JPH0485314A - Resin composition for optical three-dimensional formation - Google Patents

Abstract

PURPOSE: To obtain a composition small in change of the elasticity of a shaped article over a wide range of temperature by mixing a silicone urethane (meth) acrylate, a polyfunctional compound having an ethylenically unsaturated bond and a polymerization initiator.

CONSTITUTION: A desired resin composition comprises (A) a silicone urethane (meth)acrylate, (B) a polyfunctional compound having an ethylenically unsaturated bond and (C) a polymization initiator. The mixing proportion of compound (A) in this composition is usually 10-80 wt.%. When this amount is less than 10 wt.%, the breaking extension of a cured product to be obtained tends to decrease and when the amount is more than 80 wt.%, the modulus of elasticity at arounad room temperature of the cure product tends to decrease. Further, the mixing proportion of compound (B) is usually 10-80 wt.% When the amount is less than 10 wt.%, the curing properties decrease and, at the same time, the modulus of elasticity at around room temperature tends to decrease and when the amount is more than 80 wt.%, the breaking extension of a cured product to be obtained tends to decrease.

COPYRIGHT: (C)1992,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is an optical technology that provides a shaped object that has a low viscosity in an uncured state, a high curing rate when irradiated with light, and small changes in physical properties over a wide temperature range. The present invention relates to a resin composition for three-dimensional modeling.

[Conventional technology]

The optical three-dimensional modeling method is, for example, disclosed in Japanese Patent Application Laid-Open No. 60-2475.
As described in Japanese Patent No. 15, this is a method of selectively supplying energy necessary for curing to a photocurable liquid material to form a three-dimensional object of a desired shape. A similar method or improvement thereof is disclosed in U.S. Patent No. 4.575.3.
No. 30 (Japanese Unexamined Patent Publication No. 62-35966), Unexamined Japanese Patent Publication No. 62-35966
It is also disclosed in JP-A-101408 and the like. A typical example of this three-dimensional modeling method is to selectively irradiate the surface of a photocurable liquid substance placed in a container with light, such as an ultraviolet laser, so as to obtain a cured layer with a desired pattern. Next, a layer of a photocurable liquid substance is supplied onto the cured layer, and then light is selectively irradiated in the same manner as above to perform a lamination operation to obtain a cured layer continuous with the above cured layer. There is a method of finally obtaining a desired three-dimensional object by repeating the process. This three-dimensional modeling method is attracting attention because even when the shape of the object to be manufactured is complex, it is possible to easily obtain the desired object in a short time.

Conventionally, photocurable liquid substances used in this three-dimensional modeling method include resins such as modified polyurethane methacrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, and amino alkyd (Japanese Patent Application Laid-Open No. 60-247515 Publication No.).

[Problem to be solved by the invention]

The resin used in such a three-dimensional modeling method is required to be able to perform modeling quickly, have a low viscosity in an uncured state, and harden quickly when irradiated with various types of light. Furthermore, objects manufactured using this three-dimensional modeling method are used as models for examining designs and as prototypes of mechanical parts. Since it is used in a temperature range, it is required that the shaped article can be used in a wide temperature range and that changes in physical properties are small.

However, conventional resins for optical three-dimensional modeling have low viscosity when uncured, and harden quickly when exposed to light.
Moreover, there was no model whose physical properties changed sufficiently from a low temperature range to a high temperature range.

Therefore, it is an object of the present invention to provide a resin composition for optical three-dimensional modeling that satisfies all of the above-mentioned properties required of a resin for optical three-dimensional modeling and exhibits a small change in the elastic modulus of a model over a particularly wide temperature range. purpose.

[Means to solve the problem]

The present invention provides (A) silicone urethane (meth)acrylate (
The present invention provides a resin composition for optical three-dimensional modeling characterized by containing B) a compound having a polyfunctional ethylenically unsaturated bond and (C) a polymerization initiator.

The silicone urethane (meth)acrylate (hereinafter referred to as "compound (A)") as the component (A) used in the present invention includes, for example, ■ a polyol having a polysiloxane structure, ■ a diisocyanate, and ■ a (meth)acrylate having a hydroxyl group. It can be obtained by reacting,
Specific examples include the following methods.

