JPH08134389A - Photocurable resin composition - Google Patents

Abstract

PURPOSE: To obtain a photocurable resin composition esp. sensitive to the transmission region for semiconductor laser among the near-infrared ray region, and capable of giving highly light-resistant prints or coated products, comprising a photocurable resin and phthalocyanlne compound(s) of specific structure. CONSTITUTION: This composition comprises (A) a photocurable resin produced from an acrylate-based monomer, oligomer, or a mixture thereof, (B) at least one kind of phthalocyanine compound of the formula [R<1> -R<8> are each a (substituted) alkyl, at least four of them each being a 1-8C alkyl; X<1> to X<8> are each a halogen, (substituted) alkoxyl, (substituted) aryloxy, (substituted) arylthio, and at least four of them each being 1-5C (substituted) alkylthio; M is a divalent metal atom, trivalent or tetravalent substituted metal atom or oxymetal] and (C) a photopolymerizatlon catalyst. This composition is esp. sensitive to the transmission region for semiconductor laser (700-850nm) among near-infrared ray region (700-1800nm) and capable of giving highly light-resistant prints or coated products.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition containing a phthalocyanine compound which is a near infrared absorber and a photocurable resin. More specifically, near infrared (7
Bank passbook, credit card, cash card, check, airline ticket, road pass ticket, ticket, admission ticket, prepaid card (for example, telephone charge card, ticket purchase card, admission ticket purchase card,
Play fee card, etc.), identification card, gift certificate, securities, etc., or confidential documents such as medical information, personal information, company information,
The present invention relates to a photocurable resin composition used for ink or the like necessary for printing for the purpose of preventing forgery of materials and information, prevention of misuse by concealment, position confirmation, prevention of malfunction of equipment and the like. This resin composition is a near-infrared cut filter that cuts a specific wavelength region by coating on glass, a transparent resin film, a transparent resin plate, or the like, a heat ray-cutting filter, or a heat ray-absorption filter that contributes to energy saving. Can also be used.

[0002]

2. Description of the Related Art There are several methods for preventing forgery of prepaid cards and the like, but the most common method is to use security ink that cannot be read by ordinary visible light sensors. In this case, usually
A near infrared absorber is used. As a specific method, a security ink containing a near infrared absorber and a binder resin is printed on the surface of the prepaid card. As the near-infrared absorbing agent, a dye having an absorption wavelength in 700 to 1800 nm is used. As the binder resin, usually, urethane-based, epoxy-based, phenol-based, polyester-based resins and the like used for coating films and papers can be used, but considering mass printing such as offset printing, or pollution-free ink, A photocurable type is desired. Here, since the thickness of 10 μ or more is sensed by the touch, it is said that the thickness of printing should be 10 μ or less.

Prepaid cards printed with the above security ink are near infrared rays (700 to 1800).
(nm) irradiates light of a wavelength in that region, so that reading is possible. That is, the recording surface is irradiated with an infrared laser to read the difference in reflection between a recorded portion and a non-recorded portion at a specific wavelength. It is possible to discriminate the authenticity by using this principle. Security inks containing these near-infrared absorbers are required to have various physical and chemical properties as shown below. (1) The near-infrared absorber is completely dissolved in the security ink. Poor dissolution may be perceived by hand if the pigment particles are large. (2) The near infrared absorber has a large molar extinction coefficient. If it is small, it is necessary to add a large amount to the ink, and the printing thickness may exceed 10 μm. (3) The security ink needs to have an absorption band in the wavelength range of 700 to 1800 nm. (4) The security ink has a small absorption in the visible region of 400 to 700 nm. If the absorption in the visible region is large, the ink is colored and does not serve as a security ink. (5) The security ink has good heat resistance and light resistance. In the case of a defect, the absorption of the wavelength in the near infrared region may be incomplete due to the change with time, which may cause a reading error. None of the known photocurable security inks satisfying all of these points has been reported. In particular, in the case of photocurable ink, since it contains an olefin monomer, which is a photocurable resin, a polymerization initiator, etc., the decomposition of the near-infrared absorbing dye due to the generation of radicals or ions is accelerated, and it is more light-resistant than ordinary gravure ink. Remarkably low.

