JPH09227640A - Photocurable resin composition excellent in heat resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable resin compsn. which can provided a three- dimensional molding having a low vol. shrinkage and an excellent dimensional stability, a high heat distortion temp. and an excellent heat resistance, and excellent clarity and mechanical characteristics. SOLUTION: This compsn. contains a urethanized acrylic compd represented by the formula [wherein R<1> is H or CH3 ; (p) is 1 or 2 provided when (p) is 2, then at least one of R<1> 's is CH3 ; A is a diol or triol residue; D is a di- or trivalent hydrocarbon group; E is a (poly)ethylene oxide residue and/or a (poly) propylene oxide residue comprising 1-4 alkylene oxide units; R<2> is H or alkyl; (q) is 1 or 2; and (r) is 3 or 4], another free-radical-polymerizable compd. in a wt. ratio to the urethanized acrylic compd. of (20:80)-(90:10), a photopolymn. initiator, and if necessary, fine solid particles and/or a whisker.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable resin composition, a method for producing the photocurable resin composition, a method for producing a three-dimensional object using the photocurable resin composition, and the photocurable resin. It relates to a urethanized acrylic compound used in the composition. More specifically, the present invention has a small volumetric shrinkage during photocuring and is excellent in dimensional accuracy, and also has a high heat distortion temperature and excellent heat resistance, and is excellent in mechanical properties such as transparency and tensile strength. A photocurable resin composition capable of obtaining a molded article, a three-dimensional molded article, etc., a method for producing the photocurable resin composition,
The present invention relates to a method for producing a molded article by an optical three-dimensional molding method using the photocurable resin composition, and a urethanated acrylic compound used in the photocurable resin composition.

[0002]

2. Description of the Related Art In general, liquid photocurable resin compositions are widely used as coatings (especially hard coating agents), photoresists, dental materials, and the like.
A method of three-dimensionally optically molding the photocurable resin composition based on the data input to D has attracted particular attention. Regarding the optical three-dimensional molding technology, a required amount of controlled light energy is supplied to a liquid photo-curable resin to cure it into a thin layer, and then a liquid photo-curable resin is further supplied thereon, and then the light is controlled. Japanese Patent Application Laid-Open No. 56-144478 discloses an optical three-dimensional modeling method for producing a three-dimensional molded product by repeating a process of irradiating and laminating and hardening into a thin layer, and further discloses a basic practical method. Showa 60-
Proposed by Japanese Patent No. 247515. After that, a number of proposals regarding optical three-dimensional modeling technology have been made, for example, JP-A-62-35966, JP-A-1-204915, JP-A-2-113925, and JP-A-2-145616. Gazette, JP-A-2-153
722, JP-A-3-15520, JP-A-3-15520
Japanese Patent Application Laid-Open No. 21432 and Japanese Patent Application Laid-Open No. 3-41126 disclose techniques relating to an optical three-dimensional printing method.

[0003] A typical method for optically producing a three-dimensional object is a computer controlled ultraviolet ray so as to obtain a desired pattern on the liquid surface of a liquid photocurable resin composition placed in a container. A laser is selectively irradiated to cure to a predetermined thickness, and then one layer of the liquid resin composition is supplied on the cured layer and similarly irradiated with an ultraviolet laser to be cured as described above. A method of manufacturing a three-dimensional structure having a final shape by repeating a laminating operation of forming a continuous cured layer by using the same is generally used widely. In this method, even if the shape of the modeled object is considerably complicated, the target three-dimensional modeled object can be manufactured easily and in a relatively short time, and thus, it has been receiving particular attention in recent years.

Photocurable resin compositions used for coatings, photoresists, dental materials and the like include unsaturated polyesters, epoxy (meth) acrylates, urethane (meth) acrylates, (meth) acrylate monomers and the like. The addition of a photopolymerization initiator to a hydrophilic resin is widely used. The photocurable resin composition used in the optical three-dimensional molding method includes a photopolymerizable modified (poly) urethane (meth) acrylate compound, an oligoester acrylate compound, an epoxy acrylate compound, an epoxy compound, and a polyimide. Compounds, one or more of photopolymerizable compounds such as aminoalkyd compounds, vinyl ether compounds, etc. as a main component, and a photopolymerization initiator added thereto, and recently,
JP-A-1-204915, JP-A-1-21330
4, JP-A-2-28261, JP-A-2-7
Various improved techniques are disclosed in JP-A-5617, JP-A-2-145616, JP-A-3-104626, JP-A-3-114732, JP-A-3-1147324, and the like.

[0005] The photocurable resin composition used in the optical three-dimensional molding method must be a low-viscosity liquid material and have a small volume shrinkage during curing from the viewpoints of handleability, molding speed, and molding accuracy. It is required that a three-dimensional structure obtained by photocuring has good mechanical properties. In recent years, there is a tendency for the demand and applications of optical three-dimensional molded articles to expand, and accordingly, in addition to the above-mentioned various properties, depending on the application, it has a high heat distortion temperature and is excellent in heat resistance and is transparent. There has been a growing demand for three-dimensional objects with excellent properties. For example, optical three-dimensional objects used to design complex heat medium circuits and optical three-dimensional objects used to analyze the heat medium behavior of complex structures have small volume shrinkage during photo-curing, Those having high transparency and excellent transparency are regarded as important.

Conventionally, a method of introducing a benzene ring into the molecule of a photocurable resin, a method of increasing the crosslink density in a photocurable material, and the like, with the aim of obtaining an optical three-dimensional structure having improved heat resistance. Have been considered. However, even in this case, the heat deformation temperature under a high load is 70 to 80 at most.
° C and its heat resistance is not sufficient. Moreover, when trying to improve the heat resistance of the photocured product, on the other hand, the volume shrinkage at the time of curing is increased, leading to a decrease in dimensional accuracy. A photocurable resin composition that simultaneously satisfies the above properties has not yet been obtained. In general, if the crosslink density in the photocurable resin composition is increased, an improvement in heat resistance can be expected.However, there is a tendency that the volume shrinkage during curing is increased by simultaneously increasing the crosslink density, Improvement and reduction of volumetric shrinkage during curing have a trade-off relationship.
Therefore, as described above, an extremely large number of photocurable resin compositions have been proposed, but they have high heat resistance such that the heat deformation temperature under high load exceeds 100 ° C. A photocurable resin composition capable of forming a molded article or a three-dimensional molded article having a small volume shrinkage and excellent transparency and mechanical properties has not yet been provided.

[0007]

The object of the present invention is to exhibit a low-viscosity liquid, which is easy to handle, can be cured in a short photocuring time, has a small volume shrinkage when cured by light, and has a high dimensional accuracy. A photo-curable resin composition that is excellent, has a high heat distortion temperature, excellent heat resistance, and also has excellent mechanical properties such as transparency and tensile strength, and that can give molded products, three-dimensional molded products, and other cured products. Object and a method of manufacturing the same. An object of the present invention is to provide a method for producing a molded article by an optical three-dimensional molding method using the photocurable resin composition. Further, it is an object of the present invention to provide a novel urethane acryl compound used in the above photocurable resin composition.

[0008]

Means for Solving the Problems The inventors of the present invention have been studying to achieve the above object. As a result, the novel urethanated acrylic compound having a specific chemical structure synthesized by the present inventors is extremely effective in achieving the above-mentioned object, and the urethanized acrylic compound contains other radical polymerizable compounds and photopolymerizable compounds. When an initiator is added, a liquid photocurable resin composition having a low viscosity and excellent handleability can be obtained, and when the photocurable resin composition is irradiated with light, it can be cured in a short time. Has a small volume shrinkage, and a three-dimensional object having a desired shape and size can be manufactured with high dimensional accuracy, and the three-dimensional object obtained by photocuring has a high heat distortion temperature of more than 100 ° C. It has been found that it has excellent heat resistance, and also has excellent transparency and mechanical properties.

Furthermore, the present inventors have found that in the photocurable resin composition containing the above-mentioned novel urethanized acrylic compound invented by the present inventors, at least one filler selected from solid fine particles and whiskers. When containing, a molded article or a molded article obtained by photocuring it is
While maintaining its good mechanical strength, it exhibits an extremely high heat distortion temperature, which is not known in conventional photocurable resin compositions of this kind, and, depending on the composition, extremely high heat distortion temperature exceeding 200 ° C. They have found that they have a temperature and are extremely excellent in heat resistance, and that they have extremely high dimensional accuracy because volume shrinkage during photocuring is greatly reduced.

The inventors of the present invention have found that the above-mentioned photocurable resin composition can be effectively used not only in the optical three-dimensional molding method, but also in the production of molded articles involving curing by light irradiation and other applications. I found it. In addition, the present inventors, in the production of the photocurable resin composition described above, when the initial reaction step of the production is carried out by using a radical polymerizable compound that does not react with an isocyanate group as a diluent, the production thereof. It has been found that the reaction can be carried out extremely smoothly, and that the product obtained thereby can be directly used as it is for the preparation of the photocurable resin composition of the present invention without removing the diluent, and the various findings described above. The present invention has been completed based on.

That is, the present invention provides (i) the following general formula (I);

[0012]

Embedded image In the formula, R ¹ is a hydrogen atom or a methyl group, p is 1 or 2, and when p is 2, one or both R ¹ are methyl groups, A is a diol or triol residue, D is
1-4 divalent or trivalent unsubstituted or substituted hydrocarbon group, E is the formula _{:-( CH 2 CH 2 O) s-} ( wherein s
A (poly) ethylene oxide group represented by the following formula:-[(CH ₂ CH (CH ₃ ) O] t-(where t represents an integer of 1 to 4) ( poly) propylene oxide group, or a group of the formula _{:-( CH 2 CH 2 O) u} [(CH 2 C
_{H (CH 3) O] v-} ( wherein u and v, respectively 1-3
(Poly) ethylene oxide propylene oxide group represented by the formula (wherein the sum of u and v is 2 to 4), R ² is a hydrogen atom or an alkyl group, q is 1 or 2, and r is 3 or A photocurable resin containing (ii) a radically polymerizable compound other than the urethanized acrylic compound; and (iii) a photopolymerization initiator. In the composition, the content ratio of the urethanated acrylic compound: the radical polymerizable compound is 80:20 to 10:90.
(Weight ratio) is a photocurable resin composition.

