JP2003268026A - Ultraviolet light-curing composition, ultraviolet light- curing ink and printed material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet light-curing composition exhibiting a high ultraviolet light-curing rate and having a good weather resistance against the ultraviolet light. <P>SOLUTION: This ultraviolet light-curing composition is provided by containing at least either one of a polymerizable monomer or a polymerizable oligomer, a photopolymerization initiator and a polymerizable UV absorber and having (1:0.55)-(1:0.02) range molar ratio of a UV-absorbing specific group of the UV absorber to the photopolymerization-initiating specific group of the photopolymerization initiator. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet curable composition having weather resistance, and relates to an ultraviolet curable ink and a printed matter using the same.

[0002]

2. Description of the Related Art Various types of UV-curable compositions are known. Particularly, UV-curable compositions containing a polymerizable monomer and a polymerizable oligomer as the main components and containing substantially no organic solvent are known. However, it does not emit organic solvent into the atmosphere during curing and is expected to have a small impact on the environment. UV-curable compositions are used for various purposes, but when used as a surface coating material, as it is, or when used outdoors, such as inks containing pigments, etc., their weather resistance and light resistance are Improvements have been made, and addition of ultraviolet absorbers that absorb ultraviolet rays that greatly affect the deterioration of polymer substances and light stabilizers (HA
LS) is being added.

For example, Japanese Patent Laid-Open No. 2001-179900 discloses a benzotriazole which absorbs a specific ultraviolet ray which causes material deterioration in an ultraviolet curable coating layer having a characteristic absorption wavelength in a wavelength band different from the ultraviolet curing wavelength of the coating layer. It is described that the weather resistance is improved by adding a UV absorber of a system type and a benzophenone type and a hindered amine type light stabilizer (HALS). In addition, Japanese Patent Laid-Open No. 11-268
Japanese Patent Laid-Open No. 201-201 discloses that a polymerizable ultraviolet absorber is used as the ultraviolet absorber to prevent the added ultraviolet absorber from bleeding and losing the effect of the ultraviolet absorber. This invention forms a coating layer of an ultraviolet curable composition having a large scratch resistance, and a large amount of ultraviolet rays for curing the ultraviolet curable composition.

Further, in Japanese Patent Laid-Open No. 10-60307, a cured film is formed on a plastic molded product by an ultraviolet curable composition in which the compounding amounts of a polymerizable ultraviolet absorber having a specific chemical structure and a photopolymerization initiator are specified. To suppress the deterioration of scratch resistance. However, in the examples of the publication, it is described that irradiation of a large amount of ultraviolet rays of 3000 mJ / cm ² is required for curing the ultraviolet curable composition. Irradiation of such a large amount of ultraviolet rays may adversely affect the base material etc. by heat emitted from the light source for ultraviolet irradiation, and when a flexible synthetic resin base material is used, the base material causes thermal deformation. There was a possibility. Even if the ultraviolet ray irradiation means used for curing is provided with a means for removing the heat generated from the light source, the amount of ultraviolet ray to be irradiated increases, so that the heat generation increases, which may cause problems such as deformation due to heat. There was a nature.

The ultraviolet absorber has a remarkable light absorption property in a wavelength band of absorbed light required for the photopolymerization initiator to decompose to generate a polymerization active species such as a radical. Even if the ultraviolet absorber is slower and does not have a large absorption coefficient in the wavelength band of absorbed light, the same trouble will occur if the amount of the ultraviolet absorber is large. Further, when the amount of the ultraviolet absorber is large, the time required for ultraviolet curing becomes long, and when the ultraviolet curable composition is an ink, the printing speed is extremely reduced and a practical printing ink cannot be obtained. There was a point. As described above, the improvement in the curing rate of the ultraviolet curable composition and the improvement in the weather resistance are incompatible with each other, the curing rate is high, and the production of the ultraviolet curable composition having excellent weather resistance was difficult. .

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an ultraviolet-curable composition which has high weather resistance, can maintain the weather resistance for a long time, requires a small amount of ultraviolet irradiation for ultraviolet curing, and has a high curing speed. The challenge is to provide.

[0007]

An object of the present invention is to provide an ultraviolet-curable composition containing at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber, The molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator is 1: 0.55 to 1:
It can be solved by an ultraviolet curable composition in the range of 0.02. Further, in the ultraviolet curable composition,
The above-mentioned ultraviolet curable composition contains 3 to 4.0% by mass of a polymerizable ultraviolet absorber. It is the above-mentioned ultraviolet curable composition containing a light stabilizer. The ultraviolet curable composition contains a polymerizable oligomer, and a part or all of the oligomer is a polymerizable urethane oligomer.