(Production method 1) (1) A method in which (meth)acrylate having a hydroxyl group is reacted with an isocyanate group of an intermediate product obtained by reacting a polyol having a polysiloxane structure and (2) a diisocyanate.

(Production method 2) A method in which (1) a polyol having a polysiloxane structure is reacted with an isocyanate group of an adduct obtained by reacting (1) a diisocyanate and (2) a (meth)acrylate having a hydroxyl group.

(Production method 3) A method in which (1) a diisocyanate, (2) a polyol having a polysiloxane structure, and (2) a (meth)acrylate having a hydroxyl group are simultaneously reacted.

(2) Examples of polyols having a polysiloxane structure include the following compounds (1) and (2).

-(OR, +T+OR Sho' Kano (1) (in the formula, R8
represents a methyl group or a phenyl group, R2o and R3 each represent an alkylene group having 1 to 12 carbon atoms, and l represents 1
~500, m represents 0 to 500, X represents 1 to 6,
y represents 0 to 6) (wherein, R1, L, l and m
is as described above, n is 2 to 500, preferably l+m is 5 to 200, and n is 2 to 0) These polyols having a polysiloxane structure are:
For example, FM4411, FM4421, FM4425 (
Above, Chisso @), Q 4-3367, Q 2-80
26 (Tore Silicone@) KF6001
, KF60 (12, KF6003 (Shin-Etsu series)
-n@), 1248 FLUID <I ft :1
It can be manually prepared as a commercially available product such as Ning@).

In addition, as diisocyanates, 2.4-tolylene diisocyanate, 2.6-)lylene diisocyanate, isophorone diisocyanate, 1.3-xylylene diisocyanate, 1.4-xylylene diisocyanate)
, 1.5-naphthalene diisocyanate, m-phenyl diisocyanate, p-phenyl diisocyanate, 3゜3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4.4'-diphenylmethane diisocyanate, 3.3 '-dimethylphenylene diisocyanate, 4.4'-biphenylene diisocyanate,
Hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated bisphenol A diisocyanate, 2
．． 2.4-Trimethylhexamethylene diisocyanate, bis(2-isocyanatoethyl) fumarate, 6-
Isoprobyl-1,3-phenyl diisocyanate, 4
-diphenylpropane diisocyanate and the like. Among these diisocyanates, 2.4-tolylene diisocyanate, inphorone diisocyanate,
Hydrogenated bisphenol A diisocyanate, 2,2.4-
) Dimethylhexamethylene diisocyanate and the like are preferred, and particularly preferred are isophorone diisocyanate, 2,4-)lylene diisocyanate and the like.

■ Examples of (meth)acrylates having hydroxyl groups include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate. meth)acrylate, trimethylolpropaque di(meth)acrylate, trimethylolethacrylate di(meth)acrylate, pentaerythritol tri(
meth)acrylate, dipentaerythritoltripenta(meth)acrylate, 1,4-butanediol mono(meth)acrylate, 4-hydroxycyclohexyl(meth)acrylate, 1.6-hebosandiol mono(meth)acrylate, Neo Pentyl glycol mono (meth)acrylate, glyceric di(meth)acrylate, (meth)acrylates represented by the following structural formulas (3) to (5), and glycidyls such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth)acrylate. Examples include compounds obtained by an addition reaction between a group-containing compound and (meth)acrylic acid.

R4 O01l (In the formula, R4 represents a hydrogen atom or a methyl group) (In the formula, R4 is the same as above, and p is 1 to 5) CC(5) 0'ゝN/'0 CH, CH2DCOCR,=CH.

(In the formula, R6 is the same as above) Among these (meth)acrylates having a hydroxyl group,
Preferred examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate,
Hydroxybutyl (meth)acrylate and (meth)acrylate represented by the above structural formula (4) can be mentioned.

A preferred embodiment of the production method 1 is shown below.

