JP2000351907A - Resin composition and three-dimensional form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new resin composition intended for optical three- dimensional forms, and capable of giving a cured product with rubber elasticity and favorable tensile properties, and to obtain a three-dimensional form composed of the above curved product. SOLUTION: This resin composition is intended for optical three-dimensional forms, being such one that a filler is dispersed in a liquid component containing a photocurable resin and a photoinitiator. This composition is capable of giving a cured product by irradiating the composition with active energy rays, and the cured product thus obtained satisfies the requirement (s) 1 and/or 2 as described below: (1) glass transition point: <=10 deg.C, and (2) work proportion of its elastic deformation: >=50%. The other objective three-dimensional form is obtained by irradiating this resin composition with active energy rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition and a three-dimensional article used in an optical three-dimensional molding method, and more particularly, to rubber elasticity and favorable tensile properties by irradiating active energy rays. The present invention relates to a resin composition capable of obtaining a cured product having the following formula, and a three-dimensionally formed product composed of such a cured product.

[0002]

2. Description of the Related Art In recent years, a process of forming a cured resin layer by selectively irradiating a photocurable liquid material with light is repeated to form a three-dimensional object in which the cured resin layer is integrally laminated. An optical three-dimensional molding method has been proposed [Japanese Unexamined Patent Publication No. 60-247515, U.S. Pat.
No. 75,330 (JP-A-62-35966), JP-A-62-101408, and JP-A-5-24119.
Reference). A typical example of this optical three-dimensional molding method will be described. Light such as an ultraviolet laser is applied to the liquid surface of a photocurable liquid material (photocurable resin composition) contained in a container, for example, by input CAD data. And forming a cured resin layer having a predetermined pattern. Next, on this cured resin layer, one layer of the photocurable resin composition is supplied, and by selectively irradiating the liquid surface with light, the cured resin layer formed on the previously formed cured resin layer is A new cured resin layer is integrally formed so as to be continuous. Then, the above process is repeated a predetermined number of times while changing or not changing the pattern to be irradiated with light, whereby a three-dimensional object formed by integrally laminating a plurality of cured resin layers is formed. This optical three-dimensional shaping method has attracted attention because it can easily and quickly obtain a target three-dimensional object having a complicated shape.

Conventionally, photocurable resin compositions used in optical three-dimensional molding methods include the following [A] to
Resin compositions such as (c) are known. [A] A resin composition containing a radical polymerizable organic compound such as urethane (meth) acrylate, oligoester (meth) acrylate, epoxy (meth) acrylate, thiol and ene compound, and photosensitive polyimide (for example, JP-A-1-204915) JP, JP-A-2-208
305, JP-A-3-160013). [B] A resin composition containing a cationically polymerizable organic compound such as an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl ether compound (for example, JP-A-1-213304) Gazette). [C] A resin composition containing a radically polymerizable organic compound and a cationically polymerizable organic compound (for example, JP-A-2-28
No. 261; Japanese Patent Application Laid-Open No. 2-75618;
-228413).

[0004] With the recent diversification of characteristics required for three-dimensional objects, models such as tires, vibration-proof materials, hoses, packing parts, O-rings, sealing materials for window glasses of automobiles, dust-proof or gas-proof masks, etc. , Various mechanical parts,
It has been studied to apply the three-dimensional object to a vacuum casting mold or the like. However, when a conventionally known resin composition is applied to an optical three-dimensional molding method, a cured product (rubber-like) having rubber elasticity and having tensile properties (tensile elastic modulus and elongation property) required for a rubber product is obtained. (A three-dimensional shape having the above mechanical properties) could not be formed.

[0005]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. A first object of the present invention is to provide a novel resin composition used for an optical three-dimensional printing method. A second object of the present invention is to provide a resin composition capable of obtaining a cured product having rubber elasticity and having tensile properties required for a rubber product by irradiating an active energy ray. is there. A third object of the present invention is to provide a three-dimensional object which is faithful to the design data and has no distortion or bending even when the object is used for forming a three-dimensional object having a support portion on which a load is easily concentrated or a complex three-dimensional object. It is an object of the present invention to provide a resin composition capable of forming a shape. A fourth object of the present invention is to provide a three-dimensionally formed article made of a cured product having rubber elasticity and having tensile properties required for a rubber product.

[0006]

The resin composition of the present invention comprises:
A resin composition used for an optical three-dimensional modeling method, wherein a filler is dispersed and contained in a liquid component including a photocurable resin and a photoinitiator, and a cured product glass obtained by irradiating active energy rays is provided. The transition point is 10 ° C. or less.

Further, the resin composition of the present invention is a resin composition used for an optical three-dimensional molding method, wherein a filler is dispersed and contained in a liquid component containing a photocurable resin and a photoinitiator, The ratio of the work of elastic deformation in the cured product obtained by irradiating active energy rays is 50% or more.

The following forms are preferred in the resin composition of the present invention. [1] The tensile modulus of the cured product obtained by irradiating active energy rays is 0.05 kgf / mm ² or more, and
Elongation of the cured product is 50% or more. [2] The cured product obtained by irradiating with active energy rays has a tensile modulus of 0.08 to 30 kgf / mm ² and the cured product has an elongation of 60% or more. [3] The photocurable resin contains a compound represented by the following general formula (I). [4] 2 constituting a compound represented by the following general formula (I)
A urethane bond (—CONH—) is contained in the valence organic group Y. [5] The compound represented by the following general formula (I) is urethane (meth) acrylate. [6] The photocurable resin contains a monofunctional monomer in addition to a compound represented by the following general formula (I). [7] The monofunctional monomer is a (meth) acrylate compound. [8] As a filler, at least one selected from glass beads, hollow glass beads, silica particles, potassium whisker, talc and carbon black is dispersed and contained.

[9] Glass beads or silica particles are dispersed and contained as a filler.

[0009]

## STR1 general formula (I): X-Y- Z _{^{[- (R 1 -Z) m -}} (R 2 -Z) n -Y
−] _P X

Wherein X is independently an organic group having an ethylenically unsaturated group, and R ¹ and R ^{2 each} have 2 to 10 carbon atoms.
An aliphatic hydrocarbon group, Y is each independently a divalent organic group,
Z independently represents an oxygen atom or a sulfur atom. m is an integer of 1 or more; n is 0 or an integer of 1 or more;
+ N) is 6 or more. p is an integer of 1 to 100.
Further, in the group represented by-(R ¹ -Z) _m- (R ² -Z) _n -,-(R ¹ -Z)-and-(R ² -Z)-
May be combined at random or in blocks. ]

The three-dimensionally shaped article of the present invention is obtained by irradiating the resin composition of the present invention with an active energy ray.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The resin composition of the present invention is characterized in that a cured product obtained by irradiating it with an active energy ray has rubber elasticity (elasticity) and tensile properties (tensile modulus and elongation) suitable as a rubber product. Has features. here,
The “active energy ray” applied to the resin composition is not particularly limited, such as ultraviolet rays, visible rays, and electron beams.

