Title of Invention	PROCESS FOR PRODUCING INK AND RELEVANT TO THE PROCESS, INK, PRINTED MATTER AND MOLDING
Abstract	Provided is a method for manufacturing inkjet system ultraviolet curable inks which are improved in formability, adhesiveness and tackiness by selecting a combination of a monofunctional radical polymerization monomer as a major component with other polyfunctional radical polymerization oligomers and/or monofunctional radical polymerization monomers. Also, obtained is a method for manufacturing inkjet system ultraviolet curable inks in which phenoxyethylacrylate is a basic composition used as a photo polymerization reactive composition and other monofunctional radical polymerization monomers and/or polyfunctional radical polymerization oligomers are mixed within a predetermined relative quantity, if necessary, thereby realizing results in which at least two of the above-described characteristics are favorable and the remaining one is far from poor, inks according to the method, decorating printed matter and decorating sheet shaped articles using the inks, and insert molding shaped products using the decorating printed matter and the decorating sheet shaped articles.

Title of Invention

PROCESS FOR PRODUCING INK AND RELEVANT TO THE PROCESS, INK, PRINTED MATTER AND MOLDING

Abstract

Provided is a method for manufacturing inkjet system ultraviolet curable inks which are improved in formability, adhesiveness and tackiness by selecting a combination of a monofunctional radical polymerization monomer as a major component with other polyfunctional radical polymerization oligomers and/or monofunctional radical polymerization monomers. Also, obtained is a method for manufacturing inkjet system ultraviolet curable inks in which phenoxyethylacrylate is a basic composition used as a photo polymerization reactive composition and other monofunctional radical polymerization monomers and/or polyfunctional radical polymerization oligomers are mixed within a predetermined relative quantity, if necessary, thereby realizing results in which at least two of the above-described characteristics are favorable and the remaining one is far from poor, inks according to the method, decorating printed matter and decorating sheet shaped articles using the inks, and insert molding shaped products using the decorating printed matter and the decorating sheet shaped articles.

