JPH0912615A - Actinic-radiation-curing composition and cured product thereof - Google Patents

Abstract

PURPOSE: To obtain an actinic-radiation-curing composition desirable for stereolithography by mixing an ethylenically unsaturated compound with a cationically polymerizable substance and a sulfonium salt of a specified structure. CONSTITUTION: An ethylenically unsaturated compound (A) is mixed with a cationically polymerizable substance (B) and a photopolymerization initiator comprising a sulfonium salt (C) of formula I [wherein R1 to R5 are each H, OH, a 1-15C aliphatic group, a halogen, group of formula II or the like; (n) is 1-4; Z is a group of the formula: MQp or MQp-1 (OH) (wherein M is P, B, As or the like; Q is a halogen; and (p) is 4-6); and X is a group of formula II (wherein R<6> to R15 are each H, a halogen, an alkoxyl, phenyl or the like)] to obtain an actinic-radiation-curing composition. This initiator is applicable to both cationic polymerization and radical polymerization and is suited as an optical shaping composition. The component A is, for example, a hydroxylalkyl (meth)acrylate, and the component B is, for example, an epoxy resin or styrene. The component C is obtained by condensing a thioxanthone compound with a diphenyl sulfoxide compound.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photopolymerization initiator (C) comprising an ethylenically unsaturated group-containing compound (A), a cationically polymerizable substance (B) and a sulfonium salt having a specific structure.
And an energy ray-curable composition capable of being polymerized by irradiation with an energy ray, and a cured product thereof. More specifically, it relates to an energy ray-curable composition suitable for an energy ray-curable resin composition for optical modeling and a cured product thereof.

[0002]

2. Description of the Related Art Generally, a model corresponding to a product shape required at the time of mold making, or a model for cutting control of a cutting process or a model for a die-sinking electric discharge machining electrode is manufactured by hand machining.
Alternatively, it has been performed by NC cutting using an NC milling machine or the like. However, there is a problem that a lot of labor and skill are required in the case of manual machining, and in the case of NC cutting, it is necessary to create a complicated machining program in consideration of exchange and wear for changing the shape of the cutting edge of the blade. In addition, there is a problem that further finishing processing may be required in order to remove the step formed on the processed surface. Recently,
In order to solve these problems, technical development has been carried out on a method for creating a complicated model for mold making, copying, and die-sinking electric discharge machining and various fixed objects by an optical molding method. This optical modeling resin has excellent sensitivity to energy rays, good resolution of curing by energy rays, low viscosity, low volume shrinkage rate during curing, and mechanical strength of the cured product. Is excellent,
Various characteristics such as good self-adhesiveness and good curing characteristics in an oxygen atmosphere are required. For example, JP-A No. 2-80423 discloses an energy ray curability,
An optical modeling resin composition comprising a cationically polymerizable organic substance, an energy ray-sensitive cationic polymerization initiator, an energy ray-curable radical-polymerizable organic substance, and an energy ray-sensitive radical polymerization initiator has been proposed.

[0003]

Conventionally, the above-mentioned Japanese Unexamined Patent Publication (Kokai) No. 2 has been proposed.
When a cation-polymerizable organic substance and a radical-polymerizable organic substance are used in combination as in JP-A-80423, it is generally practiced to use a cation polymerization initiator and a radical polymerization initiator in combination. However, there are problems such as the problem of selection of the polymerization initiator and the increase in the price of the composition.

