JP2634018B2 - Photopolymerizable composition for optical stereolithography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition for stereolithography (hereinafter simply referred to as a photopolymerizable composition). The NC cutting method has been used to produce various models and fixed objects such as mold working models, copying machining models, sculpture electric discharge machining models, and the like. Attention has been paid to a method in which a photopolymerizable composition is irradiated with energy rays to be cured into a predetermined shape. The present invention relates to a photopolymerizable composition applied to the above-described optical three-dimensional modeling method, and more particularly to a photopolymerizable composition containing an unsaturated urethane having a specific structure.

[0002]

2. Description of the Related Art Conventionally, as a photopolymerizable composition containing an unsaturated urethane, 1) an example containing an unsaturated urethane obtained from a polyurethane diisocyanate and a hydroxyalkyl acrylate (JP-A-2-145616);
2) Examples containing unsaturated urethane obtained from polyurethane diisocyanate and triol di (meth) acrylate (JP-A-1-204915, JP-A-63-355)
50), 3) Examples containing unsaturated urethane obtained from polyurethane diisocyanate and tetraol triacrylate (Japanese Unexamined Patent Publication (Kokai) No. 61-276863), 4) Unsaturation obtained from polyurethane tri-hexa isocyanate and triol di (meth) acrylate. Examples containing saturated urethane (JP-A-63-35550), 5) Examples containing unsaturated urethane obtained from triisocyanate and diol mono (meth) acrylate or trioldi (meth) acrylate (JP-A-63-112551) ), 6)
Example containing unsaturated urethane obtained from diisocyanate and triol dimethacrylate (Japanese Patent Publication No. Sho 63-2
0203).

However, the above-described conventional example has the following disadvantages. In the case of the above-mentioned conventional examples 1) to 5), when the concentration of double bonds in the photopolymerizable composition is increased to increase the crosslink density of the obtained cured molded article, the reaction shrinkage in the photopolymerization reaction is large. Conversely, when the concentration of double bonds in the photopolymerizable composition is lowered to reduce the crosslink density of the obtained cured molded article, thermal properties are inferior, for example, only the cured molded article having a low heat distortion temperature is obtained. I can't get it. Also, in the case of the conventional example 6), since the double bond concentration in the photopolymerizable composition is originally high, the reaction shrinkage in the photopolymerization reaction is remarkably large, and further, it is based on the fact that it has a polymerizable group consisting of a methacryl group. Low photopolymerization reactivity. In the conventional example, it is impossible to simultaneously improve the photopolymerization reactivity, reduce the reaction shrinkage in the photopolymerization reaction, and improve the thermal properties of the obtained cured molded article.

[0004]

The problem to be solved by the present invention is to provide a conventional photopolymerizable composition containing an unsaturated urethane with an improvement in photopolymerization reactivity, a reduction in reaction shrinkage in a photopolymerization reaction, and The point is that it is not possible to simultaneously improve the thermal properties of the obtained cured molded article.

[0005]

Means for Solving the Problems Thus, the present inventors have
As for the photopolymerizable composition containing unsaturated urethane, as a result of studying the chemical structure of the unsaturated urethane, the relationship between the photopolymerization reactivity, the reaction shrinkage in the photopolymerization reaction, and the thermal properties of the resulting cured molded article, As the unsaturated urethane, an unsaturated urethane having a specific structure in which a polymerizable group consisting of an acryloyl group and a methacryloyl group and a hydrophobic group containing a long-chain aliphatic hydrocarbon residue are introduced into a molecule in a predetermined amount is used. It was found that the use of (meth) acrylic acid esters was correct and suitable.

That is, the present invention relates to an unsaturated urethane represented by the following formula 1 and one or more unsaturated urethanes selected from the following unsaturated urethanes represented by the following formula 2:
It comprises a (meth) acrylic ester copolymerizable with the unsaturated urethane and a photopolymerization initiator, and the unsaturated urethane / the (meth) acrylic ester = 10/90 to 9
The present invention relates to a photopolymerizable composition, which has a ratio of 0/10 (weight ratio).