Japanese Unexamined Patent Publication (Kokai) No. 4-320466 proposes a security ink containing a phthalocyanine compound having an o-aminophenylthioether group in a cyclohexanone solvent. However, since the phthalocyanine compound has a relatively large absorption in the visible region of 400 to 700 nm, coloring is conspicuous and it is insufficient for use as a security ink. Japanese Unexamined Patent Publication (Kokai) No. 3-62878 discloses a near-infrared region, particularly a semiconductor laser oscillation wavelength region (760
A phthalocyanine compound having a large absorption at ˜830 nm). However, in this publication, there is no description of a method for producing an ink layer that is excellent in light resistance and does not fall off on paper or resin by touching with hand, using this phthalocyanine compound. . JP 63
-308073 describes the preparation of security ink in its example, but it cannot be a practical ink because no binder resin is added. That is, as a security ink, no ink has been found that has high visible transparency, excellent storage stability as a printing ink, and excellent light resistance of a printed portion printed. Also,
Japanese Patent Publication No. 1-19693, Japanese Patent Publication No. 3-77230, and Japanese Patent Publication No. 4-20945 disclose that a naphthalocyanine compound is used for coloring an ink or a paint. There is no description about photocurable ink.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a printed material or a coated material which is sensitive to near-infrared rays (700 to 1800 nm), particularly 700 to 850 nm which is the emission region of a semiconductor laser, and has excellent light resistance. It is to provide a photocurable resin composition to be given.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a photocurable resin,
By using a certain phthalocyanine compound,
We found a photocurable composition that is sensitive to near infrared rays (700 to 850 nm), has little coloring in the visible region (400 to 700 nm), and in particular, can obtain a practical printed matter or coating excellent in light resistance, The present invention has been completed. That is, the present invention relates to a photocurable resin and the general formula (1)
The present invention relates to a photocurable resin composition containing at least one kind of phthalocyanine compound represented by (Chemical Formula 2).

[0007]

Embedded image [In the formula, R ^{1 to} R ⁸ each independently represent a substituted or unsubstituted alkyl group, and at least four of them are alkyl groups having 1 to 8 carbon atoms. X ^{1 to} X ⁸ each independently represent a halogen, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and at least 4 of them have 1 carbon
To 5 substituted or unsubstituted alkylthio groups. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal]

The photocurable resin composition of the present invention contains a photocurable resin and a phthalocyanine compound. The photocurable resin composition of the present invention is printed or coated with the composition, and then cured by ultraviolet irradiation from a mercury lamp or a metal halide lamp or electron beam irradiation. As the photocurable resin used in the present invention,
"Ultraviolet curing system" (Kiyoshi Kato, General Technology Center), "New, practical technology of photosensitive resin" (Supervised by Kiyoshi Akamatsu, CMC), "Light and radiation curing technology" (edited by Taiseisha editorial department), Acrylate-based, epoxy-based, vinyl ether-based generally used for photocurable inks or photocurable coatings as described in "UV / EB Curing Handbook, Raw Material Edition" (Polymer Publishing) The monomer or oligomer is not particularly limited as long as it is a monomer or oligomer, but among them, an acrylate monomer, an oligomer, or a mixture thereof is used from the viewpoint of curing characteristics, ink or coating characteristics.

Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, hydroxyethyl acrylate, 2
-(N, N-dimethylamino) ethyl acrylate, 2
-(N, N-diethylamino) ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, hydroxyethyl methacrylate,
Monofunctional group type monomers such as 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl methacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate,
Polyfunctional monomers such as trimethylolpropane trimethacrylate, adipic acid / 1,6-hexanediol oligomer diacrylate, phthalic anhydride / propylene oxide oligomer diacrylate, trimellitic acid diethylene glycol oligomer triacrylate, adipic acid / 1, 6 Hexanediol type oligomer dimethacrylate, phthalic anhydride / propylene oxide type oligomer dimethacrylate, trimellitic acid diethylene glycol type oligomer trimethacrylate and other polyfunctional polyester acrylate type oligomers, bisphenol A / epichlorohydrin type oligomer acrylate, phenol novolac / epichlorohydrin type oligomer Acrylate, cycloaliphatic epoxide and acrylic acid addition type, bispheno A / epichlorohydrin type oligomer methacrylate, phenol novolac / epichlorohydrin type oligomer methacrylate, polyfunctional epoxy acrylate such as addition type of cycloaliphatic epoxide and methacrylic acid, tolylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, An acrylic acid derivative such as a urethane acrylate derived from a urethane oligomer in which a diisocyanate such as xylylene diisocyanate or isophorone diisocyanate is reacted with a polyfunctional alcohol can be used. These may be used alone, or may be mixed and used in an appropriate ratio to adjust the viscosity.

The phthalocyanine compound represented by the formula (1) used in the present invention has a near-infrared absorbing ability and is 700 to 8
It is a compound having a strong absorption in the region of 50 nm. Specific examples of the substituents represented by R ^{1 to} R ⁸ , X ^{1 to} X ⁸ and the metal represented by M in the formula (1) are described below. As the substituted or unsubstituted alkyl group represented by R ^{1 to} R ⁸ , in order for the present phthalocyanine compound to exhibit high light resistance, at least four of the alkyl groups are substituted or unsubstituted having 1 to 8 carbon atoms. However, other than these, it may be an alkyl group having 9 or more carbon atoms and is not particularly limited. Examples of the substituent of the alkyl group include a fluorine atom, an alkoxy group, an aryl group and the like. Examples of the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group,
sec-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group,
Cyclohexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propyl group Propyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group and other linear, branched or cyclic alkyl groups, trifluoromethyl group, Fluorinated alkyl groups such as pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, methoxyethyl group, ethoxyethyl Base,
Alkoxyalkyl groups such as propoxyethyl group, butoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, benzyl group, 1-methylbenzyl group, o-
Chlorobenzyl group, m-chlorobenzyl group, p-chlorobenzyl group, o-methoxybenzyl group, m-methoxybenzyl group, p-methoxybenzyl group, o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group Groups and the like.

The substituents represented by R ^{1 to} R ⁸ are more preferably all methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. -
Butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, cyclohexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group Group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2 -Ethylhexyl group, linear, branched or cyclic alkyl groups such as 3-methyl-1-iso-propylbutyl group, more preferably all of them are methyl group, ethyl group, n-propyl group, n-butyl group. And alkyl groups such as an iso-butyl group, an n-pentyl group, an iso-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group and a 2-ethylhexyl group. If all of the substituents represented by R ^{1 to} R ⁸ have more than 8 carbon atoms, or if there are 5 or more substituents having 9 or more carbon atoms, the dye becomes unstable and the printed layer after curing or The light resistance of the coating layer tends to be significantly reduced.

As the substituents represented by X ^{1 to} X ⁸ , at least four of them are substituted or unsubstituted alkylthio groups having 1 to 5 carbon atoms so that the present phthalocyanine compound exhibits high light resistance. Other than them, halogens such as fluorine, chlorine, bromine and iodine, substituted or unsubstituted alkoxy groups having 6 to 20 carbon atoms, and 6 carbon atoms
To a substituted or unsubstituted aryloxy group having 20 to 20 carbon atoms, a substituted or unsubstituted alkylthio group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms, and is not particularly limited. Absent.

