JPH08183823A - Stereolithographic resin and stereolithographic resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin which can give a three-dimensional molding excellent in mechanical and thermal properties and dimensional accuracy by mixing a specific short-chain unsaturated urethane, a specific long-chain unsaturated urethane, and a vinyl monomer in a specific proportion. CONSTITUTION: The resin comprises a short-chain unsaturated urethane (A) represented by formula I, a long-chain unsaturated urethane (B) represented by formula II, III, or IV, and a vinyl monomer (C). In the formulae, X is the residue formed from a diisocyanate by removing the isocyanate groups; Z<1> is the residue formed from a urethane di- or triisocyanate by removing the isocyanate groups; Z<2> is the residue formed from a polyurethane di- or triisocyanate by removing the isocyanate groups; Z<3> is the residue formed from a di- or trihydric polyether or another polyol by removing the hydroxyl groups; A<1> and A<2> each is a group represented by formula V or VI; B<1> and B<2> each is a group represented by formula V; B<3> is a group represented by formula VII (wherein R<1> to R<4> each is H or CH3 ; Y<1> is the residue formed from a dihydric alcohol by removing the hydroxyl groups; Y<2> is the residue formed from a trihydric alcohol by removing the hydroxyl groups; and Y<3> is a 2-4C alkylene); and m, n, and p each is 2 or 3. Examples of the component C include (meth)acrylic morpholide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical three-dimensional modeling resin and an optical three-dimensional modeling resin composition. The NC cutting method has been used for the production of various models and fixed objects such as a model for mold making, a model for copying, and a model for die-sinking electric discharge machining. In recent years, these have photopolymerizability. Attention has been focused on an optical three-dimensional modeling method in which a resin for optical three-dimensional modeling or a composition thereof is irradiated with an energy ray to cure and mold a predetermined three-dimensional model. The present invention relates to an optical three-dimensional molding resin applied to the above-described optical three-dimensional molding method, particularly an optical three-dimensional molding resin containing unsaturated urethane and a composition thereof.

[0002]

2. Description of the Related Art Conventionally, as an optical three-dimensional molding resin containing unsaturated urethane, 1) an example containing unsaturated urethane obtained from polyurethane diisocyanate and hydroxyalkyl acrylate (JP-A-2-14561).
6) 2) Examples containing unsaturated urethane obtained from polyurethane diisocyanate and triol di (meth) acrylate (JP-A-1-204915, JP-A-63-
35550), 3) Examples containing unsaturated urethane obtained from polyurethane diisocyanate and tetraol triacrylate (JP-A-61-276863), 4).
Examples containing an unsaturated urethane obtained from polyurethane tri-hexaisocyanate and triol di (meth) acrylate (JP-A-63-35550), 5) From triisocyanate and diol mono (meth) acrylate or triol di (meth) acrylate An example containing the obtained unsaturated urethane (Japanese Patent Laid-Open No. 63-11255).
There is an example (Japanese Patent Publication No. 63-20203) containing an unsaturated urethane obtained from 1) and 6) diisocyanate and triol dimethacrylate.

In such a conventional example, an optical stereolithography resin containing a so-called short-chain unsaturated urethane, which does not have a soft segment chain in the molecule and has a relatively high content of a polymerizable group, is crosslinked. Since a three-dimensional object with high density is formed, the obtained three-dimensional object has excellent mechanical strength and thermal physical properties, but on the other hand, volumetric shrinkage due to photopolymerization reaction is large, resulting in extremely poor shape accuracy. Is known to be. Further, an optical stereolithography resin containing a so-called long-chain unsaturated urethane, which has a soft segment chain in the molecule and has a relatively low content of a polymerizable group, has a small volume shrinkage due to a photopolymerization reaction. On the other hand, it is known that the obtained three-dimensional molded item has poor thermal physical properties. And it is also known that the optical three-dimensional modeling resin containing the above-mentioned short-chain unsaturated urethane and long-chain unsaturated urethane, the obtained three-dimensional molded article will have correspondingly improved physical properties and the like. Has been.

However, even if the resin contains a short-chain unsaturated urethane and a long-chain unsaturated urethane as described above, in the conventional optical three-dimensional molding resin, as a matter of fact,
The obtained three-dimensional model does not necessarily have excellent shape accuracy. The reason is, in addition to the volume contraction based on the photopolymerization described above, the heterogeneity of the material in the resin for optical three-dimensional modeling to be used, the heterogeneity of the photopolymerization reaction, the shape of the desired three-dimensional model, and the like. This is because non-uniform strain stress is inherent in the obtained three-dimensional molded item. When such strain stress concentrates on a specific part or a specific direction in the three-dimensional model,
Deformation such as warpage, twisting, and crushing, and further structural destruction such as cracking and peeling will occur. A three-dimensional object with such a strain stress is potentially inferior in shape accuracy. In the conventional optical three-dimensional modeling resin, thermal and mechanical properties of the obtained three-dimensional model, such as tensile strength,
Tensile elongation and toughness value indicated by their product are
Compared with a three-dimensional object obtained from a thermoplastic resin that is commonly used as a plastics molding material, for example, an ABS resin, the three-dimensional object obtained is significantly inferior, and thus the obtained three-dimensional object can be used only for limited purposes.

