JPH05247134A - Resin composition for optical modeling and its cured material - Google Patents

Abstract

PURPOSE:To obtain the subject composition causing no cracks, etc., during production of cured substances of solid shape, having excellent dimensional accuracy, comprising a specific epoxy(meth)acrylate, a water-soluble reactive monomer as a diluent and a photopolymerizable initiator. CONSTITUTION:The objective composition comprising (A) an epoxy(meth)acrylate of formula I (R1 and R2 are H or 1-4C alkyl; R3 is H or methyl; (n) is 1 or >=1 integer; M is H or group of formula II), (B) a water-soluble reactive monomer (e.g. N-vinylpyrrolidone) as a diluent and (C) a photopolymerizable initiator (e.g. 2-hydroxy-2-methylpropiophenone). The component A is preferably obtained by reacting a hydantoin compound of formula III with a compound of formula IV to give a compound, reacting an alcoholic hydroxyl group of the obtained compound with epichlorohydrin to give an epoxy resin of formula V and reacting the resin with (meth)acrylic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray-curable resin composition for optical modeling.

[0002]

2. Description of the Related Art Conventionally, photocurable compositions for paints, inks, adhesives, photosensitive resin plates, etc. have been known.

[0003]

However, in the conventional photocurable composition, the composition is irradiated with a light beam to cure the irradiated part, and then to the uncured part around the cured product. When used as a resin composition for an optical molded article to obtain an optical molded article that is produced by irradiating a light flux to cure and then producing a three-dimensional cured body by repeating this, a three-dimensional cured body is produced during production. Even if a cured product is distorted or cracked or a cured product is obtained, the dimensional accuracy of the cured product is inferior.
Further, when the cured product is taken out, the uncured portion has to be washed with a solvent, which causes toxicity and contamination problems.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the cured product does not suffer from distortion or crack during the production of a three-dimensional cured product, and the dimensional accuracy is improved. In addition, the uncured portion can be washed with water, and the present invention succeeded in providing a resin composition for optical modeling suitable for producing a three-dimensional cured body and a cured body thereof.

That is, the present invention is as follows:

[0006]

[Chemical 3]

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ is a hydrogen atom or a methyl group, and n is 0 or an integer of 1 or more, M
Is a hydrogen atom or

[0008]

[Chemical 4]

[0009] ) Epoxy (meth) acrylate (A), a water-soluble reactive monomer (B) as a diluent, and a photopolymerizable initiator (C) are contained in the optical structure. And a cured product of the resin composition described in 1 above.

The epoxy (meth) acrylate (A) represented by the formula (1) used in the present invention is the same as the epoxy resin represented by the formula (2).

[0011]

[Chemical 5]

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is 0 or an integer of 1 or more, and X is a hydrogen atom or a glycidyl group. It can be obtained by reacting (meth) acrylic acid. The epoxy resin represented by the formula (2) can be obtained by various methods, but one preferable method is a compound represented by the formula (3),

[0013]

[Chemical 6]

(Wherein R ₁ , R ₂ and n have the same meanings as in formula (1)) and can be obtained by reacting the alcoholic hydroxyl group with epichlorohydrin. The compound represented by the formula (3) is a hydantoin compound represented by the formula (4),

[0015]

[Chemical 7]

(In the formula, R ₁ and R ₂ have the same meanings as in formula (1).) For example, hydantoin, 5,5-dimethylhydantoin, 5,5-dimethylhydantoin,
5-ethyl-5-methylhydantoin, 5,5-dipropylhydantoin and the like and a compound represented by the formula (5)

[0017]

[Chemical 8]

(In the formula, R ₁ and R ₂ have the same meanings as those in formula (1).) 1 mol of the compound of formula (5) to the compound of formula (4) The reaction temperature is usually 130 to 160 ° C. and the reaction temperature is usually 5 to 5 mol.
It can be obtained by reacting for 10 hours.

The amount of epichlorohydrin used in obtaining the epoxy resin represented by the formula (2) is determined by the formula (3)
It is preferable to use 1 equivalent or more with respect to 1 equivalent of the alcoholic hydroxyl group. However, if the amount exceeds 15 times the equivalent of one hydroxyl group, the effect of increasing the amount is almost lost, and the volume efficiency is deteriorated, which is not preferable. It is preferable to use a quaternary ammonium salt such as tetramethylammonium chloride or benzyltrimethylammonium chloride as a catalyst when the compound represented by the formula (3) is reacted with epichlorohydrin. The amount used is preferably 0.3 to 50 g per 1 equivalent of the alcoholic hydroxyl group in the formula (3).

