JP2844583B2 - 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 of irradiating a photopolymerizable composition with an energy beam to cure it 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. In the case of the conventional example 6), since the concentration of the double bond in the photopolymerizable composition is originally high, the reaction shrinkage in the photopolymerization reaction is remarkably large, and the polymerizable group comprising a methacryl group is present. And 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 together with a predetermined ratio. 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:
A (meth) acrylic acid ester having no urethane bond in a molecule copolymerizable with the unsaturated urethane, and a photopolymerization initiator, and the unsaturated urethane / (meth)
The present invention relates to a photopolymerizable composition, characterized in that the ratio of acrylic ester is from 10/90 to 90/10 (weight ratio).

[0007]

(Equation 1)

[0008]

(Equation 2)

In equations 1 and 2, X¹, X^Two: From tri- or tetravalent polyol to all hydroxyl groups
Residues except for Y: all isocyanate groups from diisocyanate
Excluding residue R¹, R^Four: H or CH not simultaneously the same_Three  R^Two, R⁶: An aliphatic hydrocarbon group having 5 to 21 carbon atoms R^Three: An alkylene group R having 2 to 4 carbon atoms^Five, R⁸: H or CH not simultaneously the same_Three  R⁷: An alkylene group having 2 to 6 carbon atoms or an alkylene group
A polyalkylene glycol residue having 2 or 3 carbon atoms p, q, r: X¹From trivalent polyol to all hydroxyl groups
Are all 1, X¹Is a four-valent port
If the residue is obtained by removing all hydroxyl groups from riol
1 or 2 that satisfies p + q + r = 4 s, t, u: X^TwoFrom trivalent polyol to all hydroxyl groups
Are all 1, X^TwoIs a four-valent port
If the residue is obtained by removing all hydroxyl groups from riol
1 or 2 and s + t + u = 4

The unsaturated urethane represented by the formula (1) includes 1)
Urethane compounds obtained by reacting a methacrylic acid / long chain fatty acid mixed partial ester of a polyol derived from a tri- or tetravalent polyol, methacrylic acid and a long-chain fatty acid with acryloyloxyalkyl isocyanate, 2) 3
Alternatively, a urethane compound obtained by reacting a mixed partial ester of acrylic acid and long chain fatty acid of a polyol derived from a tetravalent polyol, acrylic acid and long chain fatty acid with methacryloyloxyalkyl isocyanate is included.

The methacrylic acid / long chain fatty acid mixed partial ester of a polyol and the acrylic acid / long chain fatty acid mixed partial ester of a polyol are collectively referred to as a (meth) acrylic acid / long chain fatty acid mixed partial ester of a polyol. Examples of the tri- or tetrahydric polyol used for deriving the acrylic acid / long chain fatty acid mixed partial ester include: 1) trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; and 2) trihydric alcohols such as pentaerythritol. Polyhydric alcohols, 3) polyether polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to these trihydric or tetrahydric alcohols, 4) caprolactone, butyrolactone, etc. to these trihydric or tetrahydric alcohols Aliphatic lacquer Polyester polyols obtained by adding the emissions and the like.

The long-chain fatty acid used to derive the (meth) acrylic acid / long-chain fatty acid mixed partial ester of the polyol is a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and having a straight or branched chain. . 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) isooctanoic acid;
Branched saturated fatty acids such as isopalmitic acid and isostearic acid; 3) unsaturated fatty acids such as oleic acid and elaidic acid; and mixtures thereof.

As a method for synthesizing a (meth) acrylic acid / long chain fatty acid mixed partial ester of a polyol, a direct esterification reaction between a polyol, (meth) acrylic acid and a long chain fatty acid, a long chain fatty acid glycidyl ester and (meth) Examples include a ring-opening addition reaction with acrylic acid and a ring-opening addition reaction between glycidyl (meth) acrylate and a long-chain fatty acid, and the present invention is not particularly limited to such a synthesis method. The bonding molar ratio between (meth) acrylic acid and long-chain fatty acid is determined so that at least one free hydroxyl group remains per 1 mol of polyol.