[0005]

The problem to be solved by the present invention is that the conventional three-dimensional modeling resin and its composition have poor thermal and mechanical properties of the obtained three-dimensional model, and The point is that the shape accuracy is poor.

[0006]

However, the present inventors have
Regarding the resin for optical three-dimensional modeling containing an unsaturated urethane and the composition thereof, focusing on the unsaturated urethane obtained by mixing the short-chain unsaturated urethane and the long-chain unsaturated urethane, the unsaturated urethane and the combined use thereof As a result of studying the relationship between the chemical structure of the vinyl monomer and the shape accuracy, thermal properties, and mechanical properties of the resulting three-dimensional model, unsaturated urethane of a specific structure and (meth) acrylic acid morpholide were identified. It has been found that it is correct and suitable to use the specific vinyl monomer contained in a predetermined ratio.

That is, the present invention provides a short-chain unsaturated urethane represented by the following formula 1, a long-chain unsaturated urethane represented by the following formula 2, 3, or 4, and the following vinyl monomer. And containing the short-chain unsaturated urethane / the long-chain unsaturated urethane in a ratio of 20/80 to 80/20 (weight ratio), the short-chain unsaturated urethane and the long-chain. Type unsaturated urethane / total amount of vinyl monomer = 100/25
The present invention relates to a resin for optical stereolithography and a composition thereof, which is characterized by comprising a ratio of 100 to 150 (weight ratio).

[0008]

(Equation 1)

[0009]

(Equation 2)

[0010]

(Equation 3)

[0011]

(Equation 4)

(In formulas 1 to 4, X: a residue obtained by removing an isocyanate group from diisocyanate Z ¹ : a residue obtained by removing an isocyanate group from urethane diisocyanate or urethane triisocyanate Z ² : an isocyanate obtained from a polyurethane diisocyanate or a polyurethane triisocyanate Residue excluding the groups Z ³ : All are di- or trivalent polyether polyols,
Residues obtained by removing a hydroxyl group from a polyol selected from polyester polyols and polyether ester polyols A ¹ and A ² : groups represented by the following formula 5 or formula B ¹ and B ² : the same or different formulas below at the same time 5
Group B ^{3 represented by} the formula: the same or different groups represented by the following formula 7 m, n, p: 2 or 3)

[0013]

[Formula 5]

[0014]

[Formula 6]

[0015]

[Formula 7]

(In the formulas 5, 6 and 7, R ¹ , R ² , R ³ , R ⁴ : H or CH ₃ Y ¹ is a residue of a dihydric alcohol from which a hydroxyl group is removed. Y ^{2 is a} trihydric alcohol. Residue excluding hydroxyl group Y ³ : alkylene group having 2 to 4 carbon atoms)

Vinyl monomer: (meth) acrylic acid morpholide or a mixture of (meth) acrylic acid morpholide and diol di (meth) acrylate.

For the unsaturated urethane represented by the formula 1, 1)
Reaction product of dihydric alcohol mono (meth) acrylate / diisocyanate = 2/1 (molar ratio), 2) dihydric alcohol mono (meth) acrylate / trihydric alcohol di (meth) acrylate / diisocyanate = 1/1 / 1
(Molar ratio) reactant, 3) di (meth) of trihydric alcohol
Acrylate / diisocyanate = 2/1 (molar ratio) reactants are included.

In the present invention, the mono (meth) acrylate of dihydric alcohol means monoacrylate or monomethacrylate of dihydric alcohol. Further, di (meth) acrylate of trihydric alcohol means diacrylate, dimethacrylate or monoacrylate monomethacrylate of trihydric alcohol.

As the mono (meth) acrylate of the dihydric alcohol, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1,6
Examples include mono (meth) acrylates of dihydric alcohols having 2 to 6 carbon atoms such as hexanediol mono (meth) acrylate.

Examples of the di (meth) acrylate of trihydric alcohol include glycerin, trimethylolpropane, 5-
Methyl-1,2,4-heptanetriol, 1,2,6
Examples thereof include di (meth) acrylates of trihydric alcohols such as hexanetriol, and of these, glycerin diacrylate, glycerin dimethacrylate, and glycerin monoacrylate monomethacrylate can be advantageously used.