The ultraviolet curable ink contains at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber, and has a molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator. Is 1:
It is an ultraviolet curable ink having a range of 0.55 to 1: 0.02. The above-mentioned UV curable ink containing a colorant. The above-mentioned ultraviolet curable ink containing a light stabilizer. UV curable ink contains a polymerizable oligomer,
The ultraviolet curable ink described above, wherein a part or all of the oligomer is a polymerizable urethane oligomer.

The printed matter contains at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber, and the molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator is 1 :. 0.55
It is a printed matter printed with an ultraviolet curable ink having a range of 1: 0.02. The printed matter is printed in multiple layers,
At least the outermost printed layer is a printed material containing no light stabilizer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides an ultraviolet-curable composition containing at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber, and a photopolymerization initiator. It has been found that by setting the content of the polymerizable ultraviolet absorber to a predetermined ratio, it is possible to provide an ultraviolet curable composition having both excellent ultraviolet curability and weather resistance. In particular, in the ultraviolet curable composition of the present invention, by blending the photopolymerization initiator and the polymerizable ultraviolet absorber in a predetermined molar ratio,
It is intended to provide an ultraviolet curable composition having excellent properties satisfying both ultraviolet curability and weather resistance.

The polymerizable ultraviolet absorber is a substance containing a polymerizable functional group and a characteristic group such as a benzotriazole group and a benzophenone group, which greatly contributes to the absorption of ultraviolet rays. There are various polymerizable ultraviolet absorbers having different molecular weights. When the molecular weight is large, the number of characteristic groups that greatly contribute to ultraviolet absorption per unit weight is smaller than that when the molecular weight is small. Therefore, it is not possible to achieve the intended purpose by blending the polymerizable ultraviolet absorber based on the weight ratio, and it is effective to compare it with the photopolymerization initiator in terms of the number of moles of the ultraviolet absorber. I found it.

According to the present invention, a polymerizable ultraviolet absorber having a large molecular weight having an atomic group other than a characteristic group and a polymerizable functional group contributing to ultraviolet absorption or a polymerizable ultraviolet absorber which is an oligomer is used. Even if there is, an ultraviolet curable composition having excellent characteristics can be obtained by similarly comparing the number of moles. In addition, a group that contributes to ultraviolet absorption is included in one molecule of the polymerizable ultraviolet absorber.
Even if a special substance containing a number of groups or a group that contributes to the initiation of photopolymerization contains m number in one molecule of the photopolymerization initiator, it should be converted to nmol and mmol, respectively. Thus, it is possible to treat the molecule as if it contained one molecule.

The constituent components of the ultraviolet curable composition of the present invention will be described below. The ultraviolet curable composition of the present invention contains at least one of a polymerizable monomer and a polymerizable oligomer. As the polymerizable monomer,
Aliphatic (meth) acrylate, alicyclic (meth) acrylate, aromatic (meth) acrylate, ether (meth)
Examples thereof include acrylates, vinyl monomers, (meth) acrylamides and the like. The (meth) acrylate means one containing at least one of acrylate and methacrylate.

Specifically, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, isobornyl acrylate, ethoxy-diethylene glycol acrylate, 2-ethylhexyl-carbitol acrylate,
Phenoxyethyl acrylate, paracumylphenol ethylene oxide modified acrylate, vinylcaprolactam, acryloylmorpholine, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol polypropylene oxide modified diacrylate , Polyethylene glycol diacrylate, polytetramethylene glycol diacrylate, 2
-Butyl-2-ethyl-1,3-propanediol diacrylate, polytetramethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate and the like can be mentioned. Among these polymerizable monomers, a non-aromatic monomer is preferable because it has good weather resistance.

As the polymerizable oligomer, urethane type oligomer, polyether type oligomer, epoxy type oligomer, polyester type oligomer, acrylic type oligomer and the like can be mentioned. Specifically, as the urethane-based oligomer, EB4849, EB230, EB244, EB245, manufactured by Daicel UCB,
EB284, EB285, EB4883, EB840
2, EB8804, EB254, EB264, EB26
5, EB294, EB295, EB1259, EB48
66, EB270, EB4830, EB8800-20
R, EB1701, EB204, EB205, KRM7
595, Kyoeisha Chemical Co., Ltd. UF8001, Hitachi Chemical Co., Ltd. Hitaroid 4861, Hitaroid 4870, Hitaloid 7
471, AKCROS Actilane 200, A
ctilane200TP20, Actilane21
0TP30, Actilane230HD30, Act
ilane250HD25, Actilane250T
P25, Actilane270, Actilane2
80, Actilane 290, Actilane 16
5, Actilane167, Actilane17
0, CN961E75, CN963B8 from Sartomer
0, CN962, CN963A80, CN964, CN
964A85, CN965, CN985, CN983,
CN985B88, CN980, CN981, CROD
Company UVU-300, UVU-310, UVU-31
6, BASF UA19T, LR-8987, Toagosei Aronix M-1200, Aronix M-160
0, Kayarat MAX5100, Kayarat MAX5101, Kayarat MAX5102, Kayarat UX8101, Kayarat UX3204, Kayarat UX2201 and the like from Nippon Kayaku Co., Ltd. can be mentioned. As an example of the polyether-based oligomer, BA84 PO84F, L
R-8894 etc. can be mentioned.

