JPH04349462A - Near infrared photosensitive resin composition and optical molding formed by using this composition - Google Patents

Abstract

PURPOSE:To provide the near IR photosensitive resin compsn. which is polymerized and cured by irradiation with near IR rays and the optical molding which is cured by being irradiated with a semiconductor laser. CONSTITUTION:This compsn. contains a cation polymerizable org. compsn., such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and an aluminum salt compd. or diinmmonium salt compd. [following formula I or II] functioning as a near IR absorptive cation polymn. initiator, such as N, N, N', N'-tetraquis(p-di-n-butylaminophenyl)-p-benzoquinone-bis(inmmonium.hex afluoroantimonate), which are mixed and dissolved. The above- mentioned compsn. is cured by irradiation with the near UV rays or by heating. The optical molding is obtd. by using the semiconductor laser as a light source and using by irradiating the near IR photosensitive resin compsn. with the semiconductor laser beam by a computer-controlled optical molding method.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel composition that quickly becomes a cured product when irradiated with near-infrared rays or heated, and an optically shaped article using the composition.

0002

BACKGROUND OF THE INVENTION Highly polymerizable polymeric materials that are polymerized by energy rays, particularly light, have been actively researched, particularly in the field of paints, due to their energy-saving, space-saving, and non-polluting properties. However, most of these studies were based on the principle of radical polymerization of compounds containing double bonds by UV irradiation. Although epoxy resins are physically excellent materials, it is difficult to radically polymerize them, and methods of introducing double bonds through acrylic modification and the like have been employed for a long time.

[0003] Subsequently, US Pat. No. 3,794,576 proposed a photopolymerizable epoxy resin composition with good performance that has both favorable rheological properties and curability. This composition uses a photosensitive aromatic diazonium salt as a photopolymerization initiator. The aromatic diazonium salt is decomposed by ultraviolet irradiation, and the epoxy resin monomer is cationically polymerized by the generated Lewis acid. However, aromatic diazonium salts release nitrogen gas when photodecomposed, and therefore, if the epoxy resin obtained by polymerization exceeds 15 microns, the coating film will foam, making it unsuitable for thick coating.

[0004] To improve this point, the use of onium salt compounds such as aromatic iodonium salts and aromatic sulfonium salts as photopolymerization initiators was proposed in Japanese Patent Publication No. Sho 52.
-14277 Publication, Special Publication No. 52-14278,
Special Publication No. 54-53181, Special Publication No. 59-1958
It is disclosed in Publication No. 1, etc. Compositions of these onium salts and epoxy resins do not cause foaming when irradiated with ultraviolet rays upon photocuring, and provide cured products having appropriate storage stability. Further, by using a composite initiator of two or more components to which a sensitizer is added, the spectral sensitivity in the visible region can be increased, and a cured product can also be obtained by irradiation with visible light.

[0005] However, compositions consisting of onium salts and epoxy resins are
When producing a model using the optical modeling method described in Publication No. 7, the ultraviolet or visible laser that must be used as a light source is a helium-cadmium laser or an argon laser, and these are extremely The cost and size of the device are dominated by the laser light source, which is expensive and large, making it impossible to miniaturize the device. Furthermore, the lifespan of these lasers is as short as 2000 hours.

[0006] Subsequently, iron allene complexes were developed by K.I. As reported by Meier et al. Iron allene complexes can undergo ligand exchange with epoxides by light irradiation and initiate cationic polymerization. However, due to its small molar extinction coefficient, photocuring efficiency is poor, requiring a high-output laser light source, and it could only be used in fields where irradiation with a high-output laser is acceptable.

[0007] In JP-A-2-252765, a three-dimensional object is obtained by thermally curing a composition consisting of an onium salt and an epoxy resin using an infrared laser such as a YAG laser or a carbon dioxide laser. However, in order to thermally cure using these lasers, carbon black is used as a laser light energy absorber, and 3
Requires high output of W or more. Therefore, only a black cured product is obtained, and thermal runaway may occur, making it impossible to obtain a molded product of the desired shape. Additionally, due to the high output, there were problems with handling safety.

[0008] Therefore, if a semiconductor laser can be used, an inexpensive desk-top three-dimensional model production apparatus can be realized. However, there are no known photopolymerization initiators that can polymerize and cure cationic polymerizable organic compounds such as epoxy resins using near-infrared light with an output comparable to that of a semiconductor laser. Not obtained. Therefore, it was not possible to develop an optical modeling method using semiconductor lasers.

[0009]

[Problems to be Solved by the Invention] In view of the above circumstances, an object of the present invention is to polymerize and harden cationic polymerizable organic compounds such as epoxy using near-infrared irradiation with an output comparable to that of a semiconductor laser, thereby making it stable to heat and light. The purpose is to provide a durable cured product.

0010

[Means for Solving the Problems] The above object is to provide a near-infrared ray photosensitive material containing a cationic polymerizable organic compound and an aminium compound represented by the following general formula (1) or a diimmonium compound represented by (2) as the main components. This was achieved using a synthetic resin composition.

[0011]

[C5]

0012

[C6]

(wherein, A is

[0014]

[C7]

[0015]B is

[0016]

[Chemical formula 8]

[k represents 1 or 2], and the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or a hydroxyl group. X- represents an anion. R1 to R8 are hydrogen atoms, halogen atoms,
Substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group,
It is a substituted or unsubstituted alkynyl group, and R1 and R
2, R3 and R4, R5 and R6, and R7 and R
8 combinations of 5 substituted or unsubstituted with N
A membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring may be formed. The substituents of R1 to R8 may be the same or different).