Full Text	FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2 003 COMPLETE SPECIFICATION (See Section 10, and rule 13) 1. TITLE OF INVENTION PROCESS FOR PRODUCING INK AND RELEVANT TO THE PROCESS, INK, PRINTED MATTER AND MOLDING 2. APPLICANT(S) a) Name : TEIKOKU PRINTING INKS MFG. CO., LTD. b) Nationality : JAPANESE Company c) Address : 4-12, MITA 4-CHOME, MINATO-KU, TOKYO 108-0 073 JAPAN 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed :- [Field of the Invention] The present invention relates to a method for manufacturing ultraviolet curable inks curable by ultraviolet rays after being laminated on a sheet as a substrate by inkjet system (hereinafter, referred to as "UV inkjet inks") and also relates to UV inkjet inks on the basis of the method, decorating printed matter and decorating sheet shaped articles obtained by printing or coating with the inks, and insert molding shaped products manufactured by using the decorating printed matter and the decorating sheet shaped articles. [Background Art] An ultraviolet curable ink usually contains a photoreaction initiator and a photo polymerization reactive composition as essential constituents, to which a pigment, a dispersing agent and other additives etc., are mixed, if necessary. A method for preparing decorating printed matter by adopting the ultraviolet curable ink adopts an inkjet system in which the ink is injected into a substrate sheet to be printed by jet printing and cured by irradiation of ultraviolet rays after lamination, in addition to a method in which ultraviolet rays are irradiated after printing performed by any kind of printing method such as screen printing and offset printing. Since UV inkjet inks adopted in the above-described inkjet system are required to be low in viscosity, a monofunctional radical polymerization monomer, which is an indispensable component, is adopted as a photo polymerization reactive composition. It is, however, understood that the monofunctional radical polymerization monomer is lower in curing speed and cross-linking density, if used solely, and is inferior in formability such as forming and also insufficient in adhesiveness. In order to improve the above-described disadvantages, in most cases, a polyfunctional radical polymerization oligomer is mixed with a monofunctional radical polymerization monomer. However, there is a situation where this mixture cannot sufficiently improve the disadvantages. In Patent Document 1 of JP declaration 2004-526820, such a constitution is adopted that a polyfunctional radical polymerization monomer is given as a major component of the photo polymerization reactive composition and any one of a and P-unsaturated ether monomers is also contained, for improving the formability (tenacity) and adhesiveness. Nonetheless, the above-described constitution is excessively high in cross-linking density and also lower in such flexibility as to be deformable due to an abrupt cure, thereby posing another disadvantage of formability which is different from a case where the monofunctional radical polymerization monomer is previously used as a major component. In Patent Document 2 of JP declaration 2005-532445, in order to improve the disadvantage found in Patent Document 1, such a constitution is adopted that the monofunctional radical polymerization monomer is given as a major component of the photo polymerization reactive composition and at least one type of a and P-unsaturated ether monomers is contained as an indispensable component. The above-described constitution is certainly better in flexibility for improving deformability as compared with the constitution disclosed in Patent Document 1. However, it is not necessarily sufficient in adhesiveness or not necessarily sufficient either in decreasing tackiness, that is, stickiness on the ink surface after ultraviolet curing. [Disclosure of the Invention] As is apparent from the above-described background art, although monofunctional radical polymerization monomers are adopted as a major component in UV inkjet inks, no sufficient evaluation is made for how to select or combine them. As a result, no such improvement is attained in formability, adhesiveness or tackiness as to exhibit a higher flexibility. In view of such a situation, an object of the present invention is to provide a method for manufacturing UV inkjet inks by procedures that a specific monofunctional radical polymerization monomer, which is a photo polymerization reactive composition, is used as a basic composition and combined with other monofunctional radical polymerization monomers and polyfunctional radical polymerization oligomers, if necessary, by which, of three characteristics consisting of highly flexible formability, improved adhesiveness and tackiness, at least two of them are excellent and the remaining one is far from poor, and it is also to provide UV inkjet inks based on this method, decorating printed matter, decorating sheet shaped articles and insert molding shaped products in which the inks are used. In order to attain the object, a basic method of the present invention is constituted by the following. (1) A method for manufacturing inkjet system ultraviolet curable inks in which essential components are a photoreaction initiator and a photo polymerization reactive composition, and the method for manufacturing inkjet system ultraviolet curable inks, wherein after being mixed with a polyfunctional radical polymerization oligomer, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with two monofunctional radical polymerization monomers selected from alicyclic monofunctional radical polymerization monomers and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate and the two alicyclic monofunctional radical polymerization monomers mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to two alicyclic monofunctional radical polymerization monomers to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.7 : 0.1 to 0.7. (2) A method for manufacturing inkjet system ultraviolet curable inks wherein essential components are a photoreaction initiator and a photo polymerization reactive composition, and the method for manufacturing inkjet system ultraviolet curable inks, wherein with a mixture of a polyfunctional radical polymerization oligomer given as a precondition, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with one monofunctional radical polymerization monomer selected from alicyclic monofuncrional radical polymerization monomers, one monofunctional radical polymerization monomer selected from heterocyclic monofunctional radical polymerization monomers, and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate, the alicyclic monofunctional radical polymerization monomer and the heterocyclic monofunctional radical polymerization monomer mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to the alicyclic monofunctional radical polymerization monomer to the heterocyclic monofunctional radical polymerization monomer to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.5 : 0.1 to 0.5 : 0.1 to 1. [Effects of the Invention] As is apparent from the above-described description covering (1) and (2), in manufacturing methods of the present invention, phenoxyethylacrylate is adopted as a monofunctional radical polymerization monomer acting as a base of the photo polymerization reactive composition. In remaining constitutions of (1) and (2) in which phenoxyethylacrylate is adopted in combination with other monofunctional radical polymerization monomers, such results are obtained at an extremely high probability that at least two characteristics of formability, adhesiveness and tackiness are excellent and the remaining one is far from poor, although there may be a case where it is not favorable. Therefore, UV inkjet inks manufactured by the respective methods as well as decorating printed matter, decorating sheet shaped articles and insert molding shaped products based on these inks are to be able to exhibit favorable characteristics in general. [Best Mode for Carrying Out the Invention] As is apparent from the constitutions of (1) and (2), in the present invention, phenoxyethylacrylate is adopted as a monofunctional radical polymerization monomer in preparing UV inkjet inks as a basic composition. However, sole use of phenoxyethylacrylate as a photo polymerization reactive composition will not always provide favorable results in all characteristics of formabikty, adhesiveness and tackiness. Therefore, selection is made from various combinations of phenoxyethylacrylate with other polyfunctional radical polymerization oligomers and/or monofunctional radical polymerization monomers, thereby providing UV inkjet inks improved in the individual characteristics, at which a basic technical idea of the present invention is found. In the UV inkjet inks of the present application, although a major component is a monofunctional radical polymerization monomer which is based on phenoxyethylacrylate, a mixture with polyfunctional radical polymerization monomers and/or ultraviolet cation curable monomers is not excluded, and mixing these monomers at least to such an extent that will not undermine the effects of the present invention (specifically, such an extent that at least two characteristics of formability, adhesiveness and tackiness are favorable and the remaining one is far from poor) corresponds to a mode of utilization of the present invention. Hereinafter, it will be confirmed by tests that the methods according to the basic constitutions of (1) and (2) are clearly excellent as embodiments. (In the combinations shown in each table given below, photoreaction initiators such as bisacyl phosphine oxide and 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-1 are mixed in a quantity of about 10% as a whole on determination of the individual characteristics.) An explanation will be made for the process leading to method (1). Specifically, phenoxyethylacrylate is combined with various types of monofunctional radical polymerization monomers and also allowed to change in weight ratio, thereby it is possible to obtain the results based on a general tendency of characteristics for each type as is shown in Table 1. It is noted that various types of monofunctional radical polymerization monomers include substantially most monofunctional radical polymerization monomers actually adopted as UV inkjet inks, and such a adopting state is same in the case of constitutions of (2) it is after described in Table 2. An explanation will be made for the process leading to method (1). Specifically, any one or a plurality of an aromatic polyfunctional urethane acrylate oligomer, aliphatic urethane acrylate oligomer, epoxy acrylate oligomer and polyester acrylate oligomer are combined and mixed. Then, phenoxyethylacrylate, any two monomer selected from alicyclic monofunctional radical polymerization monomers and any one monomer selected from other assumable monofunctional radical polymerization monomets (however, excluding phenoxyethylacrylate and the two alicyclic monofunctional radical polymerization monomers mixed with phenoxyethylacrylate), that is, a total of four monofunctional radical polymerization monomers, are combined. Then, a weight ratio of the other monofunctional radical polymerization monomers to phenoxyethylacrylate is adjusted, thereby it is possible to obtain the results of individual characteristics for each type as shown in Table 1. But, the weight ratio of polyfunctional radical polymerization oligomer to phenoxyethylacrylate to two alicyclic monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.7. [Table 1] Types of monofunctional Weight ratio when Formability Adhesiveness Tackiness monomers phenoxyethylacrylate is set to be one Aromatic monofunctional radical polymerization 0.1 -0.7 o or ∆ ∆ or o o 1.2 o ∆ ∆ monomer (without hydroxyl group, however, excluding phenoxyethylacrylate) Aromatic monofunctional 0.1 -0.7 o or∆ A or ∆ o radical polymerization 1.2 o ∆ ∆ monomer (with hydroxyl group) Aliphatic monofunctional 0.1 - 0.7 o or ∆ ∆ or o 0 radical polymerization 1.2 X ∆ 0 monomer (without hydroxyl group) Aliphatic monofunctional 0.1 - 0.7 o or ∆ ∆ or o 0 radical polymerization 1.2 X ∆ 0 monomer (with hydroxyl group) Alicyclic monofunctional 0.1-0.7 o or ∆ ∆ or o o radical polymerization 1.2 o X ∆ monomer (however, excluding two acrylate monomers mixed previously together