JP2876161B2 - Optical three-dimensional molding resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition for optical three-dimensional modeling, and particularly to a resin composition for optical three-dimensional modeling that is liquid and has excellent defoaming properties.

[Conventional technology]

In recent years, since a so-called optical three-dimensional molding method for obtaining a three-dimensional molded object having a desired shape by selectively supplying light energy required for curing to a photocurable liquid material to a desired part has been disclosed (see Japanese Patent Application Laid-Open (JP-A) no. Japanese Patent Laid-Open No. 60-247515) and various improved techniques relating to this optical three-dimensional printing method have been disclosed.

As a typical example of the conventional optical three-dimensional molding method, light such as an ultraviolet laser is selectively applied to a liquid surface of a liquid photocurable resin placed in a container so that a cured layer having a desired pattern is obtained. Irradiation to obtain a cured layer, and then supply one layer of liquid photocurable resin on the cured layer, similarly selectively irradiate light to cure, and cure the cured layer continuous with the cured layer. A method of finally obtaining a desired three-dimensional object by repeating the lamination operation of

[Problems to be solved by the invention]

By the way, in the conventional optical three-dimensional molding method, a liquid photocurable resin is used in a large container, and a large amount of bubbles are generated when the container is filled with the resin. In addition, when the cured layer is laminated, the cured product is moved up and down in the resin. In this case, bubbles may be generated. When curing is performed by selectively irradiating light with such bubbles remaining, it is preferable to perform the curing after the generated bubbles disappear because the dimensional accuracy of the obtained molded article is reduced. ,
In the conventional liquid photocurable resin, it takes a long time (usually 30 minutes or more) to eliminate generated bubbles.

On the other hand, as a method for eliminating such bubbles, it is conceivable to add an antifoaming agent.Generally, commercially available antifoaming agents have poor compatibility with the liquid photocurable resin and become cloudy, It had drawbacks such as an increase in viscosity, and a sufficient defoaming effect could not be obtained.

Accordingly, an object of the present invention is to provide a resin composition for optical three-dimensional modeling that exhibits excellent defoaming properties in a liquid state.

[Means for Solving the Problems] The present invention relates to a polymer (A) obtained by reacting a polyol compound with a polyisocyanate compound and a compound having an ethylenically unsaturated group (hereinafter referred to as “component (A)”). "
(B) a monomer having ethylenic unsaturation (hereinafter referred to as
5 to 84% by weight (C) polymerization initiator (hereinafter referred to as "(C) component") 0.05 to 10% by weight and (D) general formula (I) (Wherein, R ¹ , R ² and R ³ represent a methyl group, an ethyl group or a phenyl group, R ⁴ and R ⁵ represent an alkylene group having 1 to 12 carbon atoms, and R ⁶ represents a C 1 to C 12 alkyl group) An alkyl group or a phenyl group, x, y, m and n each represent an integer of 1 to 500) (hereinafter referred to as "component (D)") 0.005 to 1% by weight as an essential component To provide a resin composition for optical three-dimensional modeling.

As the component (A) used in the resin composition of the present invention, a polymer having an ester skeleton, an ether skeleton, a urethane skeleton or an epoxy skeleton and an ethylenically unsaturated group can be exemplified.

Specifically, for example, a polymer obtained by reacting a polyol compound such as polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polyepoxy polyol with a polyisocyanate compound and a compound having an ethylenically unsaturated group. Can be mentioned.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, polydecamethylene glycol, polyalkylene oxide adduct diol of bisphenol A, tricyclo Polyalkylene oxide adduct of decane dimethanol,
Examples include polyether polyols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds.

Here, as the ion-polymerizable cyclic compound, for example, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane , Tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl (meth) acrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane,
Cyclic ethers such as vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate;

Further, the above ion-polymerizable cyclic compound was subjected to ring-opening copolymerization with a cyclic imine such as ethyleneimine, a cyclic lactone such as p-propiolactone, glycolic acid lactide or a cyclic siloxane such as dimethylcyclopolysiloxane. Polyether polyols can also be used.
Examples of combinations of two or more ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and the like. . Also, at this time, the ring-opening copolymer of two or more ion-polymerizable cyclic compounds binds randomly or to a block.