■The amount of diisocyanate used per equivalent of the hydroxyl group of the polyol having a polysiloxane structure is approximately 0.5 to
Preferably it is 1 mol. In this reaction, a catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, or triethylamine is usually added in an amount of 0.01 to 1 part by weight per 100 parts by weight of the total amount of reactants.
The reaction is carried out using parts by weight. The reaction temperature in this reaction is usually 0 to 80°C. Also, ■ has a hydroxyl group (
The amount of meth)acrylate used is approximately 0.8 to 1.2 equivalents of hydroxyl groups per equivalent of incyanate group of the intermediate product, and the reaction conditions are the same as those for the synthesis of the intermediate product described above. It is.

Next, a preferred embodiment of the production method 2 will be described.

■ Contains a hydroxyl group per mole of diisocyanate (
0.5 to 1.0 mol of meth)acrylate is reacted under the same reaction conditions as in Production Method 1, and the amount of hydroxyl group of the diol having a polysiloxane structure is approximately 0.8 with respect to 1 equivalent of isocyanate group of the resulting adduct. It is used so that it becomes 1.2 equivalents, and it is made to react under the same reaction conditions as Production Method 1.

Next, a preferred embodiment of the production method 3 will be described.

■The amount of diisocyanate used is 0.5 to 1 mol per equivalent of the hydroxyl group in the diol having a polysiloxane structure, and the amount of (meth)acrylate used in the diol having a polysiloxane structure is 0.5 to 1 mol. The total amount of hydroxyl groups including the hydroxyl groups in the diisocyanate is adjusted to be 0.9 to 1.1 times equivalent to the total incyanate groups of the diisocyanate.

In the present invention, the compound (A) obtained as described above
The weight average molecular weight (hereinafter referred to as "MIll") is usually 500 to 30.000, and 1.000 to 10.0.
A range of '00 is preferred. When the h of the compound (A) is less than 500, the elongation at break of the cured product of the resulting composition decreases, and the toughness tends to decrease. In addition, the Mw amount is 30,
When it exceeds 000, the viscosity of the resulting composition increases,
It becomes difficult to handle and the manufacturing speed of the shaped object is reduced due to loss of fluidity.

The proportion of the polysiloxane structure occupied in the compound (A) is usually 50 to 99% by weight, preferably 60 to 98% by weight.

In the present invention, the blending ratio of compound (A) in the resin composition is usually 10 to 80% by weight, preferably 15 to 70% by weight.
Weight%. If it is less than 10% by weight, the elongation at break of the resulting cured product tends to decrease, and if it exceeds 80% by weight, the elastic modulus of the cured product at around room temperature tends to decrease.

In the composition of the present invention, urethane (meth)acrylates other than compound (A) can be used in combination as long as the effects of the present invention are not impaired. As the urethane (meth)acrylate other than compound (A), a compound selected from polytetramethylene polyol, polypropylene polyol, polybutylene polyol, polyethylene polyol, polycaprolactone polyol, polycarbonate polyol, and polyester polyol is used, which has the diisocyanate and the hydroxyl group. Examples include urethane (meth)acrylate obtained by reacting with (meth)acrylate.

A compound having a polyfunctional ethylenically unsaturated bond as component (B) used in the present invention (hereinafter referred to as "compound (B)")
For example, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2 -hydroxyethyl)isocyanurate tri(meth)acrylate,
trimethylolpropane tri(meth)acrylate,
Trimethylolpropane trioxyethyl (meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A diglycidyl ether with (meth)acrylic acid adduct at both ends, 1.4-butanediol di(meth)acrylate, 1. 6-hexanethiol di(
meth) acrylate, pen, taerythritol tri(
meth)acrylate, pentaerythritol tetra (
Examples include meth)acrylate, polyester di(meth)acrylate, polyethylene polyol di(meth)acrylate, and the like. As a commercially available product, coffee z-[IV
, 5A2007 (Mitsubishi Yuka@), Visco)
700 <Osaka Organic Chemistry fm), KAYARAOR
-604゜11PCA-20,-30,-60,-12
0,) IX-620, D-310, D-330 (and above,
Nippon Kayaku @), T Knixst 21o.

M-215, M-315, M-325 (hereinafter referred to as Toagosei Kagaku ■), and the like.

In the present invention, the blending ratio of compound (B) in the resin composition is usually 10 to 80% by weight, preferably 15 to 70% by weight.
Weight%. If it is less than 10% by weight, the curability tends to decrease and the elastic modulus near room temperature tends to decrease, and if it exceeds 80% by weight, the elongation at break of the cured product obtained tends to decrease.