[0007]

(Equation 1)

[0008]

(Equation 2)

In the formulas (1) and (2), X ¹ , X ² : residues of polyisocyanate selected from diisocyanate and triisocyanate, excluding isocyanate group Y ¹ , Y ² , Y ³ : hydroxyl group from trihydric alcohol Residues removed Y ⁴ : Residues obtained by removing hydroxyl groups from di- or tri-valent polyols selected from polyhydric alcohols, polyether polyols and polyester polyols R ¹ , R ³ : H or CH ₃ R ⁵ , which are not identical at the same time R ⁷ , R ⁸ : H or CH ₃ R ² , R ⁴ , R ⁶ : aliphatic hydrocarbon groups having 5 to 21 carbon atoms j, k, m, n: 1 or 2; j + k = 2 or 3, m + n = 2 or 3 p, q: 0 to 2 and p + q = 1 or 2]

The unsaturated urethane represented by the formula (1) is 1)
(Meth) acrylic acid / long chain fatty acid mixed ester monool (hereinafter simply referred to as mixed ester monool) and urethanization reaction product of diisocyanate; 2) urethanization reaction product of mixed ester monool and triisocyanate Include.

The mixed ester monol is a partial ester derived from (meth) acrylic acid, a long-chain fatty acid having 6 to 22 carbon atoms and a trihydric alcohol and having one free hydroxyl group in the molecule.

The trihydric alcohol used to derive the mixed ester monool includes glycerin, trimethylolethane, trimethylolpropane, 1,2,6-
Hexanetriol and the like can be mentioned.

The long-chain fatty acids used to derive the mixed ester monools are straight-chain or branched-chain saturated or unsaturated fatty acids having 6 to 22 carbon atoms. Examples of such long-chain fatty acids include: 1) linear saturated fatty acids such as hexanoic acid, octanoic acid, dodecanoic acid and stearic acid; 2) branched saturated fatty acids such as isooctanoic acid, isopalmitic acid and isostearic acid; 3) oleic acid , Unsaturated fatty acids such as elaidic acid, and the like, and mixtures thereof.

As a method for synthesizing the mixed ester monool, a direct esterification reaction of a trihydric alcohol with (meth) acrylic acid and a long-chain fatty acid, and a ring-opening addition of a long-chain fatty acid glycidyl ester with (meth) acrylic acid Reaction, a ring-opening addition reaction between glycidyl (meth) acrylate and a long-chain fatty acid, and the like. The present invention is not particularly limited to such a synthesis method. 1 mole of (meth) acrylic acid to
One mole of the long-chain fatty acid is ester-bonded.

The mixed ester monool thus synthesized includes: 1) glycerin monomethacrylate / monooctanoate, trimethylolpropane monoacrylate / monoisononanoate, 5-methyl-1,2,4.
-Heptanetriol monomethacrylate / monooleate, 1,2,6-hexanetriol monomethacrylate / mono-2-ethylhexoate, and the like,
Glycerin mono (meth) acrylic acid / mono long chain fatty acid mixed ester monool can be advantageously used.

The unsaturated urethane represented by the formula (2) includes: 1) a product in which a mixed ester monool, a (meth) acrylic ester monool, and a diisocyanate are formed at a ratio of 1: 1: 1 (molar ratio), and 2) A mixed ester monool, (meth) acrylic ester monool and triisocyanate in a ratio of 1: 2: 1 (molar ratio) or 2:
Includes urethane-formed products in a 1: 1 (molar ratio) ratio.

The (meth) acrylic ester monol is
1) a partial ester obtained from 1 mol of (meth) acrylic acid and 1 mol of diol, and 2) (meth) acrylic acid 2
And one mole of triol, each of which has one free hydroxyl group in the molecule.