The compound represented by the general formula (1) or (2) is a known compound, and is disclosed in US Pat. No. 35,758.
No. 71 and U.S. Patent No. 3,557,012, the maximum absorption wavelength is at 900 nm or more, and the molar extinction coefficient has a large absorption peak ranging from tens of thousands to hundreds of thousands. Using these high near-infrared absorption abilities, optical discs can be manufactured. It was known that it could be used in materials such as laser recording materials, insulation films, and sunglasses.

As a result of research on these compounds, the present inventors found that the aminium salt compound of general formula (1) and the diimmonium salt compound of general formula (2) absorb near infrared rays to generate cations, and the cations generate cations. It has been found that cationically polymerizable organic compounds such as epoxy can be polymerized and cured. Therefore, general formula (1) or (2) serves as a photocationic polymerization initiator using near infrared rays.

Furthermore, it has been discovered that these compounds can be sufficiently cured by irradiation with light equivalent to that of a semiconductor laser, and the present invention has been completed.

Furthermore, curing sensitivity can be increased by adding an onium salt to the composition of the present invention.

The present invention provides a near-infrared photosensitive resin composition comprising a combination of a cationically polymerizable organic compound such as epoxy and a near-infrared absorbing compound represented by the general formula (1) or (2). The polymer is polymerized by the light of an infrared laser such as a semiconductor laser or a YAG laser, and a cured product is obtained. Moreover, these compositions are also polymerized by heating to obtain a cured product.

Furthermore, by adding a leuco dye having a lactone ring to the composition of the present invention, a colored cured product can be obtained.

In the general formulas (1) and (2), R1
~R8 are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkynyl group, and R1 and R2, R3 and R4 , R5 and R6 and R7 and R8 may be combined together with N to form a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring. The substituents of R1 to R8 may be the same or different.

For example, halogen atoms include fluorine,
Indicates chlorine, bromine, iodine, etc. For example, alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-
Butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group, etc., and other alkyl groups such as substituted alkyl groups include, for example. , 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, 2-carboxymethyl group, 3-carboxypropyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, 2 - Indicates a chloroethyl group, etc. Examples of alkenyl groups include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups; examples of aralkyl groups include benzyl, p-chlorobenzyl, p-methylbenzyl, and
- Phenylmethyl group, 2-phenylpropyl group, 3-phenylpropyl group, α-naphthylmethyl group, β-naphthylethyl group, etc. Examples of the alkynyl group include propargyl group, butynyl group, bentynyl group, hexynyl group, etc. . Substituted or unsubstituted 5-membered hetero rings include pyrrolidine rings, substituted or unsubstituted 6-membered rings include piperidine rings, morpholine rings, tetrahydropyridine rings, etc., and substituted or unsubstituted 7-membered rings include cyclohexylamine. Tamaki et al.

X- is a non-nucleophilic anion and has the formula MQ
n - (M is B, P, As, Sb, Fe, Al, Sn
, Zn, Ti, Cd, Mo, W, and Zr, preferably B, P, As, and Sb. Q is a halogen atom, and n is a number from 1 to 6. ) can be shown. Preferred anions include BF4 − , P
Examples include F6-, AsF6-, SbF6-, and the like. Particularly preferred is SbF6 − . Moreover, the formula MQn-1 (OH)- (wherein, M, X,
n is the same as above) as an anion represented by SbF5
(OH)- etc.

Other anions include perchlorate ion, trifluoromethyl sulfite ion, fluorosulfonate ion, p-toluenesulfonate ion, trinitrobenzenesulfonate ion, and the like.

General formula (1) or (2) in the present invention
The method for producing the compound shown in is described in U.S. Patent No. 32518
No. 81, U.S. Patent No. 3,484,467, U.S. Patent No. 35
Methods described in JP-A-61-69991 and the like can be used. For example, it can be manufactured as follows.

[0029]

[Chemical formula 9]

After selectively alkylating the amino compound obtained by the above Ullmann reaction and reduction, the final product can be obtained by oxidation.

Next, specific examples of compounds used in general formulas (1) and (2) will be given. For simplicity, the general formula (
1) A, X, (R1 R2 )(
R3 R4 ) (R5 R6 ) (R7 R8 ), the compound represented by general formula (2) is B,
)(R3 R4)(R5 R6)(R7 R8
).

For example, in general formula (1), A is

[0033]

[Chemical formula 10]

When k=1, X- is SbF6-, and R1 to R8 are iso-propyl groups,

[
0035

[Chemical formula 11]

, SbF6 − , (iso-C3 H
It is written as 7 iso-C3 H7 )4.

[0037] Furthermore, in general formula (1), B is

[0038]

[Chemical formula 12]

[0039] When k=1, X- is SbF6-, R1 and R2 are ethyl groups, and R3 to R8 are n-butyl groups,

[0040]

[Chemical formula 13]

, SbF6 − , (n-C4 H9
n-C4 H9 )3 (C2 H5 C2
H5).

[0042]

[Chemical formula 14]

[0043]

[Chemical formula 15]

[0044]

[Chemical formula 16]

[0045]

[Chemical formula 17]

[0046]

[Chemical formula 18]

Examples of the cationic polymerizable organic compound that can be polymerized into a high molecular weight state used in the present invention include epoxy compounds, cyclic ether compounds, cyclic lactone compounds,
Examples include compounds consisting of one type or a mixture of two or more of cyclic acetal compounds, cyclic thioether compounds, spiro-orthoester compounds, and vinyl compounds. Among such cationic polymerizable organic compounds, compounds having at least two or more epoxy groups in one molecule are:
Preferred examples include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

Here, preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A, bisphenol F, or their alkylene oxides. Examples include glycidyl ether resins produced by reaction of adducts with epichlorohydrin.

