JP2000290328A - Resin composition and three-dimensional object - Google Patents

Abstract

(57) [Problem] To provide a novel resin composition for optical three-dimensional modeling. Provided is a resin composition capable of obtaining a cured product having rubber elasticity. The provision of a three-dimensional object composed of a cured product having rubber elasticity. SOLUTION: The resin composition of the present invention is a resin composition used for an optical three-dimensional molding method, wherein a cured product obtained by irradiating an active energy ray has a glass transition point of 10 ° C. or less. And In addition, the resin composition of the present invention is a resin composition used for an optical three-dimensional molding method, and a ratio of work of elastic deformation in a cured product obtained by irradiating active energy rays is 50% or more. Features. The three-dimensional object of the present invention is obtained by irradiating the resin composition of the present invention with an active energy ray.

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 for use in an optical three-dimensional molding method, and more particularly, to a cured article which exhibits rubber elasticity by irradiating active energy rays. The present invention relates to a resin composition that can be obtained, 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 having rubber elasticity (a three-dimensional product having rubber-like mechanical properties) cannot 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 by irradiating active energy rays.
A third object of the present invention is to provide a three-dimensional object made of a cured product having rubber elasticity.

[0006]

Means for Solving the Problems The resin composition of the present invention comprises:
A resin composition used for an optical three-dimensional molding method, wherein a glass transition point of a cured product obtained by irradiating active energy rays is 10 ° C. or less. In addition, the resin composition of the present invention is a resin composition used for an optical three-dimensional molding method, and a ratio of work of elastic deformation in a cured product obtained by irradiating active energy rays is 50% or more. Features.

The resin composition of the present invention preferably contains a compound represented by the following formula (1).

[0008]

Formula (1): XZ- (R ¹ -Z) _m- (R ^2-
Z) _n -X

Wherein X is an organic group having an ethylenically unsaturated group each independently, and R ¹ and R ^{2 each} have 2 to 10 carbon atoms.
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 or more. 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. ]

[0010] The resin composition of the present invention preferably contains a compound represented by the following formula (2). Further, 2 which constitutes a compound represented by the following formula (2)
It is preferable that a urethane bond (—CONH—) is contained in the valence organic group Y. Also, the compound represented by the following formula (2) is preferably urethane (meth) acrylate.

[0011]

Formula (2): XYZ [-(R ¹ -Z) _m-
(R ² -Z) _n -Y-] _p X

Wherein X is independently ethylenically unsaturated
An organic group having a sum group, R¹And R^TwoHas 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, and (m
+ N) is 6 or more. p is an integer of 1 to 100.
Also,-(R¹-Z)_m− (R^Two-Z)_nShown by -Y-
-(R ¹-Z)-and-(R^Two−
Z)-may be each independently bonded
However, they may be combined in a block shape. ]

The three-dimensional object of the present invention is characterized by being obtained by irradiating the resin composition of the present invention with active energy rays.

[0014]

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 the resin composition with active energy rays has rubber elasticity (elasticity). 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, the main glass transition point needs to be 10 ° C. or less, and all the glass transition points are 10 ° C. or less. Is preferred. The cured product having a glass transition point of 10 ° C. or less has a suitable rubber elasticity, and can quickly restore its original shape even if the solid product made of such a cured product is deformed by applying a load. Can be.

<Proportion of Work of Elastic Deformation of Cured Product> The cured product of the resin composition of the present invention has a work rate of elastic deformation (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 (during 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.

<Suitable Resin Component> As a preferred resin component constituting the resin composition of the present invention, a compound represented by the above formula (1) or (2) can be mentioned. In the above formulas (1) and (2), X is each independently a monovalent organic group having an ethylenically unsaturated group. Examples of the organic group (X) include a (meth) acryloyl group and a vinyl ether And vinyl groups. Preferably, at least one of the two organic groups (X) is a (meth) acryloyl group,
It is particularly preferred that both organic groups (X) are (meth) acryloyl groups.

