JP2007277509A - Photocurable varnish - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable varnish which controls the bleeding of a photopolymerization initiator, its decomposition product, a sensitizer and other compositions in printed matter, smells little and prevents the deterioration of the hardness of the cured film and the curability. <P>SOLUTION: The photocurable varnish comprises a resin, a monomer and a photopolymerization initiator as expresses by the general formula shown in the figure. In the formula, R<SP>1</SP>-R<SP>4</SP>are each an alkyl group, an aryl group or the like; X is a divalent condensed aromatic ring group optionally containing a heteroatom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photocurable varnish containing a photopolymerization initiator that is cured by light irradiation, and more specifically, a photopolymerization initiator, a photopolymerization initiator decomposition product, a sensitizer, and the like from the surface of the film after varnish curing. The present invention relates to a photocurable varnish capable of suppressing oozing and odor of the composition such as volatilization and elution.

  Photocurable coating compositions, especially UV curable coating compositions are printing inks, clear varnishes, paints, photosensitive resins for printing plates, adhesives, adhesives, color filter resists, printed circuit board resists, semiconductor photoresists. Research has been actively conducted in the fields of hologram materials, molding resins, casting resins, optical modeling resins, sealants, various devices, and the like. These include photopolymerization initiators, resins (including both radically polymerizable resins and non-radically polymerizable resins), radically polymerizable monomers, pigments (not included in clear varnish), additives, etc. Become. Commonly used photopolymerization initiators include benzophenone series such as methyl o-benzoylbenzoate, Darocur 1173, Darocur 2959, Irgacure 184, Irgacure 907 (Irgacure and Darocur are trademarks of Ciba Specialty Chemicals), etc. Hydrogen donation systems such as acetophenone, benzoin such as Irgacure 651, thioxanthone, EAB (Hodogaya Chemical Co., Ltd.), Seikol PAA (Seiko Chemical Co., Ltd.), Kayacure EPA (Nihon Kayaku Co., Ltd.) are used. , Photopolymer Society, “Sensitive Material List Book”, pages 55-72, 1996 (Bunshin Publishing).

  In recent years, researches on photopolymerization initiators having higher sensitivity than those of commercially available photopolymerization initiators have been actively conducted, and an example thereof is an α-aminoacetophenone derivative (Patent Document 1). When the derivative has a substituent containing a sulfur atom or an oxygen atom at the 4-position of the phenyl group, the derivative is particularly used as a photocuring initiator for photocuring system containing a pigment such as photocurable ink. It is known to be appropriate (Patent Documents 2 and 3). It is also known that an α-aminoacetophenone derivative having an amino group at the 4-position of a phenyl group is used in combination with a photosensitizer of an aromatic carbonyl compound (Patent Document 4). An α-aminoketone derivative in which the phenyl group of the α-aminoacetophenone derivative is an N-substituted carbazole group is also known (Patent Document 5). It is known that the polymerizable composition containing the α-aminoacetophenone derivative is a highly sensitive polymerizable composition that can be cured with a small amount of light irradiation. Moreover, a polymerizable composition containing α-aminoacetophenone containing at least one allyl group or aralkyl group (arylalkyl group) at the α-position as a highly sensitive photopolymerization initiator has been proposed (Patent Document 6). ). In addition, α-aminoacetophenone derivatives containing two functional groups in the same molecule have also been proposed as highly sensitive photopolymerization initiators. It is known that an α-aminoacetophenone derivative containing two functional groups in the same molecule exhibits high activity (Patent Document 7). Photocurable coating compositions containing these photopolymerization initiators are known to exhibit high curability, but from the photocurable coating composition after curing, photopolymerization initiators, photopolymerization initiator decomposition products, It has been difficult to prevent bleeding (bleeding) and volatilization of the photosensitizer and other compositions.

JP-A-54-99185 JP 58-157805 A JP 59-167546 A JP-A-60-84248 JP 61-21104 A Japanese Unexamined Patent Publication No. 63-264560 JP-T-2002-530372

  Since general photopolymerization initiators may be low molecular weight compounds, various disadvantages are caused when they are used. For example, photocuring initiators, photopolymerization initiator decomposition products, photosensitizers, and other compositions may bleed or volatilize from the photocurable coating composition after curing. This is not preferable. In addition, bleed and volatilization of photopolymerization initiators, photopolymerization initiator decomposition products, photosensitizers, and other compositions may cause odors in printing, coating sites or printed materials, and coatings. There is a problem that the hardness is deteriorated. The object of the present invention is to prevent photopolymerization initiators, photopolymerization initiator decomposition products and sensitizers in printed materials, bleed suppression, volatilization prevention, low odor, cured film hardness, and curable deterioration of other compositions. It is.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, this invention relates to the photocurable varnish which consists of resin, a monomer, and the photoinitiator represented by following General formula (1).