Preferred examples of the alicyclic epoxy resin include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring or cyclohexene;
Alternatively, examples include cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidizing a cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid. Typical examples of alicyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3
,4-epoxycyclohexanecarboxylate,2
-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, 4
-vinylepoxycyclohexane, methylenebis(3,
4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, and di-2-ethylhexyl epoxyhexahydrophthalate.

Preferred aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. Representative examples include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and diglycidyl ether of polyethylene glycol. Examples include glycidyl ethers and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these, glycidyl esters of higher fatty acids,
Examples include epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, and epoxidized polybutadiene.

Examples of cationically polymerizable organic compounds other than epoxy compounds include trimethylene oxide, 3,3-
Oxetane compounds such as dichloromethyloxetane; oxolane compounds such as tetrahydrofuran, 2,3-dimethyltetrahydrofuran; trioxane, 1,3-
Cyclic acetal compounds such as dioxolane and 1,3,6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone;
Thiirane compounds such as ethylene sulfide, thioepichlorohydrin; 1,3-propylsulfide, 3,
Examples include thietane compounds such as 3-dimethylthietane; and vinyl ether compounds such as ethylene glycol divinyl ether.

These cationic polymerizable compounds can be used alone or in combination of two or more kinds depending on the desired performance.

Particularly preferred among these cationic polymerizable organic compounds are alicyclic epoxy resins having at least two or more epoxy groups in one molecule, which have excellent cationic polymerization reactivity, low viscosity, and ultraviolet transparency. , exhibits good properties in terms of thick film curing, volumetric shrinkage, resolution, etc.

The onium salt used in the present invention is a compound represented by the general formula (1) or (2) that releases Lewis acid salt ions by absorbing near infrared rays and emitting heat, or by simply receiving heat from external heating. It will be done. Such onium salts are classified into three groups: sulfonium salts, ammonium salts and halonium salts.

The sulfonium salt type has the general formula:
[(R9)a (R10)b (R11)c
Z]+m[MQn]-(n-p) (in the formula, R9 is a monovalent aromatic organic group; R10 is a monovalent aliphatic group selected from an alkyl group, a cycloalkyl group, and a substituted alkyl group) is an organic group; R11 is a polyvalent organic group forming a heterocyclic or condensed ring structure selected from aliphatic groups and aromatic groups; Z is a group VIa element selected from sulfur, selenium and tellurium; M is a metal or metalloid that is the central atom of the halide complex
and B, P, As, Sb, Fe, Sn, Bi, Al
, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc.; Q is a halogen atom; a is an integer of 0, 1, 2 or 3; b is an integer of 0, 1 or 2. And ;c
is an integer of 0 or 1; a+b+c is 3 or the valence of Z; m=n-p; p is the valence of M and is an integer from 2 to 7; and n is p is an integer having a value up to 8). Preferably, Z is sulfur, consistent with the designation given herein.

The ammonium salt type has the general formula:
[(R12)d (R13)e (R14)f
Z'] + m [MQn ] - (n-p) (in the formula R12
is a monovalent aromatic organic group selected from carbocyclic groups and heterocyclic groups; R13 is a monovalent aliphatic organic group selected from alkyl groups, alkoxy groups, cycloalkyl groups and substituted derivatives thereof; R14 is a polyvalent organic group that forms an aromatic heterocycle or fused ring structure with Z';Z' is N,
It is a Va group element selected from P, As, Sb and Bi; M is a metal or metalloid which is the central atom of the halide complex, and B, P, A
s, Sb, Fe, Sn, Bi, Al, In, Ti, Zn
, Sc, V, Cr, Mn, Co, etc.; Q is a halogen atom; d is an integer from 0 to 4; e is 0 to 2.
f is an integer from 0 to 2; d+e+f
is the valence of 4 or X; m=n-p; p is the valence of M and is an integer from 2 to 7; and n is greater than p and has a value up to 8 ) is an integer with . Among these, it is preferable that Z' is a nitrogen pyridinium salt. The halonium salt type has the general formula: [(R15)g (R16)h Z'']+m [M
Qn]-(n-p) (in the formula, R15 is a monovalent aromatic organic group; R16 is a divalent aromatic organic group; Z''
is a halogen atom such as I, Br, Cl, etc., and M is a metal or metalloid (me) that is the central atom of the halide complex.
talloid), B, P, As, Sb, Fe
, Sn, Bi, Al, In, Ti, Zn, Sc, V, C
r, Mn, Co, etc.; Q is a halogen atom; g
is an integer of 0 or 2; h is an integer of 0 or 1; g+h is 2 or the valence of X; m=n−p; p is the valence of M, and 2 to 7; and n is an integer greater than p and having a value up to 8). Among these, it is preferable that Z'' is an iodonium salt of iodine. MQn − in the above general formula is a non-nucleophilic anion, and specific examples thereof include tetrafluoroborate ion (
BF4 − ), hexafluorophosphate ion (
PF6 − ), hexafluoroarsenate ion (As
F6 − ), hexafluoroantimonate ion (SbF6 − ), hexachloroantimonate ion (SbCl6 − ), and the like. Furthermore, an anion represented by the general formula MQn-1 (OH)- (M, Q, and n are the same as above) can also be used.

Other anions include perchlorate ion, trifluoromethyl sulfite ion, fluorosulfonate ion, p-toluenesulfonate ion, trinitrobenzenesulfonate ion, and the like.