In the above formulas (1) and (2), R
¹ and R ² are different aliphatic hydrocarbon groups having 2 to 10 carbon atoms. Examples of the aliphatic hydrocarbon groups (R ¹ ) and (R ² ) include ethylene, trimethylene, propylene, tetramethylene, 2-methyltetramethylene, pentamethylene, hexamethylene,
Examples include a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, and a 1,2-butylene group. In the above formulas (1) and (2), 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 formulas (1) and (2),-
The repeating number (m) of the group represented by (R ¹ -Z)-is 1
The above is preferable, and it is preferably 3 to 500. Also,-
The repeating number (n) of the group represented by (R ² -Z)-is 0
Alternatively, it is 1 or more, and preferably 3 to 500.

In the above formulas (1) and (2), the value of (m + n) needs to be 6 or more from the viewpoint of imparting suitable rubber elasticity to the finally obtained cured product. The value of (m + n) is preferably from 6 to 1,000. The number of repetitions (p) of the group represented by-(R ¹ -Z) _m- (R ² -Z) _n -Y- is 1 or more, and preferably 1 to 100. Note that-(R ¹ -Z) _m-
(R ² -Z) _n- and-(R ¹ -Z) _m- (R ^2-
In the group represented by _{Z) n -Y-, - (R} 1 -Z) -
And-(R < ² > -Z)-may be bonded at random or may be bonded in a block shape.

Specific examples of the compound represented by the above formula (1) include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and tetramethylene glycol di ( (Meth) acrylate and the like.

In the above formula (2), Y is each independently a divalent organic group, and the organic group (Y) is not particularly limited. It preferably contains 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 above formula (2) include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and thiourethane (meth) acrylate. Urethane (meth) acrylates are particularly preferred.

The urethane (meth) acrylate (compound represented by the above formula (2)) constituting the resin composition of the present invention comprises (a) a polyether having an alkyleneoxy structure in the molecule and having a number average molecular weight of 500 or more. A structural unit derived from a polyol (hereinafter also referred to as “polyether polyol (a)”), a structural unit derived from (b) an organic polyisocyanate compound, and a structural unit derived from (c) a hydroxyl group-containing (meth) acrylate. Is a urethane (meth) acrylate containing 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 ionic 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 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.

Commercially available polyether polyols (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 to obtain 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 for obtaining the 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, (meth) acrylate represented by the following formula (3); glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether and glycidyl (meth) acrylate And a compound obtained by an addition reaction of (meth) acrylic acid. These hydroxyl group-containing (meth) acrylates can be used alone or in combination of two or more.

[0034]

Embedded image H ₂ C ＝ C (R ³ ) COO—C ₂ H ₄ (OCO
-C ₅ H ₁₀₎ in _r -OH (wherein, R ³ represents a hydrogen atom or a methyl group, r is 1
~ 15. )

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 in combination], 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, di-laurate di-acid are used.
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 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 number average molecular weight of the urethane (meth) acrylate is preferably from 1,000 to 50,000, more preferably from 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.

<Suitable content ratio of resin component> The resin composition of the present invention contains at least one of the compound represented by the above formula (1) and the compound represented by the above formula (2). It is particularly preferable that both compounds are contained.

In the resin composition of the present invention containing both the compound represented by the formula (1) and the compound represented by the formula (2), the content ratio of the compound represented by the formula (1) Is preferably 10 to 90% by weight, more preferably 20 to 80% by weight. If the content is less than 10% by weight, it is difficult to impart an appropriate rubber elasticity (elastic modulus) to a cured product of the finally obtained resin composition, and the moldability tends to deteriorate. On the other hand, if the content exceeds 90% by weight, it is difficult to impart appropriate mechanical properties such as mechanical strength and toughness to a cured product of the finally obtained resin composition, and the cured product is composed of the cured product. The three-dimensional object is likely to crack or chip. Further, the content of the compound represented by the above (2) is preferably from 10 to 80% by weight, and more preferably from 20 to 60% by weight. When the content is less than 10% by weight, it is difficult to impart appropriate mechanical properties such as mechanical strength and toughness to a cured product of the finally obtained resin composition, and the solid formed from the cured product becomes difficult. Cracks and chips are likely to occur in the shape. On the other hand, when this content ratio exceeds 80% by weight, the viscosity of the resin composition becomes excessive, and the handleability and the molding accuracy tend to decrease when applied to the optical three-dimensional molding method.