The diols and triols used to derive the (meth) acrylic ester monol include 1)
Dihydric or trihydric alcohol, 2) polyether diol, polyether triol, 3) polyester diol, polyester triol.

Examples of the (meth) acryl ester monool include: 1) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 1,6-hexanediol monoacrylate, etc.
Mono (meth) acrylate of dihydric alcohol, 2) glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, 5-methyl-1,2,4-heptanetriol dimethacrylate, 1,2,6-hexanetriol Di (meth) acrylates of trihydric alcohols such as dimethacrylate,
3) Polyether diol mono (meth) acrylates such as polyethylene glycol monoacrylate and polypropylene glycol monomethacrylate; 4) ethylene glycol monoglyceryl ether dimethacrylate; (poly) ethoxylated trimethylolpropane dimethacrylate; (poly) propoxyl (Poly) ether triol di (meth) such as trimethylolpropane dimethacrylate, (poly) ethoxylated glycerin, etc.
Acrylates, 5) Polycaprolactone diol monomethacrylate, polyneopentyl adipate diol monoacrylate, etc., mono (meth) acrylates of polyester diols, 6) Polycaprolactone triol monoacrylate or monomethacrylate starting from trihydric alcohols And polyester triol di (meth) acrylate.

As the polyol used to derive the (meth) acrylic ester monol, those having a molecular weight of 200 or less per hydroxyl group contained in the molecule can be advantageously used, and those having a molecular weight of 150 or less are particularly preferred. It can be used to advantage.

Examples of the polyisocyanate to be reacted with the mixed ester monool and the (meth) acrylic ester monool as exemplified above include: 1) Various tolylene diisocyanates and aromatics such as methylene-bis- (4-phenylisocyanate). Diisocyanate, 2) aliphatic diisocyanate or alicyclic diisocyanate such as hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 3) 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane,
5-isocyanatomethyl-1-isocyanato-1,1-
Aliphatic and alicyclic diisocyanates such as dimethyl-5-methyl-cyclohexane (isophorone diisocyanate); and 3) aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate (an average of three NCO groups).

In the unsaturated urethane represented by the formula 1,
R ¹ and R ³ do not simultaneously form a hydrogen atom or a methyl group, and in the unsaturated urethane represented by the formula 2, R ⁵ , R ⁷ and R ⁸ do not simultaneously form a hydrogen atom or a methyl group. That is, the unsaturated urethane represented by the formula 1 and the unsaturated urethane represented by the formula 2 both contain an acryloyl group and a methacryloyl group as polymerizable groups.

When a diisocyanate is used as the polyisocyanate, the unsaturated urethane represented by the formula (1) and the unsaturated urethane represented by the formula (2) are both asymmetric unsaturated urethanes. As the diisocyanate used for synthesizing such an asymmetric unsaturated urethane, a diisocyanate having an isocyanate group affected by a sterically hindered substituent and an isocyanate group not affected by a sterically hindered substituent, or an aliphatic hydrocarbon It is preferable to use diisocyanates having isocyanate groups having mutually different reactivities, such as those having an isocyanate group bonded to an isocyanate group and an isocyanate group bonded to an aromatic hydrocarbon group. Examples thereof include diisocyanate, isophorone diisocyanate, and 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane.

In the present invention, the method for synthesizing the unsaturated urethane is not particularly limited, and a known method, for example, a method described in JP-A-4-53809 can be applied to the synthesis. In the synthesis of the asymmetric unsaturated urethane obtained as above, 1 mole of the mixed ester monool and 1 mole of the above-described diisocyanate having an isocyanate group having different reactivity are reacted in advance to obtain an unsaturated urethane monoisocyanate. A method of reacting different mixed ester monools or (meth) acrylic ester monols is preferred.