with phenoxyethylacrylate) Heterocyclic monofunctional radical polymerization monomer 0.1 ~ 0.7 o or ∆ o or ∆ o 1.2 ∆ o ∆ * Each of the symbols, o, A, x, is assessed according to the following criteria. Formability test o: showing a state that no cracks are found on coated film A: showing a state that fine cracks are partially found to such an extent that can be barely confirmed by visual inspection x; showing a state that cracks are found all over printed matter Adhesion test o: showing a state that no peeling is found on coated film A: showing a state that fundamentally no peeling is found on coated film but some found in the vicinity x: showing a state that peeling is found conspicuously Tack test o: showing a state that no stickiness (tackiness) is found when touched by finger A: showing a state that tackiness is found to some extent when touched by finger but no marks remain after touched x: showing a state that curing is not completed and marks remain when touched by finger Estimation criteria for each of o, A, x will be applied in the same way to the table 2. Of the individual characteristics, formability and adhesiveness are reverse for the marks of o and A, because even though one of the characteristics is A, the other is o, and there is no case where both of them are A, and further, there may also be a case where both of them are o. As is apparent from Table 1, phenoxyethylacrylate is mixed with any two monomers selected from alicyclic monofunctional radical polymerization monomers at the above-described weight ratio and then combined with any one monomer selected from monofunctional radical polymerization monomers belonging to all other assumable types. In the case where phenoxyethylacrylate is set to be 1, it has been revealed that all the characteristics are favorable for the monofunctional radical polymerization monomers belonging to all types where a weight ratio of two alicyclic monofunctional radical polymerization monomers and monofunctional radical polymerization monomers belonging to all other assumable types is respectively in a range of 0.1 to 0.7. An explanation will be made for the process leading to method (2). Specifically/ any one of an aromatic polyfunctional urethane acrylate oligomer, aliphatic urethane acrylate oligomer, epoxy acrylate oligomer and polyester acrylate oligomer or a combination thereof was mixed. Then, phenoxyethylacrylate, one monomer selected from alicyclic monofunctional radical polymerization monomers, one monomer selected from heterocyclic monofunctional radical polymerization monomers, a subtotal of three monofunctional radical polymerization monomers, and one monomer selected from other assumable monofunctional radical polymerization monomers (however, excluding phenoxyethylacrylate, the alicyclic monofunctional radical polymerization monomer mixed with phenoxyethylacrylate and heterocyclic monofunctional radical polymerization monomer), that is, a total of four monofunctional radical polymerization monomers were combined. A weight ratio of other monofunctional radical polymerization monomers to phenoxyethylacrylate is adjusted, thereby it is possible to obtain the results of individual characteristics for each type as shown in Table 2. But, the weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to the alicyclic monofunctional radical polymerization monomer to the heterocyclic monofunctional radical polymerization monomer is in the respective ranges of 0.05 to 0. 4 :1: 0.1 to 0.5 : 0.1 to 0.5. [Table 2] Types of Weight ratio when Formability Adhesiveness Tackiness monofunctional phenoxyethylacrylate monomers is set to be one Aromatic monofunctional radical 0.1-1 o or ∆ ∆ or o** o or ∆* 1.5 o ∆ ∆ polymerization monomer (without hydroxyl group, however, excluding phenoxyethylacrylate) Aromatic monofunctional radical 0.1-1 o or ∆ ∆ or o 0 1.5 ∆ 0 ∆ polymerization monomer (with hydroxyl group) Aliphatic 0.1-1 o or ∆ ∆ or o 0 monofunctional radical 1.5 0 X o polymerization monomer (without hydroxyl group) Aliphatic 0.1-1 o or ∆ ∆ or o o monofunctional acrylate 1.5 ∆ X 0 monomer (with hydroxyl group) Alicyclic 0.1-1 o or ∆ ∆or o o monofunctional radical 1.5 A 1 x o polymerization monomer (however, excluding a monomer mixed previously with phenoxyethylacrylate) Heterocyclic monofunctional radical 0.1-1 o or ∆ ∆ or o o or ∆* 1.5 0 ∆ ∆ polymerization monomer (however, excluding a monomer mixed previously with phenoxyethylacrylate) ** Of the individual characteristics, formability and adhesiveness are reverse for the marks of o and A, because even though one of the characteristics is A, the other is o, and there is also a case where both of them are o, The same item is applicable to a fact that adhesiveness and tackiness are also reverse in the marks of o and A. As is apparent from Table 2, phenoxyethylacrylate, one monomer selected from alicyclic monofunctional radical polymerization monomers and one monomer selected from heterocyclic monofunctional radical polymerization monomers, a subtotal of three monofunctional radical polymerization monomers, and any one monomer selected from monofunctional radical polymerization monomers belonging to all other assumable types, that is, a total of four monomers, are combined. In the case where phenoxyethylacrylate is set to be 1, it has been revealed that the characteristics are favorable for the monofunctional radical polymerization monomers belonging to all types where a weight ratio of other monofunctional radical polymerization monomers is in a range of 0.1 to 1. The constitution of (2) is able to provide favorable results stably in various combinations. Therefore, it may be well expected that favorable characteristics may also be obtained even when one or a plurality of the monofunctional radical polymerization monomers are mixed to the constitution of (2). Thus, a constitution in which other one or a plurality of the monofunctional radical polymerization monomers are added to and mixed with the constitution of (2) corresponds to constitution in which of (2) is utilized. Isobornyl acrylate and N-vinylcaprolactam are in most cases favorably adopted respectively as a typical example of an alicyclic monofunctional radical polymerization monomer and a heterocyclic monofunctional radical polymerization monomer to be mixed with phenoxyethylacrylate. In each of the above-described methods (1) and (2), inks to which pigments, high-polymer dispersing agents and additives etc., are added, if necessary, may provided with favorable characteristics at least for two of the individual characteristics. It is noted that these inks are from 3 to 500 cps in viscosity (determined at 25°C by using a cone-plate type viscometer), which is a viscosity favorably corresponding to inkjet printing. Therefore, decorating printed matter which form a decorating lamination layer by curing steps in which these inks are applied to a substrate by inkjet injection into or printing to give a single or a plurality of coated layers and ultraviolet rays are irradiated on the coated layers, decorating sheet shaped articles based on formation of the decorating printed matter by vacuum forming or pressure forming and insert molding shaped products integrally formed on injection of a molding resin into the decorating printed matter or the decorating sheet shaped articles by using an injection machine may manufactured in a state that cracks on a coated film, stickiness, and peeling are hardly found in a step leading to lamination. It is noted that sheets and films based on polycarbonate, (treated) polyester, (treated) polypropylene, (treated) polyethylene and an acrylic resin etc may be used as the substrate. These prepared by imparting a printed layer or a coated layer to these sheets or films by screen printing, offset printing, gravure printing, roll coating process or spray coating etc., may also be used as the substrate. In forming the insert molding shaped product, a binder layer is provided on a decorating layer by printing or coating for the purpose of increasing the adhesiveness between the molding resin and the decorating printed matter or between the molding resin and a decorating lamination layer of the decorating sheet shaped article, thereby it is possible to prepare insert molding shaped products higher in quality. Inks and paints for forming a binder layer may include IMB-003 Binder and IMB-009 Binder (product names) made by Teikoku Printing Inks Mfg. Co., Ltd., which are binder inks using thermoplastic resins such as an acrylic resin and a polyvinyl chloride vinyl acetate copolymer resin etc. Further, the molding resin may include ABS (acrylbutadiene styrol) resins, PC (polycarbonate) resins, PP (polypropylene) resins, and PA (polyamide) resins. Hereinafter, an explanation wiU. be made by referring to examples. [Example 1] Example 1 is characterized in that in the basic constitution of (1), 2-hydroxy-3-phenoxypropylacrylate is used as an aromatic monofunctional radical polymerization monomer with a hydroxyl group and two alicyclic monofunctional radical polymerization monomers are isobornyl acrylate and dicyclopentenyl oxyethylacrylate. As with Example 1, provided were a pigment, a photoreaction initiator, a high-polymer dispersing agent and an additive. 2-hydroxy-3-phenoxypropylacrylate in a predetermined mixed quantity as well as isobornyl acrylate and dicyclopentenyl oxyethylacrylate at the respective predetermined mixed quantities were mixed with a trifunctional urethane acrylate oligomer and phenoxyethylacrylate, each mixed quantity of which was predetermined as given in Table 3-1, and a test similar to Example 1 was conducted, thereby obtaining the results of individual characteristics as shown in the table. [Table 3-1] Type of Chemical Mixed Mixed Mixed Mixed Forma Adhesi Tacki monofun name quantity quantity quantity quantity of 2- bility veness ness ctional of of of hydroxy-3- monomer monofuncti onal monomer of the above chemical name (% by weight) trifunctio nal urethane acrylate oligomer (% by weight) phenox y- ethylacr ylate (% by weight) phenoxyprop ylacrylate (% by weight) Ali cyclic monofun Dicyclopenten yi oxyethylacryla te and isobornyl acrylate* Each 3.5 3.5 69.5 7.0 0 o o Each 2.4 2.4 47.0 32.8 o A 0 ctional Each 16.5 2.4 47.0 4.6 0 A o radical Each 12.4 1.8 35.6 24.8 o A o polymeri Each 2.8 21.7 54.3 5.4 A o o zation Each 2.0 15.8 39.6 27.6 o A 0 monomer Each 13.8 15.8 39.6 4.0 o A o Each 10.9 12.5 31.1 21.6 o A o * Dicyclopentenyl oxyethylacrylate and isobornyl acrylate were mixed at equal percentages with each other. In the test given in Table 3-1, a weight ratio according to the constitution of (1) was tested at various values, in particular, in combination with 2-hydroxy-3-phenoxypropylacrylate, dicyclopentenyl oxyethylacrylate and isobornyl acrylate. The test has revealed that favorable results were obtained at least in two characteristics. It is assumed that similar favorable characteristics may be obtained in combination of an aromatic monofunctional radical polymerization monomer with a hydroxyl group other than 2-hydroxy-3-phenoxypropylacrylate, dicyclopentenyl oxyethylacrylate and an alicyclic monofunctional radical polymerization monomer other than isobornyl acrylate. When the above-described assumption is taken into account, the validity of the constitution of (1) may be confirmed by referring to the test results given in Table 3-1. Then, after one of dicyclopentenyl oxyethylacrylate was mixed at 27.0% by weight as an alicyclic monofunctional radical polymerization monomer as shown in Table 3-2 and N-lvinylcaprolactam was mixed at 10.0% by weight as a heterocyclic monofunctional radical polymerization monomer, trifunctional urethane acrylate oligomer was not mixed, but phenoxyethylacrylate was mixed at 50.0% by weight, thereby obtaining the results of individual characteristics as shown in Table 3-2. [Table 3-2] Type of Chemical name Formability Adhesiveness Tackiness monofunctional monomer Alicyclic Dicyclopentenyl A o A monofunctional oxyethylacrylate radical polymerization monomer It has been revealed as apparent through comparison between Table 3-1 and Table 3-2 that where no polyfunctional radical polymerization oligomer is mixed at all, no mixture ratio required in the constitution of (1) is satisfied and one type of alicyclic monofunctional radical polymerization monomers is used, no favorable characteristics are obtained