General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or COR ⁵ Represents. R ³ and R ⁴ may be combined to form a ring.
R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted An aryloxy group or a substituted or unsubstituted heterocyclic oxy group is represented.
X represents a divalent condensed polycyclic aromatic group which may contain a hetero atom,
Ar ¹ represents the following general formula (2). )

General formula (2)

(Wherein R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted diarylamino group, substituted Properly represents the unsubstituted alkyl arylamino group, or a halogen atom. Also, R ⁶ to R ¹⁰ may form an aromatic ring together.)

  Furthermore, this invention relates to the said photocurable varnish whose X of General formula (1) is General formula (3), General formula (4), General formula (5), or General formula (6).

General formula (3)

General formula (4)

General formula (5)

General formula (6)

Wherein Y and Z are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH _2. CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms or a direct bond;
U represents —O—, —S—, or —N (R ¹¹ ) —;
V and W represent a nitrogen atom,
R ¹¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted An aryloxy group or a substituted or unsubstituted heterocyclic oxy group is represented. )

  Furthermore, this invention relates to the said photocurable varnish whose X of General formula (1) is General formula (3).

  Furthermore, this invention relates to the printed matter obtained by printing the said photocurable varnish and making it harden | cure by light irradiation.

  Furthermore, this invention relates to the manufacturing method of the printed matter which prints the said photocurable varnish on a base material, and hardens | cures by light irradiation.

  The photocurable varnish of the present invention has a photopolymerization initiator, a photopolymerization initiator decomposition product, and a photosensitizer from the surface of the film after varnish curing, compared to a photocurable varnish containing a conventional general-purpose photopolymerization initiator composition. In addition, the amount of exudation such as volatilization and elution of the composition can be suppressed. Further, as a result, the odor derived from the photopolymerization initiator, the photopolymerization initiator decomposition product, the sensitizer, and other compositions can be reduced. The printed matter using the varnish is not only excellent as a varnish for food packaging materials, but also leads to environmental improvement in the printing process.

  The photocurable varnish of the present invention comprises a resin, a monomer, and a photopolymerization initiator of the general formula (1). Various additives (for example, other polymerization initiators and photosensitizers) can be used in combination.

  First, the photopolymerization initiator will be described. The radical polymerization initiator of the present invention has a structure represented by the general formula (1), and the benzene ring portion of the α-aminoacetophenone derivative may contain a hetero atom having an aromatic acyl group. It has a characteristic structure in which it is replaced by an aromatic ring condensed group consisting of 4 to 16. By introducing this aromatic ring-fused group, the compound of the present invention can have light absorption characteristics suitable for a wavelength region of 250 nm to 450 nm, and realizes a significant increase in sensitivity to light irradiation. In addition, by having this structure, the compound of the present invention decomposes very efficiently upon light irradiation in the wavelength region, and as a result, as a highly sensitive material that efficiently generates a large amount of radicals. It is possible to function.

General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or COR ⁵ Represents. R ³ and R ⁴ may be combined to form a ring.
R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted An aryloxy group or a substituted or unsubstituted heterocyclic oxy group is represented.
X represents a divalent condensed polycyclic aromatic group which may contain a hetero atom,
Ar ¹ represents the following general formula (2). )

General formula (2)

(Wherein R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted diarylamino group, substituted Properly represents the unsubstituted alkyl arylamino group, or a halogen atom. Also, R ⁶ to R ¹⁰ may form an aromatic ring together.)

  Next, the structure of the photopolymerization initiator of the present invention will be described in detail.

  As shown in the general formula (1), the photopolymerization initiator of the present invention can introduce various substituents as long as the properties are not impaired. By introducing a substituent, the photopolymerization initiator of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as the maximum absorption wavelength and transmittance, and the solubility in the resin or solvent used together.

The substituents R ¹ and R ² in the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted group. An alkenyl group, specifically, a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or an alkenyl group, an aryl group having 6 to 24 carbon atoms, a nitrogen atom, It is a C4-C24 heterocyclic group containing an oxygen atom, a sulfur atom, and a phosphorus atom.

Here, the substituted or unsubstituted alkyl group in R ¹ and R ² is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. Examples thereof include, but are not limited to, CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

Examples of the aryl group in R ¹ and R ² include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and 1-anthryl. Group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-fluorenyl group Group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p -Dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p- Examples thereof include, but are not limited to, a droxyphenyl group, an m-carboxyphenyl group, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group. .

Examples of the heterocyclic group for R ¹ and R ² include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and a 2-thienyl group 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, Xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quino Ryl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group Group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, Imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, 4-quinolinyl group Group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the alkenyl group in R ¹ and R ² include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, and these include a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group and 2-pentenyl group. 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group , Cyclohexadienyl group, cyclopentadienyl group, and the like, but are not limited thereto.