[0004]

Means for Solving the Problems As a result of intensive research to solve the above-mentioned problems, the present inventors have found that by using a photopolymerization initiator prepared by introducing a specific sulfonium base into a thioxanthone compound, Succeeded in providing an energy ray-curable composition having good curability and its cured product by irradiating with energy rays (for example, ultraviolet rays) without using a polymerization initiator and a radical polymerization initiator together. did. That is, the present invention relates to an ethylenically unsaturated group-containing compound (A), a cationically polymerizable substance (B) and the formula (1)

[0005]

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In the formula, X is a group represented by the formula (2)

[0007]

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(In the formula, R _{6 to} R ₁₅ are each a hydrogen atom,
In the structure of halogen atom, nitro group, alkoxy group, C _{1 to} C ₂₀ , hydroxyl group, ether group, ester group, (meth)
It is a group selected from any of an acryloyl group, an epoxy group, or an aliphatic group which may have an allyl group, a phenyl group, a phenoxy group, and a thiophenoxy group. R _{1 to} R ₅ each represent a hydrogen atom, a hydroxyl group, C _{1 to} C ₁₅
Aliphatic groups, halogen atoms, nitro groups, alkoxy groups,
A group selected from a phenyl group and a group represented by the formula (2), n is 1 to 4, and Z is the formula (3) or the formula (4).

MQ _P (3) MQ _P-1 (OH) (4)

(In the formula, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Q is a halogen atom, and P is an integer of 4 to 6). } The photocurable initiator (C) which consists of the sulfonium salt shown by these is contained, The energy ray curable composition characterized by the above-mentioned, and its hardened | cured material.

Examples of the ethylenically unsaturated group-containing compound (A) used in the present invention include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and (2-hydroxybutyl (meth) acrylate; Mono or di (meth) glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol
Acrylates; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; hexane Polyhydric alcohols such as diols, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol and tris-hydroxyethyl isocyanurate, or polyhydric (meth) acrylates of adducts of ethylene oxide or propylene oxide thereof; Phenoxy (meth) acrylate, bisphenol A di (meth) acrylate, and (meth) acrylates such as ethylene oxide or propylene oxide adducts of these phenols S; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, (meth) acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine (meth) reactive monomers such as acrylates,

Epoxy resin (for example, phenol novolac resin, cresol novolac epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, polybutadiene modified epoxy resin, alicyclic epoxy resin, brominated phenol) Novolak epoxy resin, brominated bisphenol A type epoxy resin, amino group-containing epoxy resin, etc.) and epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid, and a polybasic anhydride (for example, an epoxy (meth) acrylate) (for example, , Maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) reacted carboxylic acid-modified epoxy (meth) acrylate, polyol component (eg ethylene glycol Lumpur, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6
-Hexanediol, 3-methyl-1,5-pentanediol, polyethylene glycol, polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol, etc.) and acid components (eg, maleic acid, succinic acid, adipine) Acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and other dibasic acids or dibasic acid anhydrides) (meth) acrylic acid ester of polyester polyol or polyol (eg ethylene glycol) ,
Nerpentyl glycol, polytetramethylene glycol, polyester polyol, polycaprolactone polyol, etc.) and organic polyisocyanate (eg, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.) and hydroxyl group-containing (meth) acrylate (eg, 2-hydroxyethyl). Examples thereof include reactive oligomers such as urethane (meth) acrylate, which is a reaction product of (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and the like. Examples of the cationically polymerizable substance (B) used in the present invention include cationically polymerizable vinyl compounds such as epoxy resin, styrene and vinyl ether, and further cyclic ethers such as spiro orthoester, bicyclo orthoester and spiro orthocarbonate. Is mentioned. Examples of the epoxy resin include conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, epoxide monomers, and episulfide monomers. here,
An example of the aromatic epoxy resin is a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, and is, for example, a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S or bisphenol. Glycidyl ethers produced by reacting an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of a compound with epichlorohydrin, novolac type epoxy resins (for example, phenol novolac type epoxy resin, Cresol / novolak type epoxy resin, brominated phenol / novolak type epoxy resin, etc.), trisphenol methane triglycidyl ether and the like. Further, specific examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4
-Epoxycyclohexanecarboxylate, bis-
(3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-
Spiro-3,4-epoxy) cyclohexanone-meta-
Dioxane, bis (2,3-epoxycyclopentyl)
Ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin, softening point 71 ° C.) and the like can be mentioned.