As the diisocyanate to be reacted with the mono (meth) acrylate of the dihydric alcohol or the di (meth) acrylate of the trihydric alcohol as exemplified above,
1) various tolylene diisocyanates, aromatic diisocyanates such as methylene-bis- (4-phenylisocyanate), 2) aliphatic diisocyanates or alicyclic diisocyanates such as hexamethylene diisocyanate and methylenebis (4-cyclohexyl isocyanate),
3) 4-isocyanatomethyl-1-isocyanato-1-
Methyl-cyclohexane, 5-isocyanatomethyl-1
And aliphatic / alicyclic diisocyanates such as isocyanato-1,1-dimethyl-5-methyl-cyclohexane (isophorone diisocyanate).

In the short-chain type unsaturated urethane represented by the formula 1, when mono (meth) acrylates of two different dihydric alcohols are used, and when di (meth) acrylates of two different trihydric alcohols are used, In addition, when mono (meth) acrylate of dihydric alcohol and di (meth) acrylate of trihydric alcohol are used, the resulting unsaturated urethanes are both asymmetric unsaturated urethanes. As the diisocyanate used for synthesizing the asymmetric unsaturated urethane, those having an isocyanate group that is affected by a sterically hindering substituent and an isocyanate group that is not affected by the same, or an aliphatic hydrocarbon It is preferable to use a diisocyanate having isocyanate groups having mutually different reactive groups, such as those having an isocyanate group bonded to a group and an isocyanate group bonded to an aromatic hydrocarbon group. Tolylene diisocyanate, isophorone diisocyanate, 4-isocyanatomethyl-1-
Isocyanato-1-methyl-cyclohexane and the like can be mentioned.

For the long-chain unsaturated urethane represented by the formula 2, 1) mono (meth) acrylate of dihydric alcohol /
Reaction product of urethane diisocyanate = 2/1 (molar ratio), 2) mono (meth) acrylate of dihydric alcohol /
The reaction product of urethane triisocyanate = 3/1 (molar ratio) is included.

As the mono (meth) acrylate of the dihydric alcohol used in the synthesis of the long chain unsaturated urethane represented by the formula 2, those exemplified in the case of the short chain unsaturated urethane represented by the formula 1 can be used. .

As the urethane diisocyanate or urethane triisocyanate to be reacted with the mono (meth) acrylate of the dihydric alcohol, 1) a urethanization reaction product of 1 mol of polyether diol, polyester diol or polyether ester diol and 2 mol of diisocyanate is used. And 2) polyether triol, polyester triol or polyether ester triol, and urethane triisocyanate which is a urethanization reaction product of 1 mol of diisocyanate.

Examples of the polyether diols having 2 to 6 carbon atoms such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethoxylated 1,4-butanediol, polypropoxylated 1,6-hexanediol and the like. Dihydric alcohol has 2 to 2 carbon atoms
The polyalkoxylated dihydric alcohol obtained by adding the alkylene oxide of 4 is mentioned, but the one in which propylene oxide is added as the alkylene oxide is preferable.

Examples of the above-mentioned polyether triol include polyethoxylated glycerin, polypropoxylated trimethylolpropane, polybutoxylated hexanetriol, and the like, and C3 to C6 trihydric alcohol to C2 to C4 alkylene oxide. Examples thereof include polyalkoxylated trihydric alcohols obtained by adding propylene oxide, and those having propylene oxide added as an alkylene oxide are preferable.

Further, as the above-mentioned polyester diol and polyester triol, an aliphatic lactone or an aliphatic oxycarboxylic acid having 4 to 6 carbon atoms is added to the dihydric alcohol or trihydric alcohol used in the synthesis of the polyether diol or the polyether triol. Examples thereof include those obtained by the reaction, and those obtained by reacting ε-caprolactone as the aliphatic lactone and those obtained by reacting oxypivalic acid as the aliphatic oxycarboxylic acid are preferable.

Examples of the above-mentioned polyether ester diol and polyether ester triol include those obtained by reacting the above-mentioned polyether diol or polyether triol with the above-mentioned aliphatic lactone or aliphatic oxycarboxylic acid.

Polyether diols, polyether triols, polyester diols as exemplified above,
As the diisocyanate to be reacted with the polyester triol, the polyether ester diol or the polyether ester triol, those exemplified in the case of the short chain unsaturated urethane represented by the formula 1 can be used.