Among these polyether polyols, polypropylene glycol, polytetramethylene glycol, polybutylene glycol and the like are preferred.

Further, these polyether polyols include, for example, “PTMG1000 (Mitsubishi Kasei Kogyo Co., Ltd.)”, “PTMG2000
PPG700 (Asahi Glass Co., Ltd.), PPG1000 (Asahi Orin Co., Ltd.), PPG2000 (Same), EXCENOL2020
“EXCENOL1020 (same)”, “PEG1000 (Nippon Oil & Fats Co., Ltd.)”, “Unisafe DC1100 (same)”, “Unisafe DC1800 (same)”, “Uniall DA-400 (same)”,
"Uniall DA-700 (same as above)", "Uniall DB-400"
(Same as above), PPTG2000 (Hodogaya Chemical), PPTG1000
(Same), "PTG400 (Same)", "PTGL2000 (Same)",
It can also be obtained as a commercial product such as "PBG2000 (Daiichi Kogyo Seiyaku)".

Examples of the polyester polyol include polyols such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and phthalic acid, isophthalic acid, terephthalic acid, and maleic acid. And polyester polyols obtained by reacting with a polybasic acid such as fumaric acid, adipic acid and sebacic acid.

As the polycaprolactone polyol, ε-caprolactone and, for example, ethylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4
A polycaprolactone polyol obtained by reacting a polyol such as butanediol, trimethylolpropane or pentaerythritol.

The above polycarbonate polyols include “DN-980 (Nippon Polyurethane Co., Ltd.)”, “DN-981 (same as above)”, “DN-9
82 (same), DN-983 (same), PC-8000 (US PPG
) Can be obtained as a commercial product.

As the above polyepoxy polyol, bisphenol A or an alkylene oxide adduct of bisphenol A is reacted with epichlorohydrin to form a diglycidyl ether.
Examples include polyepoxy polyols obtained by reacting acrylic acid.

As the polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate,
Methylene bis (4-cyclohexyl isocyanate),
2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate. Among these polyisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate are preferred.

Further, examples of the compound having an ethylenically unsaturated group include (meth) acrylic compounds having a hydroxyl group, a carboxyl group, an epoxy group or an acid halide group.

Examples of the (meth) acrylic compound having a hydroxyl group include hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and polyethylene glycol. Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1 , 4-Butanediol mono (meth)
Acrylate, 4-hydroxycyclohexyl (meth)
Acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerin di (meth) acrylate, (meth) acrylates represented by general formulas (II) to (IV), alkyl glycidyl ether And compounds obtained by an addition reaction of a glycidyl group-containing compound such as aryl glycidyl ether and glycidyl (meth) acrylate with (meth) acrylic acid.

(Wherein, R ⁷ represents a hydrogen atom or a methyl group;
Indicates an integer of 5) Among these (meth) acrylic compounds having a hydroxyl group, 2-hydroxyethyl acrylate is preferable.

Examples of the (meth) acrylic compound having a carboxyl group include (meth) acrylic acid. Examples of the (meth) acrylic compound having an epoxy group include:
(Meth) acrylic acid glycidyl ether and the like.

Examples of the (meth) acrylic compound having an acid halide group include (meth) acrylic halides such as (meth) acrylic chloride and (meth) acrylic bromide.

Further, as the component (A) of the present invention, a polymer in which an ethylenically unsaturated group has been introduced into a polyether resin, a polyester resin, a polyepoxy resin, or the like other than those described above can also be used.

In the present invention, the component (A) has a number average molecular weight of 300 to 300.
Those having a range of 7,000 are preferable, and those having a range of 500 to 5,000 are particularly preferable.