The polymerization initiator (C) component (hereinafter referred to as "compound (C)") in the present invention is not particularly limited, but a photopolymerization initiator or a thermal polymerization initiator can be used.

Compound (C) includes acetophenone, acetophenone diethyl ketal, anthraquinone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4°4' -diaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 2
．． 2-dimethoxy-2-phenylacetophenone, 4.
4'-dimethoxybenzophenone, thioxanthone compounds, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-(
4-(methylthio)phenyl)2-morpholino-propan-1-one, triphenylamine, 2.4.6-)
Limethylbenzoyldiphenylphosphine oxide,
1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzyl dimethyl ketal, benzaldehyde, benzoin ethyl ether,
Benzoinpropyl ether, benzophenone, Michler's ketone, 2-methyl-1-(:4- (methylthiophenyl)]-]2-morpholinopropan-1-one 3
- methylacetophenone, 3.3', 4.4' -tetra(t-butylperoxycarbonyl)benzophenone (BTTB) and combinations of BTTB with bovine santhene, thioxanthin, coumarin, ketocoumarin and other dye sensitizers, etc. Photopolymerization initiator; benzoin peroxide,
t=nibutylperoxybenzoate dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, t
Examples include thermal polymerization initiators such as -butyl peroxide and azobisisobutyronitrile.

Among these, 1-hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal, 2°4.6-)limethylbenzoyldiphenylphosphine oxide and the like are preferred.

When using a thermal polymerization initiator, it is preferable to use infrared rays as the radiation.

The blending ratio of compound (C) in the resin composition in the present invention is usually 0.05 to 10% by weight, preferably 0.1 to 8% by weight.
% by weight, particularly preferably from 0.5 to 5% by weight. 1
If it exceeds 0% by weight, it may have an adverse effect on the physical properties, curing characteristics, handling properties, etc. of the cured product, and if it is not added at 0.05% by weight, the curing speed may decrease.

In addition, if necessary, a sensitizer (polymerization accelerator) such as an amine compound such as triethanolamine, methyljetanolamine, triethylamine, or diethylamine may be used in combination with compound (C) within a range that does not interfere with the curing of the present invention. can do.

In addition to compound (A), compound (B) and compound (C), a reactive diluent having a monofunctional ethylenically unsaturated group can be used in the composition of the present invention, if necessary.

Examples of the monofunctional compound used here include acrylamide, 7-amino-3,7-dimethyloctyl (
meth)acrylate, isobutoxymethyl(meth)acrylamide, isobornyloxyethyl(meth)acrylate, inbornyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, ethyldiethylene glycol(meth)acrylate, t-octyl(meth)acrylate
Acrylamide, diacetone (meth)acrylamide,
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dicyclopentadiene (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (meth) Acrylamide, tetrachlorophenyl (meth)acrylate,
2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromo Phenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-11 nitroxyprobyl (meth)acrylate, vinylcaprolactam,
N-vinylpyrrolidone, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentapro-phenyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate , bornyl (meth)acrylate, (meth)acryloylmorpholine, methyltriethylene diglycol (meth)acrylate, and compounds represented by the following structural formulas (6) to (8).

(In the formula, R4 is the same as above, and R3 has 2 to 6 carbon atoms.
, preferably represents an alkylene group having 2 to 4 carbon atoms, R8 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to 9 carbon atoms, and r represents 0 to 12, preferably in the formula, R4 is the same as above. Yes, R1 has 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms.
represents an alkylene group, q is 1 to 8, preferably 1 to 4
) 1(4R4 (In the formula, R1, R7 and q are the same as above) Also, as a commercially available product, Aroma: Ris Mi11. M113° M114. M117 (Toagosei Chemical ■')
,KAYARADTCIIO3,R629,R644(
As mentioned above, Nippon Kayaku@), Visco) 3700 (Osaka Organic Chemistry@), etc. are mentioned.

Furthermore, vinyl ethers, vinyl sulfides, vinyl urethanes, vinyl ureas, etc. can also be used as reactive diluents.