During the reaction, alkali metal hydroxides (eg,
It is preferable to use caustic soda, caustic potash, lithium hydroxide, calcium hydroxide, etc.). The amount of the alkali metal hydroxide used is preferably approximately equivalent to 1 equivalent of the epoxidized alcoholic hydroxyl group of the compound represented by the formula (3). The alkali metal hydroxide may be solid or aqueous solution. When an aqueous solution is used, the reaction can be carried out during the reaction while distilling the water in the reaction system out of the reaction system under normal pressure or reduced pressure.

The reaction temperature is preferably 30 to 100 ° C. When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long reaction time is required. When the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable. After completion of the reaction, excess epichlorohydrin can be distilled off under reduced pressure, and then the resin can be dissolved in an organic solvent to carry out a dehydrohalogenation reaction with an alkali metal hydroxide. As the organic solvent, methyl isobutyl ketone, toluene, xylene and the like can be used, but methyl isobutyl ketone is preferably used.

The epoxy (meth) acrylate (A) is
(Meth) acrylic acid is preferably used in an amount of about 0.5 to 1. per 1 equivalent of the epoxy group of the epoxy resin represented by formula (2).
5 equivalents, particularly preferably about 0.8 to 1.1 equivalents, are reacted in a ratio, and a catalyst (for example,
(Triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, triphenylphosphine, etc.) is preferably used, and the amount of the catalyst used is 0.1 with respect to the reaction raw material mixture.
It is preferably used in the range of 10 to 10 weight. Polymerization-preventing property (for example, methoquinone, to prevent polymerization during the reaction,
Hydroquinone, phenothiazine, etc.) is preferably used, and the amount thereof is 0.0 with respect to the reaction raw material mixture.
It is preferably used in the range of 1 to 1% by weight. The reaction temperature is usually 60 to 150 ° C. The reaction time is usually 5
60 hours.

Examples of the water-soluble reactive monomer (B) used as a diluent in the resin composition of the present invention include N 2
-Vinylpyrrolidone, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol diacrylate, triethylene glycol diglycidyl ether di (meth) acrylate, pentaerythritol tri (meth) acrylate, trishydroxyethyl isocyanurate Di (meth) acrylate, glycerin di (meth) acrylate, glycerin triglycidyl ether tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methoxymethyl (meth) acrylic amide, isopropyl (meth) acrylamide, N- Mention may be made of monomers such as ethoxymethyl (meth) acrylic amide.

Next, typical examples of the photopolymerizable initiator (C) include 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 2
-Hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 2,4-diethylthioxanthone,
1-Hydroxycyclohexyl phenyl ketone isopropyl thioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and the like can be mentioned. These may be used alone or in combination of two or more.

The resin composition of the present invention is an epoxy (meth)
When the acrylate (A) is 100 parts, the water-soluble reactive monomer (B) is preferably 30 to 900 parts, particularly preferably 50 to 500 parts, and the (A) component + (B) component. When the total amount is 100 parts, the photopolymerizable initiator (C) is
It is preferably formed by mixing 0.5 to 25 parts, particularly preferably 2 to 10 parts. The resin composition of the present invention can be obtained by mixing and dissolving each component ((A), (B), (C)) at room temperature or by heating.

The resin composition of the present invention contains, if necessary, a coloring agent such as a pigment or a dye, as long as the effects of the present invention are not impaired.
A filler, an antifoaming agent, a leveling agent, a thickener, a flame retardant, a plasticizer, a solvent, a modifying resin, an antioxidant, a light stabilizer, an ultraviolet absorber and the like can be used in an appropriate amount.

The viscosity of the resin composition of the present invention is preferably 7,000 cps or less at room temperature, more preferably 5000 cps or less. If the viscosity is too high, workability tends to be poor because the time required for modeling is prolonged. In general, the molding resin composition undergoes volume shrinkage upon curing, and therefore it is required that the shrinkage is small in terms of accuracy. The volume shrinkage during curing of the resin composition of the present invention,
It is preferably 5% or less. As an embodiment of the present invention, as described in JP-A-60-247515, the resin composition for optical modeling of the present invention is housed in a container, and a light guide is used to form the container. A solid (cured product) having a desired shape can be formed by selectively supplying active energy rays required for curing from the light guide while moving relative to the light guide.