<Glass transition point of cured product> The cured product of the resin composition of the present invention has a glass transition point of 10 ° C or lower, preferably 0 ° C or lower, more preferably -5 ° C or lower. Here, the "glass transition point" of the cured product of the resin composition
Shows a peak (maximum) existing in the measurement temperature range when a vibration frequency of 3.5 Hz is applied to the cured product, and a temperature dependence curve of a loss tangent is measured using a dynamic viscoelasticity measurement device.
Can be obtained from That is, in the cured product of the resin composition of the present invention, a peak (maximum) exists in a measurement temperature region of 10 ° C. or lower. When a plurality of peaks corresponding to the glass transition point exist in the measurement temperature region, it is necessary that the main glass transition point (the glass transition point obtained from the maximum peak of the loss tangent) is 10 ° C. or less. It is preferable that all the glass transition points are 10 ° C. or less.

A cured product having a glass transition point of 10 ° C. or lower has a suitable rubber elasticity. Even if a three-dimensional product made of such a cured product is deformed by applying a load, it quickly returns to its original shape. Can be restored.

<Proportion of elastic deformation work of cured product> The cured product of the resin composition of the present invention has an elastic deformation work ratio (hereinafter referred to as "elastic deformation work rate") of 50% or more. It is preferably at least 60%, more preferably at least 70%, particularly preferably at least 80%. Here, the "elastic deformation power" of the cured product of the resin composition can be measured as follows.

(I) Using a micro-hardness tester “Fischer Scope H-100” (manufactured by Fisher Co.), a film having a diameter of 0. A compressive load is applied by a 4 mm ball-shaped indenter (compression speed: 30 μm / min), and when the compressive strain of the cured product becomes 5%, the compressive load is released, thereby obtaining a “stress” as shown in FIG. -Distortion curve
Is measured.

(Ii) In FIG. 1 showing an example of a stress-strain curve, a curve OA shows a relationship between a stress and a strain amount when a compressive load is applied, and a curve AB shows a stress after a compressive load is released (at the time of restoration). And the relationship between the amount of distortion and the amount of distortion. C
Is the intersection of the perpendicular drawn from A and the horizontal axis. Here, an area surrounded by points OAB is equivalent to the work amount W _r of the plastic deformation, the area enclosed by points BAC work amount W of the elastic deformation
corresponds to _e, the area was surrounded by a point OAC is equivalent to the total work W _t. Therefore, the elastic deformation work rate, W _e / W _t = W
_{e / (W r + W e} ) = ( area surrounded by a point BAC) /
(The area surrounded by the point OAC). A cured product having an elastic deformation power of 50% or more has a suitable rubber elasticity, and quickly restores its original shape even when a load is applied to a three-dimensional object made of such a cured product and deformed. be able to.

<Tensile Properties of Cured Product> (1) Tensile Modulus: The tensile modulus of the cured product of the resin composition of the present invention.
Tensile modulus is 0.05kgf / mm^TwoThat is all
Preferably, more preferably, 0.08 to 30 kgf / mm
^TwoAnd particularly preferably 0.1 to 20 kgf / mm^TwoAnd
You. Tensile elasticity, even with sufficient elongation properties
The rate is 0.05kgf / mm ^TwoSolid consisting of less than cured product
Shaped objects may be damaged during molding and / or use.
Part of the three-dimensional object (especially the lower layer and support)
Insufficient degrees may cause distortion or bending.

(2) Elongation (Eb): The elongation (elongation at break) of the cured product of the resin composition of the present invention is preferably at least 50%, more preferably at least 60%, particularly preferably at least 70%. Is done.

Sufficient tensile modulus (0.05 kgf / mm
⁽² or more), a three-dimensionally formed product composed of a cured product having an elongation of less than 50% is not practical because of a small allowable deformation amount, and its use as a rubber product is limited.

<Composition of Resin Composition> The resin composition of the present invention comprises a filler dispersed in a liquid component containing a photocurable resin and a photoinitiator. Hereinafter, the photocurable resin, the photoinitiator, and the filler constituting the resin composition of the present invention will be described.

<Photocurable Resin> A preferred photocurable resin constituting the resin composition of the present invention is represented by the above general formula (I)
Can be mentioned. In the general formula (I), X is a monovalent organic group each independently having an ethylenically unsaturated group. Examples of the organic group (X) include a (meth) acryloyl group, a vinyl ether group, and a vinyl group. And the like. Preferably, at least one of the two organic groups (X) is a (meth) acryloyl group, and both organic groups (X)
Is particularly preferably a (meth) acryloyl group.

In the above general formula (I), R ¹ and R
² is a different aliphatic hydrocarbon group having 2 to 10 carbon atoms. Examples of the aliphatic hydrocarbon groups (R ¹ ) and (R ² ) include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 2-methyltetramethylene group,
Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, isopropylene group, isobutylene group, sec-butylene group, tert-butylene group, 1,2-butylene group, and the like. it can.

In the above formula (I), each Z independently represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. Note that all the atoms represented by Z are present in the main chain.

In the above general formula (I),-(R ^1-
The number of repetitions (m) of the group represented by Z)-is 1 or more, and preferably 3 to 500. Further,-(R ^2-
Z) The number of repeating groups (n) represented by-is 0 or 1
The above is preferable, and it is preferably 3 to 500.

In the above general formula (I), from the viewpoint of imparting suitable rubber elasticity to the finally obtained cured product, (m
+ N) is required to be 6 or more, and (m +
The value of n) is preferably from 6 to 1,000. Also,
The number (p) of repeating groups represented by-(R ¹ -Z) _m- (R ² -Z) _n -Y- is 1 or more, and preferably 1 to
100. -(R ¹ -Z) _m- (R ² -Z) _n-
In the group represented by,-(R ¹ -Z)-and-(R
² -Z) -, respectively, ^{"- R 1 -Z-R 2 -Z} -R
¹ -ZR ² -ZR ¹ -ZR ¹ -ZR ² -ZR
² -ZR ¹ -ZR ² -Z- ”or a random bond such as“ -R ¹ -ZR ¹ -ZR ¹
-ZR ¹ -ZR ¹ -ZR ² -ZR ² -ZR ^{2
-Z-R 2 -Z-R 2} -Z- may be coupled to the block-shaped as ". Incidentally,-(R ¹ -Z)-and-
All the groups represented by (R ² -Z)-are linked linearly to form a main chain.

In the above general formula (I), Y is each independently a divalent organic group, and the organic group (Y) is not particularly limited. , A urethane bond (—CONH—). Thereby, urethane bonds are introduced into the obtained resin composition, and the mechanical strength of the cured product of the resin composition can be improved.

Specific examples of the compound represented by the general formula (I) include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and thiourethane (meth) acrylate. And urethane (meth) acrylate are particularly preferred.