The (meth) of the polyol thus synthesized
Acrylic acid / long chain fatty acid mixed partial ester
1) Mixed partial esters of trihydric alcohols such as glycerin monomethacrylate / monoisopalmitate, trimethylolpropane monomethacrylate / monolaurate, and 5-methyl-1,2,4-heptanetriol monomethacrylate / monooleate; ) Mixed partial esters of tetrahydric alcohols such as pentaerythritol monomethacrylate / monooleate, pentaerythritol diacrylate / mono-2-ethylhexoate, and pentaerythritol monomethacrylate / dilaurate;
3) Trimethylolpropane mono (2-hydroxyethyl) ether monomethacrylate monoisononanoate, polyethoxylated trimethylolpropane monoacrylate monooctanoate, pentaerythritol monomethacrylate didecanoate with ring-opening addition of ε-caprolactone, etc. And mixed partial esters of polyether polyols and polyester polyols. Among these, glycerin mono (meth) acrylic acid. Obtained by a ring-opening addition reaction of glycidyl ester of long-chain fatty acid and (meth) acrylic acid or a ring-opening addition reaction of glycidyl (meth) acrylate and long-chain fatty acid. Monolong chain fatty acid mixed partial esters can be advantageously used.

The (meth) acryloyloxyalkyl isocyanate to be reacted with the (meth) acrylic acid / long chain fatty acid mixed partial ester of a polyol is a (meth) acryloyloxyalkyl isocyanate having an alkyl group having 2 to 4 carbon atoms. Examples of the (meth) acryloyloxyalkyl isocyanate include acryloyloxyethyl isocyanate, acryloyloxy-2-methyl-ethyl isocyanate, methacryloyloxyethyl isocyanate, and methacryloyloxy-2-methyl-isocyanate.
Ethyl isocyanate and the like can be mentioned. Of these, methacryloyloxyethyl isocyanate and acryloyloxyethyl isocyanate can be advantageously used.

The unsaturated urethane represented by the formula (2) includes 1)
A urethane compound obtained by reacting the above-mentioned mixed partial ester of an acrylic acid and a long-chain fatty acid with an unsaturated urethane monoisocyanate in which 1 mol of diisocyanate and 1 mol of diol monomethacrylate are urethane-formed. Urethane compounds obtained by reacting a methacrylic acid / long chain fatty acid mixed partial ester with an unsaturated urethane monoisocyanate in which 1 mol of diisocyanate and 1 mol of diol monoacrylate are urethane-formed are included.

Diol monomethacrylate and diol monoacrylate used for obtaining unsaturated urethane monoisocyanate are collectively referred to as diol mono (meth) acrylate. The diol mono (meth) acrylate includes 1) 2-hydroxyethyl (meth) acrylate. Alkanediol mono (meth) acrylates such as acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,6-hexanediol mono (meth) acrylate; 2) diethylene glycol mono (meth) acrylate; tripropylene Polyalkylene glycol mono (meth) having 2 or 3 carbon atoms in the alkylene group such as glycol mono (meth) acrylate
Acrylates are mentioned. Among them, alkanediol mono (meth) acrylate is preferably 2-hydroxyethyl (meth) acrylate, and polyalkylene glycol mono (meth) acrylate is preferably one having an oxyalkylene group condensation number of 5 or less.

The diisocyanates used for obtaining unsaturated urethane monoisocyanates include 1) aromatic diisocyanates such as various tolylene diisocyanates and methylene-bis- (4-phenylisocyanate), and 2).
Hexamethylene diisocyanate, methylene-bis-
Aliphatic or alicyclic diisocyanate such as (4-cyclohexyl isocyanate); 3) 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane;
Aliphatic and alicyclic diisocyanates such as -isocyanatomethyl-1-isocyanato-1,1-dimethyl-5-methyl-cyclohexane (isophorone diisocyanate). Among these, diisocyanates having both isocyanate groups affected by sterically hindered substituents in the molecule and isocyanate groups not affected by the same, and isocyanate groups directly bonded to aliphatic hydrocarbon groups and aromatic A diisocyanate having both an isocyanate group directly bonded to a hydrocarbon group is preferable. Such diisocyanates include 2,4-tolylene diisocyanate, isophorone diisocyanate, 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane, and the like.

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.

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 which are preferable for obtaining photopolymerization reactivity and thermal properties suitable for practical use have a molecular weight of 150 to 45 per polymerizable group.
0, and more preferred unsaturated urethane is the polymerizable group 1
The molecular weight per unit is 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 16 to 19 carbon atoms are preferred. The number of long-chain aliphatic hydrocarbon groups to be introduced is one in the case of unsaturated urethane using a trivalent polyol as a raw material, and one in the case of unsaturated urethane using a tetravalent polyol as a raw material. Alternatively, the number of long-chain aliphatic hydrocarbon groups in one molecule of the unsaturated urethane is preferably 10 to 45% by weight, more preferably 15 to 40% by weight.