For the long-chain unsaturated urethane represented by the formula 3, 1) mono (meth) acrylate of dihydric alcohol /
Reaction product of polyurethane diisocyanate = 2/1 (molar ratio), 2) Mono (meth) acrylate of dihydric alcohol / polyurethane triisocyanate = 3/1 (molar ratio)
The reactants of are included.

In the present invention, the polyurethane diisocyanate is defined by n moles of diol and diisocyanate (n + 1).
It is a polyurethane having free isocyanate groups at both ends, which is obtained by a urethanization reaction with moles. Here, as the diol, 1) alkane diol having 2 to 12 carbon atoms, 2) the above-mentioned polyether diol, polyester diol, polyether ester diol, 3)
These mixtures are mentioned.

In the present invention, the polyurethane triisocyanate is obtained by the urethanization reaction of 3 mol of the above-mentioned urethane diisocyanate or polyurethane diisocyanate and 1 mol of triol, and is a polyurethane having 3 isocyanate groups as terminal groups. . Here, as a triol, 1) 3 to 3 carbon atoms
12 alkane triols, 2) the above-mentioned polyether triols, polyester triols, polyether ester triols, 3) mixtures thereof.

As the mono (meth) acrylate of the dihydric alcohol used in the synthesis of the long chain unsaturated urethane represented by the formula 3, those exemplified in the case of the short chain unsaturated urethane represented by the formula 1 can be used. .

The unsaturated urethane represented by the formula 4 is a urethanization reaction product of a polyol and a (meth) acryloyloxyalkylisocyanate, and includes 1) diol / (meth) acryloyloxyalkylisocyanate = 1/2. (Molar ratio) of reactants, 2) triol /
(Meth) acryloyloxyalkyl isocyanate =
1/3 (molar ratio) of reactants are included.

As the polyols, the diols and triols exemplified in the synthesis of the above-mentioned urethane diisocyanate and urethane triisocyanate can be used.

The (meth) acryloyloxyalkyl isocyanate to be reacted with the polyol is a (meth) acryloyloxyalkyl isocyanate having an alkyl group having 2 to 4 carbon atoms. Examples of such (meth) acryloyloxyalkyl isocyanate include acryloyloxyethyl isocyanate and acryloyloxy-2-
Examples thereof include methyl-ethyl isocyanate, methacryloyloxyethyl isocyanate, methacryloyloxy-2-methyl-ethyl isocyanate, and of these, methacryloyloxyethyl isocyanate and acryloyloxyethyl isocyanate can be advantageously used.

The present invention is not particularly limited to the method for synthesizing unsaturated urethane, and a known method, for example, the method described in JP-A-4-53809 can be applied to the synthesis, but the method is asymmetric. The following methods can be applied to the synthesis of form unsaturated urethane. For example, among the short-chain unsaturated urethanes represented by the formula 1, for the synthesis of the asymmetric unsaturated urethane, the mono (meth) alcohol of the dihydric alcohol is previously prepared.
An unsaturated urethane monoisocyanate is prepared by reacting 1 mol of an acrylate or a di (meth) acrylate of a trihydric alcohol with 1 mol of the above-mentioned diisocyanate having an isocyanate group having a different reactivity, and then divalent alcohol mono ( There is a method of reacting a (meth) acrylate or a di (meth) acrylate of a trihydric alcohol.

According to the present invention, it is preferable that the short-chain unsaturated urethane represented by the formula 1 has 3 or 4 polymerizable groups in the molecule, and that the polymerizable groups include an acryloyl group and a methacryloyl group. Those having both are more preferable. In this case, the ratio of the acryloyl group and the methacryloyl group as the polymerizable group contained in the molecule is not particularly limited, but when the number of the polymerizable groups is 3, the ratio of acryloyl group / methacryloyl group = 2/1, When the number of polymerizable groups is 4, acryloyl group / methacryloyl group =
A ratio of 2/2 to 3/1 is preferable.

According to the present invention, the formula 2, the formula 3, or the formula 4 is also used.
In the long-chain unsaturated urethane represented by, those in which m, n or p are 3 are preferable, and in this case, the number of polymerizable groups contained in the molecule is 3, but among these unsaturated urethanes, Particularly preferred are those in which at least two of the three polymerizable groups are acryloyl groups.

Further in accordance with the present invention, equation 2, equation 3 or equation 4
In the long-chain unsaturated urethane represented by, the molecular weight per polymerizable group contained in the molecule is 400 to 1000.
It is preferable that

In the resin for optical three-dimensional modeling of the present invention,
As the unsaturated urethane, a short-chain unsaturated urethane and a long-chain unsaturated urethane are used. The ratio of the short-chain unsaturated urethane and the long-chain unsaturated urethane is as follows: short-chain unsaturated urethane / long-chain unsaturated urethane = 20/80 to 80/20
(Weight ratio), but preferably 20/80 to 50/50 (weight ratio).