In the resin composition of the present invention containing only the compound represented by the formula (1), the content of the compound is preferably 10 to 90% by weight, more preferably 20 to 90% by weight. ８０80% by weight. Also,
In the resin composition of the present invention containing only the compound represented by the formula (2), the content ratio of the compound is 1
It is preferably from 0 to 80% by weight, and more preferably from 20 to 80% by weight.

Further, in the resin composition of the present invention containing the above urethane (meth) acrylate as the compound represented by the formula (2), the content ratio of the urethane (meth) acrylate is usually 10-80
%, Preferably 20 to 80% by weight, more preferably 30 to 70% by weight. This content ratio is 10
If the amount is less than 10% by weight, a cured product of the finally obtained resin composition cannot have appropriate mechanical properties such as mechanical strength and toughness, so that a three-dimensional product made of the cured product may be cracked or chipped. And other problems occur. On the other hand, when this content ratio exceeds 80% by weight, the viscosity of the obtained resin composition increases, and disadvantages such as deterioration of the moldability are likely to occur.

<Optional Components> In the resin composition of the present invention, the above essential components [in the above formula (1) or (2)] as long as the photocurability and the rubber elasticity of the obtained cured product are not impaired. Ingredients other than the represented compound] can be contained. Such an optional component is a radically polymerizable organic compound such as an acrylic compound or an unsaturated polyester compound, other than the compound represented by the above formula (1) or (2); a radical photopolymerization initiator A cationic polymerizable organic compound such as an epoxy compound, a vinyl ether compound or a cyclic ether compound; a cationic photopolymerization initiator such as an onium salt; a photosensitizer (polymerization accelerator) composed of an amine compound or the like; thioxanthone, a derivative of thioxanthone , Anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene,
Photosensitizers composed of perylene derivatives, benzophenone, benzoin isopropyl ether and the like; reactive diluents such as vinyl ethers, vinyl sulfides, vinyl urethanes, urethane acrylates and vinyl ureas;
Epoxy resin, polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine oligomer, silicone oligomer, polysulfide Polymers or oligomers such as a system oligomer; phenothiazine, 2,6-di-
polymerization inhibitors such as t-butyl-4-methylphenol; other polymerization initiation aids; antioxidants; leveling agents; wetting improvers; surfactants; plasticizers; ultraviolet stabilizers; Agents; pigments; dyes; inorganic fillers; organic fillers. Of these, it is preferable to include a radical photopolymerization initiator (photoinitiator). Examples of such photoinitiators include acetophenones such as diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin ethers such as isobutyl benzoin ether and isopropyl benzoin ether; benzyldimethyl ketal; Benzyl ketals such as hydroxycyclohexyl phenyl ketone; benzophenone, 2-
Ketone photoinitiators such as chlorothioxanthone can be exemplified.

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 50 to 30,000 cps, more preferably 100 to 20,000 cps. When the viscosity (25 ° C.) of the obtained photocurable resin composition is too small, the planarity of the resin liquid surface may be lost due to vibration of the apparatus or the like, while the viscosity of the photocurable resin composition may be lost. When (25 ° C.) is excessive, it is difficult to supply a smooth thin layer, and a high-precision modeled product may not be obtained in some cases.

<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 employed. 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 after removing the resin composition remaining on the surface thereof, washing is performed as necessary. 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 has the mechanical properties (tensile strength, elongation, and hardness) required for the elastomer.・ Elastic modulus, bending resistance, bending rigidity). Moreover, the three-dimensional object has high dimensional accuracy. The three-dimensional object of the present invention is used for applications requiring rubber elasticity, for example, tires, vibration-proof materials, hoses, packing parts, O-rings, sealing materials for window glasses of automobiles,
It is suitable for models such as dust-proof or gas-proof masks, various mechanical parts, and molds for vacuum casting.