As an example of the epoxy-based oligomer,
EB604, EB3500 of Daicel UCB
EB3600, EB3700-20H, EB3702,
Examples thereof include Crodamer UVE-150 manufactured by CRODA. Examples of the polyester-based oligomer include EB524 and EB80 manufactured by Daicel UCB. Examples of acrylic oligomers are EB1701 and EB75 from Daicel UCB.
4, Actlane 890 from AKCROS, CN130 from Sartomer, Hitaroid AA-G from Hitachi Chemical
6, Hitaroid AA-G7, Hitaloid AA-G9, Hitaloid AA-G1 and the like. Particularly, non-aromatic urethane oligomers are preferable because they have good weather resistance.

As the photopolymerization initiator, aryl ketones such as acetophenone type, benzophenone type, alkylaminobenzophenone type, benzyl type, benzoin type, benzoin ether type, benzyl dimethyl ketal type, benzoyl benzoate type, α-acyloxime ester type, etc. Examples thereof include sulfur-containing photopolymerization initiators such as system photopolymerization initiators, sulfide series and thioxanthone series, and acylphosphine oxide series photopolymerization initiators such as acyldiarylphosphine oxide.

Specifically, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,2-dimethoxy-2-phenylacetone phenone, 2,4-diethylthioxanthone, isopropyl Thioxanthone, 2,4
6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, bis-2,
4,6-Trimethylbenzoylphenylphosphine oxide, 4-phenoxydichloroacetophenone, 4-
t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-
(4-dodecylphenyl) -2-methylpropane-1-
On, 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methyl-propan-1-one, 2-methyl-1- {4- (methylthio) phenyl}
-2-morpholinopropan-1-one, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone Acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone, 9,10-phenanthrenequinone, camphorquinone, dibenzos Bellon, 2-ethylanthraquinone,
4 ′, 4 ″ -diethylisophthalophenone, α-acyloxime ester, 4-benzoyl-4′-methyldiphenylsulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Dichlorothioxanthone,
2,4-diisopropylthioxanthone and the like can be mentioned.

In addition to the photopolymerization initiator, a photopolymerization initiation aid may be used in combination. Examples of the photopolymerization initiation assistant that can be used in combination include amines, and specifically, triethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, methyldiethanolamine and the like. Can be mentioned. The polymerizable ultraviolet absorber used in the present invention contains one or more groups that contribute to ultraviolet absorption, such as a benzophenone skeleton, a benzotriazole skeleton, a phenyltriazine skeleton, a salicylic acid skeleton, and a cyanoacrylate skeleton.
A polymerizable benzophenone-based UV absorber, a polymerizable benzotriazole-based UV absorber, a polymerizable phenyltriazine-based UV absorber having one or more polymerizable functional groups such as an acryloyl group, a methacryloyl group and a vinyl group,
Examples thereof include polymerizable salicylic acid type ultraviolet absorbers and polymerizable cyanoacrylate type ultraviolet absorbers.

As the polymerizable benzophenone type ultraviolet absorber, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3- (meth) acryloyloxypropyl) benzophenone, 2- Hydroxy-4- (2- (meth) acryloyloxyethoxy) benzophenone, 2-hydroxy-4- (2-acryloyloxypropoxy) benzophenone, 2-hydroxy-4- (2-hydroxy-3)
-(Meth) acryloyloxypropoxy) benzophenone, 2,2'-dihydroxy-4- (meth) acryloyloxybenzophenone, 2,2'-dihydroxy-
4- (2- (meth) acryloyloxyethoxy) benzophenone can be mentioned.

