JP2007262401A - Active energy ray-curable resin composition for optical stereolithography and optical stereolithography product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition for optical stereolithography, which does not include poisonous metals and has excellent storage stability; and also to provide an optical stereolithography product. <P>SOLUTION: The active energy ray-curable resin composition for an optical stereolithography comprises a cationic polymerization initiator (1) and a cation polymerizable compound as essential components, wherein the initiator (1) is an onium fluorinated alkyl fluorophosphoric acid salt represented by formula (3). In the formula: A is an element of atomic valence m belonging to groups VIA-VIIA; m=1-2; n=0-3; R is an organic group; D is represented by formula (4); E is a divalent group; G is -O-, -S-, -SO-, -SO<SB>2</SB>-, -NH-, -NR'-, -CO-, -COO-, -CONH- and 1-3C alkylene or phenylene; a=0-5; X<SP>-</SP>is represented by formula (5); and Rf represents an alkyl whose 80% of H atoms are substituted with fluorine atoms; and b=1-5. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable resin composition for optical three-dimensional modeling using a specific onium fluorinated alkyl fluorophosphate as an active energy ray cationic polymerization initiator, and an optically shaped article obtained by curing the resin composition About.

  Optics that form a three-dimensional object in which the cured resin layer is integrally laminated by repeating the process of selectively irradiating the active energy ray-curable liquid composition with active energy rays to form a cured resin layer. Three-dimensional modeling methods are known (see Patent Documents 1 to 4). A typical example of this optical three-dimensional modeling method will be described. By selectively irradiating the active energy ray curable liquid resin composition contained in a container with an active energy ray such as an ultraviolet laser. Then, a cured resin layer having a predetermined pattern is formed. Next, a single layer of an active energy ray-curable liquid resin composition is supplied onto the cured resin layer, and the liquid surface is selectively irradiated with active energy rays to form a cured resin layer formed in advance. A new cured resin layer is integrally laminated so as to be continuous therewith. Then, by repeating the above process a predetermined number of times while changing or not changing the pattern irradiated with the active energy rays, a three-dimensional object formed by integrally laminating a plurality of cured resin layers is formed. This optical three-dimensional modeling method can be obtained easily and in a short time even if the target three-dimensional object has a complicated shape. This technology is extremely useful in the trial production process of new product development in the automobile and home appliance industries, and is becoming an indispensable means for shortening the development period and reducing costs.

Conventionally, as the active energy ray-curable composition used in the optical three-dimensional modeling method, the cationically polymerizable compound such as the following (1) and (2), which is excellent in modeling accuracy and mechanical properties of the obtained model A composition containing as a main component is known.
(1) A resin composition containing a cationically polymerizable compound such as an epoxy compound, a cyclic ether compound, a cyclic lactone compound, or a vinyl ether compound (see Patent Document 5).
(2) A resin composition containing a cationically polymerizable compound and a radically polymerizable compound (see Patent Documents 6 to 11).
In these compositions, a cationic polymerization initiator that decomposes by active energy rays to generate a cationic species is used as an essential component, and has an initial strength (green strength) after photocuring and SbF ₆ ⁻ that has a high modeling speed. Onium salt is used.
The polymerization initiation ability of the onium salt is different in the kind of counter ^{_{anion, BF 4 - <PF 6 -}} <AsF 6 - <SbF 6 - in becomes better in order, good polymerization initiation ability AsF ₆ ^-, SbF ₆ ^- onium salts of Or since the composition containing it contains the toxic metals As and Sb, there is a concern about its handling and environmental impact.
On the other hand, PF ₆ ^- In the onium salt, for example, SbF ₆ ^- and to obtain the same degree of physical properties of the cured product must be added in an amount 10 times more of the latter, the unreacted amount of addition is increased initiator, initiator As the residual amount of solvent or initiator decomposition products used to dissolve the agent increases, the mechanical strength of the stereolithography decreases, and the absorption of active energy rays by the onium salt itself is large. Therefore, there is a problem that a necessary curing depth cannot be obtained.

Thus free of toxic metals, SbF ₆ ^- composition having a stereolithography resin composition comparable or better performance with salt as a cationic polymerization initiator has been desired.
JP 60-247515 A JP-A-62-35966 JP 62-101408 A Japanese Patent Laid-Open No. 5-24119 JP-A-1-213304 JP-A-2-28261 Japanese Patent Laid-Open No. 2-75618 JP-A-6-228413 Japanese Patent Laid-Open No. 11-310626 JP 11-228610 A JP-A-11-240939

The present invention relates to an active energy ray-curable resin composition for optical three-dimensional modeling, which does not contain a toxic metal, has good storage stability, is excellent in mechanical properties of the obtained optical modeling object, and has high transparency. An object of the present invention is to provide an optically shaped object obtained by curing

As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the active energy ray-curable resin composition for optical three-dimensional modeling comprises the cationic polymerization initiator (1) and the cationic polymerizable compound (2) as essential components. The active energy ray-curable resin composition for optical three-dimensional modeling characterized in that (1) is an onium fluorinated alkyl fluorophosphate represented by the following general formula (3): The present invention has been reached by finding out that it satisfies the requirements.

[In the formula (3), A is an element having a valence m of VIA group to VIIA group. m = 1-2. n = 0-3. R is an organic group bonded to A. D is the following general formula (4)

[In the formula (4), E represents a divalent group, G represents —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO] -, -CONH, an alkylene or phenylene group having 1 to 3 carbon atoms. a = 0-5. Is a structure represented by
X ⁻ represents the following general formula (5)

[Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b = 1-5. ] The fluorinated alkyl fluorophosphate anion represented by this. ]

The active energy ray-curable resin composition for optical three-dimensional modeling of the present invention does not contain a toxic metal such as arsenic and antimony, has good storage stability, good modeling accuracy, excellent mechanical properties, and transparency. High stereolithography can be obtained.
The application field of the composition of the present invention is not particularly limited, but as a typical application field, a model for verifying the appearance design in the middle of the design, a model for checking the functionality of the part, and a mold are manufactured. Resin molds, base models for producing molds, direct molds for prototype molds, and the like. In particular, the resin composition for stereolithography can exhibit power in producing a model of a precise part. More specifically, for example, design models and working models such as precision parts, electrical / electronic parts, furniture, building structures, automobile parts, various containers, castings, mother molds, machining applications, surgical simulations, etc. It can be effectively used for medical applications such as orthodontics, microparts, nanotechnology, functional parts such as functional parts.

In the formula (3) representing the cationic polymerization initiator (1) of the composition of the present invention, A represents an element of VIA group to VIIA group (CAS notation) and is bonded to organic groups R and D to form an onium [A ⁺ ] Is formed. Among the elements of Group VIA to VIIA, preferred are S, I and Se, which are excellent in cationic polymerization initiating ability, and particularly preferred are S and I. m represents the valence of the element A and is 1 or 2.

R is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, It may be substituted with at least one selected from the group consisting of alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and halogen. The number of R is m + n (m−1) +1, and may be the same as or different from each other. In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, carbon number A ring structure containing element A may be formed by bonding via 1 to 3 alkylene or phenylene groups. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

  In the above, the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as phenyl groups and condensed naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone, etc. And a polycyclic aryl group.

  Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 hetero atoms such as oxygen, nitrogen and sulfur, which may be the same or different. Are monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl , Carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl, It is below.

  Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like, isopropyl, isobutyl, sec-butyl, tert-butyl, Branched alkyl groups such as isopentyl, neopentyl, tert-pentyl, isohexyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl, naphthylmethyl, anthracenylmethyl, 1-phenylethyl, 2-phenylethyl Aralkyl groups. Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, and 1-methyl-2- Propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, Linear or branched such as 3-methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 1-decenyl, 2-decenyl, 8-decenyl, 1-dodecenyl, 2-dodecenyl, 10-dodecenyl Cycloalkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl, and arylalkenyl groups such as styryl and cinnamyl. It is. Further, examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2 Linear or branched such as -propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-decynyl, 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl, 10-dodecynyl Or arylalkynyl groups such as phenylethynyl.

  The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms is at least 1 The alkyl group may have various substituents, and examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, okdadecyl, and the like. Branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl; cycloalkyl having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl Group; hydroxy group; methoxy, ethoxy, propoxy, isopropoxy, butoxy , Isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, etc., a straight or branched alkoxy group having 1 to 18 carbon atoms; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbuta Straight chain or branched alkylcarbonyl groups having 2 to 18 carbon atoms such as noyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl and octadecanoyl; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; methoxycarbonyl, Ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl A linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms such as octadecyloxycarbonyl; an aryloxycarbonyl group having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; a carbon number such as phenylthiocarbonyl and naphthoxythiocarbonyl 7-11 arylthiocarbonyl groups; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyl Straight chain or branched acyloxy groups having 2 to 19 carbon atoms such as oxy and octadecylcarbonyloxy; phenylthio, 2-methylphenylthio, 3-methylphenylthio 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenyl Thio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] Phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4- Benzoyl -Chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methyl) Arylthio groups having 6 to 20 carbon atoms such as benzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio; methylthio, ethylthio, propylthio, Linear or branched alkylthio group having 1 to 18 carbon atoms such as isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio Aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl , Carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl and the like, a phenoxy, naphthyloxy Aryloxy groups having 6 to 10 carbon atoms such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropyls Linear or branched alkylsulfinyl having 1 to 18 carbon atoms such as rufinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl Groups: phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl and the like arylsulfinyl groups having 6 to 10 carbon atoms; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentyl Sulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl Throat linear or branched alkylsulfonyl group having 1 to 18 carbon atoms; phenylsulfonyl, tolylsulfonyl (tosyl group), an arylsulfonyl group having 6 to 10 carbon atoms such as naphthylsulfonyl;

  An alkyleneoxy group represented by the general formula (9) (Q represents a hydrogen atom or a methyl group, k is an integer of 1 to 5); an unsubstituted amino group and an alkyl having 1 to 5 carbon atoms and / or a carbon number; Amino group mono- or di-substituted with 6 to 10 aryl (specific examples of alkyl groups having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl; isopropyl, isobutyl, Branched alkyl groups such as sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, etc., and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, etc. Specific examples of aryl groups having 6 to 10 carbon atoms include phenyl Cyano group; nitro group; halogen such as fluorine, chlorine, bromine, iodine, etc. It is below.

The two or more R may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '- (R' is an alkyl group or a carbon number of 1 to 5 carbon atoms An aryl group having 6 to 10. Specific examples of the alkyl group having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, etc., isopropyl, isobutyl, sec-butyl, tert-butyl, Branched alkyl groups such as isopentyl, neopentyl, tert-pentyl, etc .; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, etc. Specific examples of aryl groups having 6 to 10 carbon atoms include phenyl, naphthyl and the like), Examples of ring structures containing element A by bonding through —CO—, —COO—, —CONH—, C 1-3 alkylene or phenylene group include the following: Door can be.

[A is an element of VIA group to VIIA group (CAS notation), L is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—,
-CO-, -COO-, -CONH- are represented. R ′ is the same as described above. ]

  In the formula (3), m + n (m−1) +1 R bonded to the element A of the valence m group VIA to VIIA (CAS notation) may be the same or different, At least one of R, more preferably all of R is an aryl having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, which may have the substituent.

D in the formula (3) is represented by the structure of the following formula (4),

  E in the formula (4) is a linear, branched or cyclic alkylene group having 1 to 8 carbon atoms such as methylene, ethylene and propylene; arylene having 6 to 20 carbon atoms such as phenylene, xylylene, naphthylene, biphenylene and anthracenylene. Groups: 8 carbon atoms such as dibenzofurandiyl, dibenzothiophenediyl, xanthenediyl, phenoxathiindiyl, thianthrangeyl, bithiophenediyl, bifuranyl, thioxanthonediyl, xanthonediyl, carbazolediyl, acridinediyl, phenothiazinediyl, phenazinediyl Represents a divalent group of ˜20 heterocyclic compounds. Here, the divalent group of the heterocyclic compound refers to a divalent group formed by removing one hydrogen atom from two different ring carbon atoms of the heterocyclic compound.

  The alkylene group, arylene group or divalent group of the heterocyclic compound may have at least one substituent, and specific examples of the substituent include carbon such as methyl, ethyl, propyl, butyl, pentyl, octyl and the like. A linear alkyl group having 1 to 8 carbon atoms; a branched alkyl group having 1 to 8 carbon atoms such as isopropyl, isobutyl, sec-butyl and tert-butyl; a cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl and cyclohexyl; Alkoxy groups having 1 to 8 carbon atoms such as ethoxy, propoxy, butoxy, hexyloxy; aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl; hydroxy groups; cyano groups; nitro groups or fluorine, chlorine, bromine, iodine, etc. Halogen is mentioned.

G in the formula (4) is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′— (R ′ is the same as above), —CO—, —COO—, —CONH— represents an alkylene or phenylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms include linear or branched alkylene groups such as methylene, ethylene and propylene.

  A in Formula (4) is an integer of 0-5. a + 1 E and a G may be the same as or different from each other.

A typical example of D represented by the formula (4) is shown below.
When a = 0

When a = 1

When a = 2

When a = 3

  Of these D, the following groups are particularly preferred.

N in the formula (3) represents the number of repeating units of the [D-A ⁺ Rm _- 1] bond, and is an integer of 0 to 3, preferably 0 or 1.

Preferred examples of the onium ion [A ⁺ ] in the formula (3) are sulfonium, iodonium, and selenium, and typical examples thereof include the following.

  Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluorophenyl). ) Sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium, 4 -(4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) phenylbis ( 4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio } Phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4- Methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- ( 4-Benzoylphenylthio) phenylbis (4-fluorophenyl) sulfur 4-, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo -10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4- tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio)] phenyldi-p-tolylsulfonium , 4- [4- (Benzoylphenylthio)] phenyldiphenyl Sulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2,4,6-trimethyl) Triarylsulfonium such as phenyl) thiaanthrhenium; diarylsulfonium such as diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4 -Methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthy Rumethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphena Monoarylsulfonium such as silsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethyl Examples include trialkylsulfonium such as phenacylsulfonium, and these are described in the following literature. It has been mounting.

Regarding triarylsulfonium, U.S. Pat. No. 4,231,951, U.S. Pat. No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922, JP-A-8- 27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, JP-A-10-287463. JP-A-10-245378, JP-A-8-157510, JP-A-10-204083, JP-A-8-245656, JP-A-8-157451, JP-A-7-324069, JP-A-9-268205. JP, 9-278935, JP 2001-288205, JP 11-80118, JP JP-A-10-182825, JP-A-10-330353, JP-A-10-152495, JP-A-5-239213, JP-A-7-333834, JP-A-9-12537, JP-A-8-325259, JP-A-8-160606. JP, 2000-186071 (U.S. Pat. No. 6,368,769), JP 2005-263696, etc . ; with respect to diarylsulfonium , JP-A-7-300504 , JP-A-64-45357 , JP-A- 64-29419 Monoarylsulfonium is disclosed in JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6,097,753), JP-A-2-196812, and JP-A-2-1470. JP-A-2-196812, JP-A-3-237107, JP-A-3-1 No. 101, JP-A-6-228086, JP-A-10-152469, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; For trialkylsulfonium, JP-A-4-308563, JP 5-140210, JP 5-140209, JP 5-230189, JP 6-271532, JP 58-37003, JP 2-178303, JP 10-338688, JP-A-9-328506, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, US Patent 6031014 etc. are mentioned.