The present invention provides a photopolymerizable composition capable of improving the photopolymerization reactivity and the thermal properties of the resulting cured product. Therefore, in the present invention, an unsaturated urethane having both an acryloyl group and a methacryloyl group as a polymerizable group is used. Having such two different polymerizable groups is extremely effective in improving the photopolymerization reactivity and the thermal properties of the resulting cured molded article. The relationship between the number of the polymerizable groups contained in one molecule of the unsaturated urethane and the molecular weight of the unsaturated urethane per one polymerizable group also affects the improvement of the photopolymerization reactivity and the thermal properties. Unsaturated urethanes having a molecular weight of 150 to 450 per polymerizable group are preferable for obtaining photopolymerization reactivity and thermal properties suitable for practical use, and more preferable are those having a molecular weight per polymerizable group. Are 200 to 400.

The present invention also provides a photopolymerizable composition capable of reducing the reaction shrinkage in the photopolymerization reaction. Therefore, in the present invention, a long-chain aliphatic hydrocarbon group having 5 to 21 carbon atoms is introduced into the molecule of the unsaturated urethane. The long-chain aliphatic hydrocarbon group has 7 to 7 carbon atoms.
An alkyl group having 17 and an alkenyl group having 15 to 19 carbon atoms are preferred. The proportion of the long-chain aliphatic hydrocarbon group in one molecule of the unsaturated urethane is preferably from 10 to 45% by weight, more preferably from 15 to 40% by weight.

The (meth) acrylate used in combination with the unsaturated urethane represented by the formulas 1 and 2 includes 1) alkyl acrylates such as butyl acrylate and 2-ethylhexyl acrylate, and 2) methyl methacrylate and methacrylic. Alkyl methacrylates such as ethyl acrylate and isobutyl methacrylate; 3) ethylene glycol diacrylate;
Dihydric alcohol diacrylates such as 4-butanediol diacrylate; 4) dihydric alcohol dimethacrylates such as 1,2-propylene glycol dimethacrylate and 1,6-hexanediol dimethacrylate;
5) trihydric alcohol triacrylate such as glycerin triacrylate and trimethylolpropane triacrylate; 6) trihydric alcohol trimethacrylate such as glycerin trimethacrylate and trimethylolethane trimethacrylate; 7) trimethylolpropane diacrylate. Mixed (meth) acrylate of trihydric alcohol such as monomethacrylate, glycerin monoacrylate / dimethacrylate, 8) pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate
Tetraesters of tetrahydric alcohols such as dimethacrylate; 9) polyether polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to the aforementioned dihydric alcohols, and acrylic acid, methacrylic acid, and mixtures thereof Esters of polyether polyols obtained from acids and 10)
Esters of polyester polyols obtained from the polyester polyol obtained by adding an aliphatic lactone such as caprolactone and butyrolactone to the above-mentioned dihydric alcohol and acrylic acid, methacrylic acid, and a mixed acid thereof are exemplified.

As the (meth) acrylic ester exemplified above, a mixture of an acrylic ester and a methacrylic ester is preferably used, and a mixed ester using two kinds of acrylic acid and methacrylic acid is preferably used. More preferred. In this case, the ratio of the acryl group to the methacryl group is preferably such that the acryl group / methacryl group = 9/1 to 1/9 (molar ratio) in both the mixture and the mixed ester, and 8/2. More preferably, it is set to be about 5/5 (molar ratio).

In the photopolymerizable composition of the present invention, an unsaturated urethane and a (meth) copolymerizable with the unsaturated urethane
The ratio of the unsaturated urethane to the (meth) acrylic ester = 10/90 to 90/10
(Weight ratio), preferably 30/70 to 70/30
(Weight ratio). The ratio of both is 10/90 (weight ratio)
When the amount is less than the above, the physical properties of the cured molded article obtained by the photopolymerization reaction are inferior. On the other hand, when the ratio exceeds 90/10 (weight ratio), the viscosity of the photopolymerizable composition becomes too high and the optical molding operation becomes difficult.