In addition, the resin composition of the present invention may contain other additives such as epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene/butadiene/styrene block copolymer, etc., as necessary. Polymers or oligomers such as styrene/isoprene/styrene block copolymers can be blended. Petroleum resins, xylene resins, ketone resins, fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, etc. can also be blended. Polymerization inhibitors such as phenothiazine and 2,6-sheet-t-butyl-4-methylphenol can also be blended. Furthermore, various additives other than those mentioned above, such as sensitizers, polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers,
Resin particles, pigments, dyes, etc. may also be blended.

The viscosity of the resin composition of the present invention is usually 20 to 5000c.
ps (25°C), preferably 20-2000 cps.

Particularly preferred is 20 to 5C1Ocps.

The resin composition of the present invention can be suitably used as a curable liquid substance in optical stereolithography. That is, by selectively irradiating the resin composition of the present invention with light such as visible light, ultraviolet light, or infrared light at specific locations and supplying the energy necessary for curing, a three-dimensional object with a desired shape is obtained. be able to.

The method of selectively irradiating light to a specific location of the resin composition is not limited, and examples include a method of irradiating a specific location with laser light, focused light obtained using a lens, mirror, etc., and non-focused light. For example, a method of irradiating the light through a partially patterned mask can be mentioned. However, when placing importance on microprocessability and processing accuracy, which are some of the characteristics of the resin composition of the present invention, it is preferable to minimize the size of the focused light, and in such cases, the laser beam is It is preferable to use Furthermore, the specific location to be irradiated with light may be the liquid level of the resin composition placed in the container, the surface in contact with the side wall or lower wall of the container, or even in the liquid. In order to irradiate the liquid surface of the resin composition or the surface in contact with the container wall, the light may be irradiated from the outside directly or through the transparent container wall.In order to irradiate the light to a specific location in the liquid, For example, by a light guide such as an optical fiber,
It can be irradiated.

In this optical three-dimensional modeling method, after curing a desired specific area, the irradiation position is moved continuously or stepwise from the cured area to the adjacent uncured area, so that the cured area is cured. can be grown into a desired three-dimensional shape. Various methods are possible for moving the irradiated position, such as moving one or more of the light source, the container, and the cured portion, or adding an uncured liquid curable substance to the container.

A typical method for obtaining a shaped object from the resin composition of the present invention is to selectively irradiate the liquid composition of the present invention with light to form a cured layer with a desired pattern. Then, the uncured composition layer adjacent to the cured layer is irradiated with light in the same manner to form a new cured layer continuous with the previous cured layer.The lamination operation is repeated to finally achieve the desired result. A method for obtaining a three-dimensional, that is, a three-dimensional shaped object is mentioned.

More specific embodiments of the above method include the following examples.

After the first cured layer is formed, the uncured composition of the next cured portion is additionally supplied onto the obtained first cured layer,
A method of repeating the process of further irradiating light to form the next hardened layer.

■ Submerge the bottom plate in the composition by the depth of the first hardened layer 1
After the first cured layer is formed, the bottom plate is further submerged to a partial depth to allow a portion of the uncured composition to flow onto the first cured layer, which is then irradiated with light to form the next layer. A method of repeating operations to form a hardened layer.

■ A box with a transparent bottom plate is submerged in the composition placed in a container, and the composition layer formed in the gap between the bottom plate and the bottom of the container is made to have the same thickness as the first cured layer. , the composition layer is irradiated with light through the transparent bottom plate of the box, and the first
After forming a cured layer, the case is raised to allow the composition to flow into the gap between the first cured layer and the transparent bottom plate of the case,
A method of repeating the process of irradiating light in the same way to form the next hardened layer.

■ Submerge the plate in the composition placed in a container with a transparent bottom, and make the composition layer formed in the gap between the iron plate and the bottom of the container the same thickness as the first hardened layer. After irradiating the composition layer with light through the transparent bottom of the container to form a first cured layer, a portion of the uncured composition is removed by raising the plate by one layer thickness. A method of repeating the operation of causing the first cured layer to flow into the gap between the first cured layer and the plate, and then irradiating with light in the same manner as described above to form the next cured layer.