The present invention is the above-mentioned photocurable resin composition characterized by further containing at least one filler selected from solid fine particles and whiskers. Furthermore, the present invention is an optical three-dimensional modeling resin composition comprising the above photocurable resin composition. Further, the present invention includes a method for producing a three-dimensional object by an optical three-dimensional method using the above resin composition for optical three-dimensional object formation.

The present invention includes (1) the following general formula (II);

[0015]

Embedded image (Wherein R ¹ , A, a and p each represent the same group or number as described above) (meth) acrylate (II) and the following general formula (III);

[0016]

Embedded image The polyisocyanate compound (III) represented by D- (NCO) q + 1 (III) (wherein D and q represent the same groups or numbers as described above) is replaced by 1 in the polyisocyanate compound (III). Used in such a quantitative ratio that each isocyanate group remains, the reaction is carried out in the presence or absence of a diluent comprising a radically polymerizable compound having no reactivity with an isocyanate group, and the following general formula ( IV);

[0017]

Embedded image (Wherein R ¹ , A, D, p and q each represent the same group or number as described above), or a reaction product of the monoisocyanate compound (IV) A step of producing a reaction product containing the radically polymerizable compound together with the compound (IV); (2) a reaction product obtained by the step (1), with the following general formula (V);

[0018]

In embedded image (H-O-E-CH 2) r -C- (R 2) 4-r (V) ( wherein represents the same group or number and each R ^2, E and r above) The polyol compound (V) represented is mixed and reacted at a ratio such that the residual isocyanate group in the monoisocyanate compound (IV) and the hydroxyl group in the polyol compound (V) react at a ratio of 1: 1 to react, and the above general formula (3) a step of producing a reaction product comprising the urethanated acrylic compound (I) represented by (I) or a reaction product containing the above radically polymerizable compound together with the urethanized acrylic compound (I); If the reaction product obtained in the step (2) does not contain a radically polymerizable compound or the content of the radically polymerizable compound is small, is it the same as that used in the step (1)? Or a different boom Urethane acrylate compound as a mixture of one or more polymerizable compounds (I): the total radically polymerizable compound = 80: 20 to 10:
90 (weight ratio), and the step of adding a photopolymerization initiator; and the method for producing a photocurable resin composition described above.

And, in the present invention, in the above-mentioned method for producing a photocurable resin composition, following the step (3),
The method for producing a photocurable resin composition includes a step of further adding at least one of solid fine particles and whiskers.

The present invention also has the following general formula (I):

[0021]

Embedded image (In the formula, R ¹ , R ² , A, D, E, p, q, and r each represent the same group or number as described above), which is a urethanated acrylic compound.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the urethanated acrylic compound (I) represented by the general formula (I) used in the photocurable resin composition of the present invention will be described. In the urethanated acrylic compound (I) represented by the above general formula (I), R ¹ is a hydrogen atom or a methyl group, and p is 1 or 2, and when p is 2, two ^{_{group; CH 2 = C (R 1}} ) -C
It is necessary that the radical R ¹ in one or both radicals of OO— is a methyl radical. In the urethanated acrylic compound (I), when p is 2, two groups; CH ₂ =
When both groups R ¹ of C (R ¹ ) -COO- are hydrogen atoms, they must pass through glycerin diacrylate, which is a synthetically extremely toxic, carcinogenic and skin irritant, and is practically usable. No, it is not preferable.

The urethane-modified acrylic compound (I)
In formula (I), the group A is a diol or triol residue (that is, a group obtained by removing a hydroxyl group from a diol or triol). Examples of the group A include diols and triol residues such as aliphatic diols having 2 to 5 carbon atoms, alicyclic diols, aromatic diols, aliphatic triols, alicyclic triols, and aromatic triols. Among them, the group A is a diol residue such as ethylene glycol, propylene glycol, butylene glycol, ethoxylated bisphenol A, spiro glycol, glycerin, trimethylolpropane, 5-methyl-1,2,2,
It is preferably a triol residue such as 4-heptanetriol or 1,2,6-hexanetriol, more preferably an alcohol residue of ethylene glycol or glycerin, and more preferably an alcohol residue of glycerin. More preferred.

In the urethanated acrylic compound (I), the group D is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and the group D is an unsubstituted or substituted group having 6 to 20 carbon atoms. It is preferably an aliphatic, aromatic or alicyclic divalent or trivalent hydrocarbon group. And the urethane acryl compound (I)
As described in detail below, the (meth) acrylic acid ester (II) represented by the general formula (II) and the general formula (II
It can be preferably produced by using the polyisocyanate compound (III) represented by I), and in this respect, the group D is the polyisocyanate compound used for producing the urethanated acrylic compound (I), that is, the diisocyanate compound or It is preferably a divalent or trivalent residue excluding the isocyanate group of the triisocyanate compound.
More specifically, preferred examples of the group D in the urethanated acrylic compound (I) include an isophorone group, a tolylene group, a 4,4′-diphenylmethane group, a naphthylene group,
Xylylene group, phenylene group, 3,3'-dichloro-
4,4'-phenylmethane group, toluylene group, hexamethylene group, 4,4'-dicyclohexylmethane group, hydrogenated xylylene group, hydrogenated diphenylmethane group, triphenylenemethane group, tetramethylxylene group and the like. it can. Among them, it is more preferable that the group D is an isophorone group and / or a tolylene group, and in that case, a three-dimensional structure or molding obtained from the photocurable resin composition of the present invention containing the urethanated acrylic compound (I). It becomes easy to balance the volumetric shrinkage rate and the heat resistance when curing a photocured product such as a product. The urethane-modified acrylic compound (I)
In the above, when the group D is a divalent hydrocarbon group, q = 1
And when the group D is a trivalent hydrocarbon, q = 2
become. That is, in the case of using the diisocyanate compound represented by the general formula; D- (NCO) ₂ (wherein D is the same as the above) as the polyisocyanate compound (III) in preparing the urethanated acrylic compound (I) Is q = 1
When a triisocyanate compound represented by the general formula; D- (NCO) ₃ (wherein D is the same as above) is used, q = 2.

In the urethanized acrylic compound (I), the group E is a (poly) ethylene represented by the formula:-(CH ₂ CH ₂ O) s- (where s represents an integer of 1 to 4). oxide groups, the _{formula: - [(CH 2 CH (} CH 3) O] t- (t wherein is an integer of 1 to 4) (poly) propylene oxide group, or a group of the formula :-( CH ₂ CH ₂ O) u
_{[(CH 2 CH (CH 3} ) O] v- ( wherein u and v total an integer of each 1 to 3 u and v are represented by a 2 to 4) (poly) ethylene oxide In the group E, that is, the (poly) ethylene oxide group or the (poly) propylene oxide group represented by the above formula, s or t is preferably an integer of 1 to 3, and 1 or 2 is a propylene oxide group. In addition, in the (poly) ethylene oxide propylene oxide group represented by the above formula, the sum of u and v is 2
Alternatively, it is preferably 3, and more preferably 2. In particular, urethane acrylate compound (I) in the group E has the _{formula: - [(CH 2 CH (} CH 3) O] t- ( wherein t is preferably 1 to 3, represented by a more preferably 1 to 2) When it is a (poly) propylene oxide group, the heat-deformation temperature is higher, the heat resistance is more excellent, the volume shrinkage during curing is smaller, and a relatively low-viscosity photocurable resin composition is obtained. It is possible because it is possible.

In the above group E, if s and t are larger than 4, the photocurable resin composition obtained by using the photocurable resin composition is selected, even if a suitable radical polymerizable compound is selected. The heat distortion temperature of the product is not sufficiently high, and the heat resistance does not reach the desired level. On the other hand, s or t
Is 0, that is, a urethanized acrylic compound (I)
When does not have an ethylene oxide group or a propylene oxide group, although improved heat resistance is observed,
Due to the large volume shrinkage during photocuring, it is not possible to manufacture the desired molded product or three-dimensional molded item with high dimensional accuracy, and gelation tends to occur when synthesizing the urethanized acrylic compound. The viscosity of the urethanized acrylic compound obtained becomes abnormally high, and it cannot be used in the photocurable resin composition of the present invention.

The urethane-modified acrylic compound (I)
In, the group R ² is a hydrogen atom or an alkyl group, and r is 3 or 4. The group R ² is preferably a lower alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

Although not limited, examples of the urethanated acrylic compound (I) usable in the photocurable resin composition of the present invention include the following. In the above general formula (I), p is 1, R ¹ is a hydrogen atom or a methyl group, q is 1, and D is a divalent unsubstituted or substituted aromatic, aliphatic or alicyclic hydrocarbon group, r Is a urethanized acrylic compound (I) of 4, wherein one of the carbon atoms is the center and its carbon atom has the formula: CH ₂ ＣC (R ¹ )
COO-A-OOC-NH-D-NH-COO-EC
A urethane acrylate compound in which four urethane acrylate groups represented by H ₂ — are bonded.

In the above general formula (I), p is 1,
R ¹ and R ² are a hydrogen atom or a methyl group, q is 1, and D is a divalent unsubstituted or substituted aromatic, aliphatic or alicyclic hydrocarbon group, and r is a urethane-containing acrylic compound (I ) comprising the formula for the carbon atoms around a single carbon atom (i.e. the carbon atom to which the remainder of the radicals R ² are _{attached): CH 2 = C (R} 1) COO-a-OOC- NH-D-
_{NH-COO-E-CH 2} - with urethane acrylate compound urethane acrylate group is three bond represented.

In the above general formula (I), p is 2
Wherein ^one of the two R ¹ is a hydrogen atom and the other is a methyl group, q is 1 and D is a divalent unsubstituted or substituted aromatic, aliphatic, alicyclic hydrocarbon group, r Is a urethane-containing acrylic compound (I) having a carbon atom centered on one carbon atom and having the formula: [CH ₂ ＣC (R ¹ ) CO
O] ₂ -A-OOC-NH-D-NH-COO-EC
A urethane acrylate compound in which four urethane acrylate groups represented by H ₂ — are bonded [ie, a urethane acrylate compound (I) having eight (meth) acrylate groups in one molecule].