As the polymerizable benzotriazole type ultraviolet absorber, 2- [2-hydroxy-5-((meth) acryloyloxy) phenyl] benzotriazole, 2- [2-hydroxy-3-methyl-5-] is used. ((Meth) acryloyloxy) phenyl] benzotriazole, 2- [2-hydroxy-3-t-butyl-5- (3
-(Meth) acryloyloxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-5- (2-
(Meth) acryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-5- (3- (meth) acryloyloxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-3-t-butyl-
5- (2- (meth) acryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-
t-butyl-5- (3- (meth) acryloyloxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-3-methyl-5- (2- (meth) acryloyloxyethyl) phenyl] benzotriazole, 2 −
[2-Hydroxy-3-methyl-5- (3- (meth) acryloyloxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-5- (2- (meth) acryloyloxyethyl) phenyl] -5- Chlorobenzotriazole, 2- [2-hydroxy-5- (2- (meth) acryloyloxyethyl) phenyl] -5-methylbenzotriazole, 2- [2-hydroxy-5-
(2- (2- (meth) acryloyloxyethoxycarbonyl) ethyl) phenyl] benzotriazole, 2-
[2-hydroxy-5- (2- (meth) acryloyloxyethoxy) phenyl] benzotriazole, 2-
Mention may be made of [2-hydroxy-5- (2- (meth) acryloyloxypropoxy) phenyl] benzotriazole.

As the polymerizable phenyltriazine-based UV absorber, 2- [4-[(2-hydroxy-3-
Methacryloyloxy) -2-hydroxyphenyl]-
4,6-bis (2,4-dimethylphenyl) -1,3,
5-triazine, 2- [4-[(2-hydroxy-3-
Acryloyloxy) -2-hydroxyphenyl]-
4,6-bis (2,4-dimethylphenyl) -1,3,
5-triazine can be mentioned. Of these, compounds represented by the following chemical structural formulas are preferable.

[0023]

[Chemical 1]

Particularly, a polymerizable benzotriazole type ultraviolet absorber is preferable. In addition to the polymerizable ultraviolet absorber, a non-polymerizable ultraviolet absorber may be added,
Examples of the UV absorber that can be added include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylic acid-based UV absorbers, and phenyltriazine-based UV absorbers.
Octyl 3- [3- (2H-benzotriazole-2-
Yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2- (3,5-di-t-pentyl-2-
Hydroxyphenyl) benzotriazole, 2- (2-
Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-
3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, pt-butylphenyl salicylate can be mentioned.

In the ultraviolet curable composition of the present invention, the molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator is 1:
0.55 to 1: 0.02 is preferable,
The range of 1: 0.5 to 1: 0.03 is more preferable. With such a blending amount, the action of the photopolymerization initiator does not become insufficient at the time of curing the ultraviolet curable composition, and rapid curing is possible even with a relatively low dose of ultraviolet irradiation. Becomes

Further, when the amount of the polymerizable ultraviolet absorber in the ultraviolet curable composition is large, the ultraviolet curing reaction is hindered even if the mixing ratio of the photopolymerization initiator increases.
It may be difficult to obtain a weather-resistant ultraviolet-curable composition having a high curing rate. Therefore, the compounding amount of the polymerizable ultraviolet absorber in the ultraviolet curable composition is preferably 0.3 to 4.0% by mass.

In addition to the ultraviolet absorber, a light stabilizer may be added in order to improve the stability against light. Examples of the light stabilizer include a hindered amine light stabilizer, and a hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine residue is preferable. Specifically, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) sebacate, 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
-2-n-butylmalonate bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) and the like. When the light stabilizer is blended, the blending amount in the ultraviolet curable composition is preferably 1.3 to 0.3% by mass. If a light stabilizer is used more than this, it may have an adverse effect such as a decrease in the curing rate of the ultraviolet curable composition.

Further, the ultraviolet curable composition of the present invention comprises
Antioxidants, stabilizers such as thermal polymerization inhibitors, leveling agents, defoamers, thickeners, antisettling agents, pigment dispersants, antistatic agents, surfactants such as antifog agents, near infrared absorbers You may mix these. Furthermore, fine particles such as pigments and silica may be dispersed. Further, a non-polymerizable organic solvent may be added to improve the coating property and printability on the substrate or to adjust the viscosity, or a synthetic resin may be added.
Examples of the organic solvent include lower alcohols, ketones, ethers, cellosolves, n-butyl acetate, esters such as diethylene glycol monoacetate, halogenated hydrocarbons, hydrocarbons and the like.

The UV-curable composition of the present invention can be used for UV-curable molding materials, transparent protective film-compatible materials, paints, inks, etc., and contains pigmented colored paints, colored inks, pigments. It can be used for transparent paints and transparent inks containing no. In particular, it is possible to exert a great effect in improving the weather resistance of a protective film, a thin film of ink or the like.

When the ultraviolet curable composition of the present invention is an ultraviolet curable ink, it can be applied to printing on paper, glass, metal, various synthetic resin films and synthetic resin moldings. In particular, since the ink of the present invention does not need to be irradiated with a large amount of ultraviolet rays and can be cured under relatively mild conditions, even when applied to a base material having a small thickness or a flexible base material, the base material is not deformed. Since it does not occur, it is suitable for printing synthetic resin sheets, synthetic resin films and the like used outdoors, and is effective for producing various signs, advertisements and the like.