The photopolymerizable composition of the present invention comprises an unsaturated urethane, a (meth) acrylate and a photopolymerization initiator. In the present invention, the kind of the photopolymerization initiator to be used is not particularly limited. Examples of the photopolymerization initiator include: 1) carbonyl compounds such as benzoin, α-methylbenzoin, anthraquinone, chloranthraquinone, acetophenone, and 2) diphenyl. Sulfur compounds such as sulfide, diphenyl disulfide and dithiocarbamate; and 3) polycyclic aromatic compounds such as α-chloromethylnaphthalene and anthracene. The content of these photopolymerization initiators in the photopolymerizable composition is usually 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the unsaturated urethane and the (meth) acrylate. .
Along with the photopolymerization initiator, a photosensitizer such as n-butylamine, triethanolamine, N, N-dimethylaminobenzenesulfonic acid diallylamide, and N, N-dimethylaminoethyl methacrylate can be used.

The photopolymerizable composition of the present invention may contain solid fine particles in addition to the unsaturated urethane, (meth) acrylate and photopolymerization initiator. The content ratio of the solid fine particles is 300 parts by weight or less, preferably 100 parts by weight or less, per 100 parts by weight of the total amount of the unsaturated urethane and the (meth) acrylate.

As such solid fine particles, 1) silica,
Inorganic fine particles such as alumina; 2) organic high molecular fine particles such as polyamide, vinyl chloride, polymethylsiloxane, polystyrene, and polymethyl methacrylate; 3) polysiloxane-polyvinyl composite fine particles; and 4) milled glass fibers. Particle size or average fiber length is 10μm
The following are preferred, and those with 1 μm or less are more preferred.

The present invention does not particularly limit the optical three-dimensional molding method to which the photopolymerizable composition of the present invention is applied. Various optical three-dimensional modeling methods are known (JP-A-56-144478, JP-A-60-247514, JP-A-1-204915, JP-A-3-41126, etc.). After forming a cured layer, supplying an uncured composition on the cured layer, irradiating the energy beam to this to repeat the operation of forming the next cured layer,
There is a method of forming a desired cured object and post-curing as needed. Examples of the energy beam used include visible light, ultraviolet light, and electron beam, and ultraviolet light is preferable.

[0034]

【Example】

Test Category 1 (Preliminary Synthesis) The following preliminary synthesis examples 1 to 4 were performed. In addition, in each preliminary synthesis example, parts are parts by weight. Preparative Synthesis Example 1 144 parts (1.0 mol) of octanoic acid and 2 parts of triethylamine as a catalyst were placed in a reaction vessel, kept at 70 ° C., stirred, and further 142 parts of glycidyl methacrylate (1.
0 mol) was added dropwise over 30 minutes. Then, the reaction system was
It was kept at 0 ° C. for 5 hours to complete the synthesis. The oxirane oxygen content of the reaction was quantified, but hardly detected. The product obtained here is 286 parts of glycerin monomethacrylate monooctanoate and has an acid value of 0.1.
7, hydroxyl value 198, saponification value 390.

Preparative Synthesis Example 2 The same operation as in Preparative Synthesis Example 1 was carried out using 144 parts (1.0 mol) of octanoic acid, 2 parts of triethylamine and 128 parts (1.0 mol) of glycidyl acrylate. The product obtained here has 272 parts of glycerin monoacrylate.
Monooctanoate, acid value 0.9, hydroxyl value 20
5, saponification number 412.

Preparative Synthesis Example 3 The procedure of Preparative Synthesis Example 1 was repeated using 256 parts (1.0 mol) of isopalmitic acid, 3 parts of triethylamine and 142 parts (1.0 mol) of glycidyl methacrylate. The product obtained here is 398 parts of glycerin monomethacrylate / monoisopalmitate and has an acid value of 1.
1, the hydroxyl value was 140, and the saponification value was 281.

