JP2020075941A - Photosetting resin composition for optical solid molding used for forming a solid molded article for surgical guide - Google Patents

Abstract

To enable forming a solid molded article having good toughness and strength by optical solid molding using a photosetting resin composition.SOLUTION: There is disclosed a photosetting resin composition for optical solid molding containing a photopolymerization component and a photoinitiator and used for forming a solid molded article for surgical guide. The photopolymerization component is represented by the following formula (I): Rrepresents a hydrogen atom or a methyl group, m+n is 6 to 40, and modified bisphenol A dimethacrylate and a reactive oligomer having 2 or more methacryloyloxy groups are contained.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable resin composition for optical three-dimensional modeling used for forming a three-dimensional molded article for a surgical guide.

  In dental implant surgery, a surgical guide having a guide hole for guiding an implant drill in the oral cavity is used. This surgical guide needs to have a precisely controlled three-dimensional shape, and may be produced by optical three-dimensional modeling (for example, Patent Document 1). According to the optical three-dimensional modeling, the surgical guide can be manufactured in a short time with high dimensional accuracy.

JP, 2014-133134, A

  The conventional surgical guide formed by optical three-dimensional modeling may cause cracks or defects due to, for example, dropping or contact with an implant drill, and improvement in toughness and strength is required.

  Therefore, an object of one aspect of the present invention is to enable the formation of a three-dimensional object having good toughness and strength by optical three-dimensional object formation using a photocurable resin composition.

で表される変性ビスフェノールＡジメタクリレートと、２個以上の（メタ）アクリロイルオキシ基を有する反応性オリゴマーと、を含む。式（Ｉ）中、Ｒ^１は水素原子又はメチル基を示し、同一分子中の複数のＲ^１は同一でも異なっていてもよく、ｍ及びｎはそれぞれ独立に１以上の整数を示し、ｍ＋ｎが６〜４０である。 One aspect of the present invention provides a photocurable resin composition for optical three-dimensional modeling, which contains a photopolymerizable component and a photopolymerization initiator and is used for forming a three-dimensional molded article for a surgical guide. The photopolymerizable component has the following formula (I):

The modified bisphenol A dimethacrylate represented by and a reactive oligomer having two or more (meth) acryloyloxy groups are included. In formula (I), R ¹ represents a hydrogen atom or a methyl group, a plurality of R ¹ in the same molecule may be the same or different, m and n each independently represent an integer of 1 or more, and m + n is 6 to 40.

  In another aspect, the present invention includes a step of forming a three-dimensional molded article for a surgical guide by repeating optical three-dimensional modeling by photo-curing a layer of the photo-curable resin composition for optical three-dimensional modeling, A method of manufacturing a surgical guide is provided.

  According to the present invention, a three-dimensional object having good toughness and strength can be obtained by optical three-dimensional modeling.

  Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The photocurable resin composition according to one embodiment contains a photopolymerizable component and a photopolymerization initiator, and is used to form a three-dimensional object for a surgical guide. The photopolymerizable component is at least the following formula (I):

で表される変性ビスフェノールＡジメタクリレートと、２個以上の（メタ）アクリロイルオキシ基（ＣＨ_２＝Ｃ（ＣＨ_３）Ｃ（＝Ｏ）Ｏ−、ＣＨ_２＝ＣＨＣ（＝Ｏ）Ｏ−）を有する反応性オリゴマーと、を含む。式（Ｉ）中のＲ^１は水素原子又はメチル基を示し、同一分子中の複数のＲ^１は同一でも異なっていてもよく、ｍ及びｎはそれぞれ独立に１以上の整数を示し、ｍ＋ｎが６〜４０である。変性ビスフェノールＡジメタクリレートは、式（Ｉ）中のＲ^１が水素原子であるとき、エチレンオキサイド変性ビスフェノールＡジメタクリレートと称されることがあり、Ｒ^１がメチル基であるとき、プロプレンオキサイド変性ビスフェノールＡジメタクリレートと称されることがある。

A modified bisphenol A dimethacrylate represented in, the two or more (meth) acryloyloxy groups _{(CH 2 = C (CH 3} ) C (= O) O-, CH 2 = CHC (= O) O-) And a reactive oligomer having. R ¹ in formula (I) represents a hydrogen atom or a methyl group, a plurality of R ¹ in the same molecule may be the same or different, m and n each independently represent an integer of 1 or more, and m + n is 6 to 40. The modified bisphenol A dimethacrylate is sometimes referred to as ethylene oxide modified bisphenol A dimethacrylate when R ¹ in the formula (I) is a hydrogen atom, and propylene oxide modified when R ¹ is a methyl group. Sometimes referred to as bisphenol A dimethacrylate.