The urethane (meth) acrylate (compound represented by the above general formula (I)) constituting the resin composition of the present invention comprises (a) a poly (alkyleneoxy) structure having a number average molecular weight of 500 or more in the molecule. Ether polyol (hereinafter, also referred to as “polyether polyol (a)”)
(B) a structural unit derived from an organic polyisocyanate compound, and (c) a structural unit derived from a hydroxyl group-containing (meth) acrylate in a molecule.

Here, examples of the polyether polyol (a) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol. Polyether diols obtained by ring-opening copolymerization of at least one kind of ion-polymerizable cyclic compound can also be suitably used.

Examples of the ion-polymerizable cyclic compound for obtaining the polyether polyol (a) include ethylene oxide, propylene oxide, butene-1-oxide (1,2-butylene oxide), isobutene oxide, and 3,3-bischloro. Methyl oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate,
Examples include cyclic ethers such as allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate.

Specific combinations of the ionic polymerizable cyclic compounds for obtaining the polyether polyol (a) include:
For example, a combination of tetrahydrofuran and propylene oxide, a combination of tetrahydrofuran and 2-methyltetrahydrofuran, a combination of tetrahydrofuran and 3-methyltetrahydrofuran, a combination of tetrahydrofuran and ethylene oxide, a combination of butene-1-oxide and ethylene oxide, a mixture of tetrahydrofuran and butene A combination of -oxide and ethylene oxide, and a combination of tetrahydrofuran, butene-1-oxide and ethylene oxide. The polyether polyol (a) is selected from the above ion-polymerizable cyclic compounds, cyclic imines such as ethyleneimine, cyclic lactones such as β-propiolactone and glycolic lactide, and dimethylcyclopolysiloxanes. 1
A polyether diol obtained by ring-opening copolymerization with a seed can also be used. The ring-opening copolymers of these ionic polymerizable cyclic compounds may be configured to be randomly bonded, or may be configured to be bonded in a block shape.

The number average molecular weight of the polyether polyol (a) is required to be 500 or more, and preferably 2000 or more. With a polyether polyol having a number average molecular weight of less than 500, the cured product of the finally obtained resin composition does not exhibit sufficient rubber elasticity.
In addition, the resin composition containing a urethane (meth) acrylate having a structural unit derived from a polyether polyol having a number average molecular weight of less than 500 has an excessively high viscosity and is easy to handle when applied to an optical three-dimensional molding method. And the molding accuracy is reduced.

Commercial products of the polyether polyol (a) include, for example, PTMG650, PTMG1000, PTM
TMG2000 (Mitsubishi Chemical Corporation), PPG7
00, PPG1000, EXCENOL2020, 10
20 (all manufactured by Asahi Glass Urethane Co., Ltd.), PEG100
0, Unisafe DC1100, DC1800 (all manufactured by NOF Corporation), PTG650 (SN), PTG10
00 (SN), PTG2000 (SN), PTG300
0 (SN), PPTG2000, PPTG1000, P
TGL1000, PTGL2000 (all manufactured by Hodogaya Chemical Industry Co., Ltd.), Z-3001-4, Z-3001
5, PBG2000, PBG2000B (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

The organic polyisocyanate compound used for obtaining the urethane (meth) acrylate includes, for example, 2,4-tolylene diisocyanate,
6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4 ' -Diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, and the like. Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate are preferred.

The hydroxyl group-containing (meth) acrylate used to obtain the above urethane (meth) acrylate includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, formula:
^{_{H 2 C = C (R 3}} ) COO-C 2 H 4 (OCO-C 5 H
₁₀ ) (meth) represented by _r- OH (wherein R ³ represents a hydrogen atom or a methyl group, and r is a number from 1 to 15).
Acrylates include compounds obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid. These hydroxyl group-containing (meth) acrylates can be used alone or in combination of two or more.

The above urethane (meth) acrylate is
It may have a structural unit derived from a polyol compound other than the polyether polyol (a). Such polyol compounds include ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol,
Polyhydric alcohols such as 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, Polyester polyol obtained by reacting with polybasic acids such as adipic acid and sebacic acid; poly (hexanediol carbonate), poly (nonanediol carbonate), poly (3-methyl-1,5-pentamethylene carbonate)
Ε-caprolactone and ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Polycaprolactone polyol obtained by reacting with diols such as cyclohexanedimethanol and 1,4-butanediol; ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyoxy Ethylene bisphenol A
Examples include polyols such as ether, polyoxyethylene bisphenol F ether, and polyoxypropylene bisphenol F ether.

In preparing the urethane (meth) acrylate, the proportions of the polyol [polyether polyol (a) and a polyol compound that can be used together], the organic polyisocyanate compound and the hydroxyl group-containing (meth) acrylate are as follows. The isocyanate group contained in the organic polyisocyanate compound is 1.1 to 2.0 equivalents with respect to 1 equivalent of the hydroxyl group contained in the polyol, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is 0.1 equivalent.
It is preferable that the ratio be such that it becomes 1.0 equivalent.

In the reaction for preparing the above urethane (meth) acrylate, usually, copper naphthenate, cobalt naphthenate, zinc naphthenate, and dilaurate di-
A urethanization catalyst such as n-butyltin, triethylamine, triethylenediamine-2-methyltriethyleneamine is used in a ratio of 0.01 to 1% by weight based on the total amount of the reaction system. The reaction temperature is usually 10 to 90
° C, preferably 30-80 ° C.

The reaction method (reaction procedure) for preparing the urethane (meth) acrylate is as follows: (1) A polyol, an organic polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate are packaged together in a reaction vessel. (2) a method of reacting a polyol with an organic polyisocyanate compound, and reacting the obtained reaction product with a hydroxyl group-containing (meth) acrylate; (3) a method of mixing an organic polyisocyanate compound with a hydroxyl group. (4) a method of reacting (meth) acrylate with an obtained reaction product and a polyol; (4) reacting an organic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate to obtain an obtained reaction product (i) ) And a polyol, and the obtained reaction product (ii) is reacted with a hydroxyl group-containing (meth) acrylic acid. And a method of reacting a chromatography bets. Of these, the methods (2) and (3) are preferred.

The urethane (meth) acrylate preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000. When the number average molecular weight is less than 1,000,
The cured product of the finally obtained resin composition is unlikely to exhibit sufficient rubber elasticity. On the other hand, when this number average molecular weight is 5
When it exceeds 000, the viscosity of the obtained resin composition becomes excessive, and when applied to an optical three-dimensional molding method, handleability and molding accuracy may be reduced.

In the resin composition of the present invention, the content of the compound represented by the general formula (I) is 10 to 90% by weight.
And more preferably 20 to 80% by weight. When this content ratio is less than 10% by weight,
It is difficult to impart suitable rubber elasticity to the cured product of the finally obtained resin composition, and mechanical properties such as mechanical strength and toughness, and cracks and chips are likely to be generated in the three-dimensional shape made of the cured product. Become. On the other hand, when the content ratio exceeds 90% by weight, the viscosity of the resin composition becomes excessively high, and when applied to an optical three-dimensional molding method, there is a tendency that handleability and molding accuracy tend to decrease, and the resin composition has It becomes difficult to impart appropriate elongation characteristics to the cured product.