Preparative Synthesis Example 4 200 parts (1.0 mol) of glycerin diacrylate and 0.3 part of tetrabutyl titanate as a catalyst were placed in a reaction vessel, stirred at 80 ° C., and further stirred at 342 parts of ε-caprolactone ( 3.0 mol) was added dropwise over 30 minutes.
Thereafter, the reaction system was maintained at 100 ° C. for 1 hour to complete the synthesis. The product obtained here was 542 parts of glycerin tricaprolactone triol diacrylate, and had an acid value of 0.4, a hydroxyl value of 104 and a saponification value of 207.

Test Category 2 (Synthesis of Unsaturated Urethane and Preparation of Monomer Solution) The following synthesis of unsaturated urethane and preparation of a monomer solution were performed. Tables 1 and 2 show the types and amounts of the raw materials used in the synthesis, and Table 3 shows the contents of the obtained unsaturated urethanes. In the synthesis of each unsaturated urethane and preparation of the monomer solution, parts are parts by weight, and% is% by weight. -Synthesis of unsaturated urethane A-1 and monomer solution a-1
Preparation of 87 parts (0.5 mol) of 2,4-tolylene diisocyanate, 100 parts of dry toluene and 0.5 part of di-n-butyltin dilaurate are placed in a reaction vessel, stirred at 50 ° C., and 143 parts (0.5 mol) of glycerin monomethacrylate monooctanoate obtained in Synthesis Example 1
Was added dropwise over 30 minutes. During this time, the reaction temperature is set to 50-6
It was kept at 0 ° C. Thereafter, the reaction was continued at 50 to 55 ° C., and the reaction was terminated when the remaining amount of isocyanate groups in the reaction product became の of the theoretical amount calculated from the amount of diisocyanate used for the reaction. The reaction product obtained here is 2,
It is an unsaturated urethane monoisocyanate in which 4-tolylene diisocyanate and glycerin monomethacrylate / monooctanoate are combined in a 1/1 molar ratio. Next, the reaction product was stirred while being maintained at 60 ° C.
136 parts (0.5 mol) of glycerin monoacrylate / monooctanoate obtained in the above was added dropwise over 30 minutes. At this time, the reaction heat was generated, but the reaction temperature was maintained at 60 to 70 ° C. Thereafter, the temperature was maintained at 70 ° C. for 2 hours to complete the synthesis.
Further, 366 parts of triethoxylated trimethylolpropane diacrylate / monomethacrylate was added and dissolved.
The toluene was distilled off under reduced pressure to obtain a monomer solution a-1 containing 50% of unsaturated urethane A-1 and 50% of triethoxylated trimethylolpropane diacrylate / monomethacrylate.

Synthesis of unsaturated urethanes R-1 and R-2 and preparation of monomer solutions r-1 and r-2 In the same manner as in the synthesis of unsaturated urethane A-1 and the preparation of monomer solution a-1, Synthesis of saturated urethane R-1 and preparation of monomer solution r-1, synthesis of unsaturated urethane R-2 and preparation of monomer solution r-2 were performed.

Synthesis of unsaturated urethane A-2 and preparation of monomer solution a-2 272 parts (1.0 mol) of glycerin monoacrylate monooctanoate obtained in Preparative Synthesis Example 2, Preparative Synthesis Example 3
Glycerin monomethacrylate / monoisopalmitate (199 parts, 0.5 mol), polyethylene glycol (molecular weight 200) diacrylate 662 parts, and di-n
0.5 part of butyltin dilaurate is placed in a reaction vessel, and
The mixture was stirred at 0 ° C., and 191 parts (0.5 mol) of polymethylene polyphenyl isocyanate (containing an average of 3 NCO groups) was added dropwise over 30 minutes. At this time, the reaction heat was generated, but the reaction temperature was kept at 50 to 60 ° C. Thereafter, the temperature was maintained at 60 ° C. for 1 hour to complete the synthesis. Monomer solution a containing 50% of unsaturated urethane A-2 and 50% of polyethylene glycol (molecular weight 200) diacrylate
-2 was obtained.