as shown in Table 3-1, which is the constitution of (1). Each of the inks given in Table 3-1 were subjected to irradiation of ultraviolet rays under the same conditions as those of the above-described tests and cured on a substrate sheet made with a polycarbonate resin. Then, the substrate sheet was vacuum-formed and an ABS resin was laminated by using an injection machine and formed integrally to mold an insert molding shaped product In molding the shaped product, each of the inks was not in a tacky state on the substrate sheet, substantially favorable in formability and also generally favorable in adhesion with the substrate sheet, with no peeling found at all. It was, therefore, possible to obtain strong insert molding shaped products. [Example 2] Example 2 is characterized in that in the basic constitution of (2), after selection of isobornyl acrylate as an alicyclic monofunctional radical polymerization monomer, N-vinylcaprolactam as a heterocyclic monofunctional radical polymerization monomer, among monofunctional radical polymerization monomers belonging to all other types, the aromatic monofunctional radical polymerization monomer without a hydroxyl group is any one of benzyl acrylate, phenoxydiethylene glycolacrylate, phenoxytetraethylene glycolacrylate and nonyl phenol tetraethylene glycolacrylate, the aromatic monofunctional radical polymerization monomer with a hydroxyl group is 2-hydroxy-3-phenoxypropylacrylate, the aliphatic monofunctional radical polymerization monomer without a hydroxyl group is ethoxydiethylene glycolacrylate, the aliphatic monofunctional radical polymerization monomer with a hydroxy! group is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the aliphatic monofunctional radical polymerization monomer is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the alicyclic monofunctional radical polymerization monomer is any one of dicyclopentenyl acrylate and dicyclopentenyl oxyethylacrylate, and the heterocyclic monofunctional acrylate monomer is any one of acryloylmorphorine and tetrahydrofurfurylacrylate. As with Example 1, provided were a pigment a photoreaction initiator, a high-polymer dispersing agent and an additives. Isobornyl acrylate in a predetermined mixed quantity and N-vinylcaprolactam in a predetermined mixed quantity were mixed with a trifunctional urethane acrylate oligomer and phenoxyethylacrylate, each mixed quantity of which was predetermined as shown in Table 4-1, and the other monofunctional radical polymerization monomers in a predetermined mixed quantity was also mixed, thereby obtaining the results of individual characteristics as shown in the table. [Table 4-1] Type of Chemical name Mixed Mixed Mixed Mixed Mixed Forma Adhesi Tackin monofun quantity quanti quantity quant quantit bility veness ess ctional of ty of of ity of y of N- monomer mono- tri- phenox isobor vinylca function functi y- nyl pro- al onal ethylacr acryla lactam monom uretha ylate (% te (% by er of the above chemica 1 name (% by weight) ne acryla te oligo mer (% by weigh t) by weight) (% by weigh t) weight Aromatic Benzylacrylate 7.5 6.0 40.5 20.0 13.0 o o o monofun 6.6 3.2 64.0 6.6 6.6 o o 0 ctional 38.5 2.0 38.5 4.0 4.0 0 A 0 radical 5.0 2.4 49.8 5.0 24.8 0 0 o polymeri 32.8 1.7 32.8 3.3 16.4 o 0 0 zation 5.0 2.4 49.8 24.8 5.0 o A o monomer 32.8 1.7 32.8 16.4 3.3 o A o (without 5.0 2.0 40.0 20.0 20.0 o o o hydroxyl 28.5 1.5 28.6 14.2 14.2 0 0 o group) 5.2 20.4 51.0 5.2 5.2 A o 0 33.3 13.4 33.5 3.4 3.4 o o o 4.2 16.5 41.4 4.2 20.7 o o o 29.0 11.6 29.0 2.9 14.5 o 0 0 4.2 16.5 41.4 20.7 4.2 o A 0 29.0 11.6 29.0 14.5 2.9 o A 0 3.5 13.9 34.8 17.4 17.4 o 0 o 25.6 10.2 25.6 12.8 12.8 0 o 0 Phenoxy diethylene glycolacrylate 7.5 6.0 40.5 20.0 13.0 o o 0 Phenoxy tetraethylene glycolacrylate 7.5 6.0 40.5 20.0 13.0 0 o 0 Phenol EO modified (2 mol) acrylate 7.5 6.0 40.5 20.0 13.0 o 0 0 Aromatic 2-hydroxy- monofun 3—phenoxypro ctional pylacrylate radical polymeri zation 7.5 6.0 40.5 20.0 13.0 0 o 0 monomer (with hydroxyl group) Aliphatic Ethoxydiethylen monofun e glycolacrylate ctional radical polymeri 7.5 6.0 40.5 20.0 13.0 o o o zation monomer (without hydroxyl group) Aliphatic 2-hydroxy monofun ethylacrylate 7.5 6.0 40.5 20.0 13.0 o o o ctional radical polymeri zation (HOA) 2-hydroxy proplylacrylate 7.5 6.0 40.5 20.0 13.0 o o 0 2-hydroxy monomer butylacrylate (with 7.5 6.0 40.5 20.0 13.0 o o o hydroxyl group) Alicyclic Dicyclopentenyl monofun acrylate ctional radical 7.5 6.0 40.5 20.0 13.0 o 0 o polymeri zation monomer Heterocy clic Tetrahydrofurfu rylacrylate 7.5 6.0 40.5 20.0 13.0 o o 0 monofun Acryloylmorph ctional orine radical polymeri 7.5 6.0 40.5 20.0 13.0 o 0 o zation monomer As shown in Table 4-1, a weight ratio according to the constitution of (2) was tested for various required values, in particular, in combination with benzyl acrylate as a monofunctional monomer, and also tested up to a limited value. The test has revealed the characteristics, and it was confirmed that favorable results could be obtained at least in two characteristics. In this instance, it is assumed that favorable results may be obtained for other monofunctional monomers. When the above-described assumption is taken into account, the validity of the constitution of (2) may be confirmed by referring to the test results shown in Table 4-1. Then, a polyfunctional radical polymerization oligomer, phenoxyethylacrylate, isobornyl acrylate and N-vinylcaprolactam were mixed respectively at 6.0% by weight, 48.0% by weight, 24.0% by weight and 8.0% by weight, and as shown in Table 4-2, a polyfunctional radical polymerization monomer was mixed at 1.0% by weight, thereby obtaining the results of individual characteristics as shown in the table. [Table 4-2] Type of monofunctional monomer Chemical name Formabiliry Adhesiveness Tackiness Bifunctional monomer Tripropylene glycoldiacrylate ∆ 0 0 Hexanediol diacrylate X 0 0 Trifunctional monomer Trimethylol propane triacrylate X o o It has been revealed as apparent through comparison between Table 4-1 and Table 4-2 that in the basic constitution of (2) favorable results may be obtained, irrespective of types of other monofunctional radical polymerization monomers, but, where a polyfunctional radical polymerization monomer is mixed in place of these other monofunctional radical polymerization monomers, favorable characteristics as provided in the basic constitution of (2) may necessarily be lost, even if mixed only in a small quantity. The inks given in Table 4-1 were used to mold insert molding shaped products under the same conditions as those of Example 1. It was, therefore, possible to obtain strong insert molding shaped products substantially favorable in formability, adhesiveness and tackiness and also favorable in adhesion with a substrate, without any state of peeling. [Industrial Applicability] The present invention is applicable to the field of UV inkjet inks in which phenoxyethylacrylate is a basic composition used as a photo polymerization reactive composition and a major component is a monofunctional radical polymerization monomer and also applicable to the field of decorating shaped products based on the inks. We Claim: 1. A method for manufacturing inkjet system ultraviolet curable inks in which essential components are a photoreaction initiator and a photo polymerization reactive composition, the method for manufacturing inkjet system ultraviolet curable inks, wherein after being mixed with a polyfunctional radical polymerization oligomer, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with two monofunctional radical polymerization monomers selected from alicyclic monofunctional radical polymerization monomers and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate and the two alicyclic monofunctional radical polymerization monomers mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to two alicyclic monofunctional radical polymerization monomers to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.7: 0.1 to 0.7. 2. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 1, wherein the two alicyclic monofunctional radical polymerization acrylate monomers are dicyclopentenyl oxyethylacrylate and isobornyl acrylate. 3. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 2, wherein, among radical polymerization monomers belonging to all types, the aromatic monofunctional radical polymerization monomer without a hydroxyl group is any one of benzyl acrylate, phenoxydiethylene glycolacrylate, phenoxytetraethylene glycolacrylate and nonylphenol tetraethylene glycolacrylate, the aromatic monofunctional radical polymerization monomer with a hydroxy! group is 2-hydroxy-3-phenoxypropylacrylate, the aliphatic monofunctional radical polymerization monomer without a hydroxyl group is ethoxydiethylene glycolacrylate, the aliphatic monofunctional radical polymerization monomer with a hydroxyl group is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the alicyclic monofunctional radical polymerization monomer is dicyclopentenyl acrylate, and the heterocyclic monofunctional radical polymerization monomer is any one of tetrahydrofurfurylacrylate, N-vinylcaprolactam and acryloylmorphorine. 4. A method for manufacturing inkjet system ultraviolet curable inks in which essential components are a photoreaction initiator and a photo polymerization reactive composition, the method for manufacturing inkjet system ultraviolet curable inks, wherein, with a mixture of a polyfunctional radical polymerization oligomer given as a precondition, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with one monofunctional radical polymerization monomer selected from alicyclic monofunctional radical polymerization monomers, one monofunctional radical polymerization monomer selected from heterocyclic monofunctional radical polymerization monomers, and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate, the alicyclic monofunctional radical polymerization monomer and the heterocyclic monofunctional radical polymerization monomer mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to the alicyclic monofunctional radical polymerization monomer to the heterocyclic monofunctional radical polymerization monomer to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.5 : 0.1 to 0.5 : 0.1 to 1. 5. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 4, wherein, one monomer selected from alicyclic monofunctional radical polymerization monomers is isobornyl acrylate and, one monomer selected from heterocyclic monofunctional radical polymerization monomers, is N-vinylcaprolactam. 6. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 5, wherein, among monofunctional radical polymerization monomers belonging to all other types, the aromatic monofunctional radical polymerization monomer without a hydroxyl group is any one of benzyl acrylate, phenoxydiethylene glycolacrylate, phenoxytetraethylene glycolacrylate and nonylphenol tetraethylene glycolacrylate, the aromatic monofunctional radical polymerization monomer with a hydroxyl group is 2-hydroxy-3-phenoxypropylacrylate, the aliphatic monofunctional radical polymerization monomer without a hydroxyl group is ethoxydiethylene glycolacrylate, the aliphatic monofunctional radical polymerization monomer with a hydroxyl group is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the alicyclic monofunctional radical polymerization monomer is any one of dicyclopentenyl acrylate and dicyclopentenyl oxyethylacrylate, the heterocyclic monofunctional radical polymerization monomer is any one of tetrahydrofurfuryl acrylate and acryloylmorphorine. 7. Inkjet system ultraviolet curable inks manufactured according to the methods as set forth in claims 1,2, 3,4, 5, and 6. 8. Decorating printed matter which forms a decorating lamination layer by curing processes in which the inkjet system ultraviolet curable inks as set forth in claim 7 are applied to a substrate by inkjet injection or printing to give a single or a plurality of coated layers and ultraviolet rays are irradiated on the coated layers. 9. Decorating sheet shaped articles obtained by forming the decorating printed matter as set forth in claim 8 by vacuum forming or pressure forming. 10. Insert molding shaped products formed integrally by injecting a molding resin by using an injection machine to the decorating printed matter as set forth in claim 8 or the decorating sheet shaped articles as set forth in claim 9.