Further, examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and representative examples thereof include diglycidyl ethers of 1,4-butanediol, 6-Hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, ethylene glycol, propylene glycol, aliphatic polyvalents such as glycerin Examples include polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to alcohol. It is. Further, examples of the epoxide monomers include monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butylphenol, and monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these.

As the cationic polymer vinyl compound, for example, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-
Butanediol divinyl ether,

[0015]

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And

[0017]

[Chemical 6]

And the like. These cationically polymerizable organic materials may be used alone or as a mixture of two or more.

The sulfonium salt represented by the general formula (1) used in the present invention is, for example, a thioxanthone compound represented by the general formula (5).

[0020]

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(Wherein R _{1 to} R ₅ are groups selected from a hydrogen atom, a hydroxyl group, a C _{1 to} C ₁₅ aliphatic group, a halogen atom, a nitro group, an alkoxy group, an ester group and a phenyl group, respectively. A) and a substituted or unsubstituted diphenyl sulfoxide compound using a known reaction for forming a sulfonium salt (hereinafter referred to as method 1)), 2) preliminarily synthesizing a corresponding substituted or unsubstituted sulfonium salt, and then substituting Method for converting and introducing groups (hereinafter referred to as method 2)
Can be synthesized. First, the method 1) will be described in detail. A thioxanthone compound represented by the formula (5) (specific examples include 2,4-diethylthioxanthone, 2,4-dipropylthioxanthone, 2-isopropylthioxanthone, and 4-isopropyl). Thioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3,4-dimethylthioxanthone, 1-methoxythioxanthone,
2-methoxythioxanthone, 3-methoxythioxanthone, 4-methoxythioxanthone, 1-methyl-4-
Hydroxythioxanthone, 1-methyl-4-chlorothioxanthone, 1,2-dimethyl-4-chlorothioxanthone, 1,3-dimethyl-4-chlorothioxanthone, 2,3,4-trimethylthioxanthone, 3-nitrothioxanthone, 3- Ethoxythioxanthone, 1,
3,4-trimethyl-2-oxycarbonylmethylthioxanthone, 2-oxycarbonylmethyl-4-methylthioxanthone, 2-phenylthioxanthone, 1-carbonyloxymethylthioxanthone, 1-carbonyloxyethyl-3-nitrothioxanthone, 1-carbonyl Oxyethyl-3-ethoxythioxanthone and the like can be mentioned. ) And a substituted or unsubstituted diphenylsulfoxide compound (eg, diphenylsulfoxide,
4,4'-difluorodiphenyl sulfoxide, 2,
2'-difluorodiphenylsulfoxide, 3,3'-
Difluorodiphenyl sulfoxide, 4,2'-difluorodiphenyl sulfoxide, 4,4'-dibromodiphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide, 2,2 ', 4,4-tetrachlorodiphenyl sulfoxide, 4, 4'-dimethyldiphenyl sulfoxide, 4,4'-diethyldiphenyl sulfoxide,
4,4'-dimethoxydiphenylsulfoxide, 4,
4'-diethyldiphenylsulfoxide, 4-methylthiodiphenylsulfoxide, 4-phenylthiodiphenylsulfoxide, etc.) in a known method, for example, in a dehydrating agent (for example, phosphorus pentoxide, concentrated sulfuric acid, acetic anhydride, etc.) at room temperature to 10
The condensation reaction is carried out at 0 ° C., and then these reaction solutions are treated by the formula (3) or (4) (for example, NaSbF ₆ , NaP).
F ₆ , NaAsF ₆ , NaBF ₄ , NaSbF ₆ OH,
KSbF ₆ , KPF ₆ , KAsF ₆ , KSbF ₅ OH
Etc.) to obtain an sulfonium salt.