The three-dimensional structure formed by the methods (1) to (4) above is taken out from the container used for the reaction, and after removing unreacted compounds remaining on the surface of the three-dimensional structure, the three-dimensional structure is washed as necessary. As the cleaning agent used for cleaning, organic solvents typified by alcohols such as isopropyl alcohol, and thermosetting or photocurable low viscosity resins can be used.

When it is desired to impart transparency to a three-dimensional object, it is preferable to use the above-mentioned thermosetting or photocurable resin for cleaning. Further, in this case, it is necessary to perform post-curing with heat or light after cleaning, depending on the type of resin used for cleaning. Note that post-cure not only cures the resin on the surface, but also has the effect of curing unreacted resin composition that may remain inside the three-dimensional object, so it can be used even when cleaning with an organic solvent. It is preferable to do so.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Production Example 1 25.8 g of tricyclodecane dimetatool diacrylate in a reaction vessel, 2. 4-) 34.8 g of lylene diisocyanate, 0.4 g of dibutyltin dilaurate, 0.3 g of phenothiazine and 2,6-di-t-butyl-
0.2 g of 4-methylphenol was charged.

Next, while cooling the reaction vessel with ice water, 23.2 g of hydroxyethyl acrylate was added thereto while stirring the internal solution so that the internal temperature did not exceed 25°C.

After the addition, the internal temperature was maintained at 5 to 25°C and stirring was continued for 1 hour, and then silicone diol (1w2,000) was added.
(KF6001 manufactured by Shin-Etsu Silicone) 200 g was added while stirring the internal solution so that the internal temperature did not exceed 60°C.

After the addition is complete, the residual isocyanate group is 0.1 of the charged amount.
Stirring was continued until the amount was reduced to % by weight or less to obtain silicone urethane acrylate with Mw of 2600.

The obtained tricyclodecane dimetatool diacrylate solution of silicone urethane acrylate was mixed with oligomer (
1). The weight ratio of silicone urethane acrylate and tricyclodecane dimetatool diacrylate is 10.
:1.

Manufacturing example 2 56.8 g of inbornyl acrylate was added to the reaction vessel.

Inphoron diisocyanate 44.4g, silicone diol (Mw5.000) (FM4421 Chisso ■)
500g.

0.6 g of phenothiazine and 0.4 g of 2,6-di-t-butyl-4-methylphenol were charged.

Next, while cooling the reaction vessel with ice water, 0.8 g of dibutyl tin dilaure was added thereto while stirring the internal solution so that the internal temperature did not exceed 30°C.

After the addition was completed, the internal temperature was maintained at 40 to 50°C and stirring was continued for 1 hour.
g was added while stirring the internal solution so that the internal temperature did not exceed 60°C. Thereafter, the internal temperature was maintained at 60° C. and stirring was continued until the residual isocyanate group became 0.1% by weight or less of the charged amount to obtain a silicone urethane acrylate of 1w5700. The obtained inbornyl acrylate solution of silicone urethane acrylate was converted into oligomer (2).
shall be. The weight ratio of silicone urethane acrylate to inbornyl acrylate is 10:1.

Manufacturing example 3 109.9 g of isobornyl acrylate was placed in a reaction vessel.

Isophorone diisocyanate) 66, 46g, silicone:/silicone (Mw5.000) (FM442
1 f so @ 1000g.

0.8 g of phenothiazine and 0.5 g of 2,6-di-t-butyl-4-methylphenol were charged.

Next, while cooling the reaction vessel with ice water, 1.0 g of dibutyltin dilaurate was added thereto while stirring the internal solution so that the internal temperature did not exceed 30°C.

After the addition was completed, the internal temperature was maintained at 40 to 50°C and stirring was continued for 1 hour.
g was added while stirring the internal solution so that the internal temperature did not exceed 60°C. Thereafter, the internal temperature was maintained at 60° C. and stirring was continued until the residual incyanate group became 0.1% by weight or less of the charged amount to obtain a silicone urethane acrylate having a Mwlo of 900.

The obtained isobornyl acrylate solution of silicone urethane acrylate is referred to as oligomer (3).

The weight ratio of silicone urethane acrylate to isobornyl acrylate is 10:1.