  Examples of the iodonium ions include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxyphenyl). ) Iodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, etc., which are listed in Macromolecules, 10, 1307 ( 1977), JP-A-6-184170, US Pat. No. 4,256,828, US Pat. No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117, JP-A-2001-139539. No., special No. 2000-510516, disclosed in such as JP-2000-119306.

  Examples of selenium ions include triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium, tri-1- Triphenyl selenium such as naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyldiphenyl selenium, 4- (p-tolylthio) phenyldi-p-tolyl selenium; diphenylphenacyl Diaryl selenium such as selenium, diphenylbenzyl selenium, diphenylmethyl selenium; phenylmethylbenzyl selenium, 4-hydroxyphenylmethylbenzyl selenium, phenylmethyl Monoaryl selenium such as phenacyl selenium, 4-hydroxyphenylmethyl phenacyl selenium, 4-methoxyphenyl methyl phenacyl selenium; dimethyl phenacyl selenium, phenacyl tetrahydroselenophenium, dimethylbenzyl selenium, benzyl tetrahydroselenophenium, octadecyl Examples thereof include trialkyl selenium such as methylphenacyl selenium, and these are described in JP-A-50-151997, JP-A-50-151976, JP-A-53-22597, and the like.

  Of these oniums, preferred are sulfonium and iodonium, and particularly preferred are triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl. Sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl) 2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2- Ildi-p-tolylsulfonium, -Isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenyl Thiaanthrhenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium Sulfonium ions such as sodium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) Examples include iodonium ions such as phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium.

In Formula (3), X ⁻ is a counter ion. The number thereof is n + 1 per molecule, at least one of which is a fluorinated alkylfluorophosphate anion represented by the formula (5), and the rest may be other anions.
As the other anion, any conventionally known anion may be used. For example, halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ and ClSO ₃ ⁻ Sulfonic acid ions such as CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ and CF ₃ SO ₃ ⁻ ; sulfate ions such as HSO ₄ ⁻ and SO ₄ ²⁻ ; HCO ₃ ⁻ , CO ₃ ²⁻ , Carbonate ions such as: phosphate ions such as H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ , PO ₄ ³⁻ ; fluorophosphate ions such as PF ₆ ⁻ and PF ₅ OH ⁻ ; BF ₄ ⁻ , B ( Borate ions such as C ₆ F ₅ ) ₄ ⁻ and B (C ₆ H ₄ CF ₃ ) ₄ ^— ; AlCl ₄ ⁻ ; BiF ₆ ^{− and the} like. Other examples include fluoroantimonate ions such as SbF ₆ ⁻ and SbF ₅ OH ^−, and fluoroarsenate ions such as AsF ₆ ⁻ and AsF ₅ OH ⁻ , which are not preferable because they contain toxic elements. .

  In the fluorinated alkyl fluorophosphate anion represented by the formula (5), Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl; and cyclopropyl, cyclobutyl, cyclopentyl, Examples thereof include a cycloalkyl group such as cyclohexyl, and the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the fluorine atom substitution rate is less than 80%, the cationic polymerization initiating ability of the onium salt and transition metal complex salt of the present invention decreases.

Particularly preferred Rf is a linear or branched alkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, and (CF ₃ ) ₃ C.

  In the formula (5), the number b of Rf is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3. The b Rf's may be the same or different.

Specific examples of preferred fluorinated alkyl fluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [ ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ and [( CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , of which [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ and [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ Particularly preferred.

The cationic polymerization initiator (1) used in the present invention may be used alone or in combination of two or more. Moreover, you may use together with another conventionally well-known cationic polymerization initiator. Examples of other cationic initiators include onium ions such as sulfonium, iodonium, selenium, ammonium, phosphonium or salts of transition metal complex ions and various anions. Examples of anions include F ⁻ , Cl ⁻ , Br ⁻ , Halogen ions such as I ⁻ ; sulfonate ions such as OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ ; HSO ₄ ^-, SO ₄ sulfate ions such as _{^{2-; HCO 3 -, CO 3}} 2-, carbonate ions such ^{_{as; H 2 PO 4 -, HPO}} 4 2-, phosphate ions such as PO ₄ ^3-; PF Fluorophosphate ions such as ₆ ⁻ and PF ₅ OH ⁻ ; Borate ions such as BF ₄ ⁻ and B (C ₆ F ₅ ) ₄ ⁻ and B (C ₆ H ₄ CF ₃ ) ₄ ⁻ ; AlCl ₄ ^{− _{; BiF 6 -; SbF 6 -}} , SbF 5 OH - What fluoroantimonic acid _{^{ions; AsF 6 -, AsF 5 OH}} - , and the like fluoroarsenate periodate ions such as. Further, it may be used in combination with ammonium or phosphonium fluorinated alkyl fluorophosphate. However, fluoroantimonate ions and fluoroarsenate ions are not preferable because they contain toxic elements.

The sulfonium ion, iodonium ion or selenium ion includes all known ones, and typical examples and references are as described in the present specification.

  Examples of the ammonium ion include tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl-n-propylammonium, trimethylisopropylammonium, trimethyl-n-butylammonium, trimethylisobutylammonium, and trimethyl. Tetraalkylammonium such as t-butylammonium, trimethyl-n-hexylammonium, dimethyldi-n-propylammonium, dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium, methyltri-n-propylammonium, methyltriisopropylammonium; N , N-dimethylpyrrolidinium, N-eth -Pyrrolidinium such as N-methylpyrrolidinium, N, N-diethylpyrrolidinium; N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N'-methylimidazoli 1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4-methylimidazolinium, Imidazolinium such as 1,2,3,4-tetramethylimidazolinium; N, N′-dimethyltetrahydropyrimidinium, N, N′-diethyltetrahydropyrimidinium, N-ethyl-N′-methyltetrahydro Tetrahydropyrimidinium such as pyrimidinium, 1,2,3-trimethyltetrahydropyrimidinium; N, N′- Morpholinium such as methylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium; N, N-dimethylpiperidinium, N-ethyl-N′-methylpiperidinium, N Piperidinium such as N, N-diethylpiperidinium; N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, N-isopropylpyridinium, Nn-butylpyridinium, N-benzylpyridinium, N-phenacyl Pyridinium such as pyridium; N, N′-dimethylimidazolium, N-ethyl-N-methylimidazolium, N, N′-diethylimidazolium, 1,2-diethyl-3-methylimidazolium, 1,3- Diethyl-2-methylimidazolium, 1-methyl-3-n-propyl-2, Imidazolium such as 4-dimethylimidazolium; N-methylquinolium, N-ethylquinolium, Nn-propylquinolium, N-isopropylquinolium, Nn-butylquinolium, N-benzylquinolium, Quinolium such as N-phenacylquinolium; N-methylisoquinolium, N-ethylisoquinolium, Nn-propylisoquinolium, N-isopropylisoquinolium, Nn-butylisoquinolium, N -Isoquinolium such as benzylisoquinolium and N-phenacylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and arrhidium such as benzylacridium and phenacylacridium.