R ¹ and R ² may be bonded to the carbon atom of the general formula (1) at substitution positions other than those described above, and these are also in the category of the substituent represented by R ¹ and R ² of the present invention. included.

R ¹ and R ² may be combined to form a ring.

When R ¹ and R ² are combined to form a ring, the formed site is a substituted or unsubstituted alkylene group having 2 to 8 carbon atoms or oxaalkylene group having 3 to 9 carbon atoms. Or an azaalkylene group having 3 to 9 carbon atoms.

  Here, examples of the ring formed in the case of an alkylene group having 2 to 8 carbon atoms include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. However, it is not limited to these.

  Examples of the ring formed when the oxaalkylene group having 3 to 9 carbon atoms or the azaalkylene group having 3 to 9 carbon atoms include a tetrahydrofuran ring, a pyrrolidine ring, and a piperidine ring. It is not limited to.

Among the above substituents, R ¹ is preferably an alkyl group or an alkenyl group in terms of the difficulty of synthesis and sensitivity as a radical generator, and specifically includes a methyl group, an ethyl group, a benzyl group, A p-methylbenzyl group or a 2-propenyl group is particularly preferable.

The substituents R ³ and R ⁴ in the general formula (1) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted Or an unsubstituted alkenyl group, or COR ⁵ .

Examples of the alkyl group for R ³ and R ⁴ include the same substituents as those exemplified as the alkyl group for R ¹ and R ² described above, but are not limited thereto.

Examples of the aryl group in R ³ and R ⁴ include the same substituents as those exemplified as the aryl group in R ¹ and R ² described above, but are not limited thereto.

Examples of the heterocyclic group in R ³ and R ⁴ include the same substituents as those exemplified as the heterocyclic group in R ¹ and R ² described above, but are not limited thereto.

Examples of the alkenyl group for R ³ and R ⁴ include the same substituents as those exemplified as the heterocyclic group for R ¹ and R ² described above, but are not limited thereto.

R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted An aryloxy group, or a substituted or unsubstituted heterocyclic oxy group.

Examples of the alkyl group in R ⁵ include the same substituents as those exemplified as the alkyl group in R ¹ and R ² described above, but are not limited thereto.

Examples of the aryl group in R ⁵ include the same substituents as those exemplified as the aryl group in R ¹ and R ² described above, but are not limited thereto.

Examples of the heterocyclic group for R ⁵ include, but are not limited to, the same substituents as those exemplified as the heterocyclic group for R ¹ and R ² described above.

Examples of the alkenyl group for R ⁵ include the same substituents as those exemplified as the alkenyl group for R ¹ and R ² described above, but are not limited thereto.

The substituted or unsubstituted alkoxyl group in R ⁵ is a linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms, or one to one or more carbon atoms having 2 to 18 carbon atoms. And a linear, branched, monocyclic or condensed polycyclic alkoxyl group interrupted by —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxyl group having 1 to 18 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyl Oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert -Pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decyl Cyclohexyl It can be given group and the like, but not limited thereto. Specific examples of the linear or branched alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , — O—CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O—CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O— (CH ₂ —CH ₂ —O) _n — CH ₃ (where n is 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —O—CH _{2 -CH (CH 3) -O-CH} 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkoxyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include, but are not limited to: Is not to be done.

Examples of the aryloxy group in R ⁵ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and 9-anthryl. Oxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group However, it is not limited to these. Further, the aryl group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ of the present invention.

The heterocyclic oxy group in the substituent R ⁵ in the general formula (1) is a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2- Examples thereof include, but are not limited to, a carbazolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group. Further, the heterocyclic group and the oxygen atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ⁵ of the present invention.

R ³ and R ⁴ may be combined to form a ring.

When R ³ and R ⁴ are combined to form a ring, the formed site includes an alkylene group having 2 to 6 carbon atoms, an oxaalkylene group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms. Or azaalkylene group having 2 to 6 carbon atoms.

  Here, examples of the ring formed in the case of an alkylene group having 2 to 6 carbon atoms include formation of a propyleneimine ring, a pyrrolidine ring, a piperidine ring, a pipecoline ring, and the like, It is not limited to these.

  Examples of the ring formed when the oxaalkylene group having 2 to 6 carbon atoms, the thiaalkylene group having 2 to 6 carbon atoms, or the azaalkylene group having 2 to 6 carbon atoms include morpholine ring and thiomorpholine ring Examples include, but are not limited to, forming a thiazolidine ring, piperazine ring, or homopiperazine ring.