When multilayer printing is performed using the ink of the present invention, the printing layer having a slow curing rate should not contain a light stabilizer, and the printing layer having a fast curing rate should contain a light stabilizer. Is effective for improving the weather resistance without lowering the curing rate as a whole. Further, in general, by containing a light stabilizer in the lower printing layer that is exposed to a large number of ultraviolet rays and not including a light stabilizer in an upper printed layer that is exposed to a small number of ultraviolet rays, a cured product having good curability and weather resistance can be obtained. To be

Further, the ink of the present invention can be used in various printing methods such as screen printing, gravure printing and ink jet printing, and a top coat layer or the like is formed on a substrate by using a coater such as a roll coater or a blade coater. Can be used to form In particular, since the ink of the present invention can cure the ink layer with a small amount of UV irradiation light, even when the ink layer formed on a thin substrate is cured, the influence of deformation of the substrate is small. Can be one.

[0033]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. Example 1 (Preparation of UV-polymerizable composition) 70 parts by weight of oligomer A (CN963B80 manufactured by Sartomer Co., Ltd.), 5 parts by weight of monomer A (ethoxydiethylene glycol acrylate),
Monomer B (1,6-hexadiol diacrylate)
10 parts by weight, monomer C (neopentyl glycol propylene oxide modified diacrylate) 10 parts by weight, photopolymerization initiator A (2-hydroxy-2-methyl-1-phenylpropan-1-one) 2 parts by weight, photopolymerization initiation Agent B (1
-Hydroxycyclohexyl phenyl ketone) 2 parts by weight, the following polymerizable ultraviolet absorber A (2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole) 1 part by weight, defoaming agent 2 parts by weight ,
0.5 parts by weight of a heat stabilizer and 0.5 parts by weight of an extender pigment were mixed and stirred to obtain an ultraviolet curable composition. The molar ratio of the photopolymerization initiator and the polymerizable ultraviolet absorber was 1: 0.141.

[0034]

[Chemical 2]

In Table 1, the contents of the photopolymerization initiator A, the photopolymerization initiator B and the polymerizable ultraviolet absorber are shown in parts by weight, and the amount of the polymerizable ultraviolet absorber based on the total amount of the ultraviolet curable composition is shown. The content was expressed in mass%. Further, the ratio of the total number of moles of the photopolymerization initiator A and the photopolymerization initiator B in the ultraviolet curable composition to the number of moles of the polymerizable ultraviolet curable composition was expressed as a molar ratio.

(Preparation of printed matter) Using the composition thus obtained, printing was carried out on a white polyvinyl chloride sticker substrate (Hi-S cal5010SP manufactured by Nippon Carbide Co., Ltd.) with a screen printer to obtain a 10 μm printing layer. Was formed, and the coating layer was cured by changing the amount of ultraviolet rays irradiated by a metal halide lamp. The cured ultraviolet curable composition was evaluated by the following evaluation methods, and the results are shown in Table 1.

(Evaluation of Curing Property) The ultraviolet irradiation dose at which the adhesiveness was lost when the cured surface was touched with a finger was evaluated in the following stages. In addition, tacks that adhere even at 1000 mJ / cm ^{2 were} treated as tacky.

200 mJ / cm ² 400 mJ / cm ² 1000 mJ / cm ² (Evaluation of weather resistance) A printed matter was subjected to an accelerated weathering test using a xenon sunshine weather meter (Ci65 tester manufactured by Atlas Co.) to determine the exposure time at which the weather resistance is maintained as follows. The evaluation was divided into stages. 2000h or more 2000 <notation 1500 to 2000h 1500-2000 notation 1000 to 1500h 1000-1500 notation 1000h or less 1000> notation

Examples 2 to 4 Instead of oligomer A in example 1, oligomer B
(EB80 manufactured by Daicel-UCB), Oligomer C (PO84F manufactured by BASF), Oligomer D (CR
An ultraviolet-curable composition was prepared and evaluated in the same manner as in Example 1, except that Crodamer UVE-150 manufactured by ODA was used, and the same results were obtained.
The cured ultraviolet curable composition was evaluated by the following evaluation methods, and the results are shown in Table 1.

Example 5-9 Instead of the oligomer A in Example 1, an oligomer E was used.
(EB-284 manufactured by Daicel UCB) is used, and a photopolymerization initiator A (2-hydroxy-2-methyl-1-phenylpropan-1-one) and a photopolymerization initiator B are used.
(1-hydroxycyclohexyl phenyl ketone), polymerizable ultraviolet absorber A (2- [2-hydroxy-5- (2
-Methacryloyloxyethyl) phenyl] benzotriazole) was prepared in the same manner as in Example 1 except that the compounding ratio was changed to the ratio shown in Table 1 and evaluated in the same manner as in Example 1. I went. The results are shown in Table 1.