Full Text

FORM 2
THE PATENT ACT 1970 (39 of 1970)
&
The Patents Rules, 2 003 COMPLETE SPECIFICATION
(See Section 10, and rule 13)
1. TITLE OF INVENTION
PROCESS FOR PRODUCING INK AND RELEVANT TO THE PROCESS, INK, PRINTED MATTER AND MOLDING
2. APPLICANT(S)
a) Name : TEIKOKU PRINTING INKS MFG. CO., LTD.
b) Nationality : JAPANESE Company
c) Address : 4-12, MITA 4-CHOME,
MINATO-KU, TOKYO 108-0 073 JAPAN
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed :-

[Field of the Invention]
The present invention relates to a method for manufacturing ultraviolet curable inks curable by ultraviolet rays after being laminated on a sheet as a substrate by inkjet system (hereinafter, referred to as "UV inkjet inks") and also relates to UV inkjet inks on the basis of the method, decorating printed matter and decorating sheet shaped articles obtained by printing or coating with the inks, and insert molding shaped products manufactured by using the decorating printed matter and the decorating sheet shaped articles.
[Background Art]
An ultraviolet curable ink usually contains a photoreaction initiator and a photo polymerization reactive composition as essential constituents, to which a pigment, a dispersing agent and other additives etc., are mixed, if necessary.
A method for preparing decorating printed matter by adopting the ultraviolet curable ink adopts an inkjet system in which the ink is injected into a substrate sheet to be printed by jet printing and cured by irradiation of ultraviolet rays after lamination, in addition to a method in which ultraviolet rays are irradiated after printing performed by any kind of printing method such as screen printing and offset printing.
Since UV inkjet inks adopted in the above-described inkjet system are required to be low in viscosity, a monofunctional radical polymerization monomer, which is an indispensable component, is adopted as a photo polymerization reactive composition.
It is, however, understood that the monofunctional radical polymerization monomer is lower in curing speed and cross-linking density, if used solely, and is inferior in formability such as forming and also insufficient in adhesiveness.
In order to improve the above-described disadvantages, in most cases, a

polyfunctional radical polymerization oligomer is mixed with a monofunctional radical polymerization monomer. However, there is a situation where this mixture cannot sufficiently improve the disadvantages.
In Patent Document 1 of JP declaration 2004-526820, such a constitution is adopted that a polyfunctional radical polymerization monomer is given as a major component of the photo polymerization reactive composition and any one of a and P-unsaturated ether monomers is also contained, for improving the formability (tenacity) and adhesiveness.
Nonetheless, the above-described constitution is excessively high in cross-linking density and also lower in such flexibility as to be deformable due to an abrupt cure, thereby posing another disadvantage of formability which is different from a case where the monofunctional radical polymerization monomer is previously used as a major component.
In Patent Document 2 of JP declaration 2005-532445, in order to improve the disadvantage found in Patent Document 1, such a constitution is adopted that the monofunctional radical polymerization monomer is given as a major component of the photo polymerization reactive composition and at least one type of a and P-unsaturated ether monomers is contained as an indispensable component.
The above-described constitution is certainly better in flexibility for improving deformability as compared with the constitution disclosed in Patent Document 1. However, it is not necessarily sufficient in adhesiveness or not necessarily sufficient either in decreasing tackiness, that is, stickiness on the ink surface after ultraviolet curing.
[Disclosure of the Invention]
As is apparent from the above-described background art, although monofunctional radical polymerization monomers are adopted as a major

component in UV inkjet inks, no sufficient evaluation is made for how to select or combine them. As a result, no such improvement is attained in formability, adhesiveness or tackiness as to exhibit a higher flexibility.
In view of such a situation, an object of the present invention is to provide a method for manufacturing UV inkjet inks by procedures that a specific monofunctional radical polymerization monomer, which is a photo polymerization reactive composition, is used as a basic composition and combined with other monofunctional radical polymerization monomers and polyfunctional radical polymerization oligomers, if necessary, by which, of three characteristics consisting of highly flexible formability, improved adhesiveness and tackiness, at least two of them are excellent and the remaining one is far from poor, and it is also to provide UV inkjet inks based on this method, decorating printed matter, decorating sheet shaped articles and insert molding shaped products in which the inks are used.
In order to attain the object, a basic method of the present invention is constituted by the following.
(1) A method for manufacturing inkjet system ultraviolet curable inks in which essential components are a photoreaction initiator and a photo polymerization reactive composition, and the method for manufacturing inkjet system ultraviolet curable inks, wherein after being mixed with a polyfunctional radical polymerization oligomer, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with two monofunctional radical polymerization monomers selected from alicyclic monofunctional radical polymerization monomers and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate and the two alicyclic monofunctional radical polymerization monomers mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to two

alicyclic monofunctional radical polymerization monomers to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.7 : 0.1 to 0.7.
(2) A method for manufacturing inkjet system ultraviolet curable inks wherein essential components are a photoreaction initiator and a photo polymerization reactive composition, and the method for manufacturing inkjet system ultraviolet curable inks, wherein with a mixture of a polyfunctional radical polymerization oligomer given as a precondition, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with one monofunctional radical polymerization monomer selected from alicyclic monofuncrional radical polymerization monomers, one monofunctional radical polymerization monomer selected from heterocyclic monofunctional radical polymerization monomers, and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate, the alicyclic monofunctional radical polymerization monomer and the heterocyclic monofunctional radical polymerization monomer mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to the alicyclic monofunctional radical polymerization monomer to the heterocyclic monofunctional radical polymerization monomer to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.5 : 0.1 to 0.5 : 0.1 to 1.
[Effects of the Invention]
As is apparent from the above-described description covering (1) and (2), in manufacturing methods of the present invention, phenoxyethylacrylate is adopted as a monofunctional radical polymerization monomer acting as a base of the photo polymerization reactive composition. In remaining constitutions of (1) and (2) in which phenoxyethylacrylate is adopted in combination with other monofunctional radical polymerization monomers, such results are obtained at an extremely high

probability that at least two characteristics of formability, adhesiveness and tackiness are excellent and the remaining one is far from poor, although there may be a case where it is not favorable.
Therefore, UV inkjet inks manufactured by the respective methods as well as decorating printed matter, decorating sheet shaped articles and insert molding shaped products based on these inks are to be able to exhibit favorable characteristics in general.
[Best Mode for Carrying Out the Invention]
As is apparent from the constitutions of (1) and (2), in the present invention, phenoxyethylacrylate is adopted as a monofunctional radical polymerization monomer in preparing UV inkjet inks as a basic composition. However, sole use of phenoxyethylacrylate as a photo polymerization reactive composition will not always provide favorable results in all characteristics of formabikty, adhesiveness and tackiness. Therefore, selection is made from various combinations of phenoxyethylacrylate with other polyfunctional radical polymerization oligomers and/or monofunctional radical polymerization monomers, thereby providing UV inkjet inks improved in the individual characteristics, at which a basic technical idea of the present invention is found.
In the UV inkjet inks of the present application, although a major component is a monofunctional radical polymerization monomer which is based on phenoxyethylacrylate, a mixture with polyfunctional radical polymerization monomers and/or ultraviolet cation curable monomers is not excluded, and mixing these monomers at least to such an extent that will not undermine the effects of the present invention (specifically, such an extent that at least two characteristics of formability, adhesiveness and tackiness are favorable and the remaining one is far from poor) corresponds to a mode of utilization of the present invention.
Hereinafter, it will be confirmed by tests that the methods according to the

basic constitutions of (1) and (2) are clearly excellent as embodiments. (In the combinations shown in each table given below, photoreaction initiators such as bisacyl phosphine oxide and 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-1 are mixed in a quantity of about 10% as a whole on determination of the individual characteristics.)
An explanation will be made for the process leading to method (1). Specifically, phenoxyethylacrylate is combined with various types of monofunctional radical polymerization monomers and also allowed to change in weight ratio, thereby it is possible to obtain the results based on a general tendency of characteristics for each type as is shown in Table 1.
It is noted that various types of monofunctional radical polymerization monomers include substantially most monofunctional radical polymerization monomers actually adopted as UV inkjet inks, and such a adopting state is same in the case of constitutions of (2) it is after described in Table 2.
An explanation will be made for the process leading to method (1). Specifically, any one or a plurality of an aromatic polyfunctional urethane acrylate oligomer, aliphatic urethane acrylate oligomer, epoxy acrylate oligomer and polyester acrylate oligomer are combined and mixed. Then, phenoxyethylacrylate, any two monomer selected from alicyclic monofunctional radical polymerization monomers and any one monomer selected from other assumable monofunctional radical polymerization monomets (however, excluding phenoxyethylacrylate and the two alicyclic monofunctional radical polymerization monomers mixed with phenoxyethylacrylate), that is, a total of four monofunctional radical polymerization monomers, are combined. Then, a weight ratio of the other monofunctional radical polymerization monomers to phenoxyethylacrylate is adjusted, thereby it is possible to obtain the results of individual characteristics for each type as shown in Table 1.
But, the weight ratio of polyfunctional radical polymerization oligomer to

phenoxyethylacrylate to two alicyclic monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.7. [Table 1]

Types of monofunctional Weight ratio when Formability Adhesiveness Tackiness
monomers phenoxyethylacrylate is set to be one
Aromatic monofunctional radical polymerization 0.1 -0.7 o or ∆** ∆ or o** o