In the above general formula (I), p is 2
And one of the two R ¹ is a hydrogen atom, the other is a methyl group, R ² is a hydrogen atom or a methyl group, q is 1, and D is a divalent unsubstituted or substituted aromatic, aliphatic, or fat. A cyclic hydrocarbon group, a urethanized acrylic compound (I) in which r is 3, and the carbon atom is centered around one carbon atom (that is, the carbon atom to which the remaining group R ² is bonded) formula:
^{_{[CH 2 = C (R 1}} ) COO] 2 -A-OOC-NH-D-
_{NH-COO-E-CH 2} - urethane acrylate group represented by three bonds to urethane acrylate compounds are [i.e. (meth) urethane acrylate compound having 6 acrylate groups in one molecule (I)] .

In the above general formula (I), p is 1
R ¹ is a hydrogen atom or a methyl group, q is 2, D
Is a trivalent unsubstituted or substituted aromatic, aliphatic, or alicyclic hydrocarbon group, and r is 4;
With one carbon atom as the center and the formula: [CH ₂ ＣC (R ¹ ) COO-A-OOC-N
_{H] 2 -D-NH-COO} -E-CH 2 - with urethane acrylate compound urethane acrylate group is four bonds represented [i.e. (meth) urethanization having 8 acrylate groups in one molecule Acrylic compound (I)].

In the above general formula (I), p is 1
And R ¹ and R ² are a hydrogen atom or a methyl group, and q
Is 2, and D is a trivalent unsubstituted or substituted aromatic, aliphatic, or alicyclic hydrocarbon group, and the urethanated acrylic compound (I) having r is 3 is centered around one carbon atom. wherein for the carbon atoms _{Te: [CH 2 = C (R} 1) COO-A-O
_{OC-NH] 2 -D-NH} -COO-E-CH 2 - urethane acrylate group to six chromatic during three bonds to have urethane acrylate compound [i.e. (meth) acrylate groups per molecule represented by Urethaned acrylic compound (I)].

In the above general formula (I), p is 2
Wherein ^one of the two R ¹ is a hydrogen atom and the other is a methyl group, q is 2, and D is a trivalent unsubstituted or substituted aromatic, aliphatic, alicyclic hydrocarbon group, r Is a urethane-containing acrylic compound (I) having a carbon atom centered on one carbon atom and having the formula: [[CH ₂ ＣC (R ¹ ) CO
O] ₂ -A-OOC-NH｝ ₂ -D-NH-COO-E-
A urethane acrylate compound having four urethane acrylate groups represented by CH ₂ — bonded (ie, (meth)
Urethane acrylic compound (I) having 16 acrylate groups in one molecule].

In the above general formula (I), p is 2
And one of the two R ¹ is a hydrogen atom and the other is a methyl group, R ² is a hydrogen atom or a methyl group, q is 2, and D is a trivalent unsubstituted or substituted aromatic or aliphatic group. , An alicyclic hydrocarbon group, and a urethane-ized acrylic compound (I) in which r is 3 and has a formula of {[CH ₂ ═C (R ¹ )) with respect to one carbon atom. COO] ₂ -A-OOC-
NH} ₂ -D-NH-COO-E-CH ₂ -Urethanated acrylic compound in which three urethane acrylate groups are bonded [that is, a (meth) acrylate group is 1
Urethaned acrylic compound (I) having 12 in the molecule].

The photocurable resin composition of the present invention is
It contains a radical polymerizable compound (other radical polymerizable compound) other than the urethane acrylic compound (I) (hereinafter sometimes simply referred to as "radical polymerizable compound") together with the urethane acrylic compound (I). The radical-polymerizable compound is a carbon-carbon unsaturated compound capable of reacting with the urethanated acrylic compound (I) when irradiated with light and reacting with each other to form a cured product. Any radically polymerizable compound having a bond can be used, but acrylic compounds, allyl compounds and / or vinyl lactams are preferably used. The radical polymerizable compound may be either a monofunctional compound or a polyfunctional compound, or both the monofunctional compound and the polyfunctional compound may be used in combination. Further, the radical polymerizable compound may be a low molecular weight monomer, an oligomer, or, in some cases, a compound having a relatively large molecular weight. And the photocurable resin composition of this invention may contain only 1 type of radically polymerizable compound as a radically polymerizable compound, or may contain 2 or more types of radically polymerizable compounds.

Although not limited, examples of the radically polymerizable compound that can be used as the radically polymerizable compound in the photocurable resin composition of the present invention include isobornyl (meth) acrylate, bornyl (meth) methacrylate, (Meth) acrylates such as dicyclopentenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) propylene glycol mono (meth) acrylate and t-butyl (meth) acrylate Morpholine
(Meth) acrylamides such as (meth) acrylamide, monofunctional radically polymerizable compounds such as N-vinylcaprolactone, styrene; trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, ethylene Glycol di (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate,
Mention may be made of polyfunctional radically polymerizable compounds such as diallyl phthalate, diallyl fumarate and ethylene oxide modified bisphenol A diacrylate.

In addition to the radically polymerizable compound described above, an epoxy compound, a urethane-containing acrylic compound other than the urethane-containing acrylic compound (I) conventionally used in a resin composition for optical three-dimensional molding, an epoxy ( A (meth) acrylate compound, other ester (meth) acrylate, etc. can be used as a radically polymerizable compound.

In the photocurable resin composition of the present invention, the above radically polymerizable compounds may be used alone or in combination of two or more kinds. Then, among the various radically polymerizable compounds described above, in the photocurable resin composition of the present invention, morpholine (meth) acrylamide, dicyclopentenyl di (meth) acrylate, and N-vinylcaprolactam are more preferably used, In that case, when cured by light, the volume shrinkage rate is smaller and the dimensional accuracy is better, the heat deformation temperature is higher and the heat resistance is excellent, and the transparency,
It is possible to obtain a photocurable resin composition that can be formed into a molded article or a three-dimensional molded article having excellent rigidity, and further other cured products.

In the photocurable resin composition of the present invention, the content ratio of the urethanated acrylic compound (I): radical polymerizable compound is 80:20 to 10: 9 by weight.
It must be 0, preferably 65:35 to 25:75, and more preferably 60:40 to 35:65. In the photocurable resin composition, when the proportion of the urethanized acrylic compound (I) is less than 10% by weight based on the total weight of the urethanized acrylic compound (I) and the radical-polymerizable compound, heat resistance when cured by light A cured product such as a molded product or a three-dimensional molded product having excellent properties and rigidity cannot be obtained. On the other hand, when it exceeds 80% by weight, the volumetric shrinkage ratio upon photocuring becomes large and the dimensional accuracy decreases, and the photocurable resin composition Since the viscosity of the product becomes too high, the handleability, moldability, and moldability are deteriorated, and it becomes impossible to smoothly manufacture a desired three-dimensional model, particularly when used in an optical three-dimensional modeling method.

Further, the photocurable resin composition of the present invention comprises
A photopolymerization initiator is contained together with the urethane-containing acrylic compound (I) and other radically polymerizable compounds. As the photopolymerization initiator, any photoradical polymerization initiator conventionally used in photocurable resin compositions can be used and is not particularly limited. Although not limited, examples of the photopolymerization initiator that can be used in the photocurable resin of the present invention include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, diethoxyacetophenone, and acetophenone. ,
3-methylacetophenone, 2-hydroxymethyl-1
-Phenylpropan-1-one, 4'-isopropyl-
2-hydroxy-2-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, pt-butyldichloroacetophenone, pt-butyltrichloroacetophenone, p-
Azidobenzalacetophenone, 1-hydroxycyclohexylphenylketono, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, xanthone, fluorenone, fluorene, benzaldehyde, anthraquinone, triphenylamine, carbazole and the like. be able to.

When a compound having a cationically polymerizable group such as an epoxy group together with a radically polymerizable group is used as the radically polymerizable compound, a photocationic polymerization initiator is used in combination with the above-mentioned photoradical polymerization initiator. The type of the photocationic polymerization initiator in that case is not particularly limited, and conventionally known ones can be used.

The amount of the photopolymerization initiator used depends on the types of the urethane-modified acrylic compound (I) and the radical-polymerizable compound,
Although it may vary depending on the type of the photopolymerization initiator, it is generally 0.1 to 10% by weight based on the total weight of the urethanized acrylic compound (I) and the radical polymerizable compound.
And more preferably 1 to 5% by weight.

The present invention provides, within the scope of the present invention, a photocurable resin composition obtained by further containing at least one filler selected from solid fine particles and whiskers in the above photocurable resin composition. Include. In the photocurable resin composition of the present invention containing a filler selected from solid fine particles and whiskers, the volume shrinkage at the time of photocuring is further reduced, and it is possible to obtain a molded article or a molded article having more excellent dimensional accuracy. it can. Moreover, molded articles and shaped articles obtained by photo-curing a photo-curable resin composition containing at least one filler selected from solid fine particles and whiskers have extremely good mechanical properties while maintaining excellent mechanical properties. It has a high heat distortion temperature, and some of them have a heat distortion temperature of more than 200 ° C., and the heat resistance is further excellent.

The photocurable resin composition of the present invention may contain only one kind of filler selected from solid fine particles and whiskers, or may contain two or more kinds thereof. That is, the photocurable resin composition of the present invention is 1
Even if it contains only one kind or two or more kinds of solid fine particles,
It may contain only one type or two or more types of whiskers, or may contain both one type or two or more types of solid fine particles and one type or two or more types of whiskers.
And when the photocurable resin composition of the present invention contains both solid fine particles and whiskers (that is, contains one or more solid fine particles and one or more whiskers), Volume shrinkage during photocuring is further reduced, and the heat distortion temperature of the photocured product is extremely high,
It is possible to obtain a photo-cured product such as a molded product or a molded product which is further excellent in dimensional accuracy and heat resistance.