Among the above-mentioned substituents, R ³ and R ⁴ are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, R in view of synthesis difficulty and sensitivity as radical generators. ^{When 3} and R ⁴ are combined to form a ring, a substituted or unsubstituted alkylene group, a substituted or unsubstituted oxaalkylene group, a substituted or unsubstituted thiaalkylene group, a substituted or unsubstituted aza An alkylene group is preferable, and —NR ³ (R ⁴ ) is, for example, dimethylamino group, diethylamino group, bis-2-methoxyethylamino group, morpholino group, thiomorpholino group, prolidino group, piperidino group, piperazino group, or 1- A methylpiperazino group is particularly preferred.

Ar ¹ in the general formula (1) is represented by the general formula (2).

The substituents R ^{6 to} R ¹⁰ in the general formula (2) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or Unsubstituted alkenyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted Or unsubstituted alkoxycarbonyloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkyl Amino group, substituted or unsubstituted arylamino group, substituted or unsubstituted diary Amino group, a substituted or unsubstituted alkyl aryl amino group, a substituted or unsubstituted benzylamino group, a substituted or unsubstituted dibenzylamino group or a halogen atom.

Examples of the alkyl group in R ^{6 to} R ¹⁰ include the same substituents as those exemplified as the alkyl group in R ¹ and R ² described above, but are not limited thereto.

Examples of the aryl group in R ^{6 to} R ¹⁰ include the same substituents as those exemplified as the aryl group in R ¹ and R ² described above, but are not limited thereto.

Examples of the heterocyclic group in R ^{6 to} R ¹⁰ include, but are not limited to, the same substituents as those exemplified as the heterocyclic group in R ¹ and R ² described above.

Examples of the alkenyl group in R ^{6 to} R ¹⁰ include the same substituents as those exemplified as the alkenyl group in R ¹ and R ² described above, but are not limited thereto.

As the acyl group in R ^{6 to} R ¹⁰ , a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded; A carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyl group to which a monocyclic or condensed polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom; Specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl Group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoi Group, cinnamoyl group benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group and the like. Is not to be done. Further, the aryl group and the carbonyl group, the heterocyclic group and the carbonyl group may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention. .

Examples of the alkoxyl group in R ^{6 to} R ¹⁰ include the same substituents as those exemplified as the alkoxyl group in R ⁵ described above, but are not limited thereto.

Examples of the aryloxy group in R ^{6 to} R ¹⁰ include the same substituents as those exemplified as the aryloxy group in R ⁵ described above, but are not limited thereto.

Examples of the heterocyclic oxy group in R ^{6 to} R ¹⁰ include the same substituents as those exemplified as the heterocyclic oxy group in R ⁵ described above, but are not limited thereto.

As the acyloxy group in R ^{6 to} R ¹⁰ , a hydrogen atom, a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon number of 6 To a carbonyloxy group to which a monocyclic or condensed aryl group of 1 to 18 is bonded, or a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyl. Oxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexyl Carbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group , 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthacenoyloxy group, etc., but are not limited thereto. is not. In addition, the aryl group and the carbonyloxy group, the heterocyclic group and the carbonyloxy group may be bonded at positions other than those described above, and these are also in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention. included.

Examples of the alkoxycarbonyloxy group in R ^{6 to} R ¹⁰ include a carbonic acid ester group having 1 to 12 carbon atoms. Specific examples thereof include a tert-butoxycarbonyloxy group, a tert-pentyloxycarbonyloxy group, 1,1- A diethylpropyloxycarbonyloxy group, a 1-ethyl-2-cyclopentenyloxycarbonyloxy group, a 2-tetrahydropyranyloxycarbonyloxy group, a 1-ethylcyclopentyloxycarbonyloxy group, and the like can be mentioned, but are not limited thereto. It is not something.

Examples of the alkylthio group in R ^{6 to} R ¹⁰ include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms. Specific examples include methylthio group, ethylthio group, propylthio group. Groups, butylthio groups, pentylthio groups, hexylthio groups, octylthio groups, decylthio groups, dodecylthio groups, octadecylthio groups, and the like, but are not limited thereto.

Examples of the arylthio group in R ^{6 to} R ¹⁰ include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group and the like can be mentioned, but are not limited thereto. Moreover, the aryl group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention.

Examples of the heterocyclic thio group in R ^{6 to} R ¹⁰ include a monocyclic or condensed polycyclic heterocyclic thio group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group Although groups etc. can be mentioned, it is not limited to these. Moreover, the heterocyclic group and the sulfur atom may be bonded at positions other than those described above, and these are also included in the category of the substituent represented by R ^{6 to} R ¹⁰ of the present invention.

Examples of the alkylamino group in R ^{6 to} R ¹⁰ include a methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, Dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group , Neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-a , And the like Mantamino group, but not limited thereto.

Examples of the dialkylamino group in R ^{6 to} R ¹⁰ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamino group, a dihexylamino group, a diheptylamino group, a dioctylamino group, a dinonylamino group, and a didecylamino group. , Didodecylamino group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, Examples thereof include, but are not limited to, pyrrolidino group, piperidino group, piperazino group and the like.