The resin composition of the present invention containing the compound represented by the general formula (I) further includes a compound having one ethylenically unsaturated bond (C = C) in one molecule. Preferably, a functional monomer is contained. By containing such a monofunctional monomer, the viscosity of the finally obtained resin composition can be adjusted to a suitable range described later, and the cured product of the resin composition has an appropriate elongation property ( (For example, 50% or more).

Examples of such monofunctional monomers include acrylamide, (meth) acryloylmorpholine, and 7
-Amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) A) acrylate, methoxytripropylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (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, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) A) acrylate, bornyl (meth) acrylate, and methyltriethylenediglycol (meth) acrylate. These monofunctional monomers can be used alone or
More than one species can be used in combination.

Commercial products of such monofunctional monomers include, for example, Aronix M-101, M-102, M
-111, M-113, M-117, M-152, TO
-1210 (all manufactured by Toagosei Co., Ltd.), KAYARA
D TC-110S, R-564, R-128H (all manufactured by Nippon Kayaku Co., Ltd.), Biscoat 192, Biscoat 220, Biscoat 320, Biscoat 2311H
P, Viscoat 2000, Viscoat 2100, Viscoat 2150, Viscoat 8F, Viscoat 17F (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

In the resin composition of the present invention containing the compound represented by formula (I) and a monofunctional monomer, the content of the monofunctional monomer is preferably from 10 to 90% by weight. And more preferably 20 to 80% by weight. If the content is less than 10% by weight, the effect of adjusting the viscosity of the obtained resin composition and the effect of imparting elongation properties to the cured product of the resin composition may not be sufficiently exhibited. On the other hand, if the content exceeds 90% by weight, the cured product of the obtained resin composition does not have a sufficient tensile modulus as a rubber product.

The content of the photocurable resin in the resin composition of the present invention is preferably from 10 to 99% by weight,
More preferably, the content is 20 to 90% by weight. When this content ratio is too low, the viscosity of the obtained resin composition becomes excessively high, and the molding becomes difficult due to reduced handleability. It is difficult to provide mechanical properties such as strength and toughness. On the other hand, when this content ratio is excessive, the cured product of the obtained resin composition does not have a sufficient tensile modulus as a rubber product.

<Photoinitiator> The photoinitiator constituting the resin composition of the present invention is decomposed by receiving energy rays such as light to generate radicals, and the radicals cause radical polymerization of the photocurable resin. It is preferable to use a photoinitiator for radical polymerization that initiates the reaction. Specific examples of such a photopolymerization initiator for radical polymerization include, for example, acetophenone, diethoxyacetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole , Xanthone, 2-chlorothioxanthone, benzophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,
1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthones, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-2-one, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Tri-methylpentylphosphine oxide, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene,
Benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone,
Michler's ketone, 3-methylacetophenone, 3,
3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), and combinations of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other dye sensitizers, and the like. Can be used alone or in combination of two or more.

The content of the photoinitiator in the resin composition of the present invention is preferably 0.01 to 15% by weight,
More preferably, the content is 0.1 to 10% by weight. When this content ratio is too small, the radical polymerization reaction rate (curing rate) of the obtained resin composition becomes low, so that it takes a long time for molding and the resolution tends to decrease. On the other hand, when this content ratio is excessive, an excessive amount of the photoinitiator may adversely affect the curing properties of the resin composition, the physical properties of the three-dimensionally shaped article, heat resistance, handleability, and the like.

<Filler> The resin composition of the present invention comprises a filler dispersed in a liquid component containing a photocurable resin and a photoinitiator. According to the filler constituting the resin composition of the present invention, the cured product of the resin composition maintains sufficient rubber elasticity and elongation while maintaining sufficient tensile properties (0. 05kgf / mm ²
(The above tensile modulus). Such a filler may be any of an inorganic filler and an organic filler.

As the inorganic filler constituting the resin composition of the present invention, a particulate filler and a fibrous filler can be used. The average particle diameter in the particulate inorganic filler, or the average fiber length in the fibrous inorganic filler is 1 to 50 μm
And preferably 3 to 40 μm. When the average particle size (average fiber length) is 1 μm, the viscosity of the obtained resin composition becomes excessive and the curing speed decreases, and depending on the resin composition, a cured product having high dimensional accuracy is obtained. Can not do. On the other hand, when the average particle diameter (average fiber length) exceeds 50 μm, a cured product having a smooth surface cannot be obtained by the obtained resin composition.

Specific examples of such inorganic fillers include, for example, aluminum oxide, aluminum hydroxide, diatomaceous earth, glass beads, hollow glass beads, magnesium oxide, magnesium hydroxide, magnesium carbonate, silica particles, shirasu balloon, glass fiber, Examples include potassium titanate whiskers, carbon whiskers, sapphire whiskers, beryllia whiskers, boron carbide whiskers, silicon carbide whiskers, silicon nitride whiskers, talc, and carbon black. Among these, glass beads, hollow glass beads, silica particles, potassium titanate whiskers, talc, carbon black and the like are preferable. These inorganic fillers can be used alone or in combination of two or more.

The inorganic filler may be a surface-treated one with a silane coupling agent or the like.
Examples of the silane coupling agent used as a surface treating agent for the inorganic filler include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ- (methacryloxypropyl) trimethoxy. Silane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, N-
β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like can be mentioned.