The content of the fillers selected from the solid fine particles and the whiskers in the photocurable resin composition (the total content when two or more kinds are contained) depends on the types and forms of the solid fine particles and the whiskers. It can be adjusted, but is generally 3 to 70 based on the volume of the photocurable resin composition before the inclusion of solid fine particles and / or whiskers.
It is preferably volume%, more preferably 20 to 65 volume%, and further preferably 30 to 60 volume%. In particular, when the photocurable resin composition of the present invention contains only solid fine particles without containing whiskers, the content of the solid fine particles is based on the volume of the photocurable resin composition before containing it. It is preferably 3 to 70% by volume. Further, when the photocurable resin composition of the present invention contains only whiskers without containing solid fine particles, the content of the whiskers is based on the volume of the photocurable resin composition before containing it. It is preferably 3 to 30% by volume. By adjusting the content of the solid fine particles and the whiskers in the photocurable resin composition to the above range,
It becomes possible to obtain a molded product or a molded product having further excellent dimensional accuracy and heat resistance. On the other hand, if the content of the solid fine particles and the whiskers exceeds the upper limit range described above, the viscosity of the photocurable resin composition becomes too high, and the handling property, the operability during photocuring, and the like become poor, so caution is required. .

The solid fine particles contained in the photocurable resin composition have a smooth surface and hardly cause irregular reflection during light irradiation (at the time of energy beam irradiation), and are molded products obtained by photocuring. Inorganic solid fine particles and organic polymer solid fine particles that do not decompose or deteriorate at the temperature at which a photocured product such as a molded article or the like is used are preferably used. In particular, as the solid fine particles, solid fine particles having a smooth spherical shape, particularly a solid spherical solid fine particle having a relative standard deviation value of sphericity represented by the following formula (1) of 0.5 or less are used. Preferably. When the solid fine particles having a relative standard deviation value of 0.5 or less are used,
When photocuring the photocurable resin composition, the irradiation light (irradiation energy ray) is prevented from being diffusely reflected by the solid fine particles, and the photocuring is uniformly performed, and a photocured product superior in dimensional accuracy can be obtained. Moreover, excessive increase in viscosity of the photocurable resin composition is prevented.

[0049]

[Equation 1]

The solid fine particles have an average particle size of 3 to
The thickness is preferably 70 μm, more preferably 10 to 60 μm, still more preferably 15 to 50 μm. If the average particle size of the solid fine particles is less than 3 μm, the viscosity of the photocurable resin composition tends to be excessively high, while the value of 70 μm
When it exceeds m, the active energy is scattered at the time of irradiation, and the dimensional accuracy of a photocured product such as a molded product or a molded product tends to be low. Further, the solid fine particles may be transparent or opaque, and may be selected depending on the type and intended use of the target molded article or shaped article. In order to obtain a photocured product having excellent transparency while improving heat resistance, solid microparticles are made into extremely small submicron microparticles, and an appropriate surface treatment is applied to the photocurable resin composition. It is also possible to stably disperse and suppress an increase in the viscosity of the photocurable resin composition.

Examples of solid fine particles preferably used in the present invention include inorganic solid fine particles such as glass beads, talc fine particles, and silicon oxide fine particles; crosslinked polystyrene fine particles, crosslinked polymethacrylate fine particles, polyethylene fine particles, polypropylene fine particles. These solid fine particles may be used alone, in combination of two or more kinds, or in combination with whiskers.

As solid fine particles, aminosilane,
It is preferable to use one treated with one or more silane coupling agents such as epoxy silane and acryl silane, because the cured product obtained by photo-curing often has improved mechanical strength. When the polyethylene-based solid fine particles and / or the polypropylene-based solid fine particles treated with the silane coupling agent are contained in the photocurable resin composition, a polyethylene-based polymer obtained by copolymerizing an acrylic acid compound in an amount of about 1 to 10% by weight is used. It is preferable to use solid fine particles and / or polypropylene solid fine particles because the affinity with the silane coupling agent is increased.

When the photocurable resin composition contains whiskers, the diameter is 0.3 to 1 μm and the length is 10 μm.
It is preferable to use whiskers having a diameter of 0.3 to 0.7 μm and an aspect ratio of 10 to 100 μm.
m, length 20 to 50 μm and aspect ratio 20 to
More preferably, whiskers of 70 are used. When the aspect ratio of the whiskers is less than 10, it becomes difficult to obtain the effect of improving the mechanical properties and the effect of reducing the volume shrinkage due to the inclusion of the whiskers, and the viscosity of the photocurable resin composition increases. easy. On the other hand, if the aspect ratio of the whiskers is large, it is expected that the teaching of mechanical strength and the effect of reducing volume shrinkage will be expected, but if the aspect ratio is too large, the viscosity of the photocurable resin composition will increase and the fluid elasticity will increase. The aspect ratio is preferably 100 or less because the molding operation becomes difficult and the dimensional accuracy of the obtained photocured product is lowered, particularly the dimensional accuracy of the side face of the photocured product is lowered. .

Examples of whiskers which can be preferably used in the present invention include whiskers made of aluminum borate compounds, magnesium hydroxide sulfate compounds, aluminum oxide, titanium oxide compounds, silicon oxide compounds, and the like. These whiskers may be used alone, in combination of two or more kinds, or in combination with the above solid fine particles. Among the above-mentioned substances, whiskers of aluminum borate compound are preferably used. When the whiskers are treated with one or more silane coupling agents such as aminosilane, epoxysilane and acrylsilane, the mechanical strength of the cured product obtained by photocuring is improved. In many cases, it is preferable.

The photocurable resin composition of the present invention may contain a leveling agent, a surfactant, an organic polymer modifier, an organic plasticizer, etc., if necessary, in addition to the above components. Good.

The viscosity of the photocurable resin composition of the present invention can be adjusted according to the application and the mode of use, but it is generally at room temperature (25 ° C.) when measured using a rotary B-type viscometer.
Is preferably about 100 to 100,000 centipoise (cp) from the viewpoint of handleability, moldability, three-dimensional molding property, and the like, and more preferably about 300 to 50,000 cp. In particular, when the photocurable resin composition of the present invention is used for optical three-dimensional molding, the viscosity at ordinary temperature described above should be kept in the range of 300 to 5,000 cp, which is an optical handling when producing a three-dimensional molded object. This is desirable in that the properties can be improved and the target three-dimensional structure can be smoothly manufactured with high dimensional accuracy. The viscosity of the photocurable resin composition can be adjusted by selecting the type of the urethane-containing acrylic compound (I) and the radical polymerizable compound, adjusting the mixing ratio thereof, and the like.

When the photocurable resin composition of the present invention is stored in a state where it can block light, it is usually stored at a temperature of 10 to 40 ° C. for a long period of about 6 to 18 months. It can be stored while maintaining good photocuring performance while preventing denaturation and polymerization.

Urethaned acrylic compound (I) of the present invention
Of the present invention, the photocurable resin composition of the present invention containing the urethanated acrylic compound (I), and the photocurable resin composition of the present invention further containing at least one filler selected from solid fine particles and whiskers. Is not particularly limited, and the urethanated acrylic compound (I) represented by the above general formula (I), a photocurable resin composition containing the same, solid fine particles, and The above photocurable resin composition containing at least one filler selected from whiskers is included in the scope of the present invention. In particular, the urethanated acrylic compound (I) of the present invention and the photocurable resin composition containing the same can be preferably produced by the following method.

<< Representative Production Example of Urethaned Acrylic Compound (I) and Photocurable Resin Composition Containing It >> Step (1) : First, the following general formula (II);

[0060]

Embedded image (Wherein R ¹ , A, a and p each represent the same group or number as described above) (meth) acrylate (II) and the following general formula (III);

[0061]

Embedded image The polyisocyanate compound (III) represented by D- (NCO) q + 1 (III) (wherein D and q are the same groups or numbers as described above) is replaced by 1 in the polyisocyanate compound (III). The following general formula (IV) is used in such an amount ratio that isocyanate groups remain.

[0062]

Embedded image (In the formula, R ¹ , A, D, p and q each represent the same group or number as described above) to produce a monoisocyanate compound (IV).

In the step (1), when the polyisocyanate compound (III) is a diisocyanate compound, the (meth) acrylic acid ester (II) is added in an amount of about 1.0 to 1.2 with respect to 1 mol of the diisocyanate compound. By reacting at a molar ratio, a monoisocyanate compound (IV) having q = 1 in the above general formula (IV) can be obtained. In addition, polyisocyanate compound (III)
Is a triisocyanate compound, when 1 (mol) triisocyanate compound is reacted with (meth) acrylic acid ester (II) at a ratio of about 2.0 to 2.4 mol, in the above general formula (IV), A monoisocyanate compound (IV) having q = 2 can be obtained.

The polyisocyanate compound (III) used in this step (1) is not particularly limited as long as it is a diisocyanate compound or a triisocyanate compound included in the category of the above general formula (III). Among them, polyisocyanate compound (III)
As a preferred example of, isophorone diisocyanate,
Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3'-dichloro-4,4'-phenylmethane diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, triphenylmethane triisocyanate, tetramethyl xylene diisocyanate, hydrogenated 4,4'
-Diphenylmethane diisocyanate and the like can be mentioned, and these isocyanate compounds may be used alone or in combination of two or more kinds. Among the above-mentioned isocyanate compounds, isophorone diisocyanate and tolylene diisocyanate are particularly preferably used, in which case the volume at the time of photocuring in a photocured product such as a three-dimensional model obtained from the photocurable resin composition of the present invention. It becomes easy to balance the shrinkage rate and heat resistance.

This step (1) for producing the monoisocyanate compound (IV) is carried out by using a conventionally known urethanization catalyst such as an organic tin catalyst or a tertiary amine catalyst.
It is preferable to react the (meth) acrylic acid ester (II) with the polyisocyanate compound (III) at a temperature of 40 to 100 ° C.

Further, in this step (1), the (meth) acrylic acid ester (II) and the polyisocyanate compound (II
I) may be directly reacted without using a diluent or may be reacted with a diluent. Of which
Since the (meth) acrylic ester (II) used as a raw material component in this step (1) and the monoisocyanate compound (IV) obtained in this step (1) generally have a considerably high viscosity, It is preferable to carry out the reaction of step (1) using a suitable diluent that does not react with an isocyanate group. When a diluent is used, the reaction components are heated and mixed more uniformly, and the reaction proceeds smoothly, The target monoisocyanate compound (IV) can be obtained with low viscosity. The amount of the diluent used may vary depending on the type of the (meth) acrylic acid ester (II), the polyisocyanate compound (III) and the diluent, but in general,
Based on the total weight of the (meth) acrylic acid ester (II) and the polyisocyanate compound (III), about 10
It is preferable to set it to about 65% by weight.