The method 2) will be described in detail. A sulfonium salt synthesized by the method 1), for example, the formula (6)

[0023]

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[0024] (wherein, R _{1-R 5} is the same as R _{1-R 5} in formula (5), A is represented by a halogen atom, Z is the formula (3) or (4) In the presence of a basic compound (eg, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.), a large excess of mono- or polyalcohols (eg, methanol, Ethanol, carbitol, ethylene glycol, polyethylene glycol, propylene glycol,
Glycerin, trimethylolpropane, 1,4-butanediol, glycidol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl alcohol, etc.) at room temperature to 150 ° C.
Then, if necessary, by reacting in the presence of an organic solvent such as dimethyl sulfoxide, the halide portion of the halide compound, for example,

[0025]

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[0026]

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[0027]

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[0028]

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Thus, a sulfonium salt converted to the above substituents can be obtained. As typical examples of the compound represented by the general formula (1), the compounds shown in Tables 1 and 2 below can be mentioned, but the compounds are not limited to these.

[0030]

[Table 1]

[0031]

[Table 2] The proportion of each component of the curable composition of the present invention used in the ethylenically unsaturated group-containing compound (A) is preferably 5 to 80% by weight, particularly preferably 10 to 60% by weight, and the cationic polymerizable The substance (B) is preferably 5 to 95% by weight,
It is particularly preferably 40 to 90% by weight, the photopolymerization initiator (C) is preferably 0.1 to 10% by weight, and particularly preferably 1 to 5% by weight.

The curable composition of the present invention can be prepared by a method such as mixing, dissolving or kneading.

The energy ray-curable composition of the present invention contains a heat-sensitive cation and / or radical polymerization initiator, a coloring agent such as a pigment or a dye, a defoaming agent, if necessary, as long as the effects of the present invention are not impaired. , Various leveling agents, thickeners, flame retardants, antioxidants, light stabilizers, and other resin additives; silica, glass powder, ceramic powder, metal powder, and other fillers; Can be used. As the active energy ray used for curing the composition of the present invention, ultraviolet rays, electron beams, X-rays, radiation, high frequency, and the like can be used. Among these, 1800-500
Ultraviolet rays having a wavelength of 0Å are economically preferable, and as a light source thereof, an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, an alkali metal lamp or the like can be used. A preferable light source is a laser light source, and it is possible to improve the modeling accuracy by increasing the energy level to know the modeling time and utilizing good light-collecting property.

Since the composition of the present invention is cured by a cationic polymerization reaction and a radical polymerization reaction by an active energy ray, the ethylenically unsaturated group-containing compound (A) to be used is used.
Depending on the kind of the cationically polymerizable substance (B), the resin composition is treated with, for example, 30 to 1 at the time of irradiation with active energy rays.
By heating to about 00 ° C., the cross-linking curing reaction can be effectively promoted, and further, the obtained shaped product is subjected to heat treatment at a temperature of 40 to 100 ° C. or a mercury lamp. By performing the UV irradiation treatment with, for example, a molded article having more excellent mechanical strength can be obtained.

The energy ray-curable composition of the present invention is suitable as a composition for optical modeling, and is a model for examining the appearance design in the middle of the design and a model for checking the inconvenience of the combination of parts. , Wooden molds for making molds, copying models for making molds, etc.
Can be used for a wide range of applications. Specific application fields include models and processing of various curved bodies such as automobiles, electronic / electrical parts, furniture, building structures, toys, containers, castings and dolls.

The composition of the present invention is preferably used for printing inks, paints, resists, liquid registrations, adhesives, lenses, castings, etc., as well as optical molding applications.

[0037]

EXAMPLES The present invention will be specifically described below with reference to examples. Parts in Examples are parts by weight.