Commercially available inorganic fillers include, for example, glass beads GB210, GB210A, GB21
0B, GB210C, GB045Z, GB045ZA,
GB045ZB, GB045ZC, GB731, GB7
31A, GB731B, GB731C, GB731M,
GB301S, EGB210, EGB210A, EGB
210B, EGB210C, EGB045Z, EGB0
45ZA, EGB045ZB, EGB045ZC, MB
-10, MB-20, EMB-10, EMB-20, H
SC-070Q, HSC-024X, HSC-080
S, HSC-070G, HSC-075L, HSC-1
10, HSC-110A, HSC-110B, HSC-
110C (all manufactured by Toshiba Barotini Co., Ltd.); Radio Light # 100, Radio Light Fine Flow B, Radio Light Fine Flow A, Radio Light Sparkle Flow, Radio Light Special Flow, Radio Light # 300, Radio Light # 200, Radio Light Clear Flow, Radio Light # 500, Radio Light # 600, Radio Light # 2000, Radio Light # 700, Radio Light # 500S, Radio Light # 800, Radio Light # 900, Radio Light # 800S, Radio Light # 3000, Radio Radio Ace, Radio Lite Super Ace, Radio Lite High Ace, Radio Lite PC-1, Radio Lite Deluxe P-5, Radio Lite Deluxe W-50, Radio Lite Micro Fine, Jioraito F, radio light SPF, radio light GC
(The above is manufactured by Showa Chemical Industry Co., Ltd.); Heidilite H-
X, Heidilight H-21, Heidilite H-3
1, Heidilite H-32, Heidilite H-4
2, Heidilite H-42M, Heidilite H-4
3, Heidilight H-32ST, Heidilite H-
42STV, Heidilight H-42T, Heidilite H-34, Heidilite H-34HL, Heidilite H-32I, Heidilite H-42I, Heidilite H-42S, Heidilite H-210, Heidilite H-310, Heidilight H-320, Heidilite H-141, Heidilite H-241, Heidilite H-341, Heidilite H-320I,
Heidilight H-320ST, Heidilight HS-
310, Heidilight HS-320, Heidilite
HS-341, alumina A-42-6, alumina A
-42-1, alumina A-42-2, alumina A-
42-3, alumina A-420, alumina A-43
-M, Alumina A-43-L, Alumina A-50-
K, alumina A-50-N, alumina A-50-
F, alumina AL-45-H, alumina AL-45
-2, Alumina AL-45-1, Alumina AL-43
-M, Alumina AL-43-L, Alumina AL-4
3PC, alumina AL-150SG, alumina AL
-170, Alumina A-172, Alumina A-17
3. Alumina AS-10, Alumina AS-20, Alumina AS-30, Alumina AS-40, Alumina AS-50 (all manufactured by Showa Denko KK); Starmag-U, Starmag-M, Starmag-L, Starmag −
P, Starmag-C, Starmag-CX, High purity magnesia HP-10, High purity magnesia HP-10N, High purity magnesia HP-30, Starbrand-200, Starbrand-10, Starbrand-10A, Star brand magnesium carbonate Venus, star sign magnesium carbonate, two stars,
Star-marked magnesium carbonate One star, Star-marked magnesium carbonate S, Star-marked magnesium carbonate For feed, Star-marked magnesium carbonate heavy, High-purity magnesium carbonate GP-10, High-purity magnesium carbonate 30, Star brand light calcium carbonate For general use, Star brand light calcium carbonate E
C, Star brand light calcium carbonate KFW-20
0 (Kamijima Chemical Co., Ltd.), MKC silica G
S50Z, MKC silica SS-15 (all manufactured by Mitsubishi Chemical Corporation), Admafine SO-E3, Admafine SO-C3, Admafine AO-800, Admafine A0-809, Admafine AO-5
00, Admafine AO-509 (all manufactured by Admatechs); XM-220 (Mitsui Chemicals, Inc.)
Manufactured by Tismo-D, Tismo-L, Tofica Y, Tofika YN, Tofika YB, Dendor WK-20
0, Dendor WK-200B, Dendor WK-30
0, Dendor BK-200, Dendor BK-30
0, Swannite, Bali High B Super Dentol (all manufactured by Otsuka Chemical Co., Ltd.) and the like, and commercially available spherical silica particles such as Sunsphere NP-100,
NP-200 (all manufactured by Dokai Chemical Industry Co., Ltd.), Sylster MK-08, MK-15 (all manufactured by Nippon Chemical Industry Co., Ltd.), FB-48 (all manufactured by Denki Kagaku Kogyo Co., Ltd.)
Manufactured). Examples of the carbon black include FEF, SRF, HAF, ISAF, SAF, and the like. In particular, the iodine adsorption amount (IA) is 6
0 mg / g or more, the dibutyl phthalate oil absorption (DB
P) is preferably 80 ml / 100 g or more.
In addition, from the viewpoint of obtaining a three-dimensional object having good wear resistance,
It is preferable to use HAF, ISAF, and SAF.

The organic filler constituting the resin composition of the present invention includes crosslinked polystyrene-based polymer particles, crosslinked polymethacrylate-based polymer particles, polyethylene-based polymer particles, polypropylene-based polymer particles, and polybutadiene-based polymer. Examples thereof include particles, and these polymer particles may have a core-shell structure.

The content of the filler in the resin composition of the present invention is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 30 to 70% by weight.
% By weight. When the content ratio of the filler is too small, the cured product of the obtained resin composition does not have sufficient tensile modulus (0.05 kgf / mm ² or more) as a rubber product. On the other hand, when the content ratio of the filler is excessive, the viscosity of the obtained resin composition increases, and it becomes difficult to obtain a cured product having high dimensional accuracy,
The cured product has sufficient elongation properties (50%
Above) is difficult to achieve.

<Optional Components> The resin composition of the present invention contains the above-mentioned essential components [photocurable as long as the photocurability of the resin composition and the rubber elasticity and tensile properties of the obtained cured product are not impaired. Resin, photoinitiator and filler]. Such optional components include radically polymerizable organic compounds such as acrylic compounds and unsaturated polyester compounds other than the compounds represented by the above general formula (I); epoxy compounds,
Cationic polymerizable organic compounds such as vinyl ether compounds and cyclic ether compounds; cationic photopolymerization initiators such as onium salts; photosensitizers (polymerization accelerators) including amine compounds; thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone , Anthracene, anthracene derivative, perylene, perylene derivative, benzophenone, benzoin isopropyl ether, and other photosensitizers; reactive dilution of vinyl ethers, vinyl sulfides, vinyl urethanes, urethane acrylates, vinyl ureas, etc. Agent: epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene styrene block copolymer, petroleum resin, Polymers or oligomers such as a lene resin, a ketone resin, a cellulose resin, a fluorine-based oligomer, a silicone-based oligomer, and a polysulfide-based oligomer; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; Initiation assistants; antioxidants; leveling agents; wetting improvers; surfactants; plasticizers; ultraviolet stabilizers; ultraviolet absorbers; silane coupling agents; Among these optional components, it is preferable to include a coloring agent such as a pigment and a dye, whereby a colored cured product (three-dimensional shape) can be obtained, and further expansion of applications in the three-dimensional shape can be achieved. Product value can be improved. Examples of such coloring agents include conventionally known pigments (inorganic pigments / organic pigments) and dyes.

The resin composition of the present invention can be prepared by uniformly mixing the above essential components and optional components. The viscosity (25 ° C.) of the resin composition thus obtained is preferably from 10 to 30,000 cps, more preferably from 50 to 20,000 cps. Viscosity of obtained photocurable resin composition (25 ° C)
Is too small, the planarity of the surface of the resin liquid may be lost due to vibration of the apparatus or the like. On the other hand, if the viscosity (25 ° C.) of the photocurable resin composition is too large, It is difficult to supply a thin layer, and it may not be possible to obtain a high-precision model.

<Optical Stereolithography> The resin composition of the present invention obtained as described above is suitably used as a photocurable liquid resin composition in the optical stereolithography.
That is, the resin composition of the present invention, visible light, ultraviolet light, by repeating the process of selectively irradiating light such as infrared light to form a cured resin layer, the cured resin layer integrally A three-dimensional object having a desired shape can be manufactured by being laminated.