  In the modified bisphenol A dimethacrylate, when m + n (modification amount) is 6 or more, the toughness and strength of the formed three-dimensional molded article tend to be significantly improved. From the same viewpoint, m + n may be 8 or more, or 10 or more. Further, m + n may be 30 or less.

The reactive oligomer having two or more (meth) acryloyloxy groups is a photopolymerizable compound having a relatively large molecular weight. The number average molecular weight of the reactive oligomer may be 500 or more, 800 or more, or 1000 or more, and 4000 or less, 3000 or less, or 2000 or less. In the present specification, the number average molecular weight means a value measured by a method called GPC (gel permeation chromatography). In the present invention, the number average molecular weight was measured under the following conditions using a gel permeation chromatograph (GPC).
Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Tosoh Corporation TSK Guard Column SuperHZ-L
+ Tosoh Corporation TSKgel SuperHZ 4000
+ Tosoh Corporation TSKgel SuperHZ 3000
+ Tosoh Corporation TSKgel SuperHZ 2000
+ Tosoh Corporation TSKgel SuperHZ 1000
Detector; RI (refractive index), UV (ultraviolet, monitor wavelength 254 nm)
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 0.35 ml / min (Sample side), 0.175 ml / min (Ref side)
Standard; polystyrene sample; tetrahydrofuran solution of 0.5% by weight in terms of resin solid content filtered by a microfilter (injection volume 10 μl)

  The number of (meth) acryloyloxy groups contained in the reactive oligomer may be 3 or less, or 2 per molecule. This tends to further improve the toughness of the three-dimensional molded item.

  The reactive oligomer may include, for example, at least one of a urethane (meth) acrylate oligomer and an epoxy (meth) acrylate oligomer. In particular, when the reactive oligomer contains both a urethane (meth) acrylate oligomer and an epoxy (meth) acrylate oligomer, a further excellent effect is obtained in terms of flexibility and excellent strength.

  The urethane (meth) acrylate oligomer generally has a polyurethane chain formed by polycondensation of a polyisocyanate compound and a polyol compound. A (meth) acryloyloxy group may be introduced at both ends of this polyurethane chain.

  As the urethane (meth) acrylate resin used in the present invention, for example, after reacting a polyol and an organic diisocyanate so that the isocyanate group is in excess of the hydroxyl group, a urethane resin having an isocyanate group at the molecular end is prepared. Examples of the urethane (meth) acrylate resin obtained by reacting this with a hydroxyl group-containing radically polymerizable monomer. The equivalent ratio (NCO / OH) of the isocyanate group (NCO) and the hydroxyl group (OH) when reacting so that the isocyanate group is in excess of the hydroxyl group is preferably 1.5 to 2.

  The urethane (meth) acrylate resin can be prepared by using various catalysts such as dibutyltin laurate and dibutyltin acetate under the conditions of the usual urethanization reaction. At this time, if necessary, a solvent such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene or a radical-polymerizable monomer that does not contain a site that reacts with isocyanate may be used as a solvent.

Examples of the polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol. Propylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentylglycol, hydroxypivalate neo Pentyl glycol ester, cyclohexanedimethylol, 1,4-cyclohexanediol, ethylene oxide adduct of hydroquinone, propylene oxide adduct of hydroquinone, spiroglycol, tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A , Propylene oxide adducts of bisphenol A, polyols such as 1,6-hexanediol-based polycarbonate diol;
The above-mentioned polyols and various α, β-unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and chlorinated maleic acid or their anhydrides, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid , Monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, het acid, chlorendic acid, dimer acid, adipic acid, pimelic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyl Adipic acid, terephthalic acid, dimethyl terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1 Polyesters obtained by condensing saturated polycarboxylic acids such as 10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutanoic acid, hexahydrophthalic acid, and tetrabromophthalic acid, or their acid anhydrides Examples thereof include polyols and polyester polyols obtained by ring-opening polymerization of β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone and the like. The polyols may be used alone or in combination of two or more.