The (meth) acrylic acid ester used in combination with the unsaturated urethane represented by the formulas 1 and 2 includes any of the following 1) to 3) which have no urethane bond in a molecule copolymerizable with the unsaturated urethane. 10) (meth) acrylic acid esters. 1) alkyl acrylates such as butyl acrylate and 2-ethylhexyl acrylate, 2)
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isobutyl methacrylate; 3) diacrylates of dihydric alcohols such as ethylene glycol diacrylate and 1,4-butanediol diacrylate;
4) 1,2-propylene glycol dimethacrylate,
Dihydric alcohol dimethacrylate such as 1,6-hexanediol dimethacrylate, 5) trihydric alcohol triacrylate such as glycerin triacrylate, trimethylolpropane triacrylate, etc. 6) glycerin trimethacrylate, trimethylolethane trimethacrylate Trimethacrylate of trihydric alcohol, 7) mixed (meth) acrylate of trihydric alcohol such as trimethylolpropane diacrylate / monomethacrylate, glycerin monoacrylate / dimethacrylate, 8) pentaerythritol tetraacrylate, pentaerythritol tetra Tetraesters of tetrahydric alcohols such as methacrylate and pentaerythritol diacrylate / dimethacrylate;
Esters of polyether polyols obtained from polyether polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to polyhydric alcohols and acrylic acid, methacrylic acid, and mixed acids thereof. Esters of polyester polyols obtained from polyester polyols obtained by adding aliphatic lactones such as caprolactone and butyrolactone to tetrahydric alcohols, acrylic acid, methacrylic acid, and mixed acids thereof.

As the (meth) acrylates exemplified above, it is preferable to use a mixture of an acrylate and a methacrylate, and a mixed unsaturated acid ester obtained from a polyol, acrylic acid and methacrylic acid is preferably used. More preferably, it is used. 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 unsaturated acid ester. / 2 to 5/5 (molar ratio).

In the photopolymerizable composition of the present invention, the 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. The type of the photopolymerization initiator used in the present invention is not particularly limited. Examples of the photopolymerization initiator include: 1) carbonyl compounds such as benzoin, α-methylbenzoin, anthraquinone, chloranthraquinone, and 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 100% of the total amount of unsaturated urethane and (meth) acrylate.
The amount is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to parts by weight. 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 comprises an unsaturated urethane, a (meth) acrylic acid ester and a photopolymerization initiator. The photopolymerizable composition is used for the purpose of further reducing the reaction shrinkage accompanying the curing during photopolymerization. , Solid fine particles having an average particle diameter of 0.1 to 50 μm and an average fiber length of 1 to 70
A filler selected from inorganic fiber whiskers of μm can be contained. When solid fine particles are used as the filler, the average particle diameter is preferably 1 μm or less, more preferably 0.3 μm or less. Such fillers include 1) inorganic fine particles such as silica, alumina, clay, and calcium carbonate, 2) metal fine particles such as aluminum and iron, 3) polyamide, vinyl chloride, vinyl acetate,
Organic polymer fine particles such as styrene-divinylbenzene copolymer and polymethyl methacrylate; 4) solid fine particles such as polyorganosiloxane fine particles such as polymethylsilsesquioxane and polysiloxane-polyvinyl graft polymer; and 5) potassium titanate. Inorganic fiber whiskers such as fiber, magnesium sulfate fiber and carbon fiber. When these fillers are contained, the total amount of unsaturated urethane and (meth) acrylate is 100 parts by weight,
Usually, it is 300 parts by weight or less, preferably 1 to
Make up to 100 parts by weight. These fillers are 1
Species or a mixture of two or more can be used.

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-60-247515, JP-A-1-204915, JP-A-3-41126, etc.). After forming a cured layer on the cured layer, an uncured composition is supplied on the cured layer, and an operation of irradiating the composition with energy rays to form a next cured layer is repeatedly performed to obtain a desired cured molded article. There is a method of forming and post-curing as needed. Examples of the energy beam used include visible light, ultraviolet light, and electron beam, and ultraviolet light is preferable.

[0028]

【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 procedure of Preparative Synthesis Example 1 was repeated using 200 parts (1.0 mol) of lauric acid, 3 parts of triethylamine and 128 parts (1.0 mol) of glycidyl acrylate. The product obtained here was 328 parts of glycerin monoacrylate / monolaurate, and had an acid value of 0.9, a hydroxyl value of 172 and a saponification value of 343.