These are US Pat. No. 4069055, Japanese Patent Publication No. 2519480, Japanese Patent Application Laid-Open No. 5-222112, Japanese Patent Application Laid-Open No. 5-222111, Japanese Patent Application Laid-Open No. 5-262256, Japanese Patent Application Laid-Open No. 5-255256, Japanese Patent Application Laid-Open No. 7-109303, JP-A-10-101718, JP-A-2-268173, JP-A-9-328507, JP-A-5-132461, JP-A-9-221652, JP-A-7-43854, JP-A-7-43901, JP-A-5-262813, JP-A-4-327574, JP-A-2-43202, JP-A-60-203628, JP-A-57-209931, JP-A-9-221652, and the like.

  Examples of the phosphonium ion include tetraarylphosphonium such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium. Triarylphosphonium such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium; triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium Tetraal such as tributylphenacylphosphonium Ruhosuhoniumu, and the like. These are described in JP-A-6-157624, JP-A-5-105692, JP-A-7-82283, JP-A-9-202873, and the like.

The ratio in the case of using two or more kinds of the onium fluorinated alkyl fluorophosphate of (1) of the present invention is arbitrary and is not limited.
Although the use ratio in the case of using other cationic polymerization initiator together may be arbitrary, the other cationic polymerization initiator is usually 10 to 100 parts by mass of the onium fluorinated alkyl fluorophosphate of (1) of the present invention. It is 900 mass parts, Preferably it is 25-400 mass parts (In the following description, a part represents a mass part).

As the cationic polymerization initiator (1) of the present invention, one previously dissolved in a solvent may be used in order to facilitate dissolution in the cationic polymerizable compound (2) of the present invention. Examples of the solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and isobutanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl n-propyl ketone, cyclohexane Ketones such as pentanone and cyclohexanone; ethers such as diethyl ether, ethyl-tert-butyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane; propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl Carbonates such as carbonate and diethyl carbonate; ethyl acetate, ethyl lactate, butyl cellosolve acetate, carbinol acetate, β-propiolactone, β-but Esters such as rolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Monoalkyl glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol dimethyl ether , Ethylene grease Cole diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dimethyl ether, tripropylene Dialkyl glycol ethers such as glycol diethyl ether; monoalcohols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Aliphatic glycolic acid esters of luglycol ether; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; aliphatic hydrocarbons such as hexane, octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, Petroleum solvents such as solvent naphtha; and nitriles such as acetonitrile.
The use ratio in the case of using these solvents is usually 15 to 1000 parts, preferably 30 to 500 parts, with respect to 100 parts of the cationic polymerization initiator (1) of the present invention.

  Examples of the cationically polymerizable compound (2) in the composition of the present invention include cyclic ether compounds such as epoxides and oxetanes, ethylenically unsaturated compounds such as vinyl ethers and styrene, bicycloorthoesters, and spiroorthocarbonates. And spiro orthoesters

Examples of epoxides include conventionally known epoxides, and examples of aromatic epoxides include monovalent and polyhydric phenols having at least one aromatic ring, such as phenol, cresol, xylenol, biphenol, bisphenol A, and bisphenol F. , Triphenol methane, triskresol methane, biphenol, tetramethylbiphenol, dihydroxynaphthalene, binaphthol, bis (4-hydroxyphenyl) diphenylmethane, phenol novolac, xylylene novolac, cresol novolac, xylenol novolak, biphenol novolak, bisphenol A novolak, bisphenol F novolak, triphenolmethane novolak, dicyclopentadiene phenol novolak, terpene phenol novo And glycidyl ethers of these compounds or brominated compounds thereof or compounds further added with alkylene oxide and glycidyl esters of monovalent and polyvalent carboxylic acids having at least one aromatic ring, such as diglycidyl phthalate, diglycidyl-3-methyl Examples of alicyclic epoxides include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxyl. Rate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy Chlohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5 Methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanemetadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6 -Methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), etc .; aliphatic polyhydric alcohol or alkylene oxide thereof Examples of polyglycidyl ethers of the adducts include diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and hydrogenated bisphenol A. Diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, triglycidyl ether of glycerin, diglycidyl ether, monoglycidyl ether, triglycidyl ether of trimethylolpropane, diglycidyl ether, monoglycidyl ether, tetraglycidyl ether of sorbitol, triglycidyl Of ether, diglycidyl ether, monoglycidyl ether, trimethylolpropane Liglycidyl ether, diglycidyl ether, monoglycidyl ether, tetraglycidyl ether of pentaerythritol, triglycidyl ether, diglycidyl ether, monoglycidyl ether, hexaglycidyl ether of dipentaerythritol, etc .; polyglycidyl ester of aliphatic polybasic acid, For example, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl hexahydro-3-methyl phthalate, etc .; epoxidized products of long chain unsaturated compounds such as epoxidized soybean oil, epoxidized polybutadiene; Group, 3,4-epoxy-1-cyclohexylmethyl group, 5,6-epoxy-2-bicyclo [2.2.1] heptyl group, 5 (6) -epoxyethyl-2-bisic B [2.2.1] heptyl group, 5,6-epoxy-2-bicyclo [2.2.1] heptylmethyl group, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decyl group, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyloxyethyl group, 3,4-epoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecyl group, 3,4-epoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] homopolymers of (meth) acrylates having an epoxy group such as dodecylmethyl group or copolymers of these with other unsaturated monomers, such as JP-A-11-174777, JP-A-11-15159, Those described in JP-A-2005-250067, JP-A-2004-133424, and references in the specification, and also Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28,497 (1990) And polyfunctional epoxides having a dimethylsiloxane skeleton as described in).

  As the oxetanes, conventionally known ones such as 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] Phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2- Ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3- Ethyl -Oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanyl) Methyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ) Ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, Tabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3′- (1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) Ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3 -Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3- Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl) -3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-phenoxymethyloxetane 3-ethyl-3- (4-methylphenoxy) methyloxetane, 3-ethyl-3- (4-fluorophenoxy) methyloxetane, 3-ethyl-3- (1-naphthoxy) methyloxetane, 3-ethyl-3 -(2-Naphoxy) methyloxetane, 3-ethyl-3-{[3- (ethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxetane, phenol novolac oxetane, and the like.

  Examples of the ethylenically unsaturated compound include conventionally known cationically polymerizable compounds such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4- Aliphatic groups such as hydroxybutyl vinyl ether, stearyl vinyl ether, 2-acetoxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether, 2-acryloyloxyethyl vinyl ether Monovinyl ethers; 2-phenoxyethyl vinyl ether , Phenyl vinyl ethers, aromatic monovinyl ethers such as p-methoxyphenyl vinyl ether; butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, 1,4-benzene divinyl ether, hydroquinone divinyl ether, cyclohexane dimethanol divinyl ether Polyfunctional vinyl ethers such as (1,4-bis [(vinyloxy) methyl] cyclohexane), diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether; styrene, α-methylstyrene, p-methoxystyrene, p- Examples include styrenes such as tert-butoxystyrene; cationically polymerizable nitrogen-containing monomers such as N-vinylcarbazole and N-vinylpyrrolidone. Can.

  Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxa And bicyclo- [2.2.2] octane.

  Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro [5.5] undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane, and the like. Can be mentioned.

Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane, 1,4,6-trioxas. Examples include pyro [4.5] decane.