  Examples of the organic diisocyanate include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate and 1,5-naphthalene diisocyanate. Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; hydrogenated various aromatic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane-4,4-diisocyanate The obtained diisocyanate etc. are mentioned. The organic diisocyanates may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing radically polymerizable monomer include hydroxyl groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, pentaerythritol triacrylate, and isocyanuric acid ethylene oxide-modified diacrylate. Containing (meth) acrylate, ethylene oxide adduct of hydroxyl group-containing (meth) acrylate, propylene oxide adduct of hydroxyl group-containing (meth) acrylate, tetramethylene glycol adduct of hydroxyl group-containing (meth) acrylate, hydroxyl group-containing ( Examples thereof include lactone adducts of (meth) acrylate. The hydroxyl group-containing radically polymerizable monomer may be used alone or in combination of two or more kinds.

  The epoxy (meth) acrylate oligomer has, for example, a molecular chain derived from a bisphenol type epoxy resin containing a plurality of repeating units derived from bisphenol, and (meth) acryloyloxy groups introduced at both ends thereof. The bisphenol type epoxy resin is not particularly limited, but may be a bisphenol A type epoxy resin.

  The epoxy (meth) acrylate oligomer used in the present invention can be used without limitation as long as it is obtained by reacting an epoxy resin with (meth) acrylic acid. The acid value of the epoxy (meth) acrylate oligomer is preferably less than 2 mg / KOH.

  In the above-mentioned method for producing an epoxy (meth) acrylate oligomer, as the catalyst used for the reaction between the carboxyl group and the epoxy group, various catalysts such as tertiary amine type and phosphorous acid type can be used.

  Moreover, when preparing an epoxy (meth) acrylate oligomer, the radical polymerizable monomer etc. which do not have a site | part which reacts with a carboxyl group and an epoxy group and can be used by this invention can be used as needed. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol type epoxy resin obtained by hydrogenating an aromatic ring.

  The combination of the modified bisphenol A dimethacrylate and the reactive oligomer improves the toughness and strength of the three-dimensional object. Furthermore, the photocurable resin composition containing such a combination can form a three-dimensional molded article that is not too hard and is excellent in wearing feeling in the oral cavity.

  The photopolymerizable component may further contain a monofunctional monomer having one methacryloyloxy group. This tends to improve the storage stability of the photocurable resin composition. When the photocurable resin composition having excellent storage stability has excellent storage stability, for example, the surplus composition can be easily reused after one-dimensional molding.

  The molecular weight of the monofunctional monomer may be 300 or less, 250 or less, or 200 or less from the viewpoint of storage stability, optimization of viscosity, and the like. Examples of monofunctional monomers include phenoxyethyl methacrylate, phenoxybenzyl methacrylate, cyclohexyl methacrylate, trimethylcyclohexyl methacrylate, cyclohexylmethyl methacrylate, cyclohexylethyl methacrylate, 2-ethylhexyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, and dipropylene glycol monomethacrylate. , Isobornyl methacrylate, phenol ethylene oxide-modified methacrylate, phenylphenol ethylene oxide-modified methacrylate, nonylphenol ethylene oxide-modified methacrylate, isononyl methacrylate, benzyl methacrylate, phenylbenzyl methacrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, ethoxyethoxyethyl Methacrylate, 2-methacryloyloxyethyl succinate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2- Ethyl methoxy methacrylate, 2-ethyl ethoxy methacrylate, 2-ethyl butoxy methacrylate, n-decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, butoxydiethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene Glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, Glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, 2-hydroxy-3-phenoxypropyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl meta. Acrylate, pentamethylpiperidinyl methacrylate, tetramethylpiperidinyl methacrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl methacrylate, (3-ethyloxetan-3-yl) methyl acrylate, Examples thereof include cyclic trimethylolpropane formal methacrylate and morpholine methacrylate, and at least one selected from these may be used. In particular, by combining phenoxyethyl methacrylate with the modified bisphenol A dimethacrylate and the reactive oligomer, the photocurable resin composition tends to have a viscosity suitable for optical stereolithography even though it has a weak odor. Since the three-dimensional modeling process for producing the surgical guide may be performed in the dental field, it is also important that the photocurable resin composition has a weak odor.