Examples of the substituted or unsubstituted alkylthio group having 1 to 5 carbon atoms represented by X ^{1 to} X ⁸ are methylthio group, ethylthio group, n-propylthio group, iso-propylthio group and n-butylthio group. , Iso-butylthio group, sec-butylthio group, n-pentylthio group, iso-pentylthio group, ne
Examples thereof include o-pentylthio group and 1,2-dimethyl-propylthio group. The substituents represented by X ^{1 to} X ⁸ are more preferably all alkylthio groups having 1 to 5 carbon atoms described above, and further preferably all of them are methylthio group, ethylthio group, n- A propylthio group or an i-propylthio group. When all of the substituents represented by X ^{1 to} X ⁸ have more than 5 carbon atoms or there are 5 or more substituents having 6 or more carbon atoms, the dye becomes unstable and the printed layer after curing or The light resistance of the coating layer tends to be significantly reduced.

Examples of the divalent metal represented by M include Cu (II), Zn (II), Fe (II) and Co (I
I), Ni (II), Ru (II), Rh (II), Pd (I
I), Pt (II), Mn (II), Mg (II), Ti (I
I), Be (II), Ca (II), Ba (II), Cd (I
I), Hg (II), Pb (II), Sn (II) and the like. Examples of mono-substituted trivalent metals include Al-Cl,
Al-Br, Al-F, Al-I, Ga-Cl, Ga-
F, Ga-I, Ga-Br, In-Cl, In-Br,
In-I, In-F, Tl-Cl, Tl-Br, Tl-
I, Tl-F, Al- C 6 H 5, Al-C 6 H 4 (CH
_{3), In-C 6 H} 5, In-C 6 H 4 (CH 3), I
_{n-C 6 H 5, Mn} (OH), Mn (OC 6 H 5), M
n [OSi (CH _{3) 3],} Fe-Cl, include Ru-Cl, etc.. An example of a di-substituted tetravalent metal is CrC.
l ₂ , SiCl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ ,
ZrCl ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , Ge
F ₂ , SnCl ₂ , SnBr ₂ , SnF ₂ , TiC
l ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge
(OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn
(OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , Sn
R ₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof], Si (OR ′) ₂ ,
Sn (OR ') ₂ , Ge (OR') ₂ , Ti (OR ')
₂ , Cr (OR ′) ₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof], Sn (S
R ″) ₂ , Ge (SR ″) ₂ (R ″ represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof), and the like. Examples of the oxy metal include VO, MnO,
TiO etc. are mentioned. Particularly preferred among these metals is copper or palladium.

The phthalocyanine compound used in the present invention is
It can be synthesized by the method described in JP-A-3-62878 (4th line to 15th line on the upper left of page 6). The addition amount of the phthalocyanine compound is determined according to the desired absorption amount in the near-infrared region or the thickness of the coating, so that it is not limited to a single value, with respect to the resin composition used, It is preferably used in the range of 0.01 to 50 (wt%), more preferably 0.1 to 10 (wt%).

The photocurable composition of the present invention is not particularly required when an electron beam is used as a light source during curing, but when ultraviolet rays such as a mercury lamp or a metal halide lamp are used, a photopolymerization initiator is used. Is required. As a photopolymerization initiator, "UV curing system" (Kiyomi Kato, published by General Technology Center), "New, actual technology of photosensitive resin" (supervised by Kiyoshi Akamatsu, CMC), "Light and radiation curing technology" ( Commercially available products described in Taiseisha editorial department), "UV / EB curing handbook, raw materials" (Polymer Publishing Co., Ltd.), or a mixture of these commercially available products can be used. For example, benzoin ether type such as isobutyl benzoin ether and benzoin ethyl ether, 1-phenyl-1,2-
Propane dione-2- (o-ethoxycarbonyl oxime) alpha-acyloxime ester type, such as, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, etc. acetophenone type, base benzophenone, benzyl, chlorothioxanthone, methylthioxanthone And the like. Specifically, Sandoray 100
0 (Sandoz), Trigonal P2 (AKZ
O), DEPA (Upjohn), Darocur 117
3, 1116, 953, 2227, 2959, 1664
(Merck), Irgacure 184, 907 (Ciba Geigy), Sequol Z (Seiko Chemical), Nisso Cure M
BO, TX (Nippon Soda), BEE, BIP (Osaka Organic), Sorbaslon BIBE, Benzyl (Kurokanekasei),
Daito Cure (Daito Kagaku), Irgacure 651
(Ciba Geigy), Kayacure BP, MBP, CT
X, RTX, DETX, DITX, EPA, DMBI
(Nippon Kayaku), Sanyo OBM (Sanyo Kokusaku Pulp), T
diagonal 12 (AKZO), Uvecryl
P-32 (UCB) etc. are mentioned. The amount added is 0.0001 to 10.0 (wt%), more preferably 0.1 to 10.0 (wt%), relative to the resin composition used.
Is preferred.