The means for selectively irradiating the resin composition with light is not particularly limited, and various means can be adopted. For example, means for irradiating the composition while scanning laser light or convergent light obtained using a lens or a mirror, etc., using a mask having a light transmitting portion of a predetermined pattern, and using this mask to make non-convergent light Means for irradiating the composition with light, a means for irradiating light to the composition through an optical fiber corresponding to a predetermined pattern in the light guide member using a light guide member formed by bundling a number of optical fibers, and the like. Can be. Also,
In the means using a mask, as a mask, according to a specified pattern according to the same principle as a liquid crystal display device,
A device that electro-optically forms a mask image composed of a light-transmitting region and a light-impermeable region can also be used. In the above, when the target three-dimensional object has a fine partial shape or when high dimensional accuracy is required, the spot diameter is used as a means for selectively irradiating the composition with light. It is preferable to employ means for scanning with a laser beam having a small value. The light irradiation surface of the resin composition contained in the container (for example, the scanning plane of the convergent light) may be any of the liquid surface of the resin composition and the contact surface with the container wall of the translucent container. You may. When the liquid surface of the resin composition or the contact surface with the container wall is used as the light irradiation surface, the light can be irradiated directly from the outside of the container or through the container wall.

In the optical three-dimensional molding method using the resin composition of the present invention, usually, after a predetermined portion of the resin composition is cured, the light irradiation position (irradiation surface) is moved from the already-cured portion to the light-cured portion. By moving the uncured portion continuously or stepwise, the cured portion is laminated to form a desired three-dimensional shape. Here, the movement of the irradiation position can be performed by various methods, for example, a light source, a container of a resin composition,
Examples of the method include moving any of the cured portions of the resin composition and additionally supplying the resin composition to the container. A typical example of the optical three-dimensional molding method will be described. A support stage provided so as to be able to move up and down in a container is slightly lowered (settled) from a liquid surface of a resin composition.
Then, the resin composition is supplied onto the supporting stage to form the thin layer (1). Next, the thin layer (1) is selectively irradiated with light to form a solid cured resin layer (1). Next, a resin composition is supplied on the cured resin layer (1) to form a thin layer (2), and the thin layer (2) is selectively irradiated with light, whereby the cured resin layer is formed. (1) A new cured resin layer (2) is formed thereon so as to be continuously and integrally laminated thereon. This process is repeated a predetermined number of times while changing or not changing the pattern to be irradiated with light, whereby a three-dimensional object formed by integrally laminating a plurality of cured resin layers (n) is formed.

The thus obtained three-dimensionally shaped object is taken out of the container, and the resin composition remaining on the surface is removed, and then, if necessary, washed. Here, examples of the detergent include organic solvents such as alcohols such as isopropyl alcohol and ethyl alcohol, organic solvents such as acetone, ethyl acetate, and methyl ethyl ketone, terpenes, and glycol ether esters. Examples include aliphatic organic solvents, low-viscosity thermosetting resins and resins. When a three-dimensional object having excellent surface smoothness is to be obtained, after cleaning using a thermosetting resin or a cleaning agent made of a resin, heat treatment or light irradiation is performed depending on the type of the cleaning agent. It is preferable to perform post-curing by processing. According to this post-cure, not only the resin existing on the surface of the three-dimensional object can be cured, but also the uncured resin composition which may remain inside can be cured. It is preferable to perform post-cure even if it is performed.

The three-dimensionally formed product (cured product of the resin composition of the present invention) formed as described above exhibits suitable rubber elasticity and the tensile properties (0.05 kgf / mm ²⁾ required for rubber products. It has the above tensile elastic modulus and elongation of 50% or more) and other mechanical properties (hardness, flex resistance and bending rigidity). Moreover, the three-dimensional object has high dimensional accuracy. In addition, according to the resin composition of the present invention, a cured product having a sufficient tensile modulus can be obtained. Even when subjected to a molding process of a shaped article (for example, an H-shaped article or an arch-shaped article), the resulting three-dimensional article does not generate distortion or bending due to insufficient strength. The three-dimensional object of the present invention is used for applications requiring rubber elasticity, such as tires, vibration-proof materials, hoses, packing parts, O-rings, sealing materials for window glasses of automobiles, etc., models such as dust-proof or gas-proof masks, and various mechanisms. It is suitable for parts, molds for vacuum casting, and the like.

[0064]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means “parts by weight”.

[Synthesis Example 1] 152.0% of 2,4-tolylene diisocyanate (organic polyisocyanate compound) was placed in a 3-liter separable flask equipped with a stirrer.
g, ethylene oxide having a number average molecular weight of 4000 and 1,
Opening a random copolymer of 2-butylene oxide [Formula "HO- _{[CH 2 CH (C 2 H 5} ) O ] ₄₄ - [CH ₂ C
H ₂ O] ₁₈ -H ”(this formula is expressed as“ —CH ₂ CH (C ₂ H
₅₎ O- "and" -CH ₂ CH ₂ O-, "but, 44: 18
(Molar ratio) shows linear molecules randomly bonded at a ratio of (molar ratio). 1764.7 g) and 0.5 g of 2,6-di-t-butylmethylphenol (polymerization inhibitor) are charged in ice water until the temperature of the system becomes 10 ° C. or lower. Cooled in the bath. Next, 1.6 g of dibutyltin dilaurate was added to the system to start the reaction, and the reaction was carried out for 2 hours while maintaining the temperature of the system at 20 to 35 ° C., and then stirring was continued at 35 to 50 ° C. for 1 hour. After that, 101.3 g of 2-hydroxyethyl acrylate [hydroxyl-containing (meth) acrylate] is added, and the mixture is further stirred at 50 to 70 ° C. for 5 hours to obtain a urethane acrylate oligomer having a number average molecular weight of about 4600. (Hereinafter, referred to as "urethane acrylate (A-1)"). The urethane acrylate (A-1) is a compound represented by the general formula (I) [X (two Xs): H ₂ C ＣCH—COO—C ₂ H ₄ —
O-, Y (all _{Y): - CONH-C 6} H 3 (CH 3) -
NHCO-, Z (all ^{Z): O, R 1 -Z} : -CH 2 CH (C 2 H 5) -O-, R 2 -Z: -CH 2 CH 2 -O-, m = 44, n = 18, p = 1,-(R ¹ -Z)-and-(R ² -Z)-are randomly bonded], and the specific chemical structure is shown in the following formula (1). In the following formula (1), the underlined structural units are “—CH ₂ CH (C ₂ H ₅ ) O—” and “—CH ₂
“CH ₂ O—” is a linear structural unit that is randomly bonded at a ratio of 44:18 (molar ratio).