[0051]

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 In a reaction vessel equipped with a stirrer,
2,4-tolylene diisocyanate (organic polyisocyanate)
152.0 g, having a number average molecular weight of 4000
Of ethylene oxide and 1,2-butylene oxide
Ring-opening random copolymer [formula [HO- [CH _TwoCH (C_Two
H_Five) O]₄₄− [CH_TwoCH_TwoO]₁₈−H ”(this equation
Is "-CH _TwoCH (C_TwoH_Five) O- "and" -CH_TwoC
H_TwoO- "in a ratio of 44:18 (molar ratio).
Means connected to the system. ) Poly
Ether polyol (a)] 1764.7 g, 2,6-
Di-tert-butyl-methylphenol (polymerization inhibitor) 0.5
g of ice water until the temperature of the system becomes 10 ° C or less.
Cooled in the bath. The system was then charged with dibutyltindilau.
The reaction was started by adding 1.6 g of the rate, and the temperature of the system was raised to 2 g.
The reaction was carried out for 2 hours while maintaining the temperature at 0 to 35 ° C.
After continuing stirring at 5 to 50 ° C. for 1 hour, 2-hydroxy
Ethyl acrylate [hydroxy-containing (meth) acrylate
G), add 101.3 g, and at 50 to 70 ° C. for another 5 hours
By continuing the stirring for a while, the number average molecular weight becomes about 460.
0 urethane acrylate oligomer (hereinafter, referred to as
It is called "urethane acrylate (A-1)". Get)
Was. This urethane acrylate (A-1) has the above formula
Compound represented by (2) [X (two Xs): H_TwoC = CH-COO-C_TwoH_Four−
O-, Y (all Y): -CONH-C₆H_Three(CH_Three)-
NHCO-, Z (all Z): O, R¹-Z: -CH_TwoCH (C_TwoH_Five) -O-, R^Two-Z: -CH_TwoCH_Two−O−, m = 44, n = 18, p = 1, − (R¹-Z)-and-(R^Two-Z)-is randomly
Bond], and its specific chemical structure is represented by the following formula (4).
Show. In the following formula (4), the structural unit shown by underline
The position is "-CH_TwoCH (C_TwoH_Five) O- "and" -CH_Two
CH_TwoO- "in a ratio of 44:18 (molar ratio)
A unit that is randomly linked.

[Synthesis Example 2] In a reaction vessel equipped with a stirrer,
2,4-tolylene diisocyanate (organic polyisocyanate)
(Nate compound) 107.7 g, having a number average molecular weight of 4000
Of ethylene oxide and 1,2-butylene oxide
Ring-opening random copolymer [formula [HO- [CH _TwoCH (C_Two
H_Five) O]₄₄− [CH_TwoCH_TwoO]₁₈−H ”(this equation
Is "-CH _TwoCH (C_TwoH_Five) O- "and" -CH_TwoC
H_TwoO- "in a ratio of 44:18 (molar ratio).
Means connected to the system. ) Poly
Ether polyol (a)] 1856.4 g, 2,6-
Di-tert-butyl-methylphenol (polymerization inhibitor) 0.5
g of ice water until the temperature of the system becomes 10 ° C or less.
Cooled in the bath. The system was then charged with dibutyltindilau.
The reaction was started by adding 1.6 g of the rate, and the temperature of the system was raised to 2 g.
The reaction was carried out for 2 hours while maintaining the temperature at 0 to 35 ° C.
After continuing stirring at 5 to 50 ° C. for 1 hour, 2-hydroxy
Ethyl acrylate [hydroxy-containing (meth) acrylate
G), and further added at 50 to 70 ° C. for 5 hours.
By continuing the stirring, the number average molecular weight becomes about 1300.
0 urethane acrylate oligomer (hereinafter, referred to as
It is called "urethane acrylate (A-2)". Get)
Was. This urethane acrylate (A-2) has the above formula
Compound represented by (2) [X (two Xs): H_TwoC = CH-COO-C_TwoH_Four−
O-, Y (all Y): -CONH-C₆H_Three(CH_Three)-
NHCO-, Z (all Z): O, R¹-Z: -CH_TwoCH (C_TwoH_Five) -O-, R^Two-Z: -CH_TwoCH_Two−O−, m = 44, n = 18, p = 1, − (R¹-Z)-and-(R^Two-Z)-is randomly
Bond], and its specific chemical structure is represented by the following formula (5).
Show. In the following formula (5), the structural unit shown by underline
The position is "-CH_TwoCH (C_TwoH_Five) O- "and" -CH_Two
CH_TwoO- "in a ratio of 44:18 (molar ratio)
A unit that is randomly linked.