These components (A) are present in the resin composition of the present invention in an amount of from 5 to 90%.
% By weight, especially 20 to 80% by weight.

Examples of the component (B) used in the resin composition of the present invention include the following.

Monofunctional unsaturated compound: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, 2-ethylhexyl (Meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth)
Acrylate, methyltriethylene glycol (meth)
Acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecanyloxy (Meth) acrylic compounds such as ethyl (meth) acrylate,
N-vinylpyrrolidone, N-vinylcaprolactam, vinylphenol, acrylamide, vinyl acetate, vinyl ether, styrene, compounds represented by formulas (V) to (VIII).

(Wherein, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkylene group having 1 to 6 carbon atoms, R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms, and b is an integer of 1 to 12 Indicates) (Wherein, R ⁸ and R ⁹ are as described above, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and d represents 1 to
Indicates 16 integers) (Wherein, R ⁸ is as described above, and R ¹² has 2 to 7 carbon atoms.
Represents an alkylene group, and p represents an integer of 1 to 15) Wherein R ⁸ , R ¹² and p are as described above, and R ¹³ represents a hydrogen atom or a methyl group. Polyfunctional unsaturated compound: trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol Diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tricyclodecane dimethanol diacrylate, tricyclo Decane dimethanol dimethacrylate, dicyclopentadiene diacrylate, tricyclodecanyl diacrylate, dicyclopentadiene dimethacrylate, trimethylolpropane trioxypropyl acrylate, Squirrel-2-hydroxyethyl isocyanurate tri (meth) acrylate, tris-2
Hydroxyethyl isocyanurate di (meth) acrylate, an acrylate of an ethylene oxide adduct of bisphenol A, a compound represented by the general formula (IX).

(Wherein X is a group XI; Or a group X-II; And the group XI and the group X-II may both be present.) Examples of commercially available products of the component (B) include “Biscoat
3700 (Osaka Organic Co., Ltd.), VISCOAT 700 (same), "K
AYARAD DCPA-20 (Nippon Kayaku Co., Ltd.)
(Same), "sixty-six (same)", "same-120 (same)" and the like.

Preferred among these components (B) are 2-ethylhexyl acrylate, cyclohexyl acrylate,
Phenoxyethyl acrylate, isobornyl acrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, cyclopentenyl acrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, "KAYARAD DCPA-60", "KAYARAD"
DCPA-120 "and" VISCOAT 700 ".

These components (B) are present in the resin composition of the present invention in an amount of from 5 to 84%.
% By weight, especially 10 to 70% by weight.

The component (C) used in the resin composition of the present invention is not particularly limited, and various photopolymerization initiators or thermal polymerization initiators can be used.

As the photopolymerization initiator, for example, 2,2-dimethoxy-2
-Phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, acetophenone diethyl ketal, benzoin ethyl ether, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy -2-methyl-1-phenylpropan-1-one,
Thioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2-isopropylthioxanthone, camphorquinone, trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide and the like.

Further, as the thermal polymerization initiator, benzoin peroxide, t-butylperoxybenzoate, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, t-
-Butyl peroxide, azobisisobutyronitrile and the like.

If necessary, a sensitizer (polymerization accelerator) can be used in a range that does not impair the effects of the present invention.

These components (C) are usually contained in the resin composition of the present invention in an amount of from 0.1 to 0.1%.
It can be blended in the range of 05 to 10% by weight, preferably 1 to 10% by weight.

The component (D) used in the resin composition of the present invention is represented by the general formula (I). The molecular weight of the component (D) is usually 1,000 to 10,000, preferably 2,000.
0 to 6,000, and x in the general formula (I) is generally smaller than y.

Examples of commercially available products of the component (D) include “DC-57
(Dow Corning Co., Ltd.), “DC-190 (same as above)” and the like.

These components (D) are usually used in the resin composition of the present invention.
It can be blended in the range of 0.005 to 1% by weight, preferably 0.01 to 0.5% by weight.