Examples of the arylamino group in R ^{6 to} R ¹⁰ include an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3- A biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, an indolino group, and the like can be mentioned, but are not limited thereto. It is not a thing.

Examples of the diarylamino group in R ^{6 to} R ¹⁰ include, but are not limited to, diphenylamino group, ditolylamino group, N-phenyl-1-naphthylamino group, N-phenyl-2-naphthylamino group, and the like. It is not something.

Examples of the alkylarylamino group in R ^{6 to} R ¹⁰ include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N- Examples thereof include, but are not limited to, a pentylanilino group, an N-ethylanilino group, and an N-methyl-1-naphthylamino group.

Examples of the halogen atom in R ^{6 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among the above substituents, examples of the substituent R ⁶ to R ^10, and faces the difficulty of synthesis, in view of the sensitivity of the radical generator, the substituents R ⁶ to R ¹⁰ all simultaneously hydrogen atom, a substituent R ⁶ is a methyl group and the substituents R ^{7 to} R ¹⁰ are simultaneously hydrogen atoms, the substituent R ¹⁰ is a methyl group and the substituents R ^{6 to} R ⁹ are simultaneously hydrogen atoms, the substituent R ⁸ is a methyl group and the substituent R ⁶ , The case where R ⁷ , R ⁹ and R ¹⁰ are simultaneously a hydrogen atom is particularly preferred.

When Ar ¹ is an alkyl group, it is inferior in sensitivity as compared with the radical polymerization initiator of the present invention. That is, in order to achieve high sensitivity, Ar ¹ needs to be an aromatic group as in the present invention.

  X in the general formula (1) is a divalent condensed polycyclic aromatic group which may contain a hetero atom.

  In the present invention, the condensed polycyclic aromatic group is an aromatic ring in which two or more rings are condensed and at least one ring may contain a hetero atom.

  Examples of the aromatic ring in X include aromatic rings having 4 to 30 carbon atoms, and specifically include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a naphthacene ring, a pyrenyl group, a phenyl group. Naphthalene ring, indenyl group, azulene ring, furan ring, pyrrole ring, thiophene ring, indole ring, benzofuran ring, benzothiophene ring, indene feeling, quinoline ring, isoquinoline ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, phenoxathiin Ring, phenothiazine ring, thianthrene ring, xanthene ring, thioxanthene ring, phenoxazine ring, phenazine ring, acridine ring, xanthone ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, indazole ring, 1,2-benzisoxazo Le ring, phenazine phenanthridine ring, phenanthroline ring, a pyrazine ring, a pyridazine ring, an acridone ring, there may be mentioned N- phenyl pyrrole ring, etc., but is not limited thereto.

  The divalent condensed polycyclic aromatic group that may contain a heteroatom in X is not particularly limited, and the type of heteroatom, the number of heteroatoms, and the substitution position of the heteroatom are not particularly limited.

  The kind of the hetero atom in the divalent condensed polycyclic aromatic group that may contain a hetero atom in X is not particularly limited, but a nitrogen atom, an oxygen atom, and a sulfur atom are preferable.

  The number of heteroatoms in the divalent fused polycyclic aromatic group that may contain heteroatoms in X is not particularly limited, but is preferably 0 to 4.

  The substitution position of the hetero atom in the divalent condensed polycyclic aromatic group that may contain a hetero atom in X is not particularly limited, but the aromatic ring in X and the two carbonyl groups in the general formula (1) It is preferable that they are bonded so as not to block the conjugation with at least one of them.

  Although carbon number in the bivalent condensed polycyclic aromatic group which may contain the hetero atom in X is not specifically limited, 4-16 carbon atoms are preferable.

  More preferable examples of the divalent condensed polycyclic aromatic group that may contain a hetero atom in X are general formula (3), general formula (4), general formula (5), and general formula (6). .

The substituent R ¹¹ in the general formula (3), general formula (4), general formula (5), or general formula (6) is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or An unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy group.

Examples of the alkyl group for R ¹¹ include the same substituents as those exemplified as the alkyl group for R ¹ and R ² described above, but are not limited thereto.

Examples of the aryl group in R ¹¹ include the same substituents as those exemplified as the aryl group in R ¹ and R ² described above, but are not limited thereto.

Examples of the heterocyclic group for R ¹¹ include the same substituents as those exemplified as the heterocyclic group for R ¹ and R ² described above, but are not limited thereto.

Examples of the alkenyl group for R ¹¹ include the same substituents as those exemplified as the alkenyl group for R ¹ and R ² described above, but are not limited thereto.

Examples of the alkoxyl group in R ¹¹ include the same substituents as those exemplified as the alkoxyl group in R ⁵ described above, but are not limited thereto.

Examples of the aryloxy group for R ¹¹ include, but are not limited to, the same substituents as those exemplified as the aryloxy group for R ⁵ described above.