Synthesis of unsaturated urethane R-3 and preparation of monomer solution r-3 In the same manner as in the synthesis of unsaturated urethane A-2 and the preparation of monomer solution a-2, the synthesis of unsaturated urethane R-3 and A monomer solution r-3 was prepared.

Synthesis of unsaturated urethane B-1 and preparation of monomer solution b-1 111 parts (0.5 mol) of isophorone diisocyanate,
100 parts of dry toluene and 0.5 part of di-n-butyltin dilaurate are placed in a reaction vessel, kept at 50 ° C. and stirred, and further mixed with diethylene glycol monomethacrylate 87.
(0.5 mol) was added dropwise over 30 minutes. During this time, the reaction temperature was maintained at 50-60 ° C. Then 50-55 ° C
The reaction was continued when the remaining amount of the isocyanate group in the reaction product became 1/2 of the theoretical amount calculated from the amount of the diisocyanate used for the reaction. The reaction product obtained here is an unsaturated urethane monoisocyanate in which 1 mol of isophorone diisocyanate and 1 mol of diethylene glycol monomethacrylate are bonded. Next, this reaction product was stirred while being kept at 60 ° C., and 136 parts (0.5 mol) of glycerin monoacrylate / monooctanoate obtained in Preparative Synthesis Example 1 were added dropwise over 30 minutes. At this time, the reaction heat was generated, but the reaction temperature was maintained at 60 to 70 ° C. Thereafter, the temperature was maintained at 70 ° C. for 2 hours to complete the synthesis.
Further, 334 parts of triethoxylated trimethylolpropane diacrylate / monomethacrylate were added and dissolved,
The toluene was distilled off under reduced pressure to obtain a monomer solution b-1 containing 50% of unsaturated urethane B-1 and 50% of triethoxylated trimethylolpropane diacrylate / monomethacrylate.

Synthesis of unsaturated urethanes B-2 and R-4 and preparation of monomer solutions b-2 and r-4 Unsaturated urethanes B-2 and R-4 were prepared in the same manner as in the synthesis of unsaturated urethane B-1 and the preparation of monomer solutions b-1. Synthesis of saturated urethane B-2, preparation of monomer solution b-2, synthesis of unsaturated urethane R-4, and preparation of monomer solution r-4 were performed.

Synthesis of Unsaturated Urethanes B-3 and R-5 and Preparation of Monomer Solutions b-3 and r-5 As a (meth) acrylic ester, polyethylene glycol (molecular weight 200) diacrylate was used instead of triethoxylation. Other than using trimethylolpropane diacrylate / monomethacrylate, unsaturated urethane A-2
In the same manner as in the preparation of the monomer solution a-2, the synthesis of the unsaturated urethane B-3, the preparation of the monomer solution b-3, the synthesis of the unsaturated urethane R-5, and the monomer solution r-.
Preparation 5 was made.

[0045]

[Table 1]

[0046]

[Table 2]

In Tables 1 and 2, numerical value: part Numeric value in parentheses: mole * 1: polyethylene glycol (molecular weight: 200) diacrylate * 2: triethoxylated trimethylolpropane diacrylate / monomethacrylate *** 1: glycerin monoacrylate * Monooctanoate ** 2: glycerin monomethacrylate * monooctanoate ** 3: glycerin monomethacrylate * monoisopalmitate ** 4: diethylene glycol monomethacrylate ** 5: glycerin tricaprolactone triol diacrylate ** 6: Hydroxyethyl acrylate ** 7: 2,4-tolylene diisocyanate ** 8: polymethylene polyphenyl isocyanate (N
** 9: isophorone diisocyanate

[0048]

[Table 3]