Synthesis Example 3 In a reaction vessel equipped with a stirrer,
489.6 g of tolylene diisocyanate, 1.6 g of di-n-butyltin dilaurate, 2,6-di-t-butyl-
Methylphenol (polymerization inhibitor) 0.5 was charged, and the system was cooled until the temperature reached 5 to 10 ° C. Next, the temperature of this system was maintained at 30 ° C. or lower, and 2-hydroxy-3-phenyloxypropyl acrylate 3 was stirred with stirring.
12.4 g was added dropwise and reacted at 30 ° C. for 1 hour. Thereafter, 914.4 g of polytetraethylene glycol having a number average molecular weight of 650 was added to the system and reacted at 50 ° C. for 1 hour. Then, 281.4 g of an ethylene oxide adduct of bisphenol A was added. ~ 70 ° C
By continuing the stirring for 5 hours, an oligomer of urethane acrylate represented by the following formula (6) (hereinafter, referred to as “urethane acrylate (A-3)”) was obtained.

[0055]

Embedded image

<Examples 1-3 and Comparative Examples 1-2> Table 1
A resin component and a photopolymerization initiator were charged into a reaction vessel equipped with a stirrer according to the formulation shown in
By stirring for a time, a transparent liquid composition (resin composition) was prepared. For each of the resulting liquid compositions,
Table 1 shows the viscosities (25 ° C.) measured by a B-type viscometer.

<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 (1) exhibited the same feeling as rubber (elastomer). On the other hand, the cured films according to Comparative Examples 1 and 2 did not have rubber elasticity.

(2) Measurement of glass transition point: Using a dynamic viscoelasticity measuring device “Leo Vibron” (manufactured by Orientec Co.), a forced vibration having a vibration frequency of 3.5 Hz and an amplitude of 10 μm was applied in the length 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.

<Elastic Deformation Power of Cured Product> (1) Preparation of Test Specimen: Each of the resin compositions obtained in the above Examples and Comparative Examples was applied on a glass preparation using an applicator bar of 254 μm. And about 1 thick
A 00 μm coating was formed. For the formed coating,
Under a nitrogen atmosphere, ultraviolet light of 1.0 J / cm ² was irradiated to form a cured film (about 100 μm in thickness). This is called temperature 2
A test piece was prepared by being left under an environment of 3 ° C. and a relative humidity of 50% for 24 hours.

(2) Measurement of stress-strain curve: The surface of the cured film was measured at room temperature (23 ° C.) using an ultra-micro hardness tester “Fisherscope H-100” (manufactured by Fischer). 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. Here, the compression load-strain curve (stress-strain curve) for the cured film according to Example 2 is shown in FIG. 2, and the compression load-strain curve (stress-strain curve) for the cured film according to Comparative Example 1.
Is shown in FIG. 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 The curve (corresponding to the curve AB in FIG. 1) matches, and the elastic deformation power (W _e / W _t ) is 1
00%.

(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.

[0062]

[Table 1]

* 1) NK-ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd., m + n = 9) * 2) Biscoat 312 (manufactured by Osaka Organic Chemical Industry Co., Ltd., m +
n = 7) * 3) NK-ester APG700 (manufactured by Osaka Organic Chemical Industry Co., Ltd., m + n = 12) * 4) New Frontier PHE (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) * 5) VR-77 (manufactured by Showa Polymer Co., Ltd.) * 6) VISCOAT 700 (manufactured by Osaka Organic Chemical Industry) * 7) VISCOAT 260 (manufactured by Osaka Organic Chemical Industry) * 8) Irgacure 184 (manufactured by Ciba Specialty Chemicals)

<Preparation of Three-Dimensional Shaped Product> Using each of the resin compositions according to Examples 1 to 3, an optical molding device “Solid Creator JSC-2000” (manufactured by Sony Corporation) was used.
According to the following molding conditions, the box body 1 as shown in FIG.
And the lid 2 was formed. In any of the three-dimensionally shaped 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 to third embodiments can be performed.
It has been confirmed that according to the resin composition according to the above, a three-dimensional object having high dimensional accuracy can be produced.