  These cationically polymerizable compounds are described in JP-A-11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, JP-A-10-212343, JP 2000-119306, JP 10-67812, JP 2000-186071, JP H08-85775, JP 08-134405, US 2005/0147918, US 2005/0260522, JP 2005-250067. , JP2005-26396, JP10-62991, JP3033549, Photopolymer social gathering "Photopolymer Handbook" (1989, Industrial Research Committee), General Technology Center "UV / EB Curing Technology" (1982, General Technology Center), Radte Study Group “UV / EB Curing Materials” (1992, CMC), Technical Information Institute “UV Curing Failure / Inhibition Causes and Countermeasures” (2003, Technical Information Association), Epoxy Resin Technology Association "Review Epoxy Resin Vol. 1 Basic I" (2003, Epoxy Resin Technology Association), Coloring Materials, 68, (5), 286-293 (1995), Fine Chemicals, 29, (19), 5-14 (2000 ) Etc.

  Among these cationically polymerizable compounds, compounds having two or more epoxy groups in one molecule are preferable, and alicyclic epoxides are particularly preferable. These cationically polymerizable compounds may be used alone or in combination of two or more.

  The proportion of the cationic polymerization initiator (1) used relative to the cationic polymerizable compound (2) is usually 0.05 to 30 parts, preferably 0.1 to 15 parts, per 100 parts of the cationic polymerizable compound (2). However, the appropriate use ratio is determined by considering various factors such as the nature of the cationically polymerizable compound, the type and amount of radiation, temperature, curing time, curing depth, and humidity. When the proportion of the cationic polymerization initiator used is less than 0.05 parts, the polymerization of the cationic polymerizable compound becomes insufficient, and when it is more than 30 parts, the properties of the cured product deteriorate due to the unreacted cationic polymerization initiator and its decomposition product. In addition, the amount of radiation absorbed by the cationic polymerization initiator itself may increase, and the curing depth may decrease.

  A radically polymerizable compound (6) and a radiation-sensitive radical polymerization initiator (7) as necessary for the resin composition for optical three-dimensional modeling comprising the cationic polymerization initiator (1) and the cationically polymerizable compound (2) of the present invention. ) Can be blended. Examples of the radically polymerizable compound (6) include conventionally known compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Monofunctional monomers such as 1,6-hexanediol mono (meth) acrylate, styrene, vinylcyclohexene, isobutylene, butadiene; dihydric alcohols such as ethylene glycol, propylene glycol, bisphenol A or hydrides thereof, or alkylene oxides thereof Bifunctional monomers such as adduct di (meth) acrylate or divinylbenzene; polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, or alkylene oxide adducts thereof (meta Polyfunctional monomers such as acrylates; Epoxy (meth) acrylates obtained by reacting epoxides such as aromatic epoxides, cycloaliphatic epoxides, and aliphatic epoxides with (meth) acrylic acid; phthalic acid, isophthalic acid, terephthalic Aromatic polybasic acids such as acid, trimellitic acid and pyromellitic acid, and aliphatic polybasic acids such as succinic acid, adipic acid, and sebacic acid, and ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol , Neopentyl glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, bisphenol and Polyester (meth) acrylates obtained by esterifying hydroxy-terminated polyesters obtained from polyhydric alcohols such as these alkylene oxide adducts with (meth) acrylic acid; alicyclic rings such as isophorone diisocyanate and dicyclohexylmethane diisocyanate Isocyanates, polyisocyanates such as aliphatic isocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, aromatic isocyanates such as toluene diisocyanate, phenylene diisocyanate and diphenylmethane diisocyanate, and ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene Glycol, neopentyl glycol, polytetramethylene glycol 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, bisphenol, hydrogenated bisphenol and polycaprolactone diol, polyester diol, polycarbonate diol, etc. Isocyanate-terminated prepolymer obtained from polyhydric alcohol and hydroxy such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate Examples include urethane (meth) acrylates obtained by reaction with group-containing (meth) acrylates. Of these radically polymerizable compounds, compounds having at least one (meth) acryl group in one molecule are preferable. The radically polymerizable compound of the present invention may be used alone or in combination of two or more.

  Examples of these radically polymerizable compounds include JP-A No. 2006-16411, JP-A No. 2005-26396, JP-A No. 2000-186071, edited by the photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), Comprehensive Technology Center “UV / EB Curing Technology” (1982, Comprehensive Technology Center), Radtech Study Group “UV / EB Curing Material” (1992, CMC), Technical Information Association “UV Curing Failure / "Inhibition Causes and Countermeasures" (2003, Technical Information Association).

The radical polymerization initiator (7) in the composition of the present invention may be any as long as it generates radical active species by active energy rays in order to increase the molecular weight of the radical polymerizable compound by radical polymerization. . Examples of such radical polymerization initiators include those conventionally known. For example, acetophenone compounds such as acetophenone, p-tert-butyltrichloroacetophenone, 2,2-diethoxyacetophenone; benzophenone, methyl o-benzoylbenzoate Benzophenone compounds such as 4-benzoyl-4′-methyldiphenyl sulfide; Michler ketone compounds such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; benzoin and benzoin methyl ether Benzoin compounds such as thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone Ton compounds; acyl phosphine compounds such as monoacyl phosphine oxide and bisacyl phosphine oxide.
Examples of these radical polymerization initiators include JP-A No. 2006-16411, JP-A No. 2005-26396, JP-A No. 2000-186071, edited by Photopolymer Social Meeting “Photopolymer Handbook” (1989, Industrial Research Committee), Comprehensive Technology Center “UV / EB Curing Technology” (1982, Comprehensive Technology Center), Radtech Study Group “UV / EB Curing Material” (1992, CMC), Technical Information Association “UV Curing Failure / "Inhibition Causes and Countermeasures" (2003, Technical Information Association).

  The usage-amount of these radical polymerization initiators (7) is 0.01-30 parts normally with respect to 100 parts of radically polymerizable compounds (6), Preferably it is 0.1-15 parts. These radical polymerization initiators may be used alone or in combination of two or more.

  When the radical polymerizable compound (6) and the radical polymerization initiator (7) are further added to the resin composition for optical three-dimensional modeling comprising the cationic polymerization initiator (1) and the cationic polymerizable compound (2) of the present invention, The blending ratio of the cationically polymerizable compound (2) and the radically polymerizable compound (6) is such as the viscosity of the resin composition after blending, the reaction speed, the modeling speed, the dimensional accuracy of the resulting three-dimensional modeled object, and the mechanical characteristics. From the viewpoint, it is preferable to contain the cationically polymerizable compound (2): radically polymerizable compound (6) = 90: 10-30: 70 in a mass ratio of 80: 20-40: 60. Is particularly preferred.

  The composition of the present invention may further contain an OH group-containing compound (8). The OH group-containing compound is a compound having at least two OH groups in one molecule. For example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene Glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2,4-butanetriol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4- Cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3,5-cyclohexanetrimethanol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cycl Looctanediol, 1,5-cyclooctanediol, tricyclodecane dimethanol, 2,3-nobornanediol, 2 (3) -hydroxy-5, 6-bis (hydroxymethyl) norbornane, 2,3-dihydroxy- 5 (6) -Hydroxymethylnorbornane, 1,4-anhydroerytriol, L-arabinose, L-arabitol, D-cellobiose, cellulose, 1,5-decalindiol, glucose, galactose, lactose, maltose, mannose, mannanitol Polycaprolactone polyol, trimethylolpropane, glycerin, pentaerythritol, polyester diol, polycarbonate diol, bisphenol described in US Pat. Lumpur A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, phenol novolac resins, and cresol novolac resin and the like and their alkylene oxide adducts. Examples of these OH group-containing compounds are described in JP-A Nos. 2005-267396 and 2000-186071.