The resin for optical three-dimensional modeling of the present invention comprises the short chain unsaturated urethane represented by the formula 1, the formula 2, the formula 3 or the formula 4
A long-chain unsaturated urethane represented by and a vinyl monomer, and the vinyl monomer is a single system of (meth) acrylic acid morpholide or (meth) acrylic acid morpholide and diol di (meth). It is composed of a mixed system with acrylate.

As (meth) acrylic acid morpholide,
Acrylic acid morpholide and methacrylic acid morpholide are mentioned, but acrylic acid morpholide is preferable.

As the diol di (meth) acrylate used when mixed with (meth) acrylic acid morpholide, 1) ethylene glycol, propylene glycol,
1,4-butanediol, neopentyl glycol,
A diacrylate or dimethacrylate of an alkanediol having 2 to 6 carbon atoms such as 1,6-hexanediol,
2) Diacrylates or dimethacrylates of diols having an alicyclic hydrocarbon group having 6 to 12 carbon atoms such as cyclohexanedimethanol, cyclohexene dimethanol, dicyclopentyl dimethanol, and 3) Alkane diols and diols described above. Obtained by reacting an aliphatic lactone or an aliphatic oxycarboxylic acid having 4 to 6 carbon atoms,
Diacrylates or dimethacrylates of (poly) ester diols, such as diacrylates or dimethacrylates of 1,6-hexanediol hydroxycaprate, diacrylates or dimethacrylates of neopentyl glycol hydroxypivalate, 4) 2,2-bis Alkoxyl group having 2 to 3 carbon atoms such as (hydroxyethoxyphenyl) propane, 2,2-bis (hydroxydiethoxyphenyl) propane, bis (hydroxypropoxyphenyl) methane and bis (hydroxydipropoxyphenyl) methane. Examples thereof include bisphenol diacrylate or dimethacrylate.

In the present invention, when a mixed system of (meth) acrylic acid morpholide and diol di (meth) acrylate is used as the vinyl monomer, (meth) acrylic acid morpholide accounts for 50% by weight or more in the vinyl monomer. The content is preferably contained in a proportion, and more preferably 60% by weight or more.

In the resin for optical three-dimensional modeling of the present invention,
The ratio of the unsaturated urethane and the vinyl monomer is the total amount of the short-chain unsaturated urethane represented by the formula 1 and the long-chain unsaturated urethane represented by the formula 2 or the formula 3 / vinyl monomer = 100.
/ 25 to 100/150 (weight ratio), and preferably 100/40 to 100/100 (weight ratio).

The resin composition for optical three-dimensional modeling of the present invention comprises
In addition to the resin for optical three-dimensional modeling as described above, solid fine particles having an average particle diameter of 0.1 to 50 μm and an average fiber length of 1 to 7
1 of filler selected from 0 μm inorganic fiber whiskers
One or two or more kinds are contained. When using solid fine particles as the filler, those having an average particle diameter of 3 μm or more are preferable, and when using inorganic fiber whiskers as the filler, those having a fiber diameter of 0.3 to 1 μm and an average fiber length of 10 μm or more are preferable. . Examples of such fillers are 1) inorganic solid fine particles such as silica, alumina, clay, calcium carbonate and glass beads, 2) organic solid fine particles such as crosslinked polystyrene, polymethylmethacrylate and polymethylsiloxane, 3) potassium titanate fiber, sulfuric acid. Magnesium fiber, magnesium borate fiber,
Inorganic fiber whiskers such as aluminum borate fiber and carbon fiber can be used. When these fillers are contained, the proportion of the filler is 50 to 400 parts by weight per 100 parts by weight of the above-mentioned optical three-dimensional modeling resin. These fillers may be used alone or in combination of two or more, but it is preferable to use both inorganic solid fine particles and inorganic fiber whiskers as the filler. In this case, 50 to 300 parts by weight of inorganic solid fine particles and inorganic fiber whiskers are used. It is more preferable to use 10 to 100 parts by weight.

When the resin for optical three-dimensional modeling of the present invention and the composition thereof are subjected to optical three-dimensional modeling, a photopolymerization initiator is previously contained in them. The present invention does not limit the kind of the photopolymerization initiator to be used, but as the photopolymerization initiator, 1) benzoin, α-methylbenzoin,
Carbonyl compounds such as anthraquinone, chloranthraquinone and acetophenone, 2) diphenyl sulfide,
Examples thereof include sulfur compounds such as diphenyl disulfide and dithiocarbamate, and 3) polycyclic aromatic compounds such as α-chloromethylnaphthalene and anthracene. The content of the photopolymerization initiator in the resin for optical three-dimensional modeling and the composition thereof is usually 0.1 to 10 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the resin for optical three-dimensional modeling.
It should be 5 parts by weight. N- with the photopolymerization initiator
Butylamine, triethanolamine, N, N-dimethylaminobenzenesulfonic acid diallylamide, N, N-
A photosensitizer such as dimethylaminoethyl methacrylate can be used.