Preparative Synthesis Example 3 200 parts (1.0 mol) of glycerin diacrylate and 3 parts of boron trifluoride etherate complex as a catalyst were placed in a reaction vessel, stirred at 70 ° C., and further stirred with 338 parts of glycidyl oleate. (1.0 mol) was added dropwise over 30 minutes. Thereafter, the reaction system was maintained at 70 ° C. for 5 hours to complete the synthesis. The oxirane oxygen was quantified for the reaction,
Little was detected. The product obtained here was 537 parts of diglycerin diacrylate monooleate, having an acid value of 0.2, a hydroxyl value of 105 and a saponification value of 314.

Preparative Synthesis Example 4 58 parts (0.5 mol) of 2-hydroxyethyl acrylate, 150 parts of dry toluene and 0.2 part of tetrabutyl titanate as a catalyst were placed in a reaction vessel, and the mixture was stirred at 80 ° C. Further, 442 parts of ε-caprolactone (3.9)
Mol) was added dropwise over 30 minutes. Then, the reaction system was
The synthesis was terminated by holding at 0 ° C. for 1 hour. Toluene was distilled off from the reaction system under reduced pressure to obtain 495 parts of 2-hydroxyethyl acrylate adduct of ε-caprolactone.

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. Table 1 summarizes the types and amounts of the raw materials used in the synthesis, and Table 2 summarizes the contents of the obtained unsaturated urethane. 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
Reaction of 143 parts (0.5 mol) of glycerin monomethacrylate monooctanoate obtained in Preparative Synthesis Example 1, 214 parts of polyethylene glycol (molecular weight 200) diacrylate and 0.5 part of di-n-butyltin dilaurate Place in a container, stir at 50 ° C. and further add 71 parts (0.5 mol) of acryloyloxyethyl isocyanate to 30 parts.
Dropped over 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. 50% of unsaturated urethane A-1;
A monomer solution a-1 containing 50% of polyethylene glycol (molecular weight: 200) diacrylate was obtained.

.Unsaturated urethanes A-2, A-3, R-
Synthesis of 1, R-2 and monomer solution a-2, a-3, r
Preparation of -1, r-2 Synthesis of unsaturated urethane A-2, preparation of monomer solution a-2, and unsaturated urethane A in the same manner as in the synthesis of unsaturated urethane A-1 and the preparation of monomer solution a-1. -3 and Preparation of Monomer Solution a-3, Unsaturated Urethane R-1
And the preparation of a monomer solution r-1, the synthesis of an unsaturated urethane R-2, and the preparation of a monomer solution r-2.

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 58 parts (0.5 mol) of 2-hydroxyethyl acrylate are added dropwise over 30 minutes. did. During this time, the reaction temperature was maintained at 50-60 ° C. Thereafter, the reaction is continued at 50 to 55 ° C., and the remaining amount of isocyanate group in the reaction product is 1 of the theoretical amount calculated from the amount of diisocyanate used for the reaction.
The reaction was terminated when the value became / 2. The reaction product obtained here is an unsaturated urethane monoisocyanate in which 1 mol of isophorone diisocyanate and 1 mol of 2-hydroxyethyl acrylate are bonded. The reaction is then
The mixture was stirred at 0 ° C., and 143 parts (0.5 mol) of glycerin monomethacrylate / monooctanoate obtained in Preparative Synthesis Example 1 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. Furthermore, triethoxylated trimethylolpropane diacrylate.
368 parts of monomethacrylate was added and dissolved, and toluene was distilled off under reduced pressure to obtain 50% of unsaturated urethane B-1.
Monomer solution containing 50% of triethoxylated trimethylolpropane diacrylate / monomethacrylate b-
1 was obtained.

.Unsaturated urethanes B-2, B-3, R-
3, Synthesis of R-4 and monomer solutions b-2, b-3, r
Preparation of -3, r-4 Synthesis of unsaturated urethane B-2, preparation of monomer solution b-2, and unsaturated urethane B in the same manner as in the synthesis of unsaturated urethane B-1 and the preparation of monomer solution b-1. -3 and the preparation of monomer solution b-3, unsaturated urethane R-3
And the preparation of a monomer solution r-3, the synthesis of an unsaturated urethane R-4, and the preparation of a monomer solution r-4.