Example 10 Oligomer E was used instead of Oligomer A in Example 1.
(Either EB284 manufactured by Daicel UCB), monomer A (ethoxydiethylene glycol acrylate), monomer B (1,6-hexadiol diacrylate), monomer C (neopentyl glycol propylene oxide modified diacrylate), photopolymerization initiation Agent A (2-hydroxy-2-methyl-1-phenylpropan-1-one), photopolymerization initiator B (1-hydroxycyclohexyl phenyl ketone), polymerizable ultraviolet absorber A (2- [2-hydroxy-5 An ultraviolet-curable composition was prepared in the same manner as in Example 1 except that the compounding ratio of-(2-methacryloyloxyethyl) phenyl] benzotriazole) was changed to the ratio shown in Table 1. It evaluated similarly. The results are shown in Table 1.

Examples 11-12 Instead of the oligomer A in Example 1, the oligomer E is used.
(EBELL manufactured by Daicel UCB) was used, and 5 parts by weight of monomer C (neopentyl glycol propylene oxide-modified diacrylate) was used, and a photopolymerization initiator A (2-hydroxy-2-methyl-1-phenylpropane-1) was used. -On), the photopolymerization initiator B (1-hydroxycyclohexyl phenyl ketone), and the polymerizable ultraviolet absorber A (2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole) in a mixing ratio of Example 1 except that the ratios shown in Table 1 were changed.
An ultraviolet curable composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 13 Instead of the oligomer A in Example 1, an oligomer E was used.
(EB284 manufactured by Daicel UCB) was used, and 10 parts by weight of a monomer B (1,6-hexadiol diacrylate) and 5 parts by weight of a monomer C (neopentyl glycol propylene oxide modified diacrylate) were used as a monomer. Polymerization initiator A (2-hydroxy-2-methyl-1-phenylpropan-1-one), photopolymerization initiator B (1-hydroxycyclohexyl phenyl ketone), polymerizable ultraviolet absorber A (2- [2-
Hydroxy-5- (2-methacryloyloxyethyl)
An ultraviolet-curable composition was prepared in the same manner as in Example 1 except that the compounding ratio of (phenyl] benzotriazole) was changed to the ratio shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Example 14 Instead of Oligomer A in Example 1, Oligomer E
(EB284 manufactured by Daicel UCB) was used, and as a monomer, 10 parts by weight of monomer A (ethoxydiethylene glycol acrylate), 5 parts by weight of monomer B (1,6-hexadiol diacrylate), and monomer D (phenoxyethyl acrylate). 10
Photopolymerization initiator A (2-hydroxy-2-
Methyl-1-phenylpropan-1-one), a photopolymerization initiator B (1-hydroxycyclohexylphenylketone), a polymerizable ultraviolet absorber A (2- [2-hydroxy-
A UV-curable composition was prepared in the same manner as in Example 1 except that the compounding ratio of 5- (2-methacryloyloxyethyl) phenyl] benzotriazole) was changed to the ratio shown in Table 1. It evaluated similarly to. The results are shown in Table 1.
Shown in.

Example 15 In place of 10 parts by weight of the monomer D (phenoxyethyl acrylate) in Example 14, a monomer E (paracumylphenol ethylene oxide modified acrylate) 1 was used.
An ultraviolet-curable composition was prepared in the same manner as in Example 14 except that 0 part by weight was used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 16 5 parts by weight of the monomer A (ethoxydiethylene glycol acrylate) and 10 parts of the monomer B (1,6-hexadiol diacrylate) were used as the monomers in Example 14.
An ultraviolet curable composition was prepared in the same manner as in Example 14 except that the amount was 10 parts by weight and the amount of the monomer F (vinylcaprolactam) was 10 parts by weight, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Example 17 5 parts by weight of the monomer in Example 14 was used as the monomer A (ethoxydiethylene glycol acrylate) and 10 parts of the monomer B (1,6-hexadiol diacrylate).
An ultraviolet-curable composition was prepared in the same manner as in Example 14 except that the amount was 10 parts by weight of the monomer G (trimethylol ropane ethylene oxide-modified triacrylate), and the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 18 5 parts by weight of the monomer in Example 14 was used as the monomer A (ethoxy-diethylene glycol acrylate) and 10 parts of the monomer B (1,6-hexadiol diacrylate).
An ultraviolet-curable composition was prepared in the same manner as in Example 14 except that the amount was 10 parts by weight of the monomer H (acryloylmorpholine), and the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 19 Instead of Oligomer A in Example 1, Oligomer E
(EB-284 manufactured by Daicel UCB) is used, and a polymerizable ultraviolet absorber A (2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] is used.
In the same manner as in Example 1, a UV curable composition was prepared in the same manner as in Example 1 except that the amount of the following polymerizable UV absorber B having a phenyltriazine skeleton was blended in place of benzotriazole). It evaluated similarly to. The results are shown in Table 1.