The present invention does not particularly limit the optical three-dimensional modeling method to which the resin for optical three-dimensional modeling of the present invention or the composition thereof is applied. Various methods are known as such an optical three-dimensional modeling method (JP-A-56-144478, JP-A-60-247515, JP-A-1-204915, JP-A-3-41126, etc.). First, a cured layer of an optical three-dimensional modeling resin or a composition thereof is formed,
Next, there is a method of forming a desired three-dimensional model by repeating the operation of newly supplying an optical three-dimensional modeling resin or a composition thereof onto the cured layer to form the cured layer. This three-dimensional object can be further post-cured if necessary. Examples of energy rays used for curing include visible rays, ultraviolet rays, and electron rays, and ultraviolet rays are preferable.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, parts mean parts by weight and% means% by weight unless otherwise specified.

[0053]

【Example】

Test Category 1 (Preparation of Resin for Optical Stereoscopic Modeling) -Examples 1 to 11 and Comparative Examples 1 to 8 Short-chain unsaturated urethane A-1 (according to the synthesis method described in JP-A-4-53809). 1 / 2,4-tolylene diisocyanate, glycerin monoacrylate monomethacrylate and hydroxyethyl acrylate
(Reacted at a molar ratio of 1/1) was synthesized. Separately, a long-chain type unsaturated urethane B-1 {glycerin propylene oxide (10 mol) adduct, hydroxyethyl acrylate and isophorone diisocyanate is 1/3 / in accordance with the synthesis method described in JP-A-2-73817.
Were reacted at a molar ratio of 3}. 30 parts of the synthesized short-chain unsaturated urethane A-1, 70 parts of the long-chain unsaturated urethane B-1, and 10 parts of acrylic acid morpholide.
0 parts and 0 parts were mixed and dissolved at room temperature to prepare an optical three-dimensional modeling resin of Example 1. In the same manner as in Example 1, Examples 2 to 2
Resins for optical stereolithography of 9 and Comparative Examples 1 to 8 were prepared. The compositions are shown in Tables 1 and 2.

[0054]

[Table 1]

[0055]

[Table 2]

In Table 1, A-1: a reaction product of glycerin monoacrylate monomethacrylate / hydroxyethyl acrylate / 2,4-tolylene diisocyanate = 1/1/1 (molar ratio) A-2: hydroxyethyl methacrylate / hydroxy Propyl methacrylate / isophorone diisocyanate = 1/1/1 (molar ratio) reaction product A-3: Hydroxyethyl acrylate / isophorone diisocyanate = 2/1 (molar ratio) reaction product B-1: GPO-6-3T / hydroxy Reaction product of ethyl acrylate = 1/3 (molar ratio) B-2: GCL-8-3I / hydroxyethyl acrylate / hydroxyethyl methacrylate = 1/2/1
(Mole ratio) of reaction product B-3: PPG-TDI / hydroxyethyl acrylate / glycerin monoacrylate monomethacrylate =
1/1/1 (molar ratio) reactant B-4: glycerin propylene oxide (15 mol)
Adduct / Acryloyloxyethyl isocyanate = 1
/ 3 (molar ratio) of the reaction product (however, GPO-6-3T; glycerin propylene oxide (6 mol) adduct / 2,4-tolylene diisocyanate = 1/3 (molar ratio) of urethane tri Isocyanate GCL-8-3I; glycerol caprolactone (8 mol) adduct / isophorone diisocyanate = 1/3 (molar ratio), urethane triisocyanate PPG-TDI; polyoxypropylene glycol (average molecular weight 200) / 2, Polyurethane diisocyanate which is a reaction product of 4-tolylene diisocyanate = 3/4 (molar ratio) C-1: Morpholide acrylic acid C-2: Morpholide methacrylic acid D-1: Dicyclopentyl dimethylene diacrylate D-2: Neopentyl Glycol hydroxypivalate diacreate D-3: neopentyl glycol diacrylate