Examples of the heterocyclic oxy group for R ¹¹ include the same substituents as those exemplified as the heterocyclic oxy group for R ⁵ described above, but are not limited thereto.

  As general formula (3), general formula (4), general formula (5), or general formula (6), benzofuranyl group, benzothienyl group, indenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, Fluorenyl group dibenzo [b, e] [1,4] dioxinyl group, phenoxathinyl group, phenothiazinyl group, thianthenyl group, xanthenyl group, thioxanthenyl group, phenoxazinyl group, benzoxazolyl group, benzothiazolyl group, benzimidazolyl group , An indazolyl group, a 1,2-benzisoxazolyl group, an iminostilbenyl group, a xanthonyl group, and the like, but are not limited thereto.

  Of the general formula (3), general formula (4), general formula (5), or general formula (6), a carbazolyl group and dibenzofura are preferred in terms of synthesis difficulty and sensitivity as a radical generator. Nyl group, dibenzothiophenyl group, fluorenyl group dibenzo [b, e] [1,4] dioxinyl group, phenoxathinyl group, phenothiazinyl group, thiantenyl group, xanthenyl group, thioxanthenyl group, phenoxazinyl group, benzoxazolyl A group, a benzothiazolyl group, a benzimidazolyl group, and an indazolyl group are particularly preferable.

Examples of the substituent that R ^{1 to} R ¹¹ in the general formula (1) may have include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, Acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylaryl Examples thereof include an amino group, a benzylamino group, a dibenzylamino group, and combinations thereof.

Among these substituents of R ^{1 to} R ¹¹ , a halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, complex Examples of the ring thio group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group and alkylarylamino group may include the same substituents as those described above, but are not limited thereto. It is not something.

  Specific examples of particularly preferable photopolymerization initiators described above are shown below, but the structure of the radical polymerization initiator of the present invention is not limited thereto.

  As the resin of the photocurable varnish used in the present invention, there are a resin having radical polymerization and a resin having no radical polymerization. As the resin having radical polymerizability, alkyd (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or the like is used.

  Resins having no radical polymerizability include resins having a softening point of 70 to 120 ° C., and more specifically polyesters, epoxy esters, urethanes, diallyl phthalate resins, and the like, but the present invention is limited to these. It is not a thing.

  The monomer in the photocurable varnish of the present invention is a monomer having an ethylenically unsaturated bond capable of radical polymerization, and the monomer having an ethylenically unsaturated bond capable of radical polymerization is capable of radical polymerization in the molecule. Any monomer having at least one ethylenically unsaturated bond may be used. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the intended characteristics.

Examples of monomers having such an ethylenically unsaturated bond capable of radical polymerization include
Examples include acrylic acid derivatives, methacrylic acid derivatives, itaconic acid derivatives, crotonic acid derivatives, isocrotonic acid derivatives, unsaturated carboxylic acid derivatives such as maleic acid derivatives, and radically polymerizable monomers such as styrene derivatives. Is not to be done.

  Specific radical polymerizable monomers include (hydrogenated) bisphenol (A or F) alkylene oxide adduct diacrylate, (alkyl) phenol or polyhydric phenol alkylene oxide adduct acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl. Acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) butane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol Diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, Acrylic acid derivatives such as N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, (hydrogenated) bisphenol (A or F) alkylene oxide adduct dimethacrylate, (alkyl) phenol or polyhydric phenol alkylene oxide adduct methacrylate, Methyl methacrylate, N-butyl methacrylate Rate, 2-hexyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol ethanetri Methacrylic acid derivatives such as methacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of aryl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. More specifically, edited by Shinzo Yamashita et al., “Crosslinking agent handbook” (1981, Taiseisha) and Kato Seikatsu, “UV / EB Curing Handbook (raw material)” (1985, Polymer Publications), Radtech Research Group, “Application and Market of UV / EB Curing Technology”, 79, (1989, CMC), edited by Kiyoshi Akamatsu, “New / Sensitive Resin Technology” (1987, CMC), Shinichiro Takiyama, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun) Examples include radically polymerizable or crosslinkable monomers, oligomers and polymers known in the art or in the industry, but the present invention is not limited thereto.

  The photocurable varnish of the present invention can be used in combination with other polymerization initiators for the purpose of further improving sensitivity.