[0050]

[Chemical 3]

Example 20 Instead of Oligomer A in Example 1, Oligomer E
(EB-284 manufactured by Daicel UCB) and 1 part by weight of a hindered amine light stabilizer (TINUVIN 123) as a light stabilizer, and a polymerizable ultraviolet absorber A (2- [2-hydroxy-5
An ultraviolet-curable composition was prepared in the same manner as in Example 1 except that-(2-methacryloyloxyethyl) phenyl] benzotriazole) was used in the compounding amount shown in Table 1, and evaluated in the same manner as in Example 1. I went. The results are shown in Table 1.

Example 21 Instead of Oligomer A in Example 1, Oligomer E
(EB284 manufactured by Daicel UCB) 40 parts by weight are used, and as monomers, 10 parts by weight of monomer A (ethoxydiethylene glycol acrylate), 15 parts by weight of monomer B (1,6-hexadiol diacrylate), and monomer C (neo) Pentyl glycol propylene oxide modified diacrylate) 10 parts by weight,
8 parts by weight of monomer F (vinyl caprolactam), 3 parts by weight of photopolymerization initiator C (2,4,6-trimethylbenzoyldiphenylphosphine oxide), and photopolymerization initiator D
2 parts by weight of (2,4-diethylthioxanthone) was added, and the polymerizable ultraviolet absorber A (2- [2-hydroxy-5
-(2-methacryloyloxyethyl) phenyl] benzotriazole) 1 part by weight and a red pigment (IRGAZIN D
Example 1 except that 10 parts by weight of PP RED BO) was used.
An ultraviolet curable composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 22 An ultraviolet-curable composition was prepared in the same manner as in Example 21, except that 1 part by weight of a hindered amine light stabilizer (TINUVIN 123) was added as a light stabilizer. And evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 The photopolymerization initiator A (2-hydroxy-) in Example 9 was used.
2-Methyl-1-phenylpropan-1-one).
5 parts by weight, instead of the polymerizable ultraviolet absorber A (2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole), the amount of the non-polymerizable ultraviolet absorber shown in Table 1 (2- (2-hydroxy-3,
An ultraviolet-curable composition was prepared in the same manner as in Example 9 except that 5-di-t-amyl-phenyl) -2H-benzotriazole) was used, and was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The non-polymerizable ultraviolet absorber (2- (2-
Hydroxy-3,5-di-t-amyl-phenyl) -2
An ultraviolet-curable composition was prepared in the same manner as in Comparative Example 1 except that the amount of H-benzotriazole) was changed, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 The photopolymerization initiator A (2-hydroxy-) in Example 9 was used.
2-Methyl-1-phenylpropan-1-one).
An ultraviolet curable composition was prepared in the same manner as in Example 9 except that the amount was 5 parts by weight and no polymerizable ultraviolet absorber was added, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 4 The polymerizable ultraviolet absorber A (2- [2-
Hydroxy-5- (2-methacryloyloxyethyl)
An ultraviolet-curable composition was prepared in the same manner as in Example 6 except that the amount of phenyl] benzotriazole) was changed to the amount shown in the table, and then evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5 The polymerizable ultraviolet absorber A (2- [2
A UV-curable composition was prepared in the same manner as in Example 11 except that the amount of -hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole) was changed to the amount described in the table. Evaluation was performed in the same manner as 1. The results are shown in Table 1.

Comparative Example 6 5 parts by weight of the photopolymerization initiator B (1-hydroxycyclohexyl phenyl ketone), and the polymerizable UV absorber C (2- [2-Hydroxy-5- (2-acryloyloxyethyl) phenyl] benzotriazole) An ultraviolet curable composition was prepared in the same manner as in Example 11 except that the amount was changed to 5 parts by weight, and the same as in Example 1. Was evaluated. The results are shown in Table 1.