Production example 4 200 g of isobornyl acrylate in a reaction vessel.

2.4-)lylene diisocyanate) 79 g, polydimethylsiloxane having hydroxyl groups (Mw 5.700) (
DOW CORNINGO1284FL [lID, Dow Corning■) 868g, phenothiazine 0.8g
and 0.5 g of 2,6-di-t-butyl-4-methylphenol. Next, while cooling the reaction vessel with ice water, 1.0 g of dibutyl tin dilaure was added thereto while stirring the internal solution so that the internal temperature did not exceed 20°C.

After the addition was completed, the internal temperature was maintained at 20 to 30°C and stirring was continued for 1 hour, and then 53 g of hydroxyethyl acrylate was added while stirring the internal solution so that the internal temperature did not exceed 60°C. Thereafter, the internal temperature was maintained at 60° C. and stirring was continued until the residual isocyanate group became 0.1% by weight or less of the charged amount to obtain a silicone urethane acrylate with Mw of 6,600.

The obtained isobornyl acrylate solution of silicone urethane acrylate is referred to as oligomer (4).

The weight ratio of silicone urethane acrylate to inbornyl acrylate is 5:1.

Comparative Production Example 1 25.8 g of tricyclodecane dimetatool diacrylate in a reaction vessel; 2. 4-) 34.8 g of luene diisocyanate, 0.4 g of dibutyltin dilaurate.

0.3 g of phenothiazine and 0.2 g of 2,6-di-t-butyl-4-methylphenol were charged.

Next, while cooling the reaction vessel with ice water, 23.2 g of hydroxyethyl acrylate was added thereto while stirring the internal solution so that the internal temperature did not exceed 25°C.

After the addition was completed, the internal temperature was maintained at 5 to 25°C and stirring was continued for 1 hour, and then polytetramethylene glycol (1w2.
000) was added while stirring the internal solution so that the internal temperature did not exceed 60°C. Thereafter, stirring was continued until the residual isocyanate groups became 0.1% by weight or less of the charged amount. The obtained tricyclodecane dimetatool diacrylate solution of polytetramethylene glycol urethane acrylate oligomer with Mw of 2600 is designated as oligomer (5). The weight ratio of polytetramethylene glycol urethane acrylate to tricyclodecane dimetatool diacrylate is 10:1.

Examples 1 to 5, Comparative Examples 1 to 2 The components shown in Table 1 below were stirred at 40 to 50°C for 2 hours to obtain transparent resin compositions.

The following margin test examples Using each resin composition obtained in Examples 1 to 5 and Comparative Examples 1 to 2, test pieces were prepared according to the following method, and Young's modulus, elongation at break, and dynamic viscoelasticity were measured. I did it. The results are shown in Table-2.

(1) Preparation of test piece Use an applicator to spread the resin composition onto a glass plate for 25 minutes.
Coated to a thickness of 0μm, 0.5J/Cn! (Wavelength 350
A cured film was obtained by irradiating ultraviolet rays (nm). Then,
The cured film was peeled off from the glass plate and conditioned at 23° C. and 50% relative humidity for 24 hours to obtain a test piece.

(2) Measurement of Young's modulus and elongation at break.
The Young's modulus of the test piece at
+nin and 25mm between gauge lines, and 2
The elongation at break of the test piece at 3°C was measured at a tensile speed of 50 m.
The measurement was performed under the conditions of o+/min and a distance between gauge lines of 25 mm.

(3) Dynamic viscoelasticity measurement The storage modulus (E') of the test piece was measured using a dynamic viscoelasticity tester (Pyblon, Toyo Baldwin@). The temperature increase rate was 2° C./min, and the vibration frequency was 35 Hz.

Margin below [Effects of the invention] The resin composition for optical three-dimensional modeling of the present invention has a low viscosity,
The resin composition is suitable for use as a resin composition for optical three-dimensional modeling, as it has the characteristic that the physical properties of the modeled object do not change much over a wide temperature range.

that's all

Claims (1)

[Claims] 1. Optical three-dimensional modeling characterized by containing (A) silicone urethane (meth)acrylate, (B) a compound having a polyfunctional ethylenically unsaturated bond, and (C) a polymerization initiator. Resin composition for use.