  The photopolymerizable component is a compound different from the modified bisphenol A dimethacrylate and the reactive oligomer, and may further contain other polyfunctional monomer having two or more methacryloyloxy groups. Examples of other polyfunctional monomers include 1-6 hexanediol dimethacrylate, 1-4 butanediol dimethacrylate, 1-3 butylene glycol dimethacrylate, 1-9 nonanediol dimethacrylate, 1-10 decanediol dimethacrylate, Neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene oxide modified 1-6 hexanediol dimethacrylate, hydroxypivalic acid neopentyl glycol dimethacrylate, propylene oxide modified Neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene oxide modified dimethacrylate of bisphenol A, propylene oxide modified dimethacrylate of bisphenol A, ethylene oxide modified dimethacrylate of bisphenol F , Tricyclodecane dimethanol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified trimethacrylate of trimethylolpropane, propylene oxide modified trimethacrylate of trimethylolpropane Propylene oxide modified trimethacrylate of glycerin, pentaerythritol trimethacrylate, ethylene oxide modified tetramethacrylate of pentaerythritol, ditrimethylolpropane tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, 2-hydroxy-3-acryloyloxy Propyl methacrylate, ethylene oxide-modified dimethacrylate of bisphenoxyethanolfluorene, polytetramethylene glycol dimethacrylate, ethoxylated isocyanuric acid trimethacrylate, phenoxyethylene glycol methacrylate, stearyl methacrylate, 2-methacryloyloxyethyl succinate, trifluoroethyl methacrylate 3-methyl -1,5 pentanediol dimethacrylate etc. are mentioned. Among these, neopentyl glycol dimethacrylate may be selected from the viewpoints of viscosity adjustment, odor and the like.

  In the photocurable resin composition, the ratio of (meth) acryloyloxy groups contained in the photopolymerizable component (hereinafter sometimes referred to as “C = C concentration”) is 4.5 mmol or less per 1 g of the photopolymerizable component. It may be. When the C = C concentration is low, the toughness tends to be further improved. From the same viewpoint, the C = C concentration may be 4.2 mmol or less, 4.1 mmol or less, or 4.0 mmol or less per 1 g of the photopolymerizable component. The C = C concentration may be 3.0 mmol or more, or 3.5 mmol or more per 1 g of the photopolymerizable component. The C = C concentration is the mass contained in 1 g of the photopolymerizable component, the molecular weight, and the number of methacryloyloxy groups (the number of functional groups) contained in one molecule for each photopolymerizable compound constituting the photopolymerizable component. It can be calculated by obtaining the number (mmol) of (meth) acryloyloxy groups on the basis and summing them. Regarding the reactive oligomer, the C = C concentration can be estimated by regarding the weight average molecular weight as the molecular weight.

  The content of each reactive monomer and oligomer constituting the photopolymerizable component can be determined, for example, in the range described below, in consideration of the viewpoint of C = C concentration, viscosity and the like.

  The content of the modified bisphenol A dimethacrylate may be 15% by mass or more, 20% by mass or more, or 30% by mass or more in the photopolymerizable component (100% by mass) contained in the photocurable resin composition. , 70 mass% or less, 60 mass% or less, or 50 mass% or less.

  The content of the reactive oligomer may be 15% by mass or more, 20% by mass or more, or 30% by mass or more in the photopolymerizable component (100% by mass) contained in the photocurable resin composition, 60 It may be less than or equal to 55% by mass, less than or equal to 55% by mass or less than or equal to 40% by mass.

  The content of the monofunctional monomer may be 0% by mass or more, 5% by mass or more, or 10% by mass or more in the photopolymerizable component (100% by mass) contained in the photocurable resin composition, and 30% by mass. % Or less, 25% by mass or less, or 20% by mass or less.