Further, in the resin composition of the present invention, if necessary, various additives other than the above essential components, for example, a catalyst such as dibutyltin dilaurate, polymerization inhibition of 2,6-di-t-butyl-4-methylphenol and the like. Agent, polymerization initiator, surfactant,
Leveling agent, ultraviolet absorber, silane coupling agent,
An inorganic filler or the like can be blended.

The resin composition of the present invention comprises the above (A), (B),
Components (C) and (D) and other components as required are blended, but the blending of each of these components is carried out by a conventional method and is not particularly limited.

The viscosity of the resin composition of the present invention is usually 20 to 5000 cp.
s (25 ° C.), preferably 20 to 2000 cps (25 ° C.), particularly preferably 20 to 500 cps (25 ° C.). 5000cp viscosity
When the temperature exceeds s (25 ° C.), it becomes difficult to produce a three-dimensional molded object.

The resin composition of the present invention thus obtained is a photocurable liquid material or a thermosetting liquid material, and is cured by selectively irradiating a desired portion thereof with light.
A three-dimensional structure having a desired shape can be obtained.

Here, the light used for irradiation can be appropriately selected depending on whether the resin composition of the present invention is photo-curable or thermo-curable.
Visible light or the like is used, and in the case of thermosetting, infrared light or the like is used.

Further, the method of selectively irradiating light to a specific portion of the resin composition of the present invention is not limited, and for example, a method of irradiating a specific portion with laser light, a lens, a focused light obtained using a mirror, or the like, A method of irradiating non-focused light through a mask having a fixed pattern may be used.

A typical example of the optical three-dimensional molding method in which the resin composition of the present invention is used is to selectively irradiate light so as to obtain a cured layer having a desired pattern on the liquid resin composition of the present invention. To form a cured layer, and then repeat the operation of irradiating light similarly to the uncured resin composition layer adjacent to the cured layer to newly form a cured layer continuous with the cured layer,
This is a method of finally obtaining a target solid, that is, a molded article having a three-dimensional shape.

More specific embodiments of the above method include the following.

After the resin composition of the present invention is placed in a container and irradiated with light to form a first cured layer, then the uncured resin composition for the cured layer is obtained. A method in which an additional supply is performed on the layer and the operation of irradiating light to form a next cured layer is repeated.

The bottom plate is submerged in the resin composition of the present invention by the depth of the first cured layer, and after irradiating light to form a first cured layer, the bottom plate is further reduced by a further depth. A method in which an uncured resin composition for one layer flows into the first cured layer by sinking, and the operation of irradiating light to form the next cured layer is repeated.

A box having a transparent bottom plate is submerged in the resin composition of the present invention placed in a container, and a resin composition layer formed in a gap between the bottom plate and the bottom surface of the container is used as a first cured layer. After the first cured layer is formed by irradiating the composition layer with light through the transparent bottom surface of the box, the composition layer is further raised by increasing the thickness by one layer. Minute uncured composition flows into the gap between the first cured layer and the plate;
Next, a method of irradiating light in the same manner as described above and repeating the operation of forming the next cured layer.

The plate is submerged in the resin composition of the present invention placed in a container having a transparent bottom, and the composition layer formed in the gap between the plate and the bottom surface of the container is formed with the thickness of the first cured layer. In the same manner, after irradiating the composition layer with light through the transparent bottom of the container to form a first cured layer, the above-mentioned plate is raised by one thickness to thereby reduce the thickness of one layer. A method in which a cured resin composition is caused to flow into a gap between a first cured layer and a plate, and light is then irradiated in the same manner as described above to form a next cured layer.

After the three-dimensional object formed by the above methods 1 to 3 is removed from the container used for the reaction, the unreacted resin composition remaining on the surface of the three-dimensional object is removed, and further, if necessary, washed. As a cleaning agent used for cleaning,
Organic solvents typified by alcohols such as isopropyl alcohol and thermosetting or photocurable low-viscosity resins can be used.

In addition, it is preferable that the three-dimensional structure thus obtained is further subjected to post-curing by heat or light.