1.2 o ∆ ∆
monomer
(without hydroxyl group,
however, excluding
phenoxyethylacrylate)
Aromatic monofunctional 0.1 -0.7 o or∆** A or ∆** o
radical polymerization 1.2 o ∆ ∆
monomer
(with hydroxyl group)
Aliphatic monofunctional 0.1 - 0.7 o or ∆** ∆ or o** 0
radical polymerization 1.2 X ∆ 0
monomer
(without hydroxyl group)
Aliphatic monofunctional 0.1 - 0.7 o or ∆** ∆ or o** 0
radical polymerization 1.2 X ∆ 0
monomer
(with hydroxyl group)
Alicyclic monofunctional 0.1-0.7 o or ∆** ∆ or o** o
radical polymerization 1.2 o X ∆
monomer
(however, excluding two
acrylate monomers mixed
previously together with
phenoxyethylacrylate)

Heterocyclic
monofunctional radical polymerization monomer 0.1 ~ 0.7 o or ∆** o or ∆** o

1.2 ∆ o ∆
* Each of the symbols, o, A, x, is assessed according to the following criteria.
Formability test o: showing a state that no cracks are found on coated film
A: showing a state that fine cracks are partially found to such an extent that can be barely confirmed by visual inspection x; showing a state that cracks are found all over printed matter
Adhesion test o: showing a state that no peeling is found on coated film
A: showing a state that fundamentally no peeling is found on coated film but some found in the vicinity x: showing a state that peeling is found conspicuously
Tack test o: showing a state that no stickiness (tackiness) is found when touched by finger A: showing a state that tackiness is found to some extent when touched by finger but no marks remain after touched
x: showing a state that curing is not completed and marks remain when touched by finger
Estimation criteria for each of o, A, x will be applied in the same way to the table 2.
** Of the individual characteristics, formability and adhesiveness are reverse for the marks of o and A, because even though one of the characteristics is A, the other is o, and there is no case where both of them are A, and further, there may also be a case where both of them are o.
As is apparent from Table 1, phenoxyethylacrylate is mixed with any two

monomers selected from alicyclic monofunctional radical polymerization monomers at the above-described weight ratio and then combined with any one monomer selected from monofunctional radical polymerization monomers belonging to all other assumable types. In the case where phenoxyethylacrylate is set to be 1, it has been revealed that all the characteristics are favorable for the monofunctional radical polymerization monomers belonging to all types where a weight ratio of two alicyclic monofunctional radical polymerization monomers and monofunctional radical polymerization monomers belonging to all other assumable types is respectively in a range of 0.1 to 0.7.
An explanation will be made for the process leading to method (2). Specifically/ any one of an aromatic polyfunctional urethane acrylate oligomer, aliphatic urethane acrylate oligomer, epoxy acrylate oligomer and polyester acrylate oligomer or a combination thereof was mixed. Then, phenoxyethylacrylate, one monomer selected from alicyclic monofunctional radical polymerization monomers, one monomer selected from heterocyclic monofunctional radical polymerization monomers, a subtotal of three monofunctional radical polymerization monomers, and one monomer selected from other assumable monofunctional radical polymerization monomers (however, excluding phenoxyethylacrylate, the alicyclic monofunctional radical polymerization monomer mixed with phenoxyethylacrylate and heterocyclic monofunctional radical polymerization monomer), that is, a total of four monofunctional radical polymerization monomers were combined. A weight ratio of other monofunctional radical polymerization monomers to phenoxyethylacrylate is adjusted, thereby it is possible to obtain the results of individual characteristics for each type as shown in Table 2.
But, the weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to the alicyclic monofunctional radical polymerization monomer to the heterocyclic monofunctional radical polymerization monomer is in the respective ranges of 0.05 to 0. 4 :1: 0.1 to 0.5 : 0.1 to 0.5.

[Table 2]

Types of Weight ratio when Formability Adhesiveness Tackiness
monofunctional phenoxyethylacrylate
monomers is set to be one
Aromatic monofunctional radical 0.1-1 o or ∆** ∆ or o** o or ∆*

1.5 o ∆ ∆
polymerization
monomer
(without hydroxyl
group, however,
excluding
phenoxyethylacrylate)
Aromatic monofunctional radical 0.1-1 o or ∆** ∆ or o** 0

1.5 ∆ 0 ∆
polymerization
monomer
(with hydroxyl group)
Aliphatic 0.1-1 o or ∆** ∆ or o** 0
monofunctional radical 1.5 0 X o
polymerization
monomer
(without hydroxyl
group)
Aliphatic 0.1-1 o or ∆** ∆ or o** o
monofunctional acrylate 1.5 ∆ X 0
monomer
(with hydroxyl group)
Alicyclic 0.1-1 o or ∆** ∆or o** o

monofunctional radical
1.5 A 1 x o
polymerization
monomer
(however, excluding a
monomer mixed
previously with
phenoxyethylacrylate)
Heterocyclic monofunctional radical 0.1-1 o or ∆** ∆ or o** o or ∆*

1.5 0 ∆ ∆
polymerization
monomer (however,
excluding a monomer
mixed previously with
phenoxyethylacrylate)
** Of the individual characteristics, formability and adhesiveness are reverse for the marks of o and A, because even though one of the characteristics is A, the other is o, and there is also a case where both of them are o, The same item is applicable to a fact that adhesiveness and tackiness are also reverse in the marks of o and A.
As is apparent from Table 2, phenoxyethylacrylate, one monomer selected from alicyclic monofunctional radical polymerization monomers and one monomer selected from heterocyclic monofunctional radical polymerization monomers, a subtotal of three monofunctional radical polymerization monomers, and any one monomer selected from monofunctional radical polymerization monomers belonging to all other assumable types, that is, a total of four monomers, are combined. In the case where phenoxyethylacrylate is set to be 1, it has been revealed that the characteristics are favorable for the monofunctional radical polymerization monomers belonging to all types where a weight ratio of other monofunctional radical polymerization monomers is in a range of 0.1 to 1.
The constitution of (2) is able to provide favorable results stably in various

combinations. Therefore, it may be well expected that favorable characteristics may also be obtained even when one or a plurality of the monofunctional radical polymerization monomers are mixed to the constitution of (2).
Thus, a constitution in which other one or a plurality of the monofunctional radical polymerization monomers are added to and mixed with the constitution of (2) corresponds to constitution in which of (2) is utilized.
Isobornyl acrylate and N-vinylcaprolactam are in most cases favorably adopted respectively as a typical example of an alicyclic monofunctional radical polymerization monomer and a heterocyclic monofunctional radical polymerization monomer to be mixed with phenoxyethylacrylate.
In each of the above-described methods (1) and (2), inks to which pigments, high-polymer dispersing agents and additives etc., are added, if necessary, may provided with favorable characteristics at least for two of the individual characteristics.
It is noted that these inks are from 3 to 500 cps in viscosity (determined at 25°C by using a cone-plate type viscometer), which is a viscosity favorably corresponding to inkjet printing.
Therefore, decorating printed matter which form a decorating lamination layer by curing steps in which these inks are applied to a substrate by inkjet injection into or printing to give a single or a plurality of coated layers and ultraviolet rays are irradiated on the coated layers, decorating sheet shaped articles based on formation of the decorating printed matter by vacuum forming or pressure forming and insert molding shaped products integrally formed on injection of a molding resin into the decorating printed matter or the decorating sheet shaped articles by using an injection machine may manufactured in a state that cracks on a coated film, stickiness, and peeling are hardly found in a step leading to lamination.

It is noted that sheets and films based on polycarbonate, (treated) polyester, (treated) polypropylene, (treated) polyethylene and an acrylic resin etc may be used as the substrate.
These prepared by imparting a printed layer or a coated layer to these sheets or films by screen printing, offset printing, gravure printing, roll coating process or spray coating etc., may also be used as the substrate.
In forming the insert molding shaped product, a binder layer is provided on a decorating layer by printing or coating for the purpose of increasing the adhesiveness between the molding resin and the decorating printed matter or between the molding resin and a decorating lamination layer of the decorating sheet shaped article, thereby it is possible to prepare insert molding shaped products higher in quality.
Inks and paints for forming a binder layer may include IMB-003 Binder and IMB-009 Binder (product names) made by Teikoku Printing Inks Mfg. Co., Ltd., which are binder inks using thermoplastic resins such as an acrylic resin and a polyvinyl chloride vinyl acetate copolymer resin etc.
Further, the molding resin may include ABS (acrylbutadiene styrol) resins, PC (polycarbonate) resins, PP (polypropylene) resins, and PA (polyamide) resins.
Hereinafter, an explanation wiU. be made by referring to examples.
[Example 1]
Example 1 is characterized in that in the basic constitution of (1), 2-hydroxy-3-phenoxypropylacrylate is used as an aromatic monofunctional radical polymerization monomer with a hydroxyl group and two alicyclic monofunctional radical polymerization monomers are isobornyl acrylate and dicyclopentenyl oxyethylacrylate.