[0058] Aromatic onium salts are disclosed in Japanese Patent Application Laid-open No. 50-151.
Aromatic halonium salts described in JP-A-50-158680, JP-A-50-151997, JP-A-52-14278, JP-A-52-30899, etc.
JP-A-56-55420, JP-A-55-125105
Aromatic V described in JP-A-56-15261, etc.
Group Ia onium salts, aromatic Va group onium salts described in JP-A-50-151997, etc., JP-A-56-842
No. 8, JP-A-56-149402, JP-A-57-19
Oxosulfoxonium salts described in Publication No. 2429 etc.,
Triarylsulfonium salts and diaryliodonium salts described in JP-A-1-311103, JP-A-1-311103;
Examples include aromatic sulfonium salts or aromatic ammonium salts described in JP-A No. 294088, pyridinium salts described in JP-A-2-43202, etc., but are not limited to these. Specific examples of these include the following. It goes without saying that two or more of these onium salts may be used in combination.

Benzyltetrahydrothiophenium hexafluoroantimonate Benzyltetrahydrothiophenium hexafluoroarsenate Benzyltetrahydrothiophenium hexafluorophosphate Benzyltetrahydrothiophenium tetrafluoroborate Benzyltetrahydrothiophenium perchlorate Benzyltetrahydrothiophenium trifluoromethanesulfonate 2-Methylbenzyltetrahydrothiophenium hexafluoroantimonate 2-Methylbenzyltetrahydrothiophenium hexafluorophosphate 4-Methylbenzyltetrahydrothiophenium hexafluoroantimonate 4- Methylbenzyltetrahydrothiophenium hexafluorophosphate 2-methoxybenzyltetrahydrothiophenium hexafluoroantimonate 2-methoxybenzyltetrahydrothiophenium hexafluoroarsenate 4-methoxybenzyltetrahydrothiophenium hexafluoroantimonate 4-Methoxybenzyltetrahydrothiophenium hexafluoroarsenate 4-Methoxybenzyltetrahydrothiophenium hexafluorophosphate 2-Chlorobenzyltetrahydrothiophenium hexafluoroantimonate 2-Chlorobenzyltetrahydrothiophenium hexafluoro Phosphate 4-chlorobenzyltetrahydrothiophenium hexafluoroantimonate 4-chlorobenzyltetrahydrothiophenium hexafluorophosphate 2-nitrobenzyltetrahydrothiophenium hexafluoroantimonate 2-nitrobenzyltetrahydrothiophenium Hexafluorophosphate 4-nitrobenzyltetrahydrothiophenium hexafluoroantimonate 4-nitrobenzyltetrahydrothiophenium hexafluorophosphate 2-methylbenzyltetrahydro-2H-thiopyranium hexafluorophosphate 4-methylbenzyltetrahydro- 2H-thiopyranium hexafluoroantimonate 2-methoxybenzyltetrahydro-2H-thiopyranium hexafluoroarsenate 4-methoxybenzyltetrahydro-2H-thiopyranium hexafluoroantimonate α,α′-bis[tetrahydrothiophenium]4- Xylylene bishexafluoroantimonate α,α´
-bis[tetrahydro-2H-thiopyranium]4-xylylene bishexafluoroantimonate dimethyl-4-thiophenoxyphenylsulfonium
Hexafluoroantimonate diisopropyl-4-thiophenoxyphenylsulfonium/hexafluoroantimonate bis[4-(dimethylsulfonio)phenyl] sulfide/bishexafluoroantimonate bis[4-(diphenylsulfonio)phenyl] sulfide/bishexa Fluoroantimonate benzyl-4-hydroxyphenylmethylsulfonium ・Hexafluoroantimonate benzyl-4-hydroxyphenylmethylsulfonium ・Hexafluorophosphate benzyl-4-methoxyphenylmethylsulfonium ・
Hexafluoroantimonate brenyltetramethylenesulfonium/hexafluoroantimonate brenyltetramethylenesulfonium/hexafluoroarsenate brenyltetramethylenesulfonium/hexafluorophosphate dimethylbrenylsulfonium/hexafluoroarsenate t-butyltetramethylenesulfonium/ Hexafluoroantimonate 1-benzyl-2-chloropyridinium hexafluoroantimonate 1-benzyl-2-chloropyridinium hexafluoroarsenate 1-benzyl-2-chloropyridinium hexafluorophosphate 1-benzyl-2-chloro Pyridinium tetrafluoroborate 1-benzyl-2-chloropyridinium perchlorate 1-benzyl-2-chloropyridinium trifluoromethanesulfonate 1-(4-methoxybenzyl)-2-chloropyridinium hexafluoroantimonate 1-(4 -Methylbenzyl)-2-cyanopyridinium hexafluoroantimonate 1-benzyl-2-cyanopyridinium hexafluoroantimonate 1-benzyl-2-cyanopyridinium hexafluoroarsenate 1-benzyl-2-cyanopyridinium hexafluoroantimonate Fluorophosphate 1-benzyl-3-cyanopyridinium hexafluoroantimonate 1-benzyl-3-cyanopyridinium hexafluorophosphate 1-benzyl-4-cyanopyridinium hexafluoroantimonate 1-benzyl-4-cyanopyridinium・Hexafluorophosphate 1-benzyl-2-vinylpyridinium ・Hexafluoroantimonate 1-benzyl-4-vinylpyridinium ・Hexafluoroantimonate 1-benzyl-2-styrylpyridinium ・Hexafluoroantimonate 1-benzyl-4- Styrylpyridinium hexafluoroantimonate 1-benzyl-3,5-dichloropyridinium hexafluoroantimonate 1,1'-[1,4-phenylenebis(methylene)]bis-2-cyanopyridinium hexafluoroantimonate 1 -Benzyl-quinolinium hexafluoroantimonate 1-Benzyl-quinolinium hexafluoroantimonate 1-Benzyl-2-chloroquinolinium hexafluoroantimonate 1-Benzyl-2-chloroquinolinium hexafluoroantimonate 1 -(4-methoxybenzyl)-quinolinium hexafluoroantimonate 1-(4-methoxybenzyl)-quinolinium hexafluorophosphate 1-(4-methoxybenzyl)-2-chloroquinolinium hexafluoroantimonate 1 -(4-methoxybenzyl)-2-chloroquinolinium hexafluorophosphate

The lactone ring-containing leuco dye used in the present invention is not particularly limited, but one or more of the compounds exemplified below can be used in combination.