[Synthesis Example 2] In a 3-liter separable flask equipped with a stirrer, 120.4 tolylene diisocyanate (organic polyisocyanate compound) was added.
g, ethylene oxide having a number average molecular weight of 4000 and 1,
Opening a random copolymer of 2-butylene oxide [Formula "HO- _{[CH 2 CH (C 2 H 5} ) O ] ₄₄ - [CH ₂ C
H ₂ O] ₁₈ -H ”(this formula is expressed as“ —CH ₂ CH (C ₂ H
₅₎ O- "and" -CH ₂ CH ₂ O-, "but, 44: 18
(Molar ratio) shows linear molecules randomly bonded at a ratio of (molar ratio). ), 1844.2 g, and 2,6-di-t-butylmethylphenol (polymerization inhibitor) 0.5 g, and ice water until the temperature of the system becomes 10 ° C. or lower. Cooled in the bath. Next, 1.6 g of dibutyltin dilaurate was added to the system to start the reaction, and the reaction was carried out for 2 hours while maintaining the temperature of the system at 20 to 35 ° C., and then stirring was continued at 35 to 50 ° C. for 1 hour. After that, 53.5 g of 2-hydroxyethyl acrylate [hydroxyl-containing (meth) acrylate] is added, and the mixture is further stirred at 50 to 70 ° C. for 5 hours to obtain an oligomer of urethane acrylate having a number average molecular weight of about 8800. (Hereinafter, referred to as "urethane acrylate (A-2)"). The urethane acrylate (A-2) is a compound represented by the general formula (I) [X (two Xs): H ₂ C ＣCH—COO—C ₂ H ₄ —
O-, Y (all _{Y): - CONH-C 6} H 3 (CH 3) -
NHCO-, Z (all ^{Z): O, R 1 -Z} : -CH 2 CH (C 2 H 5) -O-, R 2 -Z: -CH 2 CH 2 -O-, m = 44, n = 18, p = 2,-(R ¹ -Z)-and-(R ² -Z)-are randomly bonded], and the specific chemical structure is shown in the following formula (2). In the following formula (2), the underlined structural units are “—CH ₂ CH (C ₂ H ₅ ) O—” and “—CH ₂
“CH ₂ O—” is a linear structural unit that is randomly bonded at a ratio of 44:18 (molar ratio).

[0067]

Embedded image

<Examples 1-3 and Comparative Examples 1-2> Table 1
A photocurable resin and a photoinitiator were charged into a reaction vessel equipped with a stirrer according to the formulation shown in
By stirring for a time, a liquid component was obtained, and a filler shown in Table 1 was dispersed and contained in the liquid component to prepare a resin composition. For each of the obtained resin compositions, the viscosity (25 ° C.) measured by a B-type viscometer is also shown in Table 1. Comparative Example 1 is a comparative example relating to a resin composition containing no filler, and Comparative Example 2 is a comparative example relating to a resin composition in which a cured product obtained does not exhibit rubber elasticity.

<Glass Transition Point of Cured Product> (1) Preparation of Test Piece: Each of the resin compositions obtained in the above Examples and Comparative Examples was applied on a glass plate using a 15 mil applicator bar. Thus, a coating film having a thickness of about 200 μm was formed. The formed coating film was irradiated with ultraviolet rays of 1.0 J / cm ^{2 in} an air atmosphere to form a cured film (thickness: about 200 μm). The obtained cured film was peeled off from the glass plate, and dried under an environment of a temperature of 23 ° C. and a relative humidity of 50%.
After standing for 4 hours, the cured film was formed into a rectangular shape (length 30 mm).
× width 3 mm) to prepare a test piece. here,
When the feel of the test piece (cured film) was examined, Examples 1 to 3 were obtained.
The cured film according to Comparative Example 1 had the same feeling as rubber (elastomer). On the other hand, Comparative Example 2
Did not have rubber elasticity.

(2) Measurement of glass transition point: Using a dynamic viscoelasticity measuring apparatus “Leo Vibron” (manufactured by Orientec), a forced vibration having a vibration frequency of 3.5 Hz and an amplitude of 10 μm was applied in the longitudinal direction of the test piece. While giving, the loss tangent was measured in a temperature range of -150 to 100 ° C at a rate of temperature rise of 3 ° C / min, and the maximum in the measured temperature range was measured to be the glass transition point. The measured value of the glass transition point of the cured film of each resin composition is also shown in Table 1 below.

<Power of Elastic Deformation of Cured Product> (1) Preparation of Test Specimen: Each of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to a 254 μm applicator bar. To form a coating having a thickness of about 100 μm. The formed coating film was irradiated with ultraviolet rays of 1.0 J / cm ² under a nitrogen atmosphere to form a cured film (thickness: about 100 μm). This was left in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours to produce a test piece.

(2) Measurement of stress-strain curve: Using an ultra-fine hardness tester “Fisherscope H-100” (manufactured by Fischer) at room temperature (23 ° C.), A compressive load is applied by a ball-shaped indenter having a diameter of 0.4 mm (compression speed: 30 μm / min), and when the compressive strain of the cured film becomes 5%, the compressive load is released, whereby a stress-strain curve is obtained. It was measured. FIG. 2 shows a compression load-strain curve (stress-strain curve) of the cured film according to the second embodiment. In the figure,
Is a stress-strain curve at the time of applying a compressive load,
Is a stress-strain curve after release of the compressive load. As shown in FIG. 2, in the cured film according to Example 2, the stress-strain curve when applying a compressive load (corresponding to curve OA in FIG. 1) and the stress-strain after releasing the compressive load Curve (corresponds to curve AB in FIG. 1)
When baseline (corresponding to workload W _r of the plastic deformation) the area enclosed by the (corresponding to a straight line BO in Fig. 1) is narrow, the elastic deformation work rate (W _e / W _t) but is as large as 88% there were.

(3) Calculation of elastic deformation power: Examples 1 to
3 and the stress-strain curves measured for the cured products according to Comparative Examples 1 and 2, the work amount W _e of the elastic deformation was obtained.
The elastic deformation power was calculated from the ratio of the area corresponding to (the area surrounded by the point BAC in FIG. 1) to the total work W _t (the area surrounded by the point OAC in FIG. 1). The elastic deformation power of the cured film according to each resin composition is also shown in Table 1 below.

<Tensile Modulus of Cured Product> (1) Preparation of Test Specimen: Each of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was coated on a glass plate using an applicator bar. By applying on top, the thickness is 2
A 00 μm coating was formed. Then, using a conveyor curing device equipped with a metal halide lamp, the surface of the coating film was irradiated with ultraviolet rays (irradiation amount 0.5 J / cm ² ),
A semi-cured resin film was produced. Thereafter, the semi-cured resin film is peeled off from the glass plate and placed on release paper, and ultraviolet light is irradiated (irradiation amount 0.5 J / cm ² ) from the surface opposite to the surface to which the ultraviolet light was first irradiated. Film. The cured resin film thus produced was allowed to stand in a thermo-hygrostat at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then cut into a rectangular shape (length 100 mm × width 6 mm) to obtain a test piece. Produced.

(2) Measurement (according to JIS K 7127): For the test piece prepared as described above,
The tensile modulus was measured in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% under the conditions of a tensile speed of 1 mm / min and a distance between marked lines of 25 mm. The results are shown in Table 1 below.

<Elongation of Cured Product> (1) Preparation of Test Specimen: Each of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was used to measure the tensile modulus. A rectangular test piece was prepared in the same manner as the test piece.