In Table 3, A: acryloyl group M: methacryloyl group

Test Category 3 (Examples and Comparative Examples and Evaluations) Examples 1 to 9 and Comparative Examples 1 to 7 Using the monomer solutions described in Tables 1 and 2, Table 4 or Table 5 was used.
A photopolymerizable composition having the composition described was prepared. Then, a three-dimensional NC table equipped with a container filled with the photopolymerizable composition and a helium-cadmium laser beam (wavelength 32
The surface of the photopolymerizable composition is irradiated with a helium-cadmium laser beam focused from the vertical direction to the surface of the photopolymerizable composition using an optical three-dimensional modeling device mainly composed of a control system (50 Å), and has a diameter of 150 mm and a thickness of 10 mm. I made a disk. For each photopolymerizable composition, the time required for molding was measured. In addition, the shaped disk is 127 mm long x 12.7
The test pieces were cut into mm using a diamond cutter. With respect to this test piece, the molding shrinkage and the heat distortion temperature were measured by the following methods. The results are shown in Table 4 or Table 5.

Molding shrinkage: The density (D ₁ ) of the test piece and the density (D ₂ ) of the photopolymerizable composition used for shaping were measured, and the shaping shrinkage was calculated by the following equation. Modeling shrinkage (%) = {(1 / D ₂ ) − (1 / D ₁ )} × 1
00 Heat deformation temperature: Measured according to JIS-K6919.

[0052]

[Table 4]

[0053]

[Table 5]

In Tables 4 and 5, * 3: 1-hydroxycyclohexyl phenyl ketone (trade name Irgacure 184, manufactured by Ciba Geigy) * 4: Silica fume having an average particle diameter of 0.1 μm * 5: Average fiber length of 10 μm Comparative Example 6: Significant cracks and warpage occurred on the shaped disc Comparative Example 7: Warping occurred on the shaped disc

[0055]

As is clear from the above, according to the present invention described above, it is possible to simultaneously improve the photopolymerization reactivity, reduce the reaction shrinkage in the photopolymerization reaction, and improve the thermal properties of the cured molded article obtained. This has the effect.

Claims (4)

(57) [Claims] An unsaturated urethane represented by the following formula (1):
And 1 selected from unsaturated urethanes represented by the following formula 2:
One or more unsaturated urethanes, and the unsaturated urethane
(Meth) acrylic acid ester copolymerizable with
And the unsaturated urethane / (meth)
Acrylic ester = 10 / 90-90 / 10 (weight
Ratio), for optical three-dimensional modeling
Photopolymerizable composition. (Equation 1)(Equation 2)[In the formulas 1 and 2, X¹, X^Two: Diisocyanate and triisocyanate
Isocyanate group from polyisocyanate selected from
Residue Y¹, Y^Two, Y^Three： Hydroxy group removed from trihydric alcohol
Residue Y^Four: Polyhydric alcohol, polyether polyol and polyether
Divalent or trivalent polio selected from ester polyols
Residue obtained by removing the hydroxyl group from the¹, R^Three: H or CH which are not the same at the same time_Three  R^Five, R⁷, R⁸: H or CH which are not the same at the same time_Three  R^Two, R^Four, R⁶: An aliphatic hydrocarbon group having 5 to 21 carbon atoms j, k, m, n: 1 or 2, and j + k = 2 or
Satisfies 3, m + n = 2 or 3 p, q: 0 to 2, and satisfies p + q = 1 or 2
Things to do] 2. The method according to claim 1, wherein the (meth) acrylate is acrylic.
A mixture of acid esters and methacrylic esters
The photopolymerizable composition for optical stereolithography according to claim 1. 3. The method according to claim 1, wherein the (meth) acrylate is a polyvalent alcohol.
Alcohol, polyether polyol and polyester
One or more polyols selected from riol
And acrylic acid and methacrylic acid.
Mixed ester The optical three-dimensional object forming light according to claim 1.
Polymerizable composition. 4. A further unsaturated urethane and (meth) per 100 parts by weight per the acrylic acid ester, according to claim 1, 2 or containing the solid fine particles in a proportion of less than 300 parts by weight
3 Symbol mounting for stereolithography photopolymerizable composition.