(Synthesis Example of Sulfonium Salt Represented by Formula (1)) Synthesis Example 1.2,4-Diethylthioxanthone 38.4
Part, 4,4'-difluorodiphenyl sulfoxide 2
3.8 parts, acetic anhydride 100 parts and methanesulfonic acid 39
8 parts were charged and the reaction was carried out at 25 ° C. with stirring for about 8 hours. Then, the reaction mixture was added to an aqueous solution of NaSbF ₆ at 619.9 parts (water 582.8 parts to NaSbF ₆ 37.1).
Part that is melted. ) Was gradually added dropwise, and the precipitated yellow solid was filtered and washed with water and ethylene ether. 93.0 parts of a yellow solid was obtained. The melting point of the product is 81.
The elemental analysis values at 1 to 87.9 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 48.10 48.02 Hydrogen 3.25 3.20 Sulfur 8.89 8.84 Antimony 16.71 16.78 Fluorine 20.99 20.95 This production Based on the method, structural formula

[0039]

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Thus, a sulfonium salt was obtained.

Synthesis Example 2 6.1 parts of 1-chloro-4-propoxythioxanthone, 46.1 parts of 4,4'-dimethyldiphenyl sulfoxide, 200 parts of acetic anhydride, and 796 parts of methanesulfonic acid were charged, and at 25 ° C. After reacting for about 8 hours, the reaction mixture is then mixed with an aqueous solution of NaSbF ₆ 86
2.8 parts (51.7 parts of NaSbF ₆ dissolved in 810.6 parts of water) was added dropwise little by little, and the precipitated yellow solid was filtered and washed with water and ethyl ether. 135.6 parts of a yellow solid was obtained. The melting point of the product is 10
The elemental analysis values at 5.2 to 111.0 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 47.84 47.80 Hydrogen 3.52 3.48 Sulfur 8.57 8.51 Antimony 16.20 16.15 Fluorine 15.15 15.12 Chlorine 4 .72 4.70 Based on this manufacturing method,

[0042]

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A sulfonium salt of was obtained. Synthesis Example 3.2 2-Isopropylthioxanthone 50.8
Parts, diphenyl sulfoxide 40.4 parts, acetic anhydride 20
0 parts and 796 parts of methanesulfonic acid were charged and reacted at 25 ° C. for about 8 hours, and then the reaction mixture was added to 560 parts of an aqueous solution of NaPF ₆ (33.6 parts of NaPF ₆ dissolved in 526.4 parts of water). It was added dropwise little by little, and the precipitated yellow solid was filtered and washed with water and ethyl ether. 105.1 parts of a yellow solid was obtained. The melting point of the product is 79.
The elemental analysis values at 1 to 85.7 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 57.49 57.53 Hydrogen 3.99 3.96 Sulfur 10.95 10.97 Phosphorus 5.28 5.30 Fluorine 19.52 19.50 This production Structural formula based on the method

[0044]

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A sulfonium salt of was obtained.

Synthesis Example 4 40 parts of the compound obtained in Synthesis Example 1,
Sodium hydroxide 4.0 parts, ethylene glycol 200
A portion was charged and reacted at room temperature for 24 hours, then poured into water and the precipitated yellow solid was filtered and dried to obtain a solid product at room temperature. The structural formula of the product is:
The results of elemental analysis agreed with the calculated values.

[0047]

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Element Measured value (wt%) Calculated value (wt%) Carbon 48.31 48.26 Hydrogen 4.10 4.05 Sulfur 8.07 8.05 Antimony 15.30 15.29 Fluorine 14.33 14. 31 Example 1. 15 parts of dipentaerythritol hexaacrylate as an ethylenically unsaturated group-containing compound (A), 55 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as a cationically polymerizable substance (B), bisphenol A An energy ray-curable composition was obtained by sufficiently dissolving and mixing 30 parts of divinyl ether and 3 parts of the sulfonium salt obtained in Synthesis Example 1 as the photopolymerization initiator (C). Using a stereolithography experiment system consisting of a three-dimensional NC (numerical control) table on which a container for containing the composition is placed, a helium-cadmium laser (wavelength 325 nm), and a control unit having an optical system and a personal computer as a main. A cone having a bottom diameter of 12 mm, a height of 15 mm and a thickness of 0.5 mm was formed from this composition. This molded article had no distortion, extremely high modeling accuracy, and excellent mechanical strength.