  Other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 907, Cure 369, IRGACURE 379, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01 (CGI124), CGI242 Chemicals), Adekaoptomer N1414, Adekaoptomer N1717 (Asahi Denka), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 6 Triazine derivatives described in JP-A-69621 and JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-2243807, JP-B-43-23684, As described in JP-B-44-6413, JP-B-47-1604 and diazonium compounds described in USP 3,567,453, USP 2,848,328, USP 2,852,379 and USP 2,940,853 Organic azide compounds, ortho-quinonediazides described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610, JP-B 55-39162, JP 59-140203 A and “Macro” Various onium compounds including iodonium compounds described in “Moleculars”, Vol. 10, page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, Metal allene complexes described in European Patent No. 109851 and European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986) , Titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) and JP-A-2-182701. Transition metal complexes containing transition metals such as ruthenium, described in JP-A-3-209477 Aluminate complex, borate compound described in JP-A-2-157760, 2,4,5-triarylimidazole dimer described in JP-A-55-127550 and JP-A-60-202437, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, carbon tetrabromide and organic halogens described in JP-A-59-107344 Compounds, JP-A-5-213861, JP-A-5-255347, JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, The sulfonium complex or oxosulfonium complex described in Japanese Patent Application No. 2004-053009 and Japanese Patent Application No. 2004-263413 JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, USP3558309 (1971), USP4202697 (1980) Oxime ester compounds described in JP-A Nos. 61-24558, 2004-534797 and 2004-359639, bifunctional photoinitiators described in JP-A 2002-530372, and the like. However, the present invention is not limited to these.

  In addition, by combining with a sensitizer that absorbs ultraviolet to near-infrared light to increase the activity for light from the ultraviolet to the near-infrared region, it is an extremely sensitive photopolymerizable composition. Is possible.

  Sensitizers that can be used in combination with the polymerizable composition of the present invention include benzophenones, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, benzyl and camphorquinone 1 , 2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, etc. Pigment, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, Liarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline Derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes and the like. Other specific examples include Okawara Shin et al., “Dye Handbook” (1986, Kodansha), The dyes and sensitizers described in Nobu Okawara et al., “Chemicals of Functional Dyes” (1981, CMC), Tadasaburo Ikemori et al., “Special Functional Materials” (1986, CMC) are listed. However, it is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region can be used. It doesn't matter. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylamino). Marine) and the like, but is not limited thereto.

  The photopolymerization initiator used in the present invention is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  The resin used in the present invention is preferably 0.01 to 600 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the monomer.

  In addition, a polymerization inhibitor can be added to the photocurable varnish of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the polymerization inhibitor that can be added to the photocurable varnish of the present invention include hydroquinone, p-methoxyphenol, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, and phenothiazine. The addition amount of the polymerization inhibitor is not particularly limited, but it is preferably used in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  Moreover, the polymerization composition of this invention can add the polymerization accelerator represented by amine, thiol, disulfide, etc. and a chain transfer catalyst for the purpose of further promoting superposition | polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP No. 4414312 Thiols described in the specification, JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples include O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

  The material used for the conventional photocurable varnish can be appropriately used for the photocurable varnish of the present invention. For example, viscosity adjusting agents, surfactants for adjusting printing properties of varnish, phosphoric acid additives for preventing sensitization of plates, and auxiliary agents for adjusting the surface of a cured film such as wax.

  In the polymerization reaction, the photocurable varnish of the present invention can be polymerized by applying energy by ultraviolet rays, visible rays, near infrared rays, electron beams or the like to obtain a desired polymer. The definitions of ultraviolet rays, visible rays, near-infrared rays and the like in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the photocurable varnish of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and helium. Neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser, etc. Polymer or cured product can be obtained.

  As a method for applying the photocurable varnish of the present invention, for example, known means such as a roll coater, a gravure coater, a flexo coater, an offset printing machine, a screen printing machine can be appropriately employed, but the application is not limited thereto. Absent.

  The photocurable varnish is printed on a substrate to form a printed material. The substrate that can be used in the present invention is not particularly limited as long as it is a substrate that is usually used for printing, such as paper, synthetic paper, plastic, metal stay, and wood. These substrates may be printed with a primer, a picture, or characters before the varnish is printed. Further, the substrate may be subjected to a treatment such as a corona treatment.

  The photocurable varnish obtained in the present invention can be printed and cured using the same technique as in the prior art. The varnish of the present invention can suppress the amount of seepage such as volatilization and elution of the photopolymerization initiator and its decomposition products and other compositions from the surface of the film after varnish curing. Furthermore, as a result, the odor derived from the photopolymerization initiator, its decomposition products, and other compositions can be reduced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all.

  Prior to the examples, the compounds of the present invention used in the examples are shown in Table 1.

Table 1

  These compounds shown in Table 1 could be obtained by using the synthesis method described in Japanese Patent Application No. 2005-022871.

Manufacture of varnish (mixture of resin, monomer, etc.) Dap tote DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.) 10%, ditrimethylolpropane tetraacrylate 89.9%, hydroquinone 0.10% are mixed and heated and melted. did.

Production of varnish Example 1 (varnish A1)
A varnish was obtained by mixing a varnish, a photopolymerization initiator (compound (1)) and a sensitizer MDA (N-methyldiethanolamine). The formulation is shown in Table 2.