Examples of the diluent include (meth) acrylic acid ester (II) and polyisocyanate compound (II
Any organic solvent capable of dissolving I) and not reacting with an isocyanate group can be used. Among them, among the above-mentioned radical polymerizable compounds used as other radical polymerizable compounds in the photocurable resin composition of the present invention, it is particularly preferable to select a radical polymerizable compound that does not react with an isocyanate group and use it as a diluent. desirable. When a radically polymerizable compound that does not react with an isocyanate group is used as a diluent, it is not necessary to remove the diluent from the reaction product, and the reaction product containing the diluent made of the radically polymerizable compound is converted into a urethanated acrylic compound. It can be used as it is in the next step (2) for producing the compound (I), and the diluent also contributes to the smooth progress of the reaction in the step (2), which is particularly desirable. Then, the reaction product containing the urethanated acrylic compound (I) and the radically polymerizable compound obtained in the next step (2) can be directly used as it is for the production of the photocurable resin composition of the present invention.

When the radical-polymerizable compound is used as the diluent in this step (1), the amount of the diluent comprising the radical-polymerizable compound depends on the photocuring amount finally obtained in the step (3) described later. It may be a part or the whole amount of the radically polymerizable compound used in the polymerizable resin composition. In short, the reaction in this step (1) proceeds smoothly and the desired photocurable resin composition is obtained. The amount of the radically polymerizable compound in the product may not exceed the allowable range.
Examples of the diluent preferably used in step (1) include, but are not limited to, radically polymerizable compounds such as morpholine acrylamide, dicyclopentanyl diacrylate, phenoxydiethyl acrylate, and N-vinylcaprolactam. These diluents may be used alone or in combination of two or more. Among them, morpholine acrylamide and dicyclopentanyl diacrylate are more preferably used.

Step (2) : Next, the above step (1)
To the reaction product comprising the monoisocyanate compound (IV) represented by the above general formula (IV), or containing a diluent such as a radically polymerizable compound together with the monoisocyanate compound (IV) The following general formula (V);

[0070]

In embedded image (H-O-E-CH 2) r -C- (R 2) 4-r (V) ( wherein represents the same group or number and each R ^2, E and r above) The polyol compound (V) represented is mixed and reacted at a ratio such that the residual isocyanate group in the monoisocyanate compound (IV) and the hydroxyl group in the polyol compound (V) react at a ratio of 1: 1 to react, and the above-mentioned general formula The urethanized acrylic compound (I) represented by (I) is produced, or a reaction product containing a radically polymerizable compound together with the urethanized acrylic compound (I) is produced.

In this step (2), when the polyol compound (V) is a triol compound (r = 3),
When the monoisocyanate compound (IV) is reacted at a ratio of about 3.0 to 3.6 mol with respect to 1 mol of the triol compound, the urethane-containing acrylic compound (I ) Can be obtained. Further, the polyol compound (V) is a tetraol compound (r
= 4), the monoisocyanate compound (IV) is used in an amount of about 4.0 to 4.
When the reaction is carried out at a ratio of about 8 mol, the urethanated acrylic compound (I) in which r = 4 in the general formula (I) can be obtained.

The polyol compound (V) is not particularly limited as long as it is a polyol compound satisfying the above-mentioned general formula (V), but as a typical example, there are four hydroxyl groups of pentaerythritol respectively. 1 to
Pentaerythritol ethylene oxide adduct having 4 moles of ethylene oxide added thereto, pentaerythritol propylene oxide adduct having 1 to 4 moles of propylene oxide added to each of four hydroxyl groups of pentaerythritol Pentaerythritol ethylene oxide propylene oxide adduct in which 1 to 4 mol of ethylene oxide and propylene oxide are respectively added to 4 hydroxyl groups, and 1 to 4 mol of ethylene to 3 hydroxyl groups of trimethylolpropane respectively Oxidized trimethylol propane ethylene oxide adduct, trimethylol propane trimethylol propane with 1 to 4 mol of propylene oxide added to each of the three hydroxyl groups Propane-propylene oxide adduct, and the like three trimethylolpropane ethylene oxide-propylene oxide adduct of 1-4 moles of ethylene oxide and propylene oxide respectively are added to the hydroxyl group of trimethylol propane.

The urethane-modified acrylic compound (I)
This step (2) for producing the compound is carried out at a temperature of generally 40 to 100 ° C. by using a cation catalyst, an anion catalyst, an organotin catalyst or the like, if necessary, to obtain a desired urethanated acrylic compound. (I) can be efficiently obtained. In some cases, the same diluent as that used in the above step (1) may be further added in this step (2) to carry out the reaction. Then, in this step (2),
The urethanized acrylic compound (I) is obtained, or a reaction product containing a radically polymerizable compound together with the urethanized acrylic compound (I) is obtained.

The urethanated acrylic compound (I) obtained in this step (2) is the urethanized acrylic compound (I).
The types of groups R ¹ , R ² , A, D and E in p,
The properties and the like vary depending on the number of q, r, s, t, etc., but generally they are in the form of a low-viscosity liquid to a high-viscosity liquid at room temperature, and particularly in this step (2), the urethanated acrylic compound (I The reaction product obtained in the form of a mixture of) and a radically polymerizable compound is in the form of a liquid having a low viscosity to a medium viscosity and is excellent in handleability.

Step (3) : And the above step (2)
In the step (3), the photocurable composition of the present invention is used in the step (3) using the reaction product comprising the urethanated acrylic compound (I) obtained in step 1 or the reaction product containing the urethanized acrylic compound (I) and a radical polymerizable compound. A resin composition is manufactured. At that time, the photocurable resin composition has the following (a) to (d)
It can be manufactured by any of the above methods.

(A) When the reaction product obtained in the above step (2) does not contain a radically polymerizable compound and consists only of the urethanized acrylic compound (I), the urethanization in this step (3) is performed. One or more radical polymerizable compounds other than the acrylic compound (I),
Urethane-ized acrylic compound (I): other radically polymerizable compound = 80: 20 to 10:90 (weight ratio) are mixed in such an amount, and a photopolymerization initiator is added to the photocurable composition of the present invention. A resin composition is manufactured.

(B) When the reaction product obtained in the above step (2) contains a diluent other than the radically polymerizable compound together with the urethanized acrylic compound (I), the diluent in this step (3) After removing the urethanated acrylic compound (I), one or more other radically polymerizable compounds are added to the urethanized acrylic compound (I):
Other radically polymerizable compound = 80: 20 to 10:90
The photo-curable resin composition of the present invention is manufactured by mixing in an amount such that (weight ratio) and adding a photo-polymerization initiator.

(C) The reaction product obtained in the above step (2) contains a radically polymerizable compound (diluent) together with the urethanated acrylic compound (I), and the content of the radically polymerizable compound is the final purpose. When the content of the radically polymerizable compound in the photocurable resin composition has already been set, the photopolymerization initiator is directly added to it, and the urethanated acrylic compound (I): other radically polymerizable compound = The photocurable resin composition of the present invention having a weight ratio of 80:20 to 10:90 is produced.

(D) The reaction product obtained in the above step (2) contains a radically polymerizable compound (diluent) together with the urethanated acrylic compound (I), but the final content of the radically polymerizable compound is When the content of the radical-polymerizable compound in the desired photocurable resin composition is less than that of the other radical-polymerizable compound, one or more other radical-polymerizable compounds are used as the urethanated acrylic compound (I): total radical-polymerizable compound. The compound is additionally mixed in an amount such that 80:20 to 10:90 (weight ratio), and a photopolymerization initiator is added to produce the photocurable resin composition of the present invention.

When the photocurable resin composition of the present invention contains at least one filler selected from solid fine particles and whiskers, the photocurable resin composition obtained in the above step (3) At least one of solid particles and whiskers may be added therein and mixed uniformly.

The photocurable resin composition of the present invention has excellent properties, particularly small volume shrinkage when cured by light, excellent dimensional accuracy, high thermal deformation temperature, and excellent heat resistance. Moreover, it can be used for various purposes by taking advantage of the property that molded articles, three-dimensional molded articles, and other cured products having excellent transparency can be used. It can be used for the production and coating of various molded products such as film-shaped products and molded products by a molding method or casting.

Among them, the photocurable resin composition of the present invention is suitable for use in the above-mentioned optical three-dimensional molding method, and in that case, while maintaining a small volume shrinkage ratio during photocuring, It is possible to smoothly manufacture a three-dimensional molded item that is excellent in accuracy, heat resistance, rigidity, and transparency. In performing optical three-dimensional modeling using the photocurable resin composition of the present invention, any of conventionally known optical three-dimensional modeling methods and apparatuses can be used. Among them, in the present invention, Ar is used as light energy for curing the resin.
It is preferable to use an active energy ray generated from a laser, a He-Cd laser, a xenon lamp, a metal halide lamp, a mercury lamp, a fluorescent lamp, and the like, and a laser beam is particularly preferably used. When a laser beam is used as the active energy beam, it is possible to increase the energy level and shorten the molding time, and to obtain a three-dimensional object with high modeling accuracy by utilizing the good light condensing property of the laser beam. be able to.

As described above, in carrying out optical three-dimensional modeling using the photocurable resin composition of the present invention, any conventionally known method or conventionally known stereolithography system apparatus can be adopted without any particular limitation. However, as a typical example of the optical stereolithography method preferably used in the present invention, a liquid photocurable resin composition containing a light energy absorber is mixed with active energy rays so that a cured layer having a desired pattern can be obtained. To form a cured layer, and then supply the uncured liquid photocurable resin composition to the cured layer, and similarly irradiate active energy rays to the cured layer continuous with the cured layer. A method of finally obtaining a desired three-dimensional molded article can be mentioned by repeating the lamination operation of newly forming. Then, even if the three-dimensional structure obtained by using it is used as it is, or in some cases, post-curing by light irradiation or post-curing by heat, etc., it is necessary to further improve its mechanical properties and shape stability etc. You may use it.