  The content of the other polyfunctional monomer may be 0% by mass or more, or 5% by mass or more, and 30% by mass or less in the photopolymerizable component (100% by mass) contained in the photocurable resin composition. Or 25% by mass or less.

  When a compound having an acryloyloxy group is used as the photopolymerizable component in the photocurable resin composition, the content of the compound containing an acryloyl group is 50% by mass in the photopolymerizable component (100% by mass). It is preferably the following or less, and more preferably 40% by mass or less. The lower limit of the content of the compound containing an acryloyl group is not particularly limited, but may be 0% by mass or more, and preferably 10% by mass or more.

  The content of the photopolymerizable component in the photocurable resin composition may be 80% by mass or more, 90% by mass or more, or 95% by mass or more based on the total amount of the photocurable resin composition.

  The photopolymerization initiator is not particularly limited as long as it is a compound capable of initiating photoradical polymerization of the photopolymerizable component. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, bis ( It may be at least one selected from 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and the like. The content of the photopolymerization initiator may be, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the photopolymerizable component.

  The photocurable resin composition may contain a solvent for the purpose of adjusting viscosity, but may be substantially solventless. For example, the ratio of the solvent to the total amount of the photocurable resin composition may be less than 5% by mass, less than 3% by mass, or less than 1% by mass.

  The photopolymerizable resin composition may contain other components, if necessary, in addition to the components described above. Other components include UV stabilizers, polymerization inhibitors, antioxidants, stabilizers, leveling agents, defoamers, thickeners, flame retardants, sensitizers, surface active agents, dyes, pigments, fluorescent dyes. , Inorganic fillers, organic fillers and the like.

  The viscosity of the photocurable resin composition can be adjusted in consideration of the processability of three-dimensional modeling. The viscosity of the photocurable resin composition may be, for example, 10 Pa · s or more, 15 Pa · s or more, or 20 Pa · s or more at 25 ° C., 100 Pa · s or less, 50 Pa · s or less, or 30 Pa · s or less. May be

  A surgical guide is easily manufactured in a short time by a method including a step of forming a three-dimensional molded article for a surgical guide by repeating optical curing of a layer of the photocurable resin composition described above. be able to. The optical three-dimensional modeling method is not particularly limited, but may be, for example, a DLP (Digital Light Processing) method. The formed three-dimensional model may be post-cured by irradiation with light. The obtained three-dimensional model has a guide hole for guiding the implant drill, and a metal cylinder is usually attached to the guide hole.

  The three-dimensional molded object formed from the photocurable resin composition of this embodiment can have good toughness. For example, the breaking energy of the three-dimensional model by a tensile test can be 0.2 J or more, or 0.3 J or more. The upper limit of this breaking energy is not particularly limited, but is usually about 2.0 J or less.

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

(Synthesis example 1)
[Synthesis of Polyester Polyol Urethane Acrylate (A)]
In a 1-liter flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, 136 parts of trimethylolpropane and 883 parts of ε-caprolactone were reacted at 200 ° C for 12 hours in the presence of an inert gas to give a solid content. A polyester resin (a) having an acid value of 0.5 and a number average molecular weight of 1000 was obtained.
Then, in a 1-liter flask newly equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, 264.5 parts of isophorone diisocyanate, 1.6 parts of tertiary butyl hydroxytoluene, 0.1 part of methoxyhydroquinone, dibutyltin. 0.1 part of dilaurate was added, the temperature was raised to 70 ° C., and 397.2 parts of the polyester resin (a) synthesized above was dividedly charged for 2 hours. After the completion of charging, the reaction was continued for 2 hours, then 138.2 parts of 2-hydroxyethyl acrylate was added dropwise over 1 hour, and the reaction was continued at 70 ° C. as it was, and the infrared absorption spectrum at 2250 cm −1 indicating an isocyanate group disappeared. The reaction was carried out until that time, and a polyester polyol urethane acrylate (A) was obtained. The polyester polyol urethane acrylate (A) had a number average molecular weight of 3,500 and a weight average molecular weight of 8,500.