The photocurable resin composition of the present invention contains a photoinitiator aid, a sensitizer, an ultraviolet absorber, and a multiplet oxygen which can be mixed with an ordinary photocurable ink or paint, if necessary. Additives such as quenchers, thermal polymerization inhibitors, oxygen polymerization inhibitors, waxes, plasticizers, thickeners, etc. may also be included.
The photocurable resin composition of the present invention can be used as an ink for photocuring type offset printing and the like. After printing, it can be cured in a short time by irradiation with a UV lamp such as a mercury lamp or a metal halide lamp or electron beam irradiation, and the printing efficiency is high.

[0018]

EXAMPLES The present invention will now be described in more detail by way of examples. The present invention is not limited thereby. Example 1 5 g of an acrylate-based monomer (light acrylate BP-4EA manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) was added to 100 m of copper phthalocyanine represented by the following formula (2) (Chemical Formula 3).
g, Photopolymerization catalyst [Kayakyu DET manufactured by Nippon Kayaku Co., Ltd.
X] 200 mg was dissolved to prepare a photocurable resin composition. This resin composition was applied to PET synthetic paper [Toray Industries, Inc.
Lumirer white type, 188 μm thick], and then was cured by irradiating it with light of 400 mJ / cm ² with a high pressure mercury lamp (using a rapid cure irradiator manufactured by USHIO INC.). Regarding the coated surface, total reflection at an incident angle of 5 ° was measured with a spectrophotometer UV3100 manufactured by Shimadzu Corporation (JIS-R-310).
According to 6, the visible light reflectance was calculated to be 70%.
Met. The minimum reflectance in the near infrared region is 21%
(765 nm). The reflectance in the near infrared region was 89% when the present photocurable resin composition was not applied. The coated surface of the synthetic paper, under the condition of 63 ℃,
A light resistance test was conducted by irradiating with a carbon arc lamp for 24 hours. After the test, when the reflectance was measured in the same manner, the visible light reflectance was 72% and the minimum reflectance was 24% (765 nm).
The minimal change in reflectance before and after the test was small, and the light resistance was good.

[0019]

Embedded image Example 2 A photocurable resin composition was prepared in the same manner as in Example 1 except that a photopolymerization catalyst was not added, and PET synthetic paper was coated in the same manner as in Example 1, and then an electron beam irradiation device (E manufactured by Iwasaki Electric Co., Ltd.
The ink was cured by irradiating light of 2 Mrad with a B device, CB250 / 15 / 180L). The reflectance of visible light was calculated to be 71%. The minimum reflectance in the near infrared region was 22% (765 nm). The coated surface of the synthetic paper was irradiated with a carbon arc lamp for 24 hours under the condition of 63 ° C. to perform a light resistance test. After the test
Similarly, when the reflectance was measured, the visible light reflectance was 73%,
The minimum reflectance was 27% (765 nm), the change in the minimum reflectance before and after the test was small, and the light resistance was good.