〔Example〕

Next, the present invention will be described more specifically with reference to Examples.
The present invention is not limited to these examples.

Example 1 (1) In a reaction vessel equipped with a stirrer, 12.4-37 g of 2,4-tolylene diisocyanate and 0.046 of dibutyltin dilaurate were placed.
g and 2,6-di-t-butyl-4-methylphenol 0.
069g was charged. Then, while cooling the reaction vessel with ice water, 8.293 g of 2-hydroxyethyl acrylate was added thereto while stirring the internal solution so that the internal temperature did not exceed 25 ° C. After completion of the addition, the mixture was stirred for 1 hour while maintaining the internal temperature at 5 to 25 ° C., and 24.995 g of a number average molecular weight polypropylene glycol (Asahi Glass Co., Ltd., PPG700) was added to the internal solution so that the internal temperature did not exceed 60 ° C. Was added with stirring. After completion of the addition, it was confirmed that the residual isocyanate was 0.1% by weight or less of the charged amount. Then, the stirring was stopped to obtain a polyether polyurethane having an ethylenically unsaturated group. Hereinafter, this reaction solution is referred to as component (A) -1.

(2) To 45.840 g of the (A) -1 component obtained in (1),
12.650 g of isobornyl acrylate (B) component, N-
16.740 g of vinylpyrrolidone and 18.195 g of trimethylolpropane trimethacrylate, 6.00 g of 1-hydroxycyclohexyl phenyl ketone of component (C) and 0.05 g of silicone compound DC-57 (Dow Corning Co., Ltd.) of component (D) were blended. The resin composition A of the present invention was prepared, and the defoaming property was evaluated. The results are shown in Table 1. The viscosity of the composition A was 300 cPS (25 ° C.).

Evaluation of defoaming property 15 ml of resin composition A was put into a 25 ml measuring cylinder, and air was flowed into the bottom of the measuring cylinder at 1 / min × 1 minute (the nozzle diameter at this time was 1 mm in inner diameter), and the height of the foam at that time was measured. The reading and the time until disappearance were measured.

Comparative Example 1 The defoaming property of the resin composition was evaluated in the same manner as in Example 1 except that the silicone compound DC-57 as the component (D) was not used. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated, except that 0.05 g of the silicone compound DC-57 (D) was replaced with a commercially available antifoaming agent Dappo SN-348 (non-silicone, Sannobuco). The defoaming property of the resin composition was evaluated. The results are shown in Table 1.

(Effects of the Invention) The resin composition for optical three-dimensional modeling of the present invention is a liquid substance and is excellent in an antifoaming agent.By using this, the molding time can be reduced in the optical three-dimensional modeling method,
It is possible to obtain a three-dimensional structure having good dimensional accuracy.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Katsushi Igarashi 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Edward Jay. Murphy United States 60005 South Michelle, Arlington Heights, Illinois 742 (56) References JP 2-198603 (JP, A) JP 2-75618 (JP, A) JP 2-75617 (JP, A) JP-A-2-28261 (JP, A) JP-T-62-502247 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 1/00-101/14 C08F 2 / 46-2/50 B01D 19/04

Claims (1)

(57) [Claims] 1. A polymer obtained by reacting (A) a polyol compound with a polyisocyanate compound and a compound having an ethylenically unsaturated group, from 5 to 90% by weight. (B) a monomer having an ethylenically unsaturated group. 5 to 84% by weight (C) 0.05 to 10% by weight of a polymerization initiator and (D) a general formula (I) (Wherein, R ¹ , R ² and R ³ represent a methyl group, an ethyl group or a phenyl group, R ⁴ and R ⁵ represent an alkylene group having 1 to 12 carbon atoms, and R ⁶ represents a C 1 to C 12 alkyl group) An alkyl group or a phenyl group, and x, y, m and n each represent an integer of 1 to 500). A resin composition for stereolithography, which contains 0.005 to 1% by weight of a silicone compound as an essential component.