(Synthesis example 2)
[Synthesis of Epoxy Acrylate (B)]
In a 1 liter flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, 578.5 parts of liquid bisphenol A type epoxy resin ("Epiclone 850, epoxy equivalent 188 g / eq." Manufactured by DIC Corporation), acrylic acid 217 0.5 parts and methoxyhydroquinone 0.1 parts were charged, the temperature was raised to 100 ° C., and then 4 parts by mass of triphenylphosphine was added.The reaction was carried out at 100 ° C. for 10 hours, and the epoxy equivalent was 18,000 g / eq. An epoxy acrylate (B) having an acid value of 0.4 mgKOH / g and a solution viscosity (butyl acetate non-volatile content 80 mass solution) of 1.8 Pa · s was obtained, the epoxy acrylate (B) having a number average molecular weight of 1,000, The weight average molecular weight was 1300.

(Synthesis example 3)
[Synthesis of Urethane Acrylate (C)]
In a 1 liter flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, 124.6 parts of isophorone diisocyanate, 1.6 parts of tert-butyl hydroxytoluene, 0.1 part of methoxyhydroquinone, 0.1 part of dibutyltin dilaurate. Parts were added, the temperature was raised to 70 ° C., and 673.5 parts of pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd .; Aronix M-305) were separately charged over 2 hours. After the completion of the charging, the reaction was continued as it was at 70 ° C., and the reaction was carried out until the infrared absorption spectrum at 2250 cm −1 showing an isocyanate group disappeared to obtain a urethane acrylate (C). The number average molecular weight of urethane acrylate (C) was 1100, and the weight average molecular weight was 2600.

(Measurement method of solid content acid value)
The solid content acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample, and was determined by the following measurement method shown in JIS K0070-1992. ..
(1) The reagents are as follows.
-0.1 mol / l hydrochloric acid According to JIS K 8001 4.5 (5.5) [0.1 mol / l hydrochloric acid (3.646 g HCl / l)].
-0.1 mol / l potassium hydroxide ethanol solution Dissolve 7 g of potassium hydroxide specified in JIS K8574 in 5 ml of water, add ethanol (95) specified in JIS K8102 to 1 l, and block carbon dioxide for 2-3 days. After standing, the supernatant is removed or filtered and stored in an alkali resistant bottle. For the standardization, all 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask using a pipette, phenolphthalein solution was added, and titrated with 0.1 mol / l potassium hydroxide ethanol solution. Ask for.
-Phenolphthalein solution According to JIS K8001 4.3 (indicator).
A solvent in which diethyl ether specified in JIS K8103 and ethanol (99.5) specified in JIS K8101 are mixed at a volume ratio of 1: 1 or 2: 1.
Immediately before use, a few drops of phenolphthalein solution are added as an indicator, and these are neutralized with 0.1 mol / l potassium hydroxide ethanol solution.
(2) Equipment and instruments Equipment and instruments are as follows.
・ Erlenmeyer flask 300 ml
・ Burette 25ml
・ Water bath or hot plate (3) operation is performed as follows.
・ Weigh an appropriate amount of sample into an Erlenmeyer flask.
Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well on a water bath until the sample is completely dissolved.
-Titrate with 0.1 mol / l potassium hydroxide ethanol solution, and make the end point when light pink color of the indicator continues for 30 seconds.
(4) The calculated acid value is calculated by the following formula.
A = (B × f × 5.611) / S
here,
A: Acid value B: Amount of 0.1 mol / l potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.1 mol / l potassium hydroxide ethanol solution S: Mass of sample (g)
5.611: Formula weight of potassium hydroxide 56.11 x 1/10

(Measurement method of number average molecular weight)
Using a gel permeation chromatograph (GPC), the weight average molecular weight and the number average molecular weight were obtained under the following conditions.
Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Tosoh Corporation TSK Guard Column SuperHZ-L
+ Tosoh Corporation TSKgel SuperHZ 4000
+ Tosoh Corporation TSKgel SuperHZ 3000
+ Tosoh Corporation TSKgel SuperHZ 2000
+ Tosoh Corporation TSKgel SuperHZ 1000
Detector; RI (refractive index), UV (ultraviolet, monitor wavelength 254 nm)
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 0.35 ml / min (Sample side), 0.175 ml / min (Ref side)
Standard; polystyrene sample; tetrahydrofuran solution of 0.5% by weight in terms of resin solid content filtered by a microfilter (injection volume 10 μl)

1. Resin composition for stereolithography

  Raw materials were mixed at the compounding ratios shown in Table 1 to obtain a resin composition for stereolithography.