Example 3 Oligoester acrylate (Toa Gosei Chemical Industry Co., Ltd.)
Aronix M-7100) 5 g, acrylate-based monomer (Toagosei Kagaku Kogyo Aronix M-1)
(01) 5 g of copper phthalocyanine of the formula (2) used in Example 1 and 200 mg of a photopolymerization catalyst [IRGACURE 907 manufactured by Ciba-Geigy] were dissolved to prepare a photocurable resin composition. After coating on PET synthetic paper in the same manner as in Example 1, UV curing was performed. The reflectance of visible light was calculated to be 69%. The minimum reflectance in the near infrared region was 17% (766 nm). The coated surface of the synthetic paper was irradiated with a carbon arc lamp for 24 hours under the condition of 63 ° C. to perform a light resistance test. After the test, when the reflectance was measured in the same manner, the visible light reflectance was 70.
%, The minimum reflectance was 22% (765 nm), the change in the minimum reflectance before and after the test was small, and the light resistance was good.

Comparative Example 1 Photocuring was performed in the same manner as in Example 1 except that the copper phthalocyanine represented by the following formula (3) (Chemical formula 4) was used in place of the copper phthalocyanine represented by the formula (2) used in Example 1. A resin composition was prepared. After coating on PET synthetic paper in the same manner as in Example 1, UV curing was performed. The reflectance of visible light was calculated to be 75%. The minimum reflectance in the near infrared region was 13% (784 nm). Apply a carbon arc lamp to the coated surface of the synthetic paper at 63 ° C.
A light resistance test was performed by irradiation for 4 hours. After the test, when the reflectance was measured in the same manner, the visible light reflectance was 76% and the minimum reflectance was 51% (784 nm). The minimum reflectance change before and after the test was large and the light resistance was poor.

[0022]

[Chemical 4] Examples 4-8 and Comparative Examples 2-5 In the phthalocyanine compound of formula (4)
An ink composition similar to that of Example 1 or Comparative Example 1 was prepared using compounds in which M, R, and Y were changed, and coated on PET synthetic paper, and then a light resistance test was performed. The minimum change in reflectance before and after the light resistance test is shown in Table-1 (Table 1).

[0023]

Embedded image

[0024]

[Table 1] In the example, the change in reflectance before and after the test was as small as 3 to 5%,
In the comparative example, the reflectance change before and after the test is large at 11 to 38%.

[0025]

By using the photocurable resin composition of the present invention,
The printed matter or coating obtained by printing and drying on paper or resin has little coloring in the visible region and can be applied and
It has excellent light resistance after photo-curing, and near infrared rays (700-1
800 nm), the sensitivity is particularly high in the range of 700 to 850 nm which is the emission region of the semiconductor laser.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display area C09D 11/10 PTX // C09B 47/20

Claims (6)

[Claims] 1. A photocurable resin and a compound represented by the general formula (1)
The photocurable resin composition containing at least 1 sort (s) of the phthalocyanine compound represented by these. Embedded image [In the formula, R ^{1 to} R ⁸ each independently represent a substituted or unsubstituted alkyl group, and at least four of them are alkyl groups having 1 to 8 carbon atoms. X ^{1 to} X ⁸ each independently represent a halogen, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and at least 4 of them have 1 carbon
To 5 substituted or unsubstituted alkylthio groups. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal] 2. A phthalocyanine represented by the general formula (1)
Compound R¹~ R⁸Are each independently substituted with 1 to 8 carbon atoms.
Or an unsubstituted alkyl group, X¹~ X ⁸Each is German
In addition, a substituted or unsubstituted alkylthio having 1 to 5 carbon atoms
The photocurable resin composition according to claim 1, which is a group. 3. The phthalocyanine compound represented by the general formula (1), wherein X ^{1 to} X ⁸ are each independently a methylthio group, an ethylthio group, an n-propylthio group, or an i-propylthio group. The photocurable resin composition described. 4. The phthalocyanine compound represented by the general formula (1) wherein M is copper or palladium.
The photocurable resin composition according to any one of 1. 5. The photocurable resin composition according to claim 1, wherein the photocurable resin is an acrylate-based monomer, an oligomer, or a mixture thereof. 6. The photocurable resin composition according to claim 1, further comprising a photopolymerization initiator.