[0060]

[Table 1] Type and amount of photopolymerization initiator, polymerizable ultraviolet absorber Curability in the composition Weather resistance Weight part Weight part Weight part Mass% Molar ratio mJ / cm ² h Example 1 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000 <Example 2 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000-1500 Example 3 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000-1500 Example 4 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000- 1500 Example 5 A 4.0 B 4.0 0.30 0.28 1: 0.021 200 1500-1000 Example 6 A 4.0 B 3.0 0.35 0.33 1: 0.028 200 2000-1500 Example 7 A 4.0 B 3.0 0.42 0.40 1: 0.033 200 2000 <Example 8 A 3.0 B 2.0 2.0 1.90 1: 0.220 400 2000 <Example 9 A 1.0 B 1.0 1.0 0.99 1: 0.281 200 2000 <Example 10 A 4.0 B 3.0 3.0 2.91 1: 0.238 200 2000 <Example 11 A 2.0 B 2.0 2.8 2.81 1: 0.394 200 2000 <Example 12 A 1.0 B 1.0 1.75 1.81 1: 0.493 400 2000 <Example 13 A 5.0 B 4.0 4.2 4.15 1: 0.260 1000 2000 <Example 14 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000-1500 Example 15 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000-1500 Example 16 A 2.0 B 2.0 1.0 0.9 7 1: 0.141 200 2000-1500 Example 17 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000-1500 Example 18 A 2.0 B 2.0 1.0 0.97 1: 0.141 200 2000-1500 Example 19 A 2.0 B 2.0 1.0 0.97 1 : 0.084 200 2000-1500 Example 20 A 2.0 B 2.0 1.0 0.96 1: 0.141 200 2000-1500 Example 21 C 3.0 D 2.0 1.0 0.96 1: 0.193 200 2000 < Example 22 C 3.0 D 2.0 1.0 0.95 1: 0.193 200 2000 < Comparative example 1 1.5 1.0 ---- --200 1000> Comparative example 2 1.5 1.0 ---- --With tack 1000> Comparative example 3 1.5 1.0 ---- --200 1000> Comparative example 4 4.0 3.0 0.2 0.19 1: 0.016 200 1000> Comparative example 5 2.0 2.0 4.3 4.24 1: 0.605 With tack 1000> Comparative example 6 0 5.0 5.0 4.85 1: 0.661 With tack 1000>

[0061]

INDUSTRIAL APPLICABILITY In a UV curable composition containing at least one of a monomer and an oligomer, a photopolymerization initiator, and a polymerizable UV absorber, each of the photopolymerization initiator and the polymerizable UV absorber, Since the molar ratio of the photopolymerization initiation characteristic group and the ultraviolet absorption characteristic group is set to a predetermined mixing ratio, it is possible to provide an ultraviolet curable composition having both rapid photopolymerization property and excellent weather resistance, When the curable ink is used, it is possible to provide a printed matter having good durability when used outdoors.

Continued front page    F-term (reference) 2H113 AA06 BC10 FA43                 4J011 QA03 QA07 QA08 QA13 QA24                       QA34 QA36 QA39 QA48 QB14                       QB16 QB19 QB23 SA01 SA21                       SA25 SA31 SA41 SA51 SA78                       SA82 TA02 UA01 VA01 WA05                 4J027 AB00 AC00 AE00 AG00 BA04                       BA07 BA17 BA19 BA20 BA23                       BA26 BA30 CB10 CC05 CD08                       CD09                 4J039 AD21 AE04 EA06

Claims (9)

[Claims] 1. An ultraviolet curable composition comprising at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber,
An ultraviolet curable composition, wherein the molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator is in the range of 1: 0.55 to 1: 0.02. 2. The ultraviolet-curable composition contains 0.3 to 4.0.
The ultraviolet-curable composition according to claim 1, which contains a mass% of a polymerizable ultraviolet absorber. 3. The ultraviolet curable composition according to claim 1, which further comprises a light stabilizer. 4. The ultraviolet curable composition according to claim 1, wherein the ultraviolet curable composition contains a polymerizable oligomer, and a part or all of the oligomer is a polymerizable urethane oligomer. 5. The ultraviolet curable ink contains at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber,
An ultraviolet curable ink, wherein the molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator is in the range of 1: 0.55 to 1: 0.02. 6. The ultraviolet curable ink according to claim 5, further comprising a light stabilizer. 7. The ultraviolet curable ink according to claim 5, wherein the ultraviolet curable ink contains a polymerizable oligomer, and a part or all of the oligomer is a polymerizable urethane oligomer. 8. The printed matter contains at least one of a polymerizable monomer and a polymerizable oligomer, a photopolymerization initiator and a polymerizable ultraviolet absorber, and the molar ratio of the polymerizable ultraviolet absorber to the photopolymerization initiator is 1: 0.55
A printed matter, which is printed with an ultraviolet curable ink having a range of 1: 0.02. 9. The printed matter according to claim 8, wherein the printed matter is multiply printed and at least the outermost printed layer does not contain a light stabilizer.