Triphenylmethane leuco dye 3,3-
Bis(p-dimethylaminophenyl)-6-dimethylaminophthalide [also known as crystal violet lactone]

006
2] Fluorane leuco dye 3-diethylamino-6-methyl-7-anilinofluoran 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl- p-toluideino)-6-methyl-
7-anilinofluoran 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluoran 3-pyrrolidino-6-methyl-7-anilinofluoran 3-piperidino-6-methyl-7- Anilinofluorane 3-(N-cyclohexyl-N-methylamino)-6-
Methyl-7-anilinofluoran 3-N,N-dibutylamino-7(o-chloroanilino)anilinofluoran 3-diethylamino-7-(m-trifluoromethylanilino)fluoran 3-(N-ethyl- N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-propylamino)-6-methyl-7-anilinofluoran 3-dibutylamino-6-methyl- 7-(o,p-dimethylanilino)fluoran 3-diethylamino-6-chloro-7-anilinofluoran 3-diethylamino-7-(o-chloroanilino)fluoran 3-dibutylamino-7-(o-chloroanilino) Fluoran 3-diethylamino-6-methylfluoran 3-cyclohexylamino-6-chlorofluoran

Azaphthalide leuco dye 3-(4-diethylamino-2
-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide 3-(4-diethylamino-2-ethoxyphenyl)-
3-(1-ethyl-2-methylindol-3-yl)
-7-Azaphthalide 3-(4-diethylamino-2-ethoxyphenyl)-
3-(1-octyl-2-methylindol-3-yl)-4-azaphthalide 3-(4-N-cyclohexyl-N-methylamino-2
-methoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide 3,3-bis(2-methyl-1-octyl-indol-3-yl)phthalide 3,3- bis(2-methyl-1-ethyl-indole-
3-yl)phthalide

Fluorene-based leuco dye 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide] 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'- Phthalide]

In the near-infrared photosensitive resin composition of the present invention, the compound represented by general formula (1) or (2) that functions as a near-infrared absorbing cationic polymerization initiator is a cationic polymerizable organic compound 100 It is sufficient to add about 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight. At the time of addition, a suitable solvent can be used to dissolve the near-infrared absorbing cationic polymerization initiator in the solvent.

Furthermore, when adding the above-mentioned onium salt, the general formula (
0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight of onium salt to 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight of the compound represented by 1) or (2). Add about parts by weight.

When adding a leuco dye having a lactone ring, 0.0 parts of the compound represented by formula (1) or (2) is added to 100 parts by weight of the cationically polymerizable organic compound.
5 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and 0.05 to 10 parts by weight, preferably 0.1 parts by weight of onium salt.
0 to 5 parts by weight of lactone ring-containing leuco dye
．． 0.01 to 5 parts by weight, preferably about 0.05 to 1 part by weight.

The near-infrared photosensitive resin composition of the present invention includes:
As long as they do not impair the curing of the present invention, various resin additives such as pigments, colorants for paints, antifoaming agents, leveling agents, thickeners, flame retardants, antioxidants, silica, glass, etc. may be added as necessary. Fillers such as powder, ceramic powder, and metal powder, and modifying resins can be mixed and used in appropriate amounts.

The energy source used for curing the near-infrared photosensitive resin composition of the present invention has an output of 10 to 50
A semiconductor laser beam having a power of 0 mW and a wavelength in the range of 600 to 1500 nm and converged by a lens is sufficient, but a semiconductor laser or a YAG laser with an output higher than this may also be used. In addition, when heating, a hot plate, thermostat, hot air, etc. can be used.

As a specific example of the use of the near-infrared photosensitive resin composition of the present invention, in order to form a shaped object, Japanese Patent Laid-Open No. 60-247515 and Japanese Patent Laid-Open No. 2-24121
-As described in JP-A-2-24127, etc., the light guide is moved at a certain distance relative to the curable composition of the present invention housed in a container or discharged from a nozzle. This can be done by irradiating semiconductor laser light necessary for curing through the light guide.

[0071] In addition, it has been difficult to distinguish between the shaped object and the resin composition because they were colorless or transparent with the same color, but by adding a leuco dye having a lactone ring to the near-infrared photosensitive resin composition of the present invention. When the object is irradiated with semiconductor laser light, a colored cured product is obtained, and the formation of the object can be judged by the vivid hue, and in the end, a colorful, hardened object with the desired shape can be obtained. .

Since the near-infrared photosensitive resin composition of the present invention is cured by cationic polymerization by near-infrared rays, depending on the type of cationically polymerizable organic compound used, the composition may have a By heating to about 60°C, the crosslinking reaction can be effectively promoted, and furthermore, by post-curing the obtained model at a temperature of 50 to 150°C, it can have even better mechanical strength. It is possible to obtain a modeled object.