Test Category 2 (Preparation of 3-D object and its evaluation) 1) Preparation of 3-D object Mainly composed of a three-dimensional NC table equipped with a container and a helium / cadmium laser light (output 25 mW, wavelength 3250 angstrom) control system. The constructed optical three-dimensional modeling apparatus was used. The above-mentioned container was filled with one in which 3 parts of 1-hydroxycyclohexyl phenyl ketone was dissolved as a photopolymerization catalyst per 100 parts of the optical three-dimensional modeling resin prepared in Test Category 1 (hereinafter, simply referred to as a mixed solution), The mixed solution was supplied from the container to a horizontal plane (XY axis plane) with a thickness of 0.10 mm, and helium was focused from a direction (Z axis direction) perpendicular to the surface (XY axis plane). -The cadmium laser beam was scanned to cure the resin for optical three-dimensional modeling. Next, a new mixed liquid having a thickness of 0.10 mm was supplied onto the cured product and cured in the same manner. Thereafter, in the same manner, a total of 200 layers were laminated to form a conical solid body having a design value of a bottom surface diameter of 200.00 mm and a height of 20.00 mm. The obtained modeled product was washed with isopropyl alcohol and then irradiated with a 3 Kw ultraviolet lamp for 30 minutes to perform post-curing to obtain a three-dimensional modeled product.

2) Measurement of mechanical properties In the same manner as 1), a dumbbell shape having a thickness of 3 mm specified in JIS K7113 was photo-molded, and the model was washed with isopropyl alcohol and then at 98 ° C. for 2 hours. A test piece was prepared by heating and post-curing. Three identical test pieces were prepared, and the tensile strength, the tensile elastic modulus, and the tensile elongation were measured at a tensile speed of 5 mm / sec according to JIS K7113. Further, a toughness value (Tf) represented by tensile strength × tensile elongation was calculated. The results are shown in Table 3 as an average value of three test pieces.

3) Measurement of thermal physical properties In the same manner as the test piece of 2), a 55 mm × 10 mm × 2 mm flat plate type test piece was prepared. The dynamic viscoelasticity of this test piece was measured, and the glass transition temperature (T
g) was determined. The results are shown in Table 3.

4) Measurement of shape Regarding the three-dimensional object obtained in 1), 2 on the XY axis plane.
The two-dimensional figure a was vertically projected, and the two-dimensional figure b was horizontally projected on 50 arbitrary planes perpendicular to the X-Y axis plane, and the following measurements were performed on these projections. The results are shown in Table 4. The two-dimensional figure a obtained here is a circle, and the two-dimensional figure b is a triangle. Two-dimensional figure a: Draw 50 arbitrary straight lines passing through the center of gravity of the projected view, measure the distance between two points intersecting the contour of the projected view,
For these measured values, the average value, maximum value, minimum value and standard deviation were calculated. Two-dimensional figure b: The area of 50 projection views was measured, and the average value, maximum value, minimum value and standard deviation were calculated for these measured values.

[0061]

[Table 3]

[0062]

[Table 4]

In Tables 3 and 4, Comparative Example 7: ABS resin (Diapet HF-5 manufactured by Mitsubishi Rayon Co., Ltd.) Incidentally, a test piece for measuring mechanical physical properties and a test for measuring thermal physical properties of Comparative Example 7. Cylinder temperature 200 ℃, mold temperature 60
Injection molded at ° C. The size and shape of the injection molded product are the same as those in 2) and 3) above.

Test Category 3 (Preparation of Resin Composition for Optical Stereoscopic Modeling) Examples 12 to 15 and Comparative Examples 8 and 9 100 parts of optical stereoscopic modeling resin of Example 1 prepared in Test Category 1 and light 3 parts of a polymerization initiator, 200 parts of inorganic solid fine particles, and 50 parts of inorganic fiber whiskers were put into a mixing tank equipped with a biaxial stirrer, and sufficiently stirred and mixed until uniform. The stirred mixture was filtered through a 50 μm filter to prepare an optical three-dimensional modeling resin composition of Example 12. Similar to Example 12, Examples 13 to 15 and Comparative Example 8,
The resin composition for optical three-dimensional modeling of 9 was prepared. The compositions are shown in Table 5.

Test Category 4 (Preparation of three-dimensional object and its evaluation) 1) Preparation of three-dimensional object Using the resin composition for optical three-dimensional object prepared in Test Section 3, preparation of three-dimensional object in Test Section 2 Similarly, a conical solid body having a design value of bottom surface diameter of 200.00 mm and height of 20.00 mm was formed. The obtained modeled product was washed with isopropyl alcohol, heated at 98 ° C. for 2 hours and post-cured to obtain a three-dimensional modeled product.

2) Measurement of mechanical properties, thermal properties and shape Test pieces prepared separately in the same manner as in Test Category 2 and 1)
The mechanical properties, thermal properties, and shape of the three-dimensional molded object manufactured in Section 3 were measured. The results are shown in Tables 6 and 7.