(2) Measurement (according to JIS K 7127): The test piece prepared as described above was pulled in a thermo-hygrostat at a temperature of 23 ° C. and a relative humidity of 50% at a pulling speed of 50 mm / min and a marked line. The elongation (Eb) was measured under the condition of a distance of 25 mm. The results are shown in Table 1 below.

<Shape retention during molding> Using each of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2, an optical molding apparatus “Solid Creator JSC-
2000 "(manufactured by Sony Corporation), and a three-dimensionally shaped object having an H-shaped shape and dimensions (thickness (front-to-rear direction in the drawing): 6.4 mm) as shown in FIG. The shape retention during molding was evaluated. As evaluation criteria, the lower part of the bridge (horizontal part)
(From the layer to the 3rd to 20th layer)), the deformation such as hanging down, or the case where the modeling could not be performed is set to “X”, and such a deformation does not occur, and a three-dimensional object faithful to the design data. Was able to be modeled as “○”. The results are shown in Table 1 below.

[Shaping Conditions] (i) Intensity of laser beam on liquid surface: 60 mW (ii) Scanning speed: curing depth of 0.3 m for each composition
(iii) Thickness of the cured resin layer to be formed: 0.2 mm

[0080]

[Table 1]

<Dimensional Accuracy of Three-Dimensional Shaped Object> Using each of the resin compositions according to Examples 1 to 3, using an optical molding apparatus “Solid Creator JSC-2000” (manufactured by Sony Corporation), according to the following molding conditions. The box main body 1 and the lid 2 were formed as shown in FIG. In any of the three-dimensional objects (the box body 1 and the lid 2) according to the first to third embodiments, the opening of the box body 1 can be reliably closed by the lid 2, and the first embodiment.
According to the resin compositions according to Nos. 1 to 3, it was confirmed that a three-dimensional object having high dimensional accuracy could be produced.

[Shaping Conditions] (i) Intensity of laser beam at liquid level: 100 mW (ii) Scanning speed: curing depth of 0.3 m for each composition
(iii) Thickness of the cured resin layer to be formed: 0.2 mm

[0083]

According to the present invention, it is possible to provide a novel resin composition used for an optical three-dimensional molding method. According to the resin composition of the present invention, by irradiating the resin composition with an active energy ray, the resin composition has rubber elasticity and the tensile properties required for rubber products (tensile elastic modulus of 0.05 kgf / mm ² or more and 50% A cured product having the above elongation can be obtained. ADVANTAGE OF THE INVENTION According to the resin composition of this invention, even if it is used for shaping of a three-dimensional object having a support part or a three-dimensional object of a complicated shape (for example, an H-shaped object, an arch-shaped object), it is faithful to design data. Thus, a three-dimensional object without distortion or bending can be formed. Since the three-dimensional object of the present invention has rubber elasticity and is composed of a cured product having a tensile property required for a rubber product, it can be applied to the field where rubber elasticity is required, It can respond to the diversification of required characteristics for three-dimensional objects by the method.

[Brief description of the drawings]

FIG. 1 is a chart showing an example of a stress-strain curve of a cured product measured using an ultra-micro hardness tester.

FIG. 2 is a chart showing a stress-strain curve of a cured film according to Example 2.

FIG. 3 is a front view showing a three-dimensionally shaped object formed to evaluate the shape retention during molding with respect to the resin compositions according to Examples and Comparative Examples.

FIG. 4 is a perspective view showing a three-dimensional object formed using the resin composition according to the example.

[Explanation of symbols]

 1 Box body 2 Lid

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yukitoshi Kato 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Takayoshi Tanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Incorporated (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Inc. F-term (reference) 2H025 AA00 AB20 AC01 AC06 AD01 BC14 BC32 BC45 BC83 CC08 FA03 4F071 AA53 AA78 AA86 AB03 AB20 AB26 AB28 AH19 BA02 BB12 BC07 4F213 AA42 AA43 AA44 AB11 AB16 AB17 AB18 AB26 WA25 WL02 WL12 WL23 WL25 WL96 4J002 AA001 AC033 BB023 BB113 BC023 BG053 CD191 CD201 CF271 CH052 CK021 CK041 DA037 DJ077 DE077 DJ077 DJ088 DEGG 147 EH156 EL066 EL098 EN088 EN098 EP016 EU016 EU026 EU028 EU236 EU238 EV028 EV308 EW148 FA067 FA087 FA107 FD013 FD017 FD158 GJ02 GM00 GN01 GP03 GR00

Claims (10)

[Claims] 1. A resin composition for use in an optical three-dimensional molding method, wherein a filler is dispersed and contained in a liquid component containing a photocurable resin and a photoinitiator. The resin composition, wherein the cured product has a glass transition point of 10 ° C. or lower. 2. A resin composition for use in an optical three-dimensional molding method, wherein a filler is dispersed and contained in a liquid component containing a photocurable resin and a photoinitiator, and is obtained by irradiating with an active energy ray. The resin composition, wherein the ratio of work of elastic deformation in the obtained cured product is 50% or more. 3. The resin composition according to claim 1 or 2, wherein the cured product obtained by irradiating with an active energy ray has a tensile modulus of 0.05 kgf / mm ² or more,
A resin composition characterized in that the cured product has an elongation of 50% or more. 4. The resin composition according to claim 1, wherein the photocurable resin contains a compound represented by the following general formula (I). A resin composition. General formula (I): X-Y- Z _{^{[- (R 1 -Z) m -}} (R 2 -Z) n -Y
-] _P X wherein X is independently an organic group having an ethylenically unsaturated group, R ¹ and R ² are an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and Y is each independently a divalent group. Each independently represents an oxygen atom or a sulfur atom. m is an integer of 1 or more, n is 0 or an integer of 1 or more, and (m + n) is 6
That is all. p is an integer of 1 to 100. Also,-
(R ¹ -Z) _m - In the group represented ^{by, - - (R 2 -Z)} n (R 1 -Z) - and - (R ² -Z) -, respectively, they are randomly bonded Alternatively, they may be combined in a block shape. ] 5. The resin composition according to claim 4, wherein
A resin composition, characterized in that the divalent organic group Y constituting the compound represented by the general formula (I) contains a urethane bond (-CONH-). 6. The resin composition according to claim 5, wherein
A resin composition, wherein the compound represented by the general formula (I) is urethane (meth) acrylate. 7. The resin composition according to claim 4, wherein the photocurable resin contains a monofunctional monomer. 8. The resin composition according to claim 7, wherein
A resin composition, wherein the monofunctional monomer is a (meth) acrylate compound. 9. The resin composition according to claim 1, wherein the filler is selected from glass beads, hollow glass beads, silica particles, potassium titanate whiskers, talc and carbon black. A resin composition, characterized in that at least one of them is dispersed and contained. 10. A three-dimensional object obtained by irradiating the resin composition according to claim 1 with an active energy ray.