As the active energy ray used for curing the composition of the present invention, ultraviolet rays, X-rays, radiation, high frequency or the like can be used. Of these, 1
Ultraviolet rays having a wavelength of 800 to 5000 angstroms are economically preferable, and as a light source thereof, an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, an alkali metal lamp or the like can be used. A particularly preferable light source is a laser light source, which increases the energy level to shorten the molding time and utilizes good light condensing property.
It is possible to improve modeling accuracy. A point light source that collects ultraviolet rays from various lamps such as a mercury lamp is also effective.

Since the resin composition of the present invention is cured by a radical polymerization reaction by an active energy ray, the crosslinking reaction is effected by heating the resin composition to about 30 to 100 ° C. such as irradiation with an active energy ray. It is also possible to accelerate the above, and further, to obtain the shaped article, which is usually 40 to 1
Heat treatment at a temperature of 00 ℃ or UV with a mercury lamp
By performing the irradiation treatment, it is possible to obtain a molded article having more excellent mechanical strength. INDUSTRIAL APPLICABILITY The resin composition for optical modeling of the present invention is very excellent for creating a three-dimensional three-dimensional model by stacking layered products, and it is possible to perform model creation processing without using a mold, and Free-form surface, etc. C
AD / CAM and docking can be used to create any shape, and the uncured product can be washed with water when the cured product is taken out, which is of great industrial value. For example, as an application field of the present resin composition, a model for examining appearance design in the middle of design, a model for checking inconvenience of mutual combination of parts, a wooden mold for producing a mold,
It can be used in a wide range of applications such as models for making molds. Specific application fields include automobiles,
Examples include models and processing of various curved bodies such as electronic electrical parts, furniture, building structures, toys, containers, castings, dolls, and the like.

[0030]

EXAMPLES The present invention will be described in more detail below with reference to examples. The parts in the synthesis examples and examples are parts by weight. Synthesis Example of Epoxy (meth) acrylate (A) Synthesis Example 1. Epoxy resin represented by the following structural formula 240
Department

[0031]

[Chemical 9]

137 parts of acrylic acid, 0.2 of methoquinone
Parts and 1.4 parts of benzyltrimethylammonium chloride were charged and reacted at 95 ° C. to obtain epoxy acrylate (A-1).

Synthetic Example 2.2,4-Diglycidyl-5,5
-Dimethylhydantoin (epoxy equivalent 137) 548
Parts, 128 parts of 5,5-dimethylhydantoin, and 2 parts of triethanolamine were mixed and stirred at 140 ° C. for 5 hours to obtain 676 parts of a reaction product (epoxy equivalent: 360, average value of n in formula (3)). 2.1, and a softening point of 76 ° C.) were dissolved in 2000 parts of epichlorohydrin, 13 parts of tetramethylammonium chloride was added, and 104 parts of 98.5% NaOH was added over 100 minutes at 70 ° C. with stirring. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Then, most of the excess unreacted epichlorohydrin was distilled off under reduced pressure, the reaction product containing the by-product salt was dissolved in 1500 parts of methyl isobutyl ketone, the by-product salt was filtered off, and then methyl isobutyl ketone was distilled. Thus, 722 parts of an epoxy resin having an epoxy equivalent of 216 and a softening point of 65 ° C. was obtained. (Calculated from the epoxy equivalent of the obtained epoxy resin, about 1.8 of 2.1 alcoholic hydroxyl groups in the formula (3) are epoxidized.) 216 parts of the obtained epoxy resin, acrylic acid Charge 68.5 parts, methoquinone 0.5 parts, and triphenylphosphine 2.0 parts, raise the temperature to 110 ° C, and carry out the reaction at 110 ° C, and the acid value (mgKOH / g) of the reaction solution is 1.0 or less. The reaction was continued for about 10 hours to obtain an epoxy acrylate (A-2).

Synthetic Example 3.2,4-Diglycidyl-5,5
-Dimethylhydantoin (epoxy equivalent 137) 822
Parts, 256 parts of 5,5-dimethylhydantoin and 3.5 parts of triethanolamine were mixed, and 1078 parts of a reaction product obtained by stirring at 140 ° C. for 7 hours, (epoxy equivalent: 5
77, the average n in the formula (3) was 4.3) dissolved in 4070 parts of epichlorohydrin, 26 parts of tetramethylammonium chloride was added thereto, and 211 parts of 98.5% NaOH was added at 70 ° C. for 100 minutes under stirring. It was added over. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Then, most of the excess unreacted epichlorohydrin was distilled off under reduced pressure, the reaction product containing a by-product salt was dissolved in 2500 parts of methyl isobutyl ketone, the by-product salt was filtered off, and then methyl isobutyl ketone was distilled. And epoxy equivalent 23
9 to obtain 1221 parts of an epoxy resin having a softening point of 81 ° C.
(Approximately 3.7 out of 4.1 alcoholic hydroxyl groups in the formula (3) of the obtained epoxy resin are epoxidized when calculated from the epoxy equivalent.) 239 parts of the obtained epoxy resin and 68 of acrylic acid .5 parts, metoquinone 0.
Charged 5 parts and 2.0 parts of triphenylphosphine 12
The reaction was carried out at 0 ° C., and the reaction was carried out for about 10 hours until the acid value (mgKOH / g) of the reaction solution became 1.0 or less to obtain an epoxy acrylate (A-3).