At this time, the structure, shape, size, etc. of the three-dimensional molded article are not particularly limited and can be determined according to each application. Typical application fields of the optical three-dimensional modeling method of the present invention include a model for verifying an external design during a design, a model for checking the functionality of parts, and a resin for producing a mold. Examples include the production of a mold, a base model for producing a mold, and a direct mold for a prototype mold. More specifically, precision parts,
Production of models for electric / electronic parts, furniture, building structures, automobile parts, various containers, castings, dies, mother dies, processing models, and the like. Especially, by taking advantage of its good heat resistance and transparency, it can be used very effectively for trial production of high-temperature parts, for example, designing complicated heat transfer medium circuits, and manufacturing parts for analysis and planning of heat transfer medium behavior with complicated structures. can do.

[0085]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the following examples.

<Synthesis Example 1> [Production of reaction product containing urethanated acrylic compound (I) and radically polymerizable compound] (1) Internal volume of 5 liter equipped with stirrer, temperature controller, thermometer and condenser In a three-necked flask, 888 g of isophorone diisocyanate and 9 of morpholine acrylamide
06 g and 1.0 g of dibutyltin dilaurate were charged and heated in an oil bath so that the internal temperature was 80 to 90 ° C. (2) A liquid in which 0.7 g of methylhydroquinone was uniformly mixed and dissolved in 856 g of glycerin monomethacrylate monoacrylate was placed in a dropping funnel with a side tube which was previously kept at 50 ° C., and the liquid in the dropping funnel was The contents in the flask of (1) above were dropped and mixed under stirring in a nitrogen atmosphere while maintaining the temperature of the flask contents at 80 to 90 ° C., and the mixture was stirred at the same temperature for 2 hours for reaction. (3) Then, after lowering the temperature of the flask contents to 60 ° C., 4 mol of propylene oxide of pentaerythritol charged in another dropping funnel (adding 1 mol of propylene oxide to each of the four hydroxyl groups of pentaerythritol) 366 g of the reaction mixture was rapidly added dropwise, the temperature of the flask contents was kept at 80 to 90 ° C., and the reaction was carried out for 4 hours to produce a reaction product containing a urethanated acrylic compound (I) and a radical polymerizable compound (morpholine acrylamide). The reaction product obtained was taken out of the flask while it was warm. (4) The resulting reaction product was a colorless viscous liquid at normal temperature (25 ° C.). The urethanated acrylic compound (I) contained in the reaction product obtained in Synthesis Example 1 has p = 2 in the above general formula (I).
It is a urethane acrylate compound in which two R ¹ = hydrogen atom and methyl group, A = glycerin residue, q = 1, D = isophorone group, E = propylene oxide group (t = 1), r = 4.

<Synthesis Example 2> [Production of reaction product containing urethanated acrylic compound (I) and radically polymerizable compound] (1) Internal volume of 5 liter equipped with stirrer, temperature controller, thermometer and condenser Into a three-necked flask, 696 g of tolylene diisocyanate, 90 morpholine acrylamide
6 g and 1.0 g of dibutyltin dilaurate were charged and heated in an oil bath so that the internal temperature was 80 to 90 ° C. (2) A liquid in which 0.7 g of methylhydroquinone was uniformly mixed and dissolved in 856 g of glycerin monomethacrylate monoacrylate was placed in a dropping funnel with a side tube which was previously kept at 50 ° C., and the liquid in the dropping funnel was The contents in the flask of (1) above were dropped and mixed under stirring in a nitrogen atmosphere while maintaining the temperature of the flask contents at 80 to 90 ° C., and the mixture was stirred at the same temperature for 2 hours for reaction. (3) Then, after lowering the temperature of the flask contents to 60 ° C., 4 mol of propylene oxide of pentaerythritol charged in another dropping funnel (adding 1 mol of propylene oxide to each of the four hydroxyl groups of pentaerythritol) 366 g of the reaction mixture was rapidly added dropwise, the temperature of the flask contents was kept at 80 to 90 ° C., and the reaction was carried out for 4 hours to produce a reaction product containing a urethanated acrylic compound (I) and a radical polymerizable compound (morpholine acrylamide). The reaction product obtained was taken out of the flask while it was warm. (4) The resulting reaction product was a colorless viscous liquid at normal temperature (25 ° C.). The urethanated acrylic compound (I) contained in the reaction product obtained in this Synthesis Example 2 has p = 2 in the above general formula (I),
A urethane-modified acrylic compound having two R ¹ = hydrogen atoms and a methyl group, A = a glycerin residue, q = 1, D = tolylene group, E = a propylene oxide group (t = 1), and r = 4.

<Synthesis Example 3> [Production of reaction product containing urethanated acrylic compound and radically polymerizable compound] (1) Isophorone was prepared in the same manner as in (1) and (2) of Synthesis Example 1 above. A reaction product containing a reaction product of diisocyanate and glycerin monomethacrylate monoacrylate and morpholine acrylamide was formed in the flask. (2) Next, after lowering the temperature of the flask contents to 60 ° C., 24 mol of propylene oxide of pentaerythritol charged in another dropping funnel (the propylene oxide is added to each of the four hydroxyl groups of pentaerythritol at an average of 6 (Added by mole) 1520 g was quickly added dropwise, and the reaction was carried out for 4 hours while maintaining the temperature of the flask contents at 80 to 90 ° C. to give a urethanated acrylic compound and a radical polymerizable compound (morpholine acrylamide).
Was produced, and the obtained reaction product was taken out of the flask while warm. (3) The resulting reaction product was colorless and was a viscous liquid at room temperature (25 ° C). The urethanated acrylic compound contained in the reaction product obtained in Synthesis Example 3 has the same general formula (I) as p = 2, two R ¹ = hydrogen atoms and a methyl group, and A = glycene phosphorus residue. A urethanated acrylic compound having a group, q = 1, D = isophorone group, E = propylene oxide group (t = 6), and r = 4.

<Synthesis Example 4> [Production of reaction product containing urethanated acrylic compound and radical-polymerizable compound] (1) Isophorone was prepared in the same manner as in (1) and (2) of Synthesis Example 1 above. A reaction product containing a reaction product of diisocyanate and glycerin monomethacrylate monoacrylate and morpholine acrylamide was formed in the flask. (2) Next, after lowering the temperature of the flask contents to 60 ° C., 135 g of pentaerythritol prepared in another dropping funnel was quickly added dropwise, and the temperature of the flask contents was kept at 80 to 90 ° C. for 4 hours. A reaction product containing a urethanated acrylic compound and a radically polymerizable compound (morpholine acrylamide) was produced by reaction, and the obtained reaction product was taken out of the flask while warm. (3) The resulting reaction product was colorless and was a viscous liquid at room temperature (25 ° C). The urethanated acrylic compound contained in the reaction product obtained in Synthesis Example 4 has the same general formula (I) as p = 2, two R ¹ = hydrogen atoms and a methyl group, and A = glycene phosphorus residue. Group, q = 1, D = isophorone group, r = 4, and no group corresponding to E (no alkylene oxide)
It is a urethane-modified acrylic compound.

<Synthesis Example 5> [Production of reaction product containing urethanated acrylic compound (I) and radical-polymerizable compound] (1) Internal volume of 5 liter equipped with stirrer, temperature controller, thermometer and condenser In a three-necked flask, 888 g of isophorone diisocyanate and 9 of morpholine acrylamide
06 g and 1.0 g of dibutyltin dilaurate were charged and heated in an oil bath so that the internal temperature was 80 to 90 ° C. (2) A solution prepared by uniformly mixing and dissolving 0.7 g of methylhydroquinone in a mixture of 232 g of 2-hydroxyethyl acrylate and 260 g of 2-hydroxyethyl methacrylate was charged into a dropping funnel with a side tube which was kept warm at 50 ° C in advance. The liquid in the dropping funnel is added dropwise to the content in the flask of (1) above under stirring while maintaining the temperature of the content of the flask at 80 to 90 ° C. under a nitrogen atmosphere,
The reaction was carried out by stirring at the same temperature for 2 hours. (3) Then, after lowering the temperature of the flask contents to 60 ° C., 4 mol of propylene oxide of pentaerythritol charged in another dropping funnel (adding 1 mol of propylene oxide to each of the four hydroxyl groups of pentaerythritol) 366 g of the reaction mixture was rapidly added dropwise, the temperature of the flask contents was kept at 80 to 90 ° C., and the reaction was carried out for 4 hours to produce a reaction product containing a urethanated acrylic compound (I) and a radical polymerizable compound (morpholine acrylamide). The reaction product obtained was taken out of the flask while it was warm. (4) The resulting reaction product was a colorless viscous liquid at normal temperature (25 ° C.). The urethanated acrylic compound (I) contained in the reaction product obtained in Synthesis Example 5 has p = 1, R in the general formula (I).
¹ = hydrogen atom, A = glycerin residue, q = 1, D = isophorone group, E = propylene oxide group (t = 1),
A urethane-modified acrylic compound having r = 4, and in the above general formula (I), p = 1, R ¹ = methyl group, A = glycene phosphorus residue, q = 1, D = isophorone group, E = propylene oxide group (T = 1), and a mixture with a urethane-modified acrylic compound in which r = 4.

Example 1 [Preparation of Photocurable Resin Composition] The urethane obtained in Synthesis Example 1 was placed in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. 2020 g of a reaction product containing a modified acrylic compound (I) and a radically polymerizable compound, 454 g of morpholine acrylamide and 1060 g of dicyclopentanyl diacrylate were charged, and degassing under nitrogen was carried out under reduced pressure. Then
118 g of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba-Geigy; photo-radical polymerization initiator) was added in an environment in which ultraviolet rays were blocked, and mixed and stirred at a temperature of 25 ° C. until completely dissolved (mixed With a stirring time of about 1 hour), a photocurable resin composition (viscosity at room temperature of about 2100 cp), which was a colorless transparent viscous liquid, was obtained.

Example 2 [Preparation of Photocurable Resin Composition] The urethane obtained in Synthesis Example 1 was placed in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. The reaction product containing the modified acrylic compound (I) and the radically polymerizable compound (2000 g), morpholine acrylamide (600 g) and dicyclopentanyl diacrylate (1400 g) were charged, and the atmosphere was deaerated under reduced pressure. Then
The same 1-hydroxycyclohexyl phenyl ketone 133 as that used in Example 1 under the environment where ultraviolet rays are blocked.
g, and mixed and stirred at a temperature of 25 ° C. until completely dissolved (mixing and stirring time of about 1 hour) to obtain a photocurable resin composition which is a colorless transparent viscous liquid (viscosity of about 2400 at room temperature).
cp) was obtained.