[0036]

[Table 1]

In Table 1, the upper value: part The lower value in parentheses: mole * 1: polyethylene glycol (molecular weight: 200) diacrylate * 2: triethoxylated trimethylolpropane diacrylate / monomethacrylate ** 1: glycerin Monomethacrylate / monooctanoate (obtained in Preparative Synthesis Example 1) ** 2: Glycerin monoacrylate / monolaurate (obtained in Preliminary Synthesis Example 2) ** 3: Diglycerin diacrylate / monooleate (Preliminary) ** 4: glycerin dimethacrylate ** 5: ε-caprolactone adduct of 2-hydroxyethyl acrylate (obtained in Preparative Synthesis Example 4) ** 6: Acryloyloxyethyl isocyanate ** 7: Methacryloyloxyethyl isocyanate ** 8: Isophorone diisocyanate Sulfonate / 2-hydroxyethyl acrylate = 1/1 (molar ratio) reaction product ** 9: isophorone diisocyanate / 2-hydroxyethyl methacrylate = 1/1 (molar ratio) reaction product

[0038]

[Table 2]

In Table 2, A: acryloyl group M: methacryloyl group

Test Category 3 (Examples and Comparative Examples and Evaluations) Examples 1 to 12 and Comparative Examples 1 to 6 Photopolymerizable having the composition shown in Table 3 or 4 using the monomer solution shown in Table 1 A composition was prepared. Then, using a three-dimensional NC table equipped with a container filled with the photopolymerizable composition and an optical three-dimensional modeling device mainly including a helium / cadmium laser beam (wavelength: 3250 Å) control system, the photopolymerizable composition is prepared. The surface was irradiated with a helium-cadmium laser beam focused from a vertical direction to form a disk having a diameter of 150 mm and a thickness of 10 mm. For each photopolymerizable composition, the time required for molding was measured. The shaped disk was cut into a length of 127 mm and a width of 12.7 mm using a diamond cutter to prepare a test piece. 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 3 or Table 4.

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 3.

(Equation 3) Heat distortion temperature: Measured according to JIS-K6919.

[0042]

[Table 3]

[0043]

[Table 4]

In Tables 3 and 4, * 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 1: Significant cracks and warpage occurred on the shaped disc Comparative Example 3: Cracks occurred on the shaped disc

[0045]

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.

Continuation of the front page (56) References JP-A-57-83562 (JP, A) JP-A-63-175019 (JP, A) JP-A-60-195538 (JP, A) JP-A-5-105732 (JP) (A) JP-A-5-255461 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 220 / 36,20 / 36 C08F 2/44-2/50 C08F 290/06

Claims (3)

(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
Copolymerizable withHas no urethane bond in the molecule
A (meth) acrylate and a photopolymerization initiator.
And the unsaturated urethane / (meth) acrylic acid ester
Ter = 10/90 to 90/10 (weight ratio)
A photopolymerizable composition for optical three-dimensional modeling. (Equation 1)(Equation 2)[In the formulas 1 and 2, X¹, X^Two: Is it a tri- or tetravalent polyol?All the waterAcid group
Y: DiisocyanateAllSocyanate group
Excluding residue R¹, R^Four: H or CH not simultaneously the same_Three  R^Two, R⁶: An aliphatic hydrocarbon group having 5 to 21 carbon atoms R^Three: An alkylene group R having 2 to 4 carbon atoms^Five, R⁸: H or CH not simultaneously the same_Three  R⁷: An alkylene group having 2 to 6 carbon atoms or an alkylene group
A polyalkylene glycol residue having 2 or 3 carbon atoms p, q, r: X ¹ From trivalent polyol to all hydroxyl groups
Are all 1, X ¹ Is a four-valent port
If the residue is obtained by removing all hydroxyl groups from riol
1Or 2AndOne p + q + r= 4S, t, u that satisfies: X ^Two From trivalent polyol to all hydroxyl groups
Are all 1, X ^Two Is a four-valent port
If the residue is obtained by removing all hydroxyl groups from riol
1Or 2AndS + t + u= 4That satisfy 2. The photopolymerizable composition for stereolithography according to claim 1, wherein the (meth) acrylate is a mixed unsaturated ester obtained from a polyol, acrylic acid and methacrylic acid. 3. Solid fine particles having an average particle diameter of 0.1 to 50 μm and an average fiber length of 1 to 70 per 100 parts by weight of the total amount of unsaturated urethane and (meth) acrylate.
The photopolymerizable composition for optical three-dimensional modeling according to claim 1, comprising one or more fillers selected from inorganic fiber whiskers of μm in a proportion of 300 parts by weight or less.