Embodiment 2 FIG. As the component (A), 20 parts of dipentaerythritol hexaacrylate, 10 parts of trimethylolpropane triacrylate, and as the component (B), 3,4-epoxycyclohexylmethyl-3,4-
45 parts of epoxycyclohexanecarboxylate, 25 parts of triethylene glycol divinyl ether, and sulfonium salt 3 obtained in Synthesis Example 2 as the photopolymerization initiator (C).
The parts were dissolved and mixed to obtain an energy ray-curable composition. Using the laser stereolithography experimental system shown in Example 1,
When a hanging-shaped shaped article was created, the shaped article had no distortion, had extremely high shaping accuracy, and had excellent mechanical strength.

Embodiment 3 FIG. 15 parts of bisphenol A epoxy acrylate, 25 parts of pentaerythritol triacrylate as component (A), 10 parts of bisphenol A diglycidyl ether as component (B), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate An energy ray-curable composition was obtained by dissolving and mixing 30 parts and 2 parts of the sulfonium salt obtained in Synthesis Example 1 as the component (C) and 1 part of the sulfonium salt obtained in Synthesis Example 3. Using the laser light modeling system shown in Example 1, a cup-shaped molded article was prepared while heating the composition to 60 ° C., and the molded article had no distortion and had excellent modeling accuracy. Was obtained.

Embodiment 4 FIG. As component (B), 50 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane caboxylate, 30 parts of trimethylolpropane trivinyl ether, and as component (A), 20 parts of dipentaerythritol hexaacrylate and (C As a component, 3 parts of the sulfonium salt obtained in Synthesis Example 4 was dissolved and mixed to obtain an energy ray-curable composition. When a hanging-shaped shaped object was created using the laser light modeling experiment system shown in Example 1, there was no distortion and excellent mechanical strength, modeling accuracy, and surface smoothness were obtained. As is clear from the results of each example, the composition of the present invention contains an ethylenically unsaturated group by using a specific thioxanthone sulfonium salt without using a radical polymerization initiator and a cationic polymerization initiator in combination. It is clear that the compound and the cation-polymerizable substance can be photopolymerized at the same time, and the curability is excellent, and the obtained cured product has no distortion and is excellent in mechanical strength, modeling accuracy, and the like.

[0052]

The energy ray-curable composition of the present invention comprises:
By using a specific sulfonium salt composed of an ethylenically unsaturated group-containing compound and a cationically polymerizable substance and having both radical polymerization initiation ability and cationic polymerization initiation ability as a polymerization initiator, excellent curability and curing It is possible to obtain a cured product which is free from distortion, is excellent in mechanical strength, modeling accuracy and the like and is particularly suitable for use in stereolithography.

Claims (2)

[Claims] 1. An ethylenically unsaturated group-containing compound (A), a cationically polymerizable substance (B) and a compound of formula (1): (In the formula, X is a group represented by the formula (2) {Wherein R ₆ -R ₁₅ are a hydrogen atom, a halogen atom,
Aliphatic group, phenyl group and phenoxy group which may have a hydroxyl group, an ether group, an ester group, a (meth) acryloyl group, an epoxy group or an allyl group in the structure of nitro group, alkoxy group and C ₁ -C ₂₀ A thiophenoxy group. ) R _{1 to} R ₅ are each selected from a hydrogen atom, a hydroxyl group, a C ₁ -C ₁₅ aliphatic group, a halogen atom, a nitro group, an alkoxy group, an ester group, a phenyl group and a group represented by the formula (2). And n is 1 to 4, Z is the formula (3) or the formula (4) MQ _P (3) MQ _P-1 (OH) (4) (wherein M is a phosphorus atom, a boron atom, It is an arsenic atom or an antimony atom, Q is a halogen atom, and P is an integer of 4 to 6.). } The energy-ray-curable composition containing the photoinitiator (C) which consists of a sulfonium salt shown by these. 2. A cured product of the composition according to claim 1.