Examples 2 to 7 (varnish A2 to A7)
A varnish was prepared in the same manner as in Example 1 except that the compound (1) of Example 1 was replaced with the compounds (2) to (7). The formulation is shown in Table 2.

Comparative examples 1 and 2 (varnish A8, A9)
A varnish was prepared in the same manner as in Example 1 except that Compound (1) of Example 1 was replaced with Irgacure 184 (Irg184) and Irgacure 907 (Irg907). The formulation is shown in Table 2.

The performance evaluation of the printing varnish was performed as follows. The results are shown in Table 3 for the varnish performance evaluations (1) to (4) of Examples 1 to 7 and Comparative Examples 1 and 2.
-(1) Curability: In the case of each photo-curing varnish, the photo-curing varnish is applied with a bar coater # 2, irradiated with ultraviolet light (high pressure mercury lamp 160W / cm1 lamp), and then rubbed with a cotton cloth to scratch the film. Judged with no conveyor speed. The larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability.
(2) Solvent resistance: The printed material cured under the same conditions as the curability was rubbed with a cotton swab containing methyl ethyl ketone and judged at a conveyor speed at which the film was not damaged. The larger the number in the conveyor speed (m / min) of the ultraviolet irradiation device, the better the solvent resistance.
・ (3) Odoriness: Printed material cured under the same conditions as the curability is finely cut and packed in a glass bottle. The panelists of 5 persons have judged the odor relatively, and 1 (bad) to 5 (good) ).
(4) Bleed amount: An unprinted paper was placed on a printed material cured under the same conditions as the curability, and left for one day at a temperature of 60 ° C. and a pressure of 15 g / cm ² , and transferred to an unprinted paper. The amount of unreacted initiator and other compositions were quantified.

Table 2

Table 3

In the case of the photocurable varnish using the photopolymerization initiator of the present invention, it is found that the photocuring type varnish has the same or better curability and solvent resistance as the case of using the photopolymerization initiator generally used. It was. Moreover, the photocurable varnish of the present invention was able to suppress the bleed amount of the photopolymerization initiator, its decomposition product, and other compositions from the surface after varnish curing. Although details are not yet clear about this result, it is presumed as follows. The photopolymerization initiator of the present invention may have a relatively large molecular weight, and its own sublimation property is low. To support this, in the photocurable varnish of the present invention, there is almost no odor considered to be caused by volatilization of a photopolymerization initiator after varnish curing or a decomposition product thereof. It can be imagined that the higher the varnish curability, the more difficult the photopolymerization initiator, its degradation products and other compositions will bleed out, but considering the results of the varnish curability test and the bleed test of the examples and comparative examples It is difficult to consider that the amount of bleed is caused only by the curability. In addition to the varnish curability, the photopolymerization initiator may have some sublimation properties, which may have caused the photopolymerization initiator and its decomposition products to hardly bleed out from the varnish.

Claims (5)

A photocurable varnish comprising a resin, a monomer, and a photopolymerization initiator represented by the following general formula (1).
General formula (1)

(Wherein R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted alkenyl group) R ¹ and R ² may be integrated to form a ring.
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, or COR ⁵ Represents. R ³ and R ⁴ may be combined to form a ring.
R ⁵ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted An aryloxy group or a substituted or unsubstituted heterocyclic oxy group is represented.
X represents a divalent condensed polycyclic aromatic group which may contain a hetero atom,
Ar ¹ represents the following general formula (2). )
General formula (2)

(Wherein R ^{6 to} R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkoxycarbonyl Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted Substituted arylamino group, substituted or unsubstituted diarylamino group, substituted Properly represents the unsubstituted alkyl arylamino group, or a halogen atom. Also, R ⁶ to R ¹⁰ may form an aromatic ring together.) The photocurable varnish according to claim 1, wherein X is the general formula (3), the general formula (4), the general formula (5), or the general formula (6).
General formula (3)

General formula (4)

General formula (5)

General formula (6)

Wherein Y and Z are each independently —O—, —S—,>S═O,> SO ₂ , —N (R ¹¹ ) —, —CO—, —CH ₂ —, —CH _2. CH ₂ —, —CH═CH—, an alkylidene group having 2 to 6 carbon atoms or a direct bond;
U represents —O—, —S—, or —N (R ¹¹ ) —;
V and W represent a nitrogen atom,
R ¹¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted An aryloxy group or a substituted or unsubstituted heterocyclic oxy group is represented. )   The photocurable varnish according to claim 2, wherein X is the general formula (3).   The printed matter obtained by printing the photocurable varnish in any one of Claims 1-3, and making it harden | cure by light irradiation. The manufacturing method of the printed matter which prints the photocurable varnish in any one of Claims 1-3 on a base material, and makes it harden | cure by light irradiation.