Each raw material described in the table is as follows.
-Modified bisphenol A dimethacrylate: ethylene oxide modified ethylenebisphenol A dimethacrylate (a compound in which R ¹ is a hydrogen atom and m + n is 10 in the formula (I))
-Urethane acrylate (A): Polyester polyol urethane acrylate (A) synthesized in Synthesis Example 1
Epoxy acrylate (B): Epoxy acrylate (B) synthesized in Synthesis Example 2
-Urethane acrylate (C): Urethane acrylate (C) synthesized in Synthesis Example 3
-TPO: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by BASF, IRGACURE TPO)

  A commercially available photocurable resin composition (Clear Guide (trade name) manufactured by Envision) that is generally used for surgical guide molding was prepared as the composition of Comparative Example 1. The resin composition for stereolithography of Example had a sufficiently weak odor as compared with the composition of Comparative Example 1.

2. Preparation and evaluation of three-dimensional object 2-1. Stereolithography A DLP (Digital Light Processing) stereolithography system (3D printer) was used to generate a stereoscopic sculpture having a predetermined shape with the photocurable resin composition. The stacking pitch for stereolithography was 0.1 mm, the irradiation wavelength was 400 to 410 nm, and the light irradiation time was 2 to 5 seconds. The formed three-dimensional object was subjected to ultrasonic cleaning in isopropanol and then post-cured by light irradiation with a high pressure mercury lamp. By this method, a three-dimensional object having the following shapes for evaluation was produced.

Modeling precision A surgical guide having a predetermined guide hole was produced by optical modeling using each photocurable resin composition. A metal cylinder, which serves as a mark for the implant drill, was embedded in the guide hole of the obtained surgical guide. At that time, it was observed whether or not the metal cylinder was smoothly embedded without generating cracks and cracks around the holes.

2-2. Tensile Test Using each photocurable resin composition, a dumbbell test piece of ISO527-1 standard was produced. The thickness direction of the dumbbell test piece was defined as the laminating direction of the stereolithography. Using the obtained dumbbell test piece, the elastic modulus, the maximum point strength, the elongation at break, and the breaking energy were obtained by a tensile test according to the ISO527-1 standard.

  As shown in Table 1, it was confirmed that the photocurable resin composition of the example could precisely form a three-dimensional molded article having good toughness and strength. In particular, the photocurable resin compositions of Examples 1 and 2 having low double bond density exhibited higher toughness than ever before. Further, it is considered that the stereolithography product of the example has an appropriate hardness and is excellent as a surgical guide in wearing feeling in the oral cavity.

Claims (6)

Contains a photopolymerizable component and a photopolymerization initiator, the photopolymerizable component,
Formula (I) below:

, R ¹ represents a hydrogen atom or a methyl group, a plurality of R ¹ in the same molecule may be the same or different, m and n each independently represent an integer of 1 or more, and m + n is 6 to 40, a modified bisphenol A dimethacrylate,
A reactive oligomer having two or more (meth) acryloyloxy groups,
Including,
Used to form a three-dimensional object for a surgical guide,
A photocurable resin composition for optical three-dimensional modeling.   The photocurable resin composition for optical stereolithography according to claim 1, wherein the ratio of the (meth) acryloyloxy group contained in the photopolymerizable component is 4.5 mmol or less per 1 g of the photopolymerizable component. .   The photocurable resin composition for optical stereolithography according to claim 1, wherein the reactive oligomer contains at least one of a urethane (meth) acrylate oligomer and an epoxy (meth) acrylate oligomer.   The photocurable resin composition for optical three-dimensional modeling according to claim 1, wherein the photopolymerizable component further contains a monofunctional monomer having one methacryloyloxy group.   The photocurable resin composition for optical three-dimensional modeling according to claim 4, wherein the monofunctional monomer contains phenoxyethyl methacrylate.   A step of forming a three-dimensional object for a surgical guide by repeating optical curing of a layer of the photocurable resin composition for optical three-dimensional object manufacturing according to any one of claims 1 to 5. And a method of manufacturing a surgical guide.