Example 3 [Preparation of Photocurable Resin Composition] A reaction product containing the urethanated acrylic compound (I) obtained in Synthesis Example 2 as the urethanized acrylic compound (I) and a radically polymerizable compound. When a photocurable resin composition was prepared in the same manner as in Example 1 except that the above was used, a photocurable resin composition (viscosity at room temperature, about 2900 cp) which was a colorless transparent viscous liquid was obtained.

Comparative Example 1 [Preparation of Photocurable Resin Composition] Instead of the reaction product used in Example 1, a reaction containing the urethanated acrylic compound obtained in Synthesis Example 3 and a radical polymerizable compound. A photocurable resin composition was prepared in the same manner as in Example 1 except that the product was used. As a result, a photocurable resin composition which was a colorless and transparent viscous liquid (viscosity at room temperature was about 2000 cp) was obtained. .

Comparative Example 2 [Preparation of Photocurable Resin Composition] Instead of the reaction product used in Example 1, a reaction product containing the urethanated acrylic compound obtained in Synthesis Example 4 and a radical polymerizable compound was obtained. A photocurable resin composition was prepared in the same manner as in Example 1 except that a viscous substance which was colorless and transparent and had poor fluidity (viscosity at room temperature of about 200,000 c
p) was obtained.

Example 4 [Manufacture of Photocured Molded Article by Molding Method] (1) Prepared in Example 1 above into a transparent silicon mold having a mold cavity in the form of a dumbbell test piece conforming to JIS 7113. After injecting the photocurable resin composition
Using a 30 W ultraviolet lamp, 1
When a molded product in the form of a dumbbell test piece hardened by irradiating ultraviolet rays for 5 minutes to cure the resin composition was obtained, a molded product having excellent transparency (dumbbell-shaped test piece) was obtained.
The molded product was taken out of the mold and its tensile properties (tensile strength, tensile elongation and tensile elastic modulus) were measured according to JIS K 7113. The results are shown in Table 1 below. (2) In addition, the heat deformation temperature of the dumbbell-shaped test piece obtained in the above (1) was measured by the method A (load: 18.5 kg / mm ² ) according to JIS K7207, and as shown in Table 1 below. Met. (3) Further, the specific gravity (d ₂ of the light before curing specific gravity of the photocurable resin composition used in the molding of Example 4 and (d _1), the resulting molded article (dumbbell-shaped test piece) ) Was measured and the volumetric shrinkage rate (%) was determined by the following mathematical formula (2). The results are shown in Table 1 below.

[0097]

## EQU00002 ## Volume shrinkage (%) = (d ₁ / d ₂ ) × 100 (2)

Example 5 [Manufacture of Three-dimensional Modeled Object by Optical Three-dimensional Modeling Method] Using the photocurable resin composition obtained in Example 1 above, an ultra-high-speed stereo modeling system (Teijin Seiki Co., Ltd.) Company-made "SO
LIFORM 500 ”) using a water-cooled Ar laser beam (output: 500 mW; wavelength: 333, 351, 364 n)
m) is irradiated perpendicularly to the surface, and the irradiation energy is 2
Under the condition of 0 to 30 mJ / cm ^2, the stereolithography is performed with a slice pitch (lamination thickness) of 0.127 mm and an average molding time of 2 minutes per layer by 2 minutes to obtain a three-dimensional molded article having a dumbbell specimen shape in accordance with JIS 7113. Manufactured. The obtained three-dimensional model was washed with isopropyl alcohol to remove the uncured resin liquid adhering to the three-dimensional model, and then irradiated with 3 KW ultraviolet light for 10 minutes and post-cured to obtain a three-dimensional model having excellent transparency. A shaped object was obtained. The tensile properties (tensile strength, tensile elongation and tensile elastic modulus) of the three-dimensional molded item (dumbbell-shaped test piece) were measured according to JIS K 7113, and the results are shown in Table 1 below. Further, the heat deformation temperature of the post-curing dumbbell-shaped test piece (three-dimensional molded article) obtained above was measured in the same manner as in Example 4, and it was as shown in Table 1 below. Furthermore, the specific gravity (d ₁ ) of the photocurable resin composition before photocuring and the specific gravity (d ₂ ) of the three-dimensional model after post-curing, which were used in the three-dimensional modeling method of Example 5, were measured, When the volumetric shrinkage rate (%) is calculated by the above mathematical expression (2),
The results are shown in Table 1 below.

<Example 6> [Production of three-dimensional object by optical three-dimensional object forming method] Optically produced in the same manner as in Example 5 except that the photocurable resin composition obtained in Example 2 was used. Three-dimensional modeling, washing of uncured resin, and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece) having excellent transparency. The tensile properties, heat deformation temperatures, and volumetric shrinkage rates of the resulting dumbbell-shaped test pieces (three-dimensional molded articles) were measured in the same manner as in Example 5, and the results were as shown in Table 1 below.

<Example 7> [Production of a three-dimensional object by an optical three-dimensional object formation method] Optically produced in the same manner as in Example 5 except that the photocurable resin composition obtained in Example 3 above was used. Three-dimensional modeling, washing of uncured resin, and post-curing were performed to manufacture a three-dimensional molded article (dumbbell-shaped test piece) having excellent transparency. The tensile properties, heat deformation temperatures, and volumetric shrinkage rates of the resulting dumbbell-shaped test pieces (three-dimensional molded articles) were measured in the same manner as in Example 5, and the results were as shown in Table 1 below.

<< Comparative Example 3 >> [Production of a three-dimensional object by an optical three-dimensional object forming method] Optically produced in the same manner as in Example 5 except that the photocurable resin composition obtained in Comparative Example 1 was used. Three-dimensional modeling, washing of uncured resin, and post-curing were performed to manufacture a transparent three-dimensional model (dumbbell-shaped test piece). The tensile properties of the dumbbell-shaped test piece (three-dimensional object) obtained as a result,
The heat distortion temperature and the volume shrinkage were measured in the same manner as in Example 5, and the results are shown in Table 1 below.

Comparative Example 4 [Production of Photocured Molded Article by Molding] The viscous photocurable resin composition obtained in Comparative Example 2 has a too high viscosity and may be used for stereolithography. Since it was difficult, the photocurable resin composition obtained in Comparative Example 2 was filled in a transparent silicone mold having a dumbbell test piece shape mold cavity according to JIS 7113 in the same manner as in Example 4. Then, photocuring was carried out in the same manner as in Example 4 to produce a dumbbell test piece-shaped molded article. The dumbbell-shaped test piece (molded product) thus obtained was evaluated for tensile properties, heat distortion temperature and volumetric shrinkage in Example 4.
When measured in the same manner as above, it was as shown in Table 1 below.

[0103]

[Table 1]

From the results shown in Table 1 above, in the case of Examples 4 to 7, the compounds of Examples 1 to 3 containing the urethanated acrylic compound within the category of the urethanated acrylic compound (I) of the present invention were included. By using the photocurable resin composition, the molded product and the three-dimensional molded product obtained there have a high heat distortion temperature significantly exceeding 100 ° C. and are extremely excellent in heat resistance. In addition, it can be seen that the volumetric shrinkage upon photocuring is small and the dimensional stability is excellent, and in addition, the tensile strength and the tensile elastic modulus are high and the mechanical properties are excellent.

On the other hand, in the case of Comparative Example 3, in the urethanated acrylic compound represented by the above general formula (I), t (the number of moles of propylene oxide added) = 6 and the urethanation of the present invention was conducted. By using the photocurable resin composition of Comparative Example 1 containing a urethanized acrylic compound which is not included in the category of acrylic compound (I),
The three-dimensional model thus obtained has a very low heat deformation temperature of 58 ° C. and is inferior in heat resistance, and has an extremely low tensile strength, a low tensile elastic modulus and inferior mechanical properties. I understand.

Further, in the urethanated acrylic compound represented by the above general formula (I), it corresponds to the group E (poly).
In the case of the photocurable resin composition of Comparative Example 2 which does not have an alkylene oxide group and therefore contains a urethanized acrylic compound which is not included in the category of the urethanized acrylic compound (I) of the present invention, the viscosity is too high and the liquid state However, it cannot be used for optical three-dimensional modeling, and the volumetric shrinkage during photocuring is large, resulting in poor dimensional accuracy. Moreover, the resulting molded product has extremely low tensile strength and poor strength. Recognize.

Example 8 [Preparation of Photocurable Resin Composition] The urethane obtained in Synthesis Example 5 was placed in a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. 2020 g of a reaction product containing a modified acrylic compound (I) and a radically polymerizable compound, 454 g of morpholine acrylamide and 1060 g of dicyclopentanyl diacrylate were charged, and degassing under nitrogen was carried out under reduced pressure. Then
118 g of the same 1-hydroxycyclohexyl phenyl ketone (photo-radical polymerization initiator) used in Example 1 was added to an environment shielded from ultraviolet rays, and mixed and stirred at a temperature of 25 ° C. until completely dissolved (mixed After stirring for about 1 hour), a photocurable resin composition (viscosity at room temperature, about 2900 cp) was obtained as a colorless transparent viscous liquid.

Example 9 [Preparation of photocurable resin composition containing filler] 2800 g of the photocurable resin composition obtained in Example 1 was mixed with a universal stirrer (Dalton Co., Ltd .; internal volume: 10). liter)
Glass beads treated with an acrylic silane coupling agent [manufactured by Toshiba Silicone; γ (methacryloxypropyl) trimethoxysilane] [average particle size = 1
5 μm, relative standard deviation value of sphericity according to the above formula (1) = 0.3] 3310 g (32% by volume based on the volume of the photocurable resin composition before adding a filler), and the same Aluminum borate whiskers treated with an acrylic silane coupling agent (“Arborex YS-4” manufactured by Shikoku Chemicals Co., Ltd .; diameter 0.5 to 0.7 μm, aspect ratio 50 to 70), 993 g (filler added) (8% by volume based on the volume of the photocurable resin composition before the addition), stirred for one day, defoamed, and added to the photocurable resin composition (viscosity at 25 ° C. of about 25 ° C.). 42000c
p) was obtained.