[0073]

[Action] The near-infrared photosensitive resin composition of the present invention has a 700%
By irradiation or heating with near-infrared rays of ~1500 nm,
Provides a durable cured product that is stable to heat and light. These mechanisms are thought to be as follows. Irradiation with near-infrared rays or heating causes the compound represented by the general formula (1) or (2) to dissociate, and the resulting Lewis acid salt ions polymerize and harden the cationically polymerizable organic compound. Furthermore, when an onium salt is added, the general formula (1) or (2) absorbs near-infrared rays when irradiated with near-infrared rays, and the onium salt decomposes due to the heat released, and the resulting Lewis acid salt ions and The compound represented by formula (1) or (2) is dissociated, and the resulting Lewis acid salt ions cooperate with each other to polymerize and harden the cationically polymerizable organic compound, resulting in improved curing sensitivity. Furthermore, when a leuco dye having a lactone ring is added, Lewis acid salt ions generated by near-infrared irradiation open the lactone ring and develop color. The lactone ring becomes a free carboxylic acid, and this carboxylic acid reacts with a cationic polymerizable organic compound, and the colored leuco dye is incorporated into the polymer, giving a durable colored cured product that is stable to heat and light. . The composition is similarly polymerized and cured by heating. EXAMPLES Hereinafter, the effectiveness of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

[0074]

【Example】

[Example 1] 3,4- as a cationic polymerizable organic compound
Bis(p-di-n-butylaminophenyl)[N,N-bis(p-di-n −
A near-infrared photosensitive resin composition of the present invention was obtained by mixing and dissolving 3 parts of (butylaminophenyl)-p-aminophenyl]aminium hexafluoroantimonate.

This near-infrared photosensitive resin composition was placed in a container 11 of a photocurable three-dimensional object system shown in FIG. A semiconductor laser (output: 150 mW, wavelength: 810 nm) is guided through the optical fiber 16, and the X-Y moving device 17 is controlled by the computer to shape the horizontal cross-section of the target object, and the light is emitted from the light emitting section 15. The composition is irradiated with the light flux 14 through the light-transmitting window 13, and the composition between the base and the light-transmitting window is cured. Next, take the base 1 with the cured product in the elevator 20.
3 is slightly raised to allow the composition to newly flow between the cured product and the light-transmitting window. By repeating this operation, from the above resin composition, the bottom diameter was 20 mm, the height was 10 mm, and the thickness was 0.2 mm.
mmm A cup-shaped object was produced. This model was free from distortion and took 120 minutes to build.

[Comparative Example 1] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
100 parts of epoxycyclohexane carboxylate,
Cyanine compound NK-201 as near-infrared absorption dye
4 (manufactured by Nippon Kanko Shiki Kenkyusho Co., Ltd.) were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

[0077] Although an attempt was made to cure the above composition in the same manner as in Example 1 using the photocurable three-dimensional shaped object system shown in FIG. 1, it was not possible to create a shaped object.

[Comparative Example 2] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
100 parts of epoxycyclohexane carboxylate,
, polymethine compound IR-8 as a near-infrared absorbing dye
20 (manufactured by Nippon Kayaku Co., Ltd.) were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

[0079] An attempt was made to cure the above composition in the same manner as in Example 1 using the photo-curable three-dimensional shaped object system shown in FIG. 1, but it was not possible to create a shaped object.

[Comparative Example 3] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
100 parts of epoxycyclohexane carboxylate,
Pyrylium compound NK-30 as a near-infrared absorption dye
27 (manufactured by Nippon Kanko Shiki Kenkyusho Co., Ltd.) were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

An attempt was made to cure the above composition in the same manner as in Example 1 using the photocurable three-dimensional object system shown in FIG. 1, but no object could be created.

[Example 2] 80 parts of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6'-cyclohexanecarboxylate and 1,4-butanediol diglycidyl as cationically polymerizable organic compounds 20 parts of ether, bis(p-di-n-butylaminophenyl) as a near-infrared absorbing cationic polymerization initiator
A near-infrared photosensitive resin composition of the present invention was obtained by mixing and dissolving 1 part of [N,N-bis(p-di-n-butylaminophenyl)-p-aminophenyl]aminium hexafluoroantimonate. .

Using the photocurable three-dimensional object system shown in FIG. 1, a cup-shaped product with a bottom diameter of 10 mm, a height of 5 mm, and a thickness of 0.2 mm was prepared from the resin composition in the same manner as in Example 1. Created a sculpture. This model has no distortion,
The molding time was 180 minutes.

[Example 3] 60 parts of vinyl cyclohexene oxide, 20 parts of bisphenol A diglycidyl ether, 20 parts of triethylene glycol divinyl ether as a cationically polymerizable organic compound, and bis(p) as a near-infrared absorbing cationic polymerization initiator. -di-n-butylaminophenyl)[N,N-bis(p-di-n-butylaminophenyl)-4'-aminobiphenyl]aminium hexafluoroantimonate is mixed and dissolved in the present invention. A near-infrared photosensitive resin composition was obtained.

[0085] Using the photocurable three-dimensional object system shown in Fig. 1, a bottom diameter of 10 mm, a height of 10 mm, and a thickness of 0.2 mm were prepared from the above resin composition in the same manner as in Example 1.
A cup-shaped object was created. This model was free from distortion and took 120 minutes to build.

[Example 4] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
80 parts of epoxycyclohexane carboxylate, 1
, 20 parts of 4-butanediol diglycidyl ether, bis(p-di-
1 part of aminium hexafluoroantimonate,
A near-infrared photosensitive resin composition of the present invention was obtained by mixing and dissolving 2 parts of brenyltetramethylenesulfonium hexafluoroantimonate as an onium salt.

[0087] Using the photocurable three-dimensional object system shown in Fig. 1, a bottom diameter of 20 mm, a height of 12 mm, and a thickness of 0.2 mm were prepared from the resin composition in the same manner as in Example 1.
A cup-shaped object was created. This model was free from distortion and took 90 minutes to build.