<Shaping Conditions> (i) Laser light intensity at liquid level: 100 mW (ii) Scanning speed: curing depth of 0.3 m for each composition
(ii) Thickness of the cured resin layer to be formed: 0.2 mm

[0066]

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, a cured product having rubber elasticity can be obtained by irradiating the resin composition with an active energy ray. Since the three-dimensional object of the present invention is composed of a cured product having rubber elasticity, the three-dimensional object can be applied to the field where rubber elasticity is required. I can respond.

[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 chart showing a stress-strain curve of a cured film according to Comparative Example 1.

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 Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/00 CER C08J 5/00 CER 4J027 C08L 101/16 C08L 101/00 4J034 // B29K 75:00 ( 72) Inventor Yukitoshi Kato 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JR Srl Co., Ltd. (72) Inventor Takayoshi Tanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd. (reference) 4F070 AA30 AA53 HA02 HB11 4F071 AA33 AA39 AA42 AE06 AF20Y BA02 BB01 BB12 BC07 4F213 AA42 AA43 AA44 WL25 WL96 WLJ WL02 CH07W CK04X CK05X 4J011 AA05 AC04 QA13 QB16 QB19 QB24 SA01 SA06 SA21 SA31 SA32 SA34 SA52 SA56 SA64 UA01 UA02 UA03 VA04 VA05 WA07 4J027 AC03 AC04 AE01 AG04 AG14 AG23 BA08 BA20 CB10 CC03 CD01 4J034 BA08 CA02 CA22 CB02 CD06 DA01 DB04 DG02 DG03 DG04 DG05 DG06 HA01 HA07 HC12 JA02 KC17

Claims (7)

[Claims] 1. A resin composition used for an optical three-dimensional molding method, wherein a cured product obtained by irradiating active energy rays has a glass transition point of 10 ° C. or lower. 2. A resin composition used in an optical three-dimensional molding method, wherein a rate of work of elastic deformation in a cured product obtained by irradiating active energy rays is 50% or more. object. 3. The resin composition according to claim 1, wherein the resin composition comprises a compound represented by the following formula (1). Formula (1): X—Z— (R ¹ —Z) _m — (R ² —Z) _n —X wherein X is an organic group each independently having an ethylenically unsaturated group, R ¹ and R ² represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and 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, and (m + n) is 6 or more. Also,-(R ¹ -Z)
_m - In the group represented ^{by, - - (R 2 -Z)} n (R 1
-Z) - and - (R ² -Z) -, respectively, may be randomly bonded, it may be bonded in a block form. ] 4. The resin composition according to claim 1 or claim 2.
Characterized in that it comprises a compound represented by the following formula (2).
Characteristic resin composition. Formula (2): XYZ [-(R¹-Z)_m− (R^Two−
Z)_n-Y-]_pX wherein X is independently an ethylenically unsaturated group
Organic group, R¹And R^TwoIs an aliphatic carbon having 2 to 10 carbon atoms
A hydrogen group, Y is each independently a divalent organic group, and Z is each independently
Stands for oxygen or sulfur atoms. m is one or more integers
The number and n are 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,-
(R¹-Z)_m− (R^Two-Z)_nA group represented by -Y-
Where-(R ¹-Z)-and-(R^Two-Z)-is
Each may be randomly combined or block
They may be joined in a lock shape. ] 5. The resin composition according to claim 4, wherein the divalent organic group Y constituting the compound represented by the formula (2) contains a urethane bond (—CONH—). A resin composition characterized in that: 6. The resin composition according to claim 5, wherein the compound represented by the formula (2) is urethane (meth) acrylate. 7. A three-dimensional object obtained by irradiating the resin composition according to claim 1 with an active energy ray.