  In the composition of the present invention, a sensitizer, a pigment, a filler, an antistatic agent, a flame retardant, an antifoaming agent, a flow regulator, and a light stabilizer are added as necessary as long as the purpose and effect of the present invention are not impaired. Additives such as antioxidants and non-reactive resins can be used.

  Conventionally known sensitizers can be used in combination with the composition of the present invention, particularly those which are cured by irradiation with active energy rays. Examples of such sensitizers are described in JP-A Nos. 11-279212 and 09-183960, and specifically include anthracene, 9,10-dibutoxyanthracene, and 9,10-dimethoxyanthracene. 2-ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9,10 -Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10 -Methylanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dip Poxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert-9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di-α-methylbenzyloxyanthracene, 2-tert-9,10-di-α-methylbenzyloxyanthracene, 2, 3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- α-methylbenzyloxy) -10-methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene, etc. Anthracenes; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone such as thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone Phenothiazine; xanthone; 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydride Roxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1'-thiobis (2-naphthol), 1,1'-bi- (2-naphthol), 4 -Naphthalenes such as methoxy-1-naphthol; dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloro Acetophenone, p-azidobenzalacetophenone, 1- Droxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2- Methyl-1-propan-1-one, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, etc. Ketones; carbazoles such as N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole; 1,4-dimethoxychrysene, 1,4-di Chrysene such as ethoxychrysene, 1,4-dipropoxychrysene, 1,4-dibenzyloxychrysene, 1,4-di-α-methylbenzyloxychrysene; 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxy Phenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,10-di-α-methylbenzyl Examples include phenanthrenes such as oxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, and 9-hydroxy-10-ethoxyphenanthrene.

  The use ratio in the case of using these sensitizers is 0.05-20 parts normally with respect to 100 parts of the compositions of this invention, Preferably it is 0.01-10 parts. Moreover, these sensitizers may be used independently or may use 2 or more types together.

Examples of the pigment include conventionally known pigments, for example, inorganic pigments such as titanium oxide, iron oxide, and carbon black, and organic pigments such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments.
The use ratio of these pigments is usually 0.1 to 50 parts, preferably 1 to 30 parts, relative to 100 parts of the composition of the present invention. These pigments may be used alone or in combination of two or more.

Examples of the filler include conventionally known ones such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.
The use ratio in the case of using these fillers is usually 5 to 100 parts, preferably 10 to 80 parts, relative to 100 parts of the composition of the present invention. Moreover, these fillers may be used independently or may use 2 or more types together.

Conventionally known antistatic agents such as glycerin fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, N, N-bis (2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, poly Nonionic types such as oxyethylene alkylamine fatty acid esters and alkyldiethanolamides; Anionic types such as alkylsulfonates, alkylbenzenesulfonates and alkylphosphates; Cationic types such as tetraalkylammonium salts and trialkylbenzylammonium salts Amphoteric types such as alkylbetaines and alkylimidazolium betaines; Styrene- (meth) acrylate copolymers containing quaternary ammonium groups, quaternary ammonium Group-containing styrene-acrylonitrile-maleimide copolymers and ionic properties such as polyethylene oxide, polyether ester amide, polyether amide imide, ethylene oxide-epichlorohydrin copolymer, methoxypolyethylene glycol (meth) acrylate copolymer, and Nonionic polymer type and the like.
When these antistatic agents are used, the proportion used is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, per 100 parts of the composition of the present invention. These antistatic agents may be used alone or in combination of two or more.

Conventionally known flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, aluminate Examples include inorganic substances such as calcium; bromines such as tetrabromophthalic anhydride, hexabromobenzene, and decabromobiphenyl ether; and phosphates such as tris (tribromophenyl) phosphate.
When using these flame retardants, the use ratio is usually 0.1 to 20 parts, preferably 0.5 to 10 parts, relative to 100 parts of the composition of the present invention. Moreover, these flame retardants may be used independently or may use 2 or more types together.

Conventionally known antifoaming agents, for example, alcohols such as isopropanol, n-butanol, octaethyl alcohol and hexadecyl alcohol; metal soaps such as calcium stearate and aluminum stearate; phosphate esters such as tributyl phosphate Fatty acid esters such as glycerin monolaurate; polyethers such as polyalkylene glycol; silicones such as dimethyl silicone oil and silica / silicone compound; and mineral oils in which silica powder is dispersed.
The proportion of use of these antifoaming agents is usually 0.01 to 10 parts, preferably 0.05 to 5 parts, relative to 100 parts of the composition of the present invention. These antifoaming agents may be used alone or in combination of two or more.

Examples of the flow control agent include conventionally known ones such as hydrogenated castor oils, polyethylene oxides, organic bentonites, colloidal silica, amide waxes, metal soaps, and acrylate polymers.
When these flow regulators are used, the amount used is generally 0.01 to 10 parts, preferably 0.05 to 5 parts, relative to 100 parts of the composition of the present invention. Moreover, these flow regulators may be used alone or in combination of two or more.

As the light stabilizer, conventionally known ones, for example, ultraviolet absorption type such as benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof; radical scavenging type represented by hindered amines; quenching type such as nickel complex, etc. It is done.
The use ratio in the case of using these light stabilizers is usually 0.005 to 40 parts, preferably 0.01 to 20 parts, relative to 100 parts of the composition of the present invention. These light stabilizers may be used alone or in combination of two or more.

Conventionally known antioxidants, for example, hindered phenolic compounds, such as pentaerythrityltyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox) 1010), thiodiethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1035FF), benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxy, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245), octadecyl-3- (3,5-t-butyl -4-hydroxyphenyl) propionate (Irganox 1076), 3,3 ', 3 , 5,5 ', 5 "-hexa-t-butyl-a, a', a"-(mesitylene-2,4,6-triyl) tri-p-cresol (Irganox 1330), 1,3,5 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Irganox 3114), 4,6 -Bis (octylthiomethyl) -o-cresol (Irganox 1520L), 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1 -Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Sumilyzer GA-80), 2,6-di-t-butyl-4-methylphenol (Sumilyzer BHT) and the like. Et (In the above, Irganox is a registered trademark of Ciba Specialty Chemicals Co., Ltd., and Sumilyzer is a registered trademark of Sumitomo Chemical Co., Ltd.) Examples of phosphorus compounds include Tris (2, 4 -Di-t-butylphenyl) phosphite (Irgaphos 168), bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid (Irgaphos 38), 6- [3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) -propoxy] -2,4,8,10-tetra-tert-butylbenz [d, f] [1,3,2] -dioxaphos Fepin (Sumilyzer GP), etc. (in the above, Irgafos is a registered trademark of Ciba Specialty Chemicals Co., Ltd., and Sumilyzer is Sumitomo) It is a registered trademark of Manabu Industry Co., Ltd.).
The use ratio in the case of using these antioxidants is usually 0.1 to 10 parts, preferably 0.1 to 5 parts, relative to 100 parts of the composition of the present invention. These antioxidants may be used alone or in combination of two or more.

Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene butadiene block copolymer, and (meth) acrylic ester co-polymer. Examples include coalescence and polyurethane. These resins have a number average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000 (the number average molecular weight is measured by a general method such as GPC).
The use ratio in the case of using these is 1-100 parts normally with respect to 100 parts of the composition of this invention, Preferably it is 5-50 parts. These non-reactive resins may be used alone or in combination of two or more.

  The composition of the present invention may be prepared only by mixing and stirring by a usual method. If necessary, it may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three roll mill. You may heat as needed.