Example 10 [Preparation of Photocurable Resin Composition Containing Filler] 2800 g of the photocurable resin composition obtained in Example 8 was mixed with a universal stirrer (Dalton Co .; internal volume 10 liter)
Glass beads treated with an acrylic silane coupling agent [manufactured by Toshiba Silicone; γ (methacryloxypropyl) trimethoxysilane] [average particle size = 1
5 μm, relative standard deviation value of sphericity according to the above equation (1) = 0.3] 3310 g (32% by volume based on the volume of the photocurable resin composition before adding a filler), and the same Aluminum borate whiskers treated with an acrylic silane coupling agent (“Arborex YS-4” manufactured by Shikoku Chemicals Co., Ltd .; diameter 0.5 to 0.7 μm, aspect ratio 50 to 70), 993 g (filler added) (8% by volume based on the volume of the photocurable resin composition before the addition), stirred for one day, defoamed, and added with the photocurable resin composition (viscosity at 25 ° C. is about 25 ° C.). 49000c
p) was obtained.

<Example 11> [Production of three-dimensional model by optical three-dimensional model] Optically produced in the same manner as in Example 5 except that the photocurable resin composition obtained in Example 9 above was used. Three-dimensional modeling, washing of uncured resin, and post-curing were performed to manufacture a three-dimensional model (dumbbell-shaped test piece) having excellent transparency. The tensile properties, heat distortion temperature, and volumetric shrinkage of the resulting dumbbell-shaped test piece (three-dimensional molded article) were measured in the same manner as in Example 5, and the results are shown in Table 2 below.

<Example 12> [Production of a three-dimensional object by an optical three-dimensional object formation method] Optically produced in the same manner as in Example 5 except that the photocurable resin composition obtained in Example 10 was used. Three-dimensional modeling, washing of uncured resin, and post-curing were performed to manufacture a three-dimensional molded article (dumbbell-shaped test piece) having excellent transparency. The tensile properties, heat distortion temperature, and volumetric shrinkage of the resulting dumbbell-shaped test piece (three-dimensional molded article) were measured in the same manner as in Example 5, and the results are shown in Table 2 below.

[0112]

[Table 2]

From the results of Table 2 above, the urethane-containing acrylic compound (I) of the present invention is included in the category of the urethane-containing acrylic compound, other radically polymerizable compound and a photopolymerization initiator, and solid fine particles Examples 11 and 1 in which a three-dimensional object is manufactured using the photocurable resin composition of Examples 9 and 10 further containing whiskers
In the case of 2, it is possible to obtain a photo-cured product (three-dimensional molded product) that has an extremely high heat distortion temperature of over 200 ° C. and that is extremely excellent in heat resistance. Moreover, the volumetric shrinkage rate during photo-curing is extremely small and the dimensional accuracy is high. It can be seen that the tensile strength and tensile elastic modulus are high and the mechanical properties are excellent.

[0114]

The photocurable resin composition of the present invention exhibits a low-viscosity liquid, has excellent handleability, and can be cured in a short curing time. It can be used effectively in the manufacture of other products. When the photocurable resin composition of the present invention is used, a molded article or a three-dimensional molded article having excellent dimensional accuracy can be obtained because of a small volume shrinkage during photocuring. Further, a photocured product such as a molded article or a three-dimensional molded article obtained by photocuring the photocurable resin composition of the present invention has a high heat distortion temperature of more than 100 ° C. and is extremely excellent in heat resistance. In addition, it has high tensile strength and tensile modulus, and has excellent mechanical properties. When the photocurable resin composition of the present invention contains at least one filler selected from solid fine particles and whiskers, the heat-deformation temperature of the obtained photocured product is further improved, and It is possible to obtain a photo-cured product such as a molded product or a molded product which is further excellent in heat resistance and dimensional accuracy because the volumetric shrinkage is further reduced.

Claims (14)

[Claims] 1. (i) The following general formula (I); In the formula, R ¹ is a hydrogen atom or a methyl group, p is 1 or 2, and when p is 2, one or both R ¹ are methyl groups, A is a diol or triol residue, D is
1-4 divalent or trivalent unsubstituted or substituted hydrocarbon group, E is the formula _{:-( CH 2 CH 2 O) s-} ( wherein s
A (poly) ethylene oxide group represented by the following formula:-[(CH ₂ CH (CH ₃ ) O] t-(where t represents an integer of 1 to 4) ( poly) propylene oxide group, or a group of the formula _{:-( CH 2 CH 2 O) u} [(CH 2 C
_{H (CH 3) O] v-} ( wherein u and v, respectively 1-3
(Poly) ethylene oxide propylene oxide group represented by the formula (wherein the sum of u and v is 2 to 4), R ² is a hydrogen atom or an alkyl group, q is 1 or 2, and r is 3 or A photocurable resin containing (ii) a radically polymerizable compound other than the above-mentioned urethanized acrylic compound; and (iii) a photopolymerization initiator. In the composition, the content ratio of the urethanated acrylic compound (I): the radical polymerizable compound is 80:20 to 1
The photocurable resin composition is 0:90 (weight ratio). 2. The photocurable resin composition according to claim 1, wherein the content of the photopolymerization initiator is 0.1 to 10% by weight based on the total weight of the urethanized acrylic compound (I) and the radically polymerizable compound. Stuff. 3. The photocurable resin composition according to claim 1, further comprising at least one filler selected from solid fine particles and whiskers. 4. The photocurable resin composition according to claim 3, which contains both solid fine particles and whiskers. 5. The photocurable resin composition according to claim 4, wherein the solid fine particles are spherical solid fine particles having a smooth surface with little irregular reflection of light. 6. The diameter is 0.3 to 1 μm, and the length is 10 to 70.
The photocurable resin composition according to any one of claims 3 to 5, wherein a whisker having a micrometer and an aspect ratio of 10 to 100 is used. 7. The photocurable resin composition according to claim 3, wherein at least one filler selected from solid fine particles and whiskers is treated with a silane coupling agent. 8. The total content of at least one filler selected from solid fine particles and whiskers is 3 based on the volume of the photocurable resin composition before containing them.
The photocurable resin composition according to any one of claims 3 to 6, which is ˜70% by volume. 9. The photocurable resin composition according to claim 1, which is a resin composition for optical three-dimensional modeling. 10. A method for producing a three-dimensional molded article by an optical three-dimensional molding method, using the photocurable resin composition according to any one of claims 1 to 9. 11. A compound represented by the following general formula (II): (Wherein R ¹ is a hydrogen atom or a methyl group, p is 1 or 2, and when p is 2, one or both of R ¹ is a methyl group, and A represents a diol or triol residue. ) (Meth) acrylic acid ester (I
I) and the following general formula (III): embedded image D- (NCO) q + 1 (III) (wherein D is a divalent or trivalent unsubstituted or substituted hydrocarbon group, and q is 1 Or 2) is used in an amount ratio such that one isocyanate group in the polyisocyanate compound (III) remains, and the polyisocyanate compound (III) does not show reactivity with the isocyanate group. The reaction is carried out in the presence or absence of a diluent comprising another radically polymerizable compound to give a compound of the following general formula (IV); (Wherein R ¹ , A, D, p and q each represent the same group or number as described above), or a reaction product of the monoisocyanate compound (IV) A step of producing a reaction product containing the above-mentioned radically polymerizable compound together with the compound (IV); (2) the reaction product obtained in the step (1) above, represented by the following general formula (V); 5] (H-O-E-CH 2) r -C- (R 2) 4-r (V) { wherein, E is the formula _{:-( CH 2 CH 2 O) s-} ( wherein s 1
To 4 of an integer) is represented by (poly) ethylene oxide group of the _{formula: - [(CH 2 CH (} CH 3) O] is represented by t-(t wherein is an integer of 1 to 4) that (poly) propylene oxide group, or a group of the formula _{:-( CH 2 CH 2 O) u} ,
_{[(CH 2 CH (CH 3} ) O] v- ( wherein u and v total an integer of each 1 to 3 u and v are represented by a 2 to 4) (poly) ethylene oxide A propylene oxide group, R ² is a hydrogen atom or an alkyl group, and r is 3 or 4}, and the remaining isocyanate group in the monoisocyanate compound (IV) and the polyol compound (V) The hydroxyl groups therein are mixed at a ratio of 1: 1 to react with each other and reacted to give the following general formula (I); (Wherein R ¹ , R ² , A, D, E, p, q and r each represent the same group or number as described above), or a reaction product of the urethanated acrylic compound (I), or A step of producing a reaction product containing the radical-polymerizable compound together with the urethanized acrylic compound (I); and (3) a radical-polymerizable compound is added to the reaction product obtained in the step (2). When it is not contained or when the content of the radical-polymerizable compound is small, one or more radical-polymerizable compounds which are the same as or different from those used in the above step (1) are further mixed to prepare a urethane-modified acrylic compound (I). : Total radical polymerizable compound = 80: 20 to 10:
90 (weight ratio), and the process of adding a photoinitiator; The manufacturing method of the photocurable resin composition of Claim 1 characterized by the above-mentioned. 12. The method according to claim 5, wherein the step (1) is carried out in the presence of another radically polymerizable compound which does not show reactivity with an isocyanate group. 13. The production method according to claim 11, further comprising a step of adding at least one filler selected from solid fine particles and whiskers after the step (3). 14. The following general formula (I): In the formula, R ¹ is a hydrogen atom or a methyl group, p is 1 or 2, and when p is 2, one or both R ¹ are methyl groups, A is a diol or triol residue, D is
1-4 divalent or trivalent unsubstituted or substituted hydrocarbon group, E is the formula _{:-( CH 2 CH 2 O) s-} ( wherein s
Of an integer) represented by (poly) ethylene oxide group of the _{formula: - [(CH 2 CH (} CH 3) O] expressed by t-(t wherein is an integer of 1 to 4) ( poly) propylene oxide group, or a group of the formula _{:-( CH 2 CH 2 O) u} , [(CH 2
_{CH (CH 3) O] v-} ( wherein u and v respectively 1
An integer of 3 and the sum of u and v is 2 to 4) represented by (poly) ethylene oxide propylene oxide group, R ² is a hydrogen atom or an alkyl group, q is 1 or 2, and r is 3 Or represents 4}.