[Comparative Example 4] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
80 parts of epoxycyclohexane carboxylate, 1
, 20 parts of 4-butanediol diglycidyl ether, cyanine compound NK-2014 as a near-infrared absorption dye
(manufactured by Nippon Kanko Shiki Kenkyusho Co., Ltd.) and 2 parts of brenyltetramethylenesulfonium hexafluoroantimonate as an onium salt were mixed and dissolved to obtain a near-infrared-sensitive resin composition of the present invention.

An attempt was made to produce a cup-shaped object similar to that in the example from the above composition using the photocurable three-dimensional object system shown in FIG. Because of the inferior quality, it was not possible to create the desired object.

[Example 5] 80 parts of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6'-methylcyclohexanecarboxylate and 20 parts of bisphenol A diglycidyl ether as cationic polymerizable organic compounds. , bis(p-di-n-butylaminophenyl) as a near-infrared absorbing cationic polymerization initiator.
1 part of [N,N-bis(p-di-n-butylaminophenyl)-p-aminophenyl]aminium hexafluoroantimonate, 4-methoxybenzyl-2-cyanopyridinium hexafluoroantimonate as onium salt Two parts were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional object system shown in FIG. 1, a bottom diameter of 20 mm, a height of 10 mm, and a thickness of 0.2 mm were prepared from the resin composition in the same manner as in Example 1.
A cup-shaped object was created. This model was free from distortion and took 90 minutes to build.

[Example 6] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
80 parts of epoxycyclohexane carboxylate, 20 parts of bisphenol A diglycidyl ether, N,N,N',N'- as a near-infrared absorbing cationic polymerization initiator
Tetrakis(p-di-n-butylaminophenyl)-
Three parts of p-benzoquinone-bis(immonium hexafluoroantimonate) were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

[0093] The semiconductor laser in Fig. 1 (output 150 mW,
Instead of YAG laser (wavelength 810 nm), YAG laser (output 8
Example 1 was prepared from the above resin composition using a photocurable three-dimensional structure system using
In the same manner as above, a cup-shaped object with a bottom diameter of 20 mm, a height of 10 mm, and a thickness of 0.5 mm was created. This model was free from distortion and took 50 minutes to build.

[Example 7] As cationically polymerizable organic compounds, 50 parts of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6'-methylcyclohexanecarboxylate, 30 parts of vinylcyclohexene oxide, 1 , 20 parts of 4-butanediol diglycidyl ether, N,N,N',N'-tetrakis(p-di-n-butylaminophenyl)-p-benzoquinone-bis( as a near-infrared absorbing cationic polymerization initiator)
A near-infrared sensitive composition of the present invention was obtained by mixing and dissolving 1 part of immonium hexafluoroantimonate. Using the photocurable three-dimensional object system shown in Example 6, a cup-shaped object with a bottom diameter of 10 mm, a height of 10 mm, and a thickness of 0.5 mm was produced from the resin composition in the same manner as in Example 1. It was created. This model was free from distortion and took 60 minutes to build.

[Example 8] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
80 parts of epoxycyclohexane carboxylate, 1
, 20 parts of 4-butanediol diglycidyl ether, N, N, N' as a near-infrared absorbing cationic polymerization initiator,
1 part of N'-tetrakis(p-di-n-butylaminophenyl)-p-benzoquinone-bis(immonium hexafluoroantimonate), 2 parts of brenyltetramethylenesulfonium hexafluoroantimonate as an onium salt By mixing and dissolving, a near-infrared sensitive composition of the present invention was obtained.

Using the photocurable three-dimensional object system shown in Example 6, a bottom diameter of 20 mm, a height of 15 mm, and a thickness of 0.5 mm were prepared from the resin composition in the same manner as in Example 1.
A cup-shaped object with a diameter of mm was created. This model was free of distortion and took 40 minutes to build.

[Example 9] 3,4-epoxycyclohexylmethyl-3,4- as a cationically polymerizable organic compound
80 parts of epoxycyclohexane carboxylate, 1
, 20 parts of 4-butanediol diglycidyl ether, bis(p-di-
1 part of aminium hexafluoroantimonate,
The near-infrared photosensitive resin composition of the present invention is prepared by mixing and dissolving 2 parts of brenyltetramethylenesulfonium hexafluoroantimonate as an onium salt and 0.5 part of crystal violet lactone as a leuco dye having a lactone ring. Obtained.

Using the photocurable three-dimensional object system shown in FIG. 1, a bottom diameter of 20 mm, a height of 12 mm, and a thickness of 0.2 mm were prepared from the resin composition in the same manner as in Example 1.
A blue-purple cup-shaped object was created. This model was free from distortion and took 120 minutes to build.

[Example 10] 3,4-epoxycyclohexylmethyl-3,4 as a cationically polymerizable organic compound
- 80 parts of epoxycyclohexane carboxylate,
20 parts of bisphenol A diglycidyl ether, N, N, N', N' as a near-infrared absorbing cationic polymerization initiator
-tetrakis(p-di-n-butylaminophenyl)
-p-benzoquinone- 1 part of bis(immonium hexafluoroantimonate), 4 parts as onium salt
- Methoxybenzyl-2-cyanopyridinium hexafluoroantimonate (3 parts), 3,3-bis(2-methyl-1-octyl-
Mix and dissolve 1 part of indol-3-yl) phthalide,
A near-infrared photosensitive resin composition of the present invention was obtained.