The composition of the present invention obtained as described above is suitably used as an active energy ray-curable resin composition in an optical three-dimensional modeling method. That is, low pressure, medium pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, fluorescent lamp, semiconductor solid state laser, argon laser, He-Cd laser, KrF excimer for the composition of the present invention. By an optical three-dimensional modeling method that selectively irradiates active energy rays in the ultraviolet to visible light region (about 100 to about 800 nm) obtained from a laser, ArF excimer laser, F ₂ laser, etc., and supplies energy necessary for curing A three-dimensional object having a desired shape can be manufactured.

  The optically shaped article of the present invention is obtained by irradiating the composition of the present invention with an active energy ray.

  The means for selectively irradiating the composition of the present invention with active energy rays is not particularly limited, and various means can be adopted. For example, a laser beam or means for irradiating the composition while scanning convergent light obtained using a lens, mirror, etc., and a mask having a light transmission part of a predetermined pattern are used, and non-convergence is performed through this mask. Use a means for irradiating the composition with light, a light guide member formed by bundling a large number of optical fibers, and a means for irradiating the composition with light via an optical fiber corresponding to a predetermined pattern in the light guide member. Can do. In the means using a mask, a mask that electro-optically forms a mask image composed of a light transmission region and a light non-transmission region according to a predetermined pattern according to a principle similar to that of a liquid crystal display device is used. You can also. In the above, when the target three-dimensional object has a fine part or is required to have high dimensional accuracy, the spot diameter is small as a means for selectively irradiating the composition with active energy rays. It is preferable to employ means for scanning with laser light. In addition, the irradiation surface (for example, the scanning plane of convergent light) of the active energy ray in the resin composition accommodated in the container is either the liquid surface of the resin composition or the contact surface with the vessel wall of the translucent container. It may be. When the liquid surface of the resin composition or the contact surface with the vessel wall is used as the active energy ray irradiation surface, the active energy ray can be irradiated directly from the outside of the container or through the vessel wall.

  In the above-mentioned optical three-dimensional modeling method, usually, after curing a specific part of the resin composition, the irradiation position (irradiation surface) of the active energy ray is continuously or stepwise from the uncured part to the uncured part. The cured portion is laminated to obtain a desired three-dimensional shape. Here, the irradiation position can be moved by various methods. For example, the light source, the container for containing the resin composition, or the cured part of the resin composition can be moved, or the resin composition can be additionally supplied to the container. The method of doing etc. can be mentioned. To explain a typical example of the optical three-dimensional modeling method, a support stage provided so as to be movable up and down in the storage container is lowered (sedimented) by a minute amount from the liquid surface of the resin composition. The resin composition is supplied to a thin layer (a). Next, an active energy ray is selectively irradiated to the thin layer (a) to form a solid cured resin layer (a). Next, an active energy ray-curable liquid resin composition is supplied onto the cured resin layer (a) to form the thin layer (a), and active energy ray irradiation is selectively performed on the thin layer (a). By doing so, a new cured resin layer (A) is formed on the cured resin layer (A) so as to be laminated continuously and integrally therewith. Then, by repeating this step a predetermined number of times while changing or not changing the pattern irradiated with the active energy ray, a three-dimensional object formed by integrally laminating a plurality of cured resin layers (n) is formed. The

  The three-dimensionally shaped product thus obtained is taken out from the container, and after removing the unreacted resin composition remaining on the surface, the solid shaped product is washed as necessary. Here, as the cleaning agent, alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone, etc .; aliphatics typified by terpenes Organic solvents; low viscosity thermosetting resins and radiation curable resins. In addition, after washing | cleaning with a cleaning agent, you may post-cure by heat irradiation or active energy ray irradiation as needed. Post-cure can cure unreacted resin composition that may remain on the surface and inside of the three-dimensional object, and can suppress the stickiness of the surface of the object, and improve the initial strength of the object. Can be made.

  The application field of the composition of the present invention is not particularly limited, but as a typical application field, a model for verifying the appearance design in the middle of the design, a model for checking the functionality of the part, and a mold are manufactured. Resin molds, base models for producing molds, direct molds for prototype molds, and the like. In particular, the resin composition for stereolithography can exhibit power in producing a model of a precise part. More specifically, for example, design models and working model applications such as precision parts, electrical / electronic parts, furniture, building structures, automobile parts, various containers, castings, mother molds, processing applications, surgical simulations, etc. It can be effectively used for medical applications such as orthodontics, microparts, nanotechnology, functional parts such as functional parts.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not intended to be limited to these examples.

(Production Example 1) Production of potassium tris (pentafluoroethyl) trifluorophosphate Tris (pentafluoroethyl) difluorophosphorane (gas chromatographic purity 97%, yield 72%) by electrolytic fluorination of triethylphosphine according to US Pat. No. 6,264,818 ) Was synthesized.
Next, 18.0 g of potassium fluoride and 600 ml of dimethoxyethane were added to a 1 L reaction vessel and suspended by stirring. While maintaining the liquid temperature at 20 to 30 ° C., 119.0 g of the resulting tris (pentafluoroethyl) difluorophosphorane was obtained. Was dripped. After stirring at room temperature for 24 hours, the reaction solution was filtered, and dimethoxyethane was distilled off from the filtrate under reduced pressure to obtain 136.0 g of a white powder. It was confirmed by ¹⁹ F and ³¹ P-NMR that this was potassium tris (pentafluoroethyl) trifluorophosphate.

(Production Example 2) Production of potassium tris (heptafluoropropyl) trifluorophosphate According to US Pat. No. 6,264,818, tris (heptafluoropropyl) difluorophosphorane (gas chromatographic purity 89%, by electrolytic fluorination of tris-n-propylphosphine Yield 52%) was synthesized.
Next, 18.0 g of potassium fluoride and 600 ml of dimethoxyethane were added to a 1 L reaction vessel and suspended by stirring. While maintaining the liquid temperature at 20 to 30 ° C., 161.0 g of the resulting tris (heptafluoropropyl) difluorophosphorane was obtained. Was dripped. After stirring for 24 hours, the reaction solution was filtered, and dimethoxyethane was distilled off from the filtrate under reduced pressure to obtain 177.0 g of a white powder. It was confirmed by ¹⁹ F and ³¹ P-NMR that this was potassium tris (heptafluoropropyl) trifluorophosphate.

Production Example 3 Production of 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate A reaction vessel was charged with 24.24 g of diphenyl sulfoxide, 18.6 g of diphenyl sulfide, and 86.0 g of methanesulfonic acid. Then, 15.8 g of acetic anhydride was added dropwise. After reacting at 40-50 ° C. for 5 hours, it was cooled to room temperature. This reaction solution was dropped into a container containing 249 g of a 20% by mass aqueous solution of tris (pentafluoroethyl) potassium trifluorophosphate produced in Production Example 1, and stirred well at room temperature for 1 hour. The precipitated yellow slightly viscous oily substance was extracted with 240 g of ethyl acetate, the aqueous layer was separated, and the organic layer was washed with 200 g of water three times. The solvent was distilled off from the organic layer, and 80 g of toluene was added to the resulting yellow residue to dissolve it. In order to remove impurities such as unreacted raw materials and by-products, 600 g of hexane was added to this toluene solution, and the mixture was allowed to stand after stirring well at 10 ° C. for 1 hour. Since the solution was separated into two layers, the upper layer was removed by liquid separation. When 300 g of hexane was added to the remaining lower layer and mixed well at room temperature, pale yellow crystals were precipitated. This was filtered off and dried under reduced pressure to obtain 49.0 g of 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate. The compound was identified by ¹ H, ¹³ C, ¹⁹ F and ³¹ P-NMR.
The obtained 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (49.0 g) was dissolved in propylene carbonate (49.0 g) to prepare a 50 mass% propylene carbonate solution.