As with Example 1, provided were a pigment, a photoreaction initiator, a high-polymer dispersing agent and an additive.
2-hydroxy-3-phenoxypropylacrylate in a predetermined mixed quantity as well as isobornyl acrylate and dicyclopentenyl oxyethylacrylate at the respective predetermined mixed quantities were mixed with a trifunctional urethane acrylate oligomer and phenoxyethylacrylate, each mixed quantity of which was predetermined as given in Table 3-1, and a test similar to Example 1 was conducted, thereby obtaining the results of individual characteristics as shown in the table.
[Table 3-1]

Type of Chemical Mixed Mixed Mixed Mixed Forma Adhesi Tacki
monofun name quantity quantity quantity quantity of 2- bility veness ness
ctional of of of hydroxy-3-
monomer monofuncti
onal
monomer
of the
above
chemical
name
(% by
weight) trifunctio
nal
urethane
acrylate
oligomer
(% by weight) phenox
y-
ethylacr ylate (% by weight) phenoxyprop ylacrylate (% by weight)
Ali cyclic monofun Dicyclopenten
yi
oxyethylacryla
te
and isobornyl
acrylate* Each 3.5 3.5 69.5 7.0 0 o o

Each 2.4 2.4 47.0 32.8 o A 0
ctional
Each 16.5 2.4 47.0 4.6 0 A o
radical
Each 12.4 1.8 35.6 24.8 o A o
polymeri
Each 2.8 21.7 54.3 5.4 A o o
zation
Each 2.0 15.8 39.6 27.6 o A 0
monomer
Each 13.8 15.8 39.6 4.0 o A o

Each 10.9 12.5 31.1 21.6 o A o

* Dicyclopentenyl oxyethylacrylate and isobornyl acrylate were mixed at equal percentages with each other.
In the test given in Table 3-1, a weight ratio according to the constitution of (1) was tested at various values, in particular, in combination with 2-hydroxy-3-phenoxypropylacrylate, dicyclopentenyl oxyethylacrylate and isobornyl acrylate. The test has revealed that favorable results were obtained at least in two characteristics.
It is assumed that similar favorable characteristics may be obtained in combination of an aromatic monofunctional radical polymerization monomer with a hydroxyl group other than 2-hydroxy-3-phenoxypropylacrylate, dicyclopentenyl oxyethylacrylate and an alicyclic monofunctional radical polymerization monomer other than isobornyl acrylate. When the above-described assumption is taken into account, the validity of the constitution of (1) may be confirmed by referring to the test results given in Table 3-1.
Then, after one of dicyclopentenyl oxyethylacrylate was mixed at 27.0% by weight as an alicyclic monofunctional radical polymerization monomer as shown in Table 3-2 and N-lvinylcaprolactam was mixed at 10.0% by weight as a heterocyclic monofunctional radical polymerization monomer, trifunctional urethane acrylate oligomer was not mixed, but phenoxyethylacrylate was mixed at 50.0% by weight, thereby obtaining the results of individual characteristics as shown in Table 3-2.
[Table 3-2]

Type of Chemical name Formability Adhesiveness Tackiness
monofunctional
monomer
Alicyclic Dicyclopentenyl A o A
monofunctional oxyethylacrylate
radical

polymerization
monomer
It has been revealed as apparent through comparison between Table 3-1 and Table 3-2 that where no polyfunctional radical polymerization oligomer is mixed at all, no mixture ratio required in the constitution of (1) is satisfied and one type of alicyclic monofunctional radical polymerization monomers is used, no favorable characteristics are obtained as shown in Table 3-1, which is the constitution of (1).
Each of the inks given in Table 3-1 were subjected to irradiation of ultraviolet rays under the same conditions as those of the above-described tests and cured on a substrate sheet made with a polycarbonate resin. Then, the substrate sheet was vacuum-formed and an ABS resin was laminated by using an injection machine and formed integrally to mold an insert molding shaped product In molding the shaped product, each of the inks was not in a tacky state on the substrate sheet, substantially favorable in formability and also generally favorable in adhesion with the substrate sheet, with no peeling found at all. It was, therefore, possible to obtain strong insert molding shaped products.
[Example 2]
Example 2 is characterized in that in the basic constitution of (2), after selection of isobornyl acrylate as an alicyclic monofunctional radical polymerization monomer, N-vinylcaprolactam as a heterocyclic monofunctional radical polymerization monomer, among monofunctional radical polymerization monomers belonging to all other types, the aromatic monofunctional radical polymerization monomer without a hydroxyl group is any one of benzyl acrylate, phenoxydiethylene glycolacrylate, phenoxytetraethylene glycolacrylate and nonyl phenol tetraethylene glycolacrylate, the aromatic monofunctional radical polymerization monomer with a hydroxyl group is 2-hydroxy-3-phenoxypropylacrylate, the aliphatic monofunctional radical polymerization monomer without a hydroxyl group is ethoxydiethylene glycolacrylate, the aliphatic

monofunctional radical polymerization monomer with a hydroxy! group is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the aliphatic monofunctional radical polymerization monomer is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the alicyclic monofunctional radical polymerization monomer is any one of dicyclopentenyl acrylate and dicyclopentenyl oxyethylacrylate, and the heterocyclic monofunctional acrylate monomer is any one of acryloylmorphorine and tetrahydrofurfurylacrylate.
As with Example 1, provided were a pigment a photoreaction initiator, a high-polymer dispersing agent and an additives. Isobornyl acrylate in a predetermined mixed quantity and N-vinylcaprolactam in a predetermined mixed quantity were mixed with a trifunctional urethane acrylate oligomer and phenoxyethylacrylate, each mixed quantity of which was predetermined as shown in Table 4-1, and the other monofunctional radical polymerization monomers in a predetermined mixed quantity was also mixed, thereby obtaining the results of individual characteristics as shown in the table.

[Table 4-1]

Type of Chemical name Mixed Mixed Mixed Mixed Mixed Forma Adhesi Tackin
monofun quantity quanti quantity quant quantit bility veness ess
ctional of ty of of ity of y of N-
monomer mono- tri- phenox isobor vinylca
function functi y- nyl pro-
al onal ethylacr acryla lactam
monom uretha ylate (% te (% by
er of the above chemica 1 name (% by weight) ne
acryla
te
oligo
mer
(% by
weigh
t) by weight) (% by weigh
t) weight
Aromatic Benzylacrylate 7.5 6.0 40.5 20.0 13.0 o o o
monofun
6.6 3.2 64.0 6.6 6.6 o o 0
ctional
38.5 2.0 38.5 4.0 4.0 0 A 0
radical
5.0 2.4 49.8 5.0 24.8 0 0 o
polymeri
32.8 1.7 32.8 3.3 16.4 o 0 0
zation
5.0 2.4 49.8 24.8 5.0 o A o
monomer
32.8 1.7 32.8 16.4 3.3 o A o
(without
5.0 2.0 40.0 20.0 20.0 o o o
hydroxyl
28.5 1.5 28.6 14.2 14.2 0 0 o
group)
5.2 20.4 51.0 5.2 5.2 A o 0

33.3 13.4 33.5 3.4 3.4 o o o

4.2 16.5 41.4 4.2 20.7 o o o

29.0 11.6 29.0 2.9 14.5 o 0 0

4.2 16.5 41.4 20.7 4.2 o A 0

29.0 11.6 29.0 14.5 2.9 o A 0

3.5 13.9 34.8 17.4 17.4 o 0 o

25.6 10.2 25.6 12.8 12.8 0 o 0

Phenoxy
diethylene glycolacrylate 7.5 6.0 40.5 20.0 13.0 o o 0

Phenoxy
tetraethylene glycolacrylate 7.5 6.0 40.5 20.0 13.0 0 o 0

Phenol EO
modified (2 mol) acrylate 7.5 6.0 40.5 20.0 13.0 o 0 0
Aromatic 2-hydroxy-
monofun 3—phenoxypro
ctional pylacrylate
radical
polymeri zation 7.5 6.0 40.5 20.0 13.0 0 o 0
monomer
(with
hydroxyl
group)
Aliphatic Ethoxydiethylen
monofun e glycolacrylate
ctional
radical
polymeri 7.5 6.0 40.5 20.0 13.0 o o o
zation
monomer
(without
hydroxyl

group)
Aliphatic 2-hydroxy
monofun ethylacrylate 7.5 6.0 40.5 20.0 13.0 o o o
ctional radical polymeri zation (HOA)