[0100] Using the photocurable three-dimensional object system shown in Fig. 1, a bottom diameter of 10 mm, a height of 10 mm, and a thickness of 0.2 mm were prepared from the resin composition in the same manner as in Example 1.
A red cup-shaped object was created. This model was free from distortion and took 120 minutes to build.

[Example 11] 50 parts of 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6'-methylcyclohexanecarboxylate and 30 parts of bisphenol A diglycidyl ether as cationically polymerizable organic compounds. , 20 parts of triethylene glycol divinyl ether, bis(p-di-n-butylaminophenyl) [as a near-infrared absorbing cationic polymerization initiator]
N,N-bis(p-di-n-butylaminophenyl)
-p-aminophenyl] 1 part of aminium hexafluoroantimonate, 3 parts of 4-methoxybenzyltetrahydrothiophenium hexafluoroantimonate as an onium salt, 3-diethylamino-6-methyl- as a leuco dye with a lactone ring A near-infrared photosensitive resin composition of the present invention was obtained by mixing and dissolving 0.8 part of 7-anilinofluorane.

[0102] Using the photocurable three-dimensional object system shown in Fig. 1, a black colored material with a bottom diameter of 10 mm, a height of 8 mm, and a thickness of 0.2 mm was prepared from the above resin composition in the same manner as in Example 1. A cup-shaped object was created. This model was free from distortion and took 120 minutes to build.

[Examples 12 to 12] The compositions of Examples 1 and 6 were thermally cured at 180°C. Furthermore, in place of the near-infrared absorbing cationic polymerization initiator in Example 1, bis(p-di-n-butylaminophenyl) was used in Example 9.
In Example 10, [N,N-bis(p-di-n-butylaminophenyl)-p-aminophenyl]aminium perchlorate was used instead of the near-infrared absorbing cationic polymerization initiator in Example 6. N,N,N',N'-tetrakis(p-di-n-butylaminophenyl)-p-
Heat curing was performed in the same manner using benzoquinone-bis(immonium perchlorate) for comparison. The results are shown in Table 1.

Similarly, the compositions of Comparative Examples 1 to 3 were
Heat curing was performed at 80°C.

[0105]

[Table 1]

[0106] The best sensitivity in thermosetting was obtained when diimmonium type (SbF6 - ) was used. Further, the curing sensitivity was influenced by the type of counter anion, and SbF6 − >ClO4 −.

The compositions of Comparative Examples 1 to 3 were thermally cured at 180°C, and cyanine-based NK-2014, polymethine-based IR-820, and pyrylium-based NK-302
When near-infrared absorbing dye No. 7 was used, it was not thermally cured.

[0108]

ADVANTAGEOUS EFFECTS OF THE INVENTION An advantage of the present invention is that it provides a near-infrared photosensitive resin composition that can be cured by near-infrared irradiation. In particular, the near-infrared photosensitive resin composition of the present invention enables three-dimensional curing molding using a semiconductor laser, which has not been possible until now. As a result, in the future, it will become possible to realize an inexpensive three-dimensional model production device using a semiconductor laser in the field of three-dimensional modeling.

In addition, we have provided a new near-infrared absorbing cationic polymerization initiator for near-infrared photosensitive resin compositions; one compound absorbs near-infrared rays, further generates cations, and generates cations. It has become possible to polymerize and cure polymerizable organic compounds.

Furthermore, when a near-infrared photosensitive resin composition containing a lactone ring-containing leuco dye is irradiated with near-infrared rays, it is possible to clearly see the start and completion of curing without physically touching it. It became possible to obtain a colored cured product with a unique hue.

[Brief explanation of drawings]

FIG. 1 is a configuration diagram of an apparatus for implementing an optical modeling method. DESCRIPTION OF SYMBOLS 1... Container, 2... Near-infrared photosensitive resin composition, 3... Translucent window, 4... Luminous flux, 5... Light emitting part, 6... Optical fiber, 7... X
-Y moving device, 8... light source, 9... base, 10... elevator, 11... computer, 12... cured product.

Claims (5)

[Claims] Claim 1: A cationic polymerizable organic compound and the following general formula (
A near-infrared photosensitive resin composition that contains a compound represented by 1) or (2) as a main component and is cured by near-infrared irradiation or heating. [Formula 1] [Formula 2] (wherein A is [Formula 3] B is [Formula 4] [k is 1 or 2], and the aromatic ring is a lower alkyl group, a lower alkoxy group, a halogen atom, or a hydroxyl group. R1 to R8 are hydrogen atoms,
A halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkynyl group, R1 and R2, R3 and R4, R5 and R6
The combination of R7 and R8 together with N may form a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring. R1 ~
The substituents for R8 may be the same or different. X- is a non-nucleophilic anion and can be represented by the formula MQn-. M is B, P, As, Sb, Fe, Al
, Sn, Zn, Ti, Cd, Mo, W, and Zr, preferably B, P, As, and Sb. Q is a halogen atom, n is a number from 1 to 6). Claim 2: A cationic polymerizable organic compound and the general formula (
A near-infrared photosensitive resin composition which contains a compound represented by (1) or (2) and an onium salt as main components and is cured by near-infrared irradiation or heating. 3. A cured product obtained by curing the near-infrared photosensitive resin composition of claim 1 or the near-infrared photosensitive resin composition of claim 2 by near-infrared irradiation or heating. 4. An optically shaped article obtained by curing the near-infrared photosensitive resin composition of claim 1 or the near-infrared photosensitive resin composition of claim 2 by irradiating it with semiconductor laser light. 5. A colored cured product comprising the near-infrared photosensitive resin composition of claim 2 and a leuco dye having a lactone ring as main components, which is colored and cured by irradiation with semiconductor laser light.