(Production Example 4) Production of 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate A 20% by mass aqueous solution of potassium tris (pentafluoroethyl) trifluorophosphate was added to potassium tris (heptafluoropropyl) trifluorophosphate. 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (53.8 g) was obtained in the same manner as in Production Example 3, except that 326 g of a 20% by mass aqueous solution was used. The compound was identified by ¹ H, ¹³ C, ¹⁹ F and ³¹ P-NMR.
The obtained 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (53.8 g) was dissolved in propylene carbonate (53.8 g) to prepare a 50% by mass propylene carbonate solution.

(Adjustment and evaluation results of resin composition for optical three-dimensional modeling)
Each component was mixed in the ratio shown in Table 1 to prepare a uniform active energy ray-curable resin for optical three-dimensional modeling, and the storage stability of the composition was evaluated by the following method. The results are shown in Table 2.

* RE-1: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (trade name: UVR-6110, manufactured by Dow Chemical Company)
RE-2: Propylene oxide-modified bisphenol A type diglycidyl ether (trade name: Rica Resin BPO-20E, manufactured by Shin Nippon Rika Co., Ltd.)
RE-3: 3-methyl-3-hydroxymethyloxetane C-1: 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) 50% propylene carbonate solution of trifluorophosphate (compound prepared in Production Example 2)
C-2: 50% propylene carbonate solution of 4- (phenylthio) phenyldiphenylsulfonium tris (heptafluoropropyl) trifluorophosphate (compound prepared in Production Example 4)
C-3: 50% propylene carbonate solution of 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate (trade name: CPI-101A, manufactured by San Apro)
RR-1: 2,2-bis [4- (acryloxydiethoxy) phenyl] propane (trade name: NK ester A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.)
RR-2: Propylene oxide modified trimethylolpropane triacrylate (trade name: NK ester A-TMPT-3PO, manufactured by Shin-Nakamura Chemical Co., Ltd.)
RR-3: Dicyclopentadienyl diacrylate (trade name: A-DCP Shin-Nakamura Chemical Co., Ltd.)
L-1: 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure-184, manufactured by Ciba Specialty Chemicals)
RR-4: propylene oxide modified pentaerythritol tetraacrylate (trade name: NK ester ATM-4P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
OH-1: Polytetramethylene glycol (number average molecular weight 2000)

<Storage stability test method>
Immediately after adjusting the compositions for optical three-dimensional modeling obtained in Examples 1 to 3 and Comparative Examples 1 to 2, the viscosity after storage for 2 months at 80 ° C. was measured at 25 ° C., and the storage stability was increased by the degree of thickening. Judgment was made according to the following evaluation criteria.
○: Less than twice the change in viscosity from the initial viscosity ×: The storage stability of the composition is better as the rate of increase in viscosity from the initial viscosity is twice or more.

  The test results are shown in Table 2.

From these results, the active energy ray-curable resin composition for optical three-dimensional modeling of the present invention does not contain toxic elements that may adversely affect handling, storage, or the environment, and may have excellent storage stability. Recognize.

Preparation of a test piece of an optically shaped object and evaluation of its mechanical properties were performed as follows.
<Mechanical property evaluation test>
1. Method for Producing Stereolithography and Test Specimen Using the compositions for optical three-dimensional modeling obtained in Examples 1 to 3 and Comparative Examples 1 and 2, Solid Creator SCS-300P (manufactured by Sony Manufacturing Systems Co., Ltd.) Use and repeat the process of forming a cured resin layer (thickness of 0.10 mm) by selectively irradiating the optical three-dimensional structure composition with laser light at a laser power of 100 mW on the irradiated surface (liquid surface). Thus, a dumbbell-shaped evaluation sample according to JISK7113 was formed. Subsequently, the sample for evaluation was taken out from the solid creator, the optical three-dimensional modeling composition adhering to the surface was washed and removed, and the test piece was left for 3 days at room temperature.
2. Characteristic Evaluation Test Method Tensile strength, tensile elongation and tensile elastic modulus were measured as a tensile property test using this test piece, and bending strength and flexural modulus were measured according to JISK7113 as a bending property test. The results are shown in Table 3.
3. Appearance evaluation method of photocured product
1. The appearance of the test piece obtained by the method shown in 1 was observed visually. The results are shown in Table 3.

  From these results, the active energy ray-curable resin composition for optical three-dimensional modeling of the present invention is quickly cured when shaped by irradiation with active energy rays, and is a comparative example in mechanical properties, appearance, and color tone. It can be seen that a three-dimensionally shaped product that is inferior to that of the composition is obtained.

  INDUSTRIAL APPLICABILITY The present invention is useful for the production of an active energy ray-curable resin composition for optical three-dimensional modeling that does not contain toxic metals such as arsenic and antimony, has good storage stability, and good modeling accuracy. In addition, it is also useful for obtaining an optically shaped article having excellent mechanical properties and high transparency.

Claims (10)

In the active energy ray-curable optical three-dimensional modeling resin composition comprising the cationic polymerization initiator (1) and the cationic polymerizable compound (2) as essential components, (1) is represented by the following general formula (3). An active energy ray-curable resin composition for optical three-dimensional modeling, which is an onium fluorinated alkyl fluorophosphate.

[In the formula (3), A is an element having a valence m of VIA group to VIIA group. m = 1-2. n = 0-3. R is an organic group bonded to A. D is the following general formula (4),

[In the formula (4), E represents a divalent group, G represents —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO] -, -CONH, an alkylene or phenylene group having 1 to 3 carbon atoms. a = 0-5. Is a structure represented by
X ⁻ represents the following general formula (5)

[Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b = 1-5. ]. ] Furthermore, the radically polymerizable compound (6) and the radical polymerization initiator (7) are contained, The active energy ray-curable resin composition for optical three-dimensional modeling according to claim 1 characterized by the above-mentioned. 3. The active energy ray-curable resin composition for optical three-dimensional modeling according to claim 1, wherein A is S or I in the compound of (1). In the compound of (1), R is a phenyl group which may have a substituent, The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of claims 1 to 3. The compound of (1), wherein D is at least one group selected from the group represented by the following, The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of claims 1 to 4.

In the compound of (1), Rf is a C1-C4 perfluoroalkyl group, and the number b is 2 or 3. The active energy ray-curable optical three-dimensional modeling according to any one of claims 1 to 5. Resin composition. The onium ion of the compound of (1) is 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio } Phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4- Benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9, 10-dihydroanthracen-2-yldiphenylsulfonium, 2-[( -P-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) Phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenylthiaanthrhenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4 The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of claims 1 to 6, which is -hydroxyphenylmethylphenacylsulfonium or octadecylmethylphenacylsulfonium. (1) counter anion of the compound of _{[(CF 3 CF 2) 3} PF 3] - or _{[(CF 3 CF 2 CF 2} ) 3 PF 3] -, any claim 1-7, characterized in that a An active energy ray-curable resin composition for optical three-dimensional modeling according to claim 1. The active energy ray-curable resin composition for optical three-dimensional modeling according to any one of claims 1 to 8, further comprising an OH group-containing compound (8). The optical modeling thing hardened | cured by irradiating an active energy ray to the active energy ray-curable resin composition for optical three-dimensional modeling in any one of Claims 1-9.