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[Table 5]

In Table 4, D-1: Aluminum borate whiskers having an average diameter of 0.8 μm × average fiber length of 20 μm (Arbolex YS-4 manufactured by Shikoku Kasei Co., Ltd.) E-1: Glass beads having an average particle diameter of 30 μm ( Toshiba Barodyni GB-730C) E-2: Aluminum hydroxide having an average particle size of 8 μm (B-103 manufactured by Nippon Light Metal Co., Ltd.) F-1: 1-hydroxycyclohexyl phenyl ketone.

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[Table 6]

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[Table 7]

In Tables 6 and 7, Comparative Examples 8 and 9: Cracks were observed on the surface of the three-dimensional molded item.

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As is apparent from the above, the present invention described above has an effect that it is possible to obtain a three-dimensional object excellent in mechanical properties and thermal properties and in shape accuracy.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B29K 101: 00

Claims (7)

[Claims] 1. A short-chain unsaturated urethane represented by the following formula 1, a long-chain unsaturated urethane represented by the following formula 2, 3, or 4, and a vinyl monomer described below. , The short-chain unsaturated urethane / the long-chain unsaturated urethane = 20 /
It is contained in a ratio of 80 to 80/20 (weight ratio), and the total amount of the short chain unsaturated urethane and the long chain unsaturated urethane / the vinyl monomer = 100/25 to 100/150
A resin for optical three-dimensional modeling, which is characterized by comprising a ratio (weight ratio). (Equation 1) (Equation 2) (Equation 3) (Equation 4) (In Formulas 1 to 4, X: a residue obtained by removing an isocyanate group from diisocyanate Z ¹ : a residue obtained by removing an isocyanate group from urethane diisocyanate or urethane triisocyanate Z ² : a residue obtained by removing an isocyanate group from polyurethane diisocyanate or polyurethane triisocyanate residues Z ^3: both divalent or trivalent polyether polyol,
Residues obtained by removing a hydroxyl group from a polyol selected from polyester polyols and polyether ester polyols A ¹ and A ² : groups represented by the following formula 5 or formula B ¹ and B ² : the same or different formulas below at the same time 5
Group B ^{3 represented by} the formula: Simultaneously the same or different, the group represented by the following formula 7 m, n, p: 2 or 3) [Formula 6] [Formula 7] (In Formula 5, Formula 6, and Formula 7, R ¹ , R ² , R ³ , R ⁴ : H or CH ₃ Y ¹ : a residue obtained by removing a hydroxyl group from a dihydric alcohol Y ² : a residue obtained by removing a hydroxyl group from a trihydric alcohol residues Y ^3: alkylene group) vinyl monomer having 2 to 4 carbon atoms :( meth) acrylic acid morpholide or (meth) mixture of acrylic acid morpholide and the diol di (meth) acrylate 2. The resin for optical stereolithography according to claim 1, wherein the short-chain unsaturated urethane represented by the formula 1 has both an acryloyl group and a methacryloyl group in the molecule. 3. The long chain unsaturated urethane represented by formula 2, formula 3 or formula 4 has three polymerizable groups in the molecule, and at least two of the polymerizable groups are The resin for optical stereolithography according to claim 1, which is an acryloyl group. 4. The vinyl monomer containing (meth) acrylic acid morpholide in an amount of 50% by weight or more.
The resin for optical three-dimensional modeling according to 2 or 3. 5. The diol di (meth) acrylate is a di (meth) acrylate of an alkanediol having 2 to 6 carbon atoms, a di (meth) acrylate of a diol having an alicyclic hydrocarbon group having 6 to 12 carbon atoms, A di (meth) acrylate of an ester diol obtained by reacting an alkanediol having 2 to 6 carbon atoms with an oxycarboxylic acid having 4 to 6 carbon atoms and a di (meth) alkoxylated bisphenol having 2 to 3 carbon atoms in an alkoxyl group. ) One or two or more selected from acrylates, The resin for optical stereolithography according to claim 1, 2, 3 or 4. 6. The average particle size of 0..100 per 100 parts by weight of the resin for optical three-dimensional modeling according to claim 1, 2, 3, 4 or 5.
Solid fine particles of 1 to 50 μm and average fiber length of 1 to 70 μm
A resin composition for optical three-dimensional modeling, containing one or more fillers selected from the inorganic fiber whiskers in a proportion of 50 to 400 parts by weight. 7. The filler is an inorganic fiber whisker 10-1.
The resin composition for optical three-dimensional modeling according to claim 6, which is composed of 00 parts by weight and 50 to 300 parts by weight of the inorganic solid fine particles.