Example 1. 60 parts of the epoxy acrylate (A-1) obtained in Synthesis Example 1, 30 parts of triethylene glycol diglycidyl ether diacrylate, 10 parts of N-vinylpyrrolidone and 5 parts of 1-hydroxycyclohexylketone were mixed and dissolved to prepare the invention. A resin composition for optical modeling was obtained. Using a three-dimensional NC (numerical control) table on which a container containing the resin composition, a helium cadmium laser, an optical system, and a stereolithography experimental system including a control unit mainly including a personal computer,
From this resin composition, the bottom surface has a diameter of 12 mm and a height of 15 mm,
A 0.5 mm thick cone was modeled. When the molded product is taken out of the container and the uncured resin composition adhering to the surface of the molded product is washed with water, the surface of the molded product becomes tack-free, and the uncured product is completely washed with water. We were able to. In addition, this molded product has no distortion and has extremely high modeling accuracy.

Example 2. 35 parts of epoxy acrylate (A-2) obtained in Synthesis Example 2, 30 parts of N-methoxymethyl acrylate, 35 parts of pentaerythritol triacrylate and 2-methyl-1- [4- (methylthio) phenyl] -2-mol Folinopropan-1-one was mixed and dissolved at a ratio of 5 parts to obtain an optical modeling resin composition of the present invention. Using this composition, a laser beam modeling experiment system shown in Example 1 was used to prepare a hanging-shaped shaped object. The modeled product was taken out of the container, and the uncured product attached to the surface of the modeled product was washed with water to obtain a modeled product having no surface tack. This model has no distortion and has extremely high modeling accuracy.

Example 3. 35 parts of epoxy acrylate (A-3) obtained in Synthesis Example 3, 35 parts of glycerin triglycidyl ether triacrylate, 20 parts of triethylene glycol diacrylate, 10 parts of isopropyl acrylamide and 7 parts of 1-hydroxycyclohexyl ketone were mixed and dissolved. Then, the resin composition for optical modeling of the present invention was obtained. Using this composition, a cup-shaped molded article was created using the laser light modeling system shown in Example 1. The modeled product was taken out of the container, and the uncured product attached to the surface of the modeled product was washed with water to obtain a modeled product having no surface tack. This model has no distortion and has extremely high modeling accuracy.

Comparative Example 1. 60 parts of pentaerythritol triacrylate, 30 parts of triethylene glycol diglycidyl ether diacrylate, 10 parts of N-vinylpyrrolidone and 5 parts of 1-hydroxycyclohexyl ketone were mixed and dissolved to obtain a resin composition for optical modeling. Using this composition, the same cone as in Example 1 was modeled using the laser optical experimental system shown in Example 1.
The modeled product was taken out of the container, and the uncured product attached to the surface of the modeled product was washed with water to obtain a modeled product having no surface tack. This model had a large strain and cracks were observed.

Comparative Example 2. 70 parts of dipentaerythritol hexaacrylate, 30 parts of trimethylolpropane triacrylate and 5 parts of 1-hydroxycyclohexyl ketone were mixed and dissolved to obtain an optical molding resin composition. This composition was used to shape the same cone as in Example 1. The modeled product was taken out of the container and the uncured product attached to the surface of the modeled product was washed with water, but the uncured product attached to the surface of the modeled product was not washed at all. In addition, this molded product had large distortion and cracks were observed.

[0040]

INDUSTRIAL APPLICABILITY According to the present invention, an uncured product on the surface of a modeled article can be washed with water, the distortion of the modeled article is small, and the dimensional accuracy is excellent. It is possible to obtain

Claims (2)

[Claims] 1. A formula (1): (In the formula, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ is a hydrogen atom or a methyl group, n is 0 or an integer of 1 or more, and M is hydrogen. Atom or Is. ) Epoxy (meth) acrylate (A), a water-soluble reactive monomer (B) as a diluent, and a photopolymerizable initiator (C) are contained in the optical structure. Resin composition 2. A cured product of the resin composition according to claim 1.