ink, three of 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate are used as a photopolymerization reactive composition. Select and mix, and if necessary, mix cyclodextrin or its derivative and print it on the substrate, and after it is cured by ultraviolet rays, the state where peeling of the formed film does not occur is considered good adhesiveness The state in which peeling does not occur but slight peeling occurs in the periphery is considered to be a state in which adhesiveness is not poor, while the state in which the coating film does not feel any stickiness (tack) due to finger touch is considered to be good tackiness. Although it feels somewhat sticky, the state in which no traces of finger touch remain is not bad for tackiness Tackiness, and either both of adhesiveness in the case where the polycarbonate substrate is good, or any one of a good, the method of manufacturing the ultraviolet-curable ink that allows printing as other is not bad In the above, as three polyfunctional radical polymerizable monomers, 1,6-hexanediol diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, and ethoxylated trimethylolpropane triacrylate were 1: 1 to 2: 0. Combined at a weight ratio of 1 to 0.5, and an ultraviolet ray based on the weight ratio of the three polyfunctional radical polymerizable monomers to cyclodextrin or a derivative thereof being 1: 0.05 to 0.3 A method for producing curable ink.   5. The method for producing an ultraviolet curable ink according to claim 1, wherein methylated cyclodextrin is employed as the cyclodextrin.   An ultraviolet curable ink produced by the method according to claim 1. The ultraviolet curable ink according to claim 6 is formed on a substrate by injection or printing based on inkjet, and a single or a plurality of coating layers are formed, and the coating layer is subjected to a curing step by irradiation with ultraviolet rays. Decorative printed matter that forms a decorative laminate. An insert molding molded product obtained by integrating a molding resin by injection from an injection molding machine with respect to the decorative printed matter according to claim 7 .