2-hydroxy proplylacrylate 7.5 6.0 40.5 20.0 13.0 o o 0

2-hydroxy
monomer butylacrylate
(with 7.5 6.0 40.5 20.0 13.0 o o o
hydroxyl
group)
Alicyclic Dicyclopentenyl
monofun acrylate
ctional
radical 7.5 6.0 40.5 20.0 13.0 o 0 o
polymeri
zation
monomer
Heterocy clic Tetrahydrofurfu rylacrylate 7.5 6.0 40.5 20.0 13.0 o o 0
monofun Acryloylmorph
ctional orine
radical
polymeri 7.5 6.0 40.5 20.0 13.0 o 0 o
zation
monomer
As shown in Table 4-1, a weight ratio according to the constitution of (2) was tested for various required values, in particular, in combination with benzyl acrylate as a monofunctional monomer, and also tested up to a limited value. The test has revealed the characteristics, and it was confirmed that favorable results could be

obtained at least in two characteristics.
In this instance, it is assumed that favorable results may be obtained for other monofunctional monomers. When the above-described assumption is taken into account, the validity of the constitution of (2) may be confirmed by referring to the test results shown in Table 4-1.
Then, a polyfunctional radical polymerization oligomer, phenoxyethylacrylate, isobornyl acrylate and N-vinylcaprolactam were mixed respectively at 6.0% by weight, 48.0% by weight, 24.0% by weight and 8.0% by weight, and as shown in Table 4-2, a polyfunctional radical polymerization monomer was mixed at 1.0% by weight, thereby obtaining the results of individual characteristics as shown in the table.
[Table 4-2]

Type of monofunctional monomer Chemical name Formabiliry Adhesiveness Tackiness
Bifunctional monomer Tripropylene glycoldiacrylate ∆ 0 0

Hexanediol diacrylate X 0 0
Trifunctional monomer Trimethylol
propane
triacrylate X o o
It has been revealed as apparent through comparison between Table 4-1 and Table 4-2 that in the basic constitution of (2) favorable results may be obtained, irrespective of types of other monofunctional radical polymerization monomers, but, where a polyfunctional radical polymerization monomer is mixed in place of these other monofunctional radical polymerization monomers, favorable characteristics as

provided in the basic constitution of (2) may necessarily be lost, even if mixed only in a small quantity.
The inks given in Table 4-1 were used to mold insert molding shaped products under the same conditions as those of Example 1. It was, therefore, possible to obtain strong insert molding shaped products substantially favorable in formability, adhesiveness and tackiness and also favorable in adhesion with a substrate, without any state of peeling.
[Industrial Applicability]
The present invention is applicable to the field of UV inkjet inks in which phenoxyethylacrylate is a basic composition used as a photo polymerization reactive composition and a major component is a monofunctional radical polymerization monomer and also applicable to the field of decorating shaped products based on the inks.

We Claim:
1. A method for manufacturing inkjet system ultraviolet curable inks in which essential components are a photoreaction initiator and a photo polymerization reactive composition, the method for manufacturing inkjet system ultraviolet curable inks, wherein after being mixed with a polyfunctional radical polymerization oligomer, the photo polymerization reactive composition is a combination of phenoxyethylacrylate with two monofunctional radical polymerization monomers selected from alicyclic monofunctional radical polymerization monomers and one other monofunctional radical polymerization monomer selected from monofunctional radical polymerization monomers belonging to all other types (however, excluding phenoxyethylacrylate and the two alicyclic monofunctional radical polymerization monomers mixed with phenoxyethylacrylate), that is, a total of four monomers, and a weight ratio of the polyfunctional radical polymerization oligomer to phenoxyethylacrylate to two alicyclic monofunctional radical polymerization monomers to the other monofunctional radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1: 0.1 to 0.7: 0.1 to 0.7.
2. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 1, wherein the two alicyclic monofunctional radical polymerization acrylate monomers are dicyclopentenyl oxyethylacrylate and isobornyl acrylate.
3. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 2, wherein, among radical polymerization monomers belonging to all types, the aromatic monofunctional radical polymerization monomer without a hydroxyl group is any one of benzyl acrylate, phenoxydiethylene glycolacrylate, phenoxytetraethylene glycolacrylate and nonylphenol tetraethylene glycolacrylate, the aromatic monofunctional radical

polymerization monomer with a hydroxy! group is 2-hydroxy-3-phenoxypropylacrylate, the aliphatic monofunctional radical polymerization monomer without a hydroxyl group is ethoxydiethylene glycolacrylate, the aliphatic monofunctional radical polymerization monomer with a hydroxyl group is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the alicyclic monofunctional radical polymerization monomer is dicyclopentenyl acrylate, and the heterocyclic monofunctional radical polymerization monomer is any one of tetrahydrofurfurylacrylate, N-vinylcaprolactam and acryloylmorphorine.
4. A method for manufacturing inkjet system ultraviolet curable inks in which
essential components are a photoreaction initiator and a photo
polymerization reactive composition, the method for manufacturing inkjet
system ultraviolet curable inks, wherein, with a mixture of a polyfunctional
radical polymerization oligomer given as a precondition, the photo
polymerization reactive composition is a combination of
phenoxyethylacrylate with one monofunctional radical polymerization
monomer selected from alicyclic monofunctional radical polymerization
monomers, one monofunctional radical polymerization monomer selected
from heterocyclic monofunctional radical polymerization monomers, and one
other monofunctional radical polymerization monomer selected from
monofunctional radical polymerization monomers belonging to all other
types (however, excluding phenoxyethylacrylate, the alicyclic monofunctional
radical polymerization monomer and the heterocyclic monofunctional radical
polymerization monomer mixed with phenoxyethylacrylate), that is, a total of
four monomers, and a weight ratio of the polyfunctional radical
polymerization oligomer to phenoxyethylacrylate to the alicyclic
monofunctional radical polymerization monomer to the heterocyclic
monofunctional radical polymerization monomer to the other monofunctional
radical polymerization monomers is in the respective ranges of 0.05 to 0.4 :1:
0.1 to 0.5 : 0.1 to 0.5 : 0.1 to 1.

5. The method for manufacturing inkjet system ultraviolet curable inks as set
forth in claim 4, wherein, one monomer selected from alicyclic
monofunctional radical polymerization monomers is isobornyl acrylate and,
one monomer selected from heterocyclic monofunctional radical
polymerization monomers, is N-vinylcaprolactam.
6. The method for manufacturing inkjet system ultraviolet curable inks as set forth in claim 5, wherein, among monofunctional radical polymerization monomers belonging to all other types, the aromatic monofunctional radical polymerization monomer without a hydroxyl group is any one of benzyl acrylate, phenoxydiethylene glycolacrylate, phenoxytetraethylene glycolacrylate and nonylphenol tetraethylene glycolacrylate, the aromatic monofunctional radical polymerization monomer with a hydroxyl group is 2-hydroxy-3-phenoxypropylacrylate, the aliphatic monofunctional radical polymerization monomer without a hydroxyl group is ethoxydiethylene glycolacrylate, the aliphatic monofunctional radical polymerization monomer with a hydroxyl group is any one of 2-hydroxy ethylacrylate, 2-hydroxy propylacrylate and 2-hydroxy butylacrylate, the alicyclic monofunctional radical polymerization monomer is any one of dicyclopentenyl acrylate and dicyclopentenyl oxyethylacrylate, the heterocyclic monofunctional radical polymerization monomer is any one of tetrahydrofurfuryl acrylate and acryloylmorphorine.
7. Inkjet system ultraviolet curable inks manufactured according to the methods as set forth in claims 1,2, 3,4, 5, and 6.
8. Decorating printed matter which forms a decorating lamination layer by curing processes in which the inkjet system ultraviolet curable inks as set forth in claim 7 are applied to a substrate by inkjet injection or printing to give a single or a plurality of coated layers and ultraviolet rays are irradiated on the coated layers.

9. Decorating sheet shaped articles obtained by forming the decorating printed matter as set forth in claim 8 by vacuum forming or pressure forming.
10. Insert molding shaped products formed integrally by injecting a molding resin by using an injection machine to the decorating printed matter as set forth in claim 8 or the decorating sheet shaped articles as set forth in claim 9.

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Patent Number

276931

Indian Patent Application Number

2816/MUMNP/2011

PG Journal Number

47/2016

Publication Date

11-Nov-2016

Grant Date

07-Nov-2016

Date of Filing

28-Dec-2011

Name of Patentee

TEIKOKU PRINTING INKS MFG. CO., LTD.

Applicant Address

4-12, MITA 4-CHOME, MINATO-KU, TOKYO 108-0073 JAPAN

Inventors:

#	Inventor's Name	Inventor's Address
1	TAKANO, KENJI	C/O. TEIKOKU PRINTING INKS MFG. CO., LTD. 4 - 12, MITA 4 - CHOME, MINATO - KU, TOKYO 108 - 0073 JAPAN
2	TORIHATA, TAKUYA	C/O. TEIKOKU PRINTING INKS MFG. CO., LTD. 4 - 12, MITA 4 - CHOME, MINATO - KU, TOKYO 108 - 0073 JAPAN
3	KIMURA, JUN	C/O. TEIKOKU PRINTING INKS MFG. CO., LTD. 4 - 12, MITA 4 - CHOME, MINATO - KU, TOKYO 108 - 0073 JAPAN

PCT International Classification Number

C09D 11/00,B05D 1/26

PCT International Application Number

PCT/JP06/310608

PCT International Filing date

2006-05-22

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2006-116810	2006-04-20	Japan
2	2006-048430	2006-02-24	Japan