JPH06128342A - Resin composition for optical three-dimensional shaping - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which is Iiq., photocurable, and excellent in toughness, heat resistance, etc., by compounding a specific urethane-acrylate deriv., a vinyl compd., and a polymn. initiator as the main components. CONSTITUTION:The compsn. is prepd. by compounding 10-80wt.% compd. of formula I wherein R1, R2, R3, and R4 are each H or lower alkyl; n is 1-10; l is 2-10; p is 0-15; Z is a group of formula II; m is 2-5; X is a group of formula III or IV; g is 0-10; and r is 0-4, 90-20wt.% vinyl compd. (e.g. 2-hydroxyethyl acrylate), and a polymn. initiator (e.g. 2,2-dimethoxy-2-phenylacetophenone) as the main components. The compsn. may further contain a leveling agent, an inorg. filler, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition for optical three-dimensional modeling, and more particularly to a resin composition for optical three-dimensional modeling excellent in mechanical properties and heat resistance after curing.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 56-144478 discloses a method for supplying a three-dimensional object by supplying a necessary amount of light energy to a photocurable resin, and further, Japanese Unexamined Patent Publication No. A basic practical method was proposed by Japanese Patent No. 247515. After that, similar or improved techniques are disclosed in JP-A-62-35966 and JP-A-1-20491.
5, JP-A-2-113925, JP-A-2-11325
145616, JP-A-2-153722,
It is disclosed in JP-A-3-15520, JP-A-3-21432, and JP-A-3-41126.

A typical example of the optical three-dimensional molding method is to selectively irradiate an ultraviolet laser controlled by a computer so that a desired pattern can be obtained on a liquid surface of a liquid photocurable resin contained in a container. By curing to a predetermined thickness, then supplying one layer of liquid resin on the cured layer, and similarly curing by irradiation with an ultraviolet laser in the same manner as described above to obtain a continuous cured layer. This is a method of finally obtaining a three-dimensional object. This optical three-dimensional modeling method has recently attracted particular attention because it can be easily obtained in a relatively short time even if the shape of a modeled object to be manufactured is quite complicated.

Conventionally, the photocurable resin used in the optical three-dimensional molding method includes modified polyurethane (meth) acrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, aminoalkyd and the like. Also, recently, JP-A-1
-204915, Japanese Patent Application Laid-Open No. 1-213304, Japanese Patent Application Laid-Open No. 2-28261, Japanese Patent Application Laid-Open No. 2-7561.
7, JP-A-2-145616, JP-A-3-
Various improved techniques are disclosed in JP-A-104626, JP-A-3-114732, JP-A-3-114733 and the like.

[0005]

In the optical three-dimensional molding method, the photocurable resin used is easy to handle,
From the viewpoint of molding speed, molding accuracy, etc., it is needless to say that the resin viscosity is relatively low, and the volume shrinkage rate upon curing is low,
Not only the mechanical properties of the obtained molded article are required to be sufficiently high, but also recently, it is required to have high heat resistance depending on the application.

However, none of the above-mentioned conventional liquid photo-curable resins have been provided with the properties, the special mechanical properties and the heat resistance. Therefore, an object of the present invention is to provide a photocurable liquid resin composition which has sufficiently high mechanical properties and provides an optical three-dimensional object excellent in heat resistance.

[0007]

The above objects of the present invention are as follows.
10 to 80% by weight of a compound represented by the following general formula [I]

[0008]

[Chemical 4]

[Wherein R ₂ and R ₃ are a hydrogen atom or a lower alkyl group, n = 1 to 10, l = 2 to 10 and p = 0.
To Z, and Z is a substituent represented by the following general formula [II].

[0010]

[Chemical 5]

Here, R ₁ is a hydrogen atom or a lower alkyl group, m is an integer of 2 to 5, and X is

[0012]

[Chemical 6]

(Wherein R ₄ is a hydrogen atom or a lower alkyl group, q = 0 to 10 and r = 0 to 4). This is achieved by a photocurable liquid three-dimensional optical three-dimensional modeling resin composition mainly containing 20 to 90% by weight of a vinyl compound and a polymerization initiator.

The present invention will be described in more detail below. The compound which is a component of the composition used in the present invention is represented by the general formula [I], and in the general formula [I], R ₁ , R ₂ R ₃ and R ₄ are hydrogen atoms or A lower alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., preferably a hydrogen atom or a methyl group. The above R ₁ , R ₂ R ₃ and R ₄ are
They may be the same or different.

The compound as the component (1) is preferably a tetrafunctional acrylic and / or methacrylic compound containing an isocyanurate ring having a urethane bond and composed of an ethylenic polyol and / or polyester as an essential component.
It has been found that a polyfunctional acrylic group and / or methacrylic group having a high heat resistance, an isocyanurate ring, and further bound with an alicyclic group and / or an aromatic group imparts high reactivity and heat resistance to the present invention. Arrived

The ethylenic and / or polyester structure can be arbitrarily selected as the soft segment depending on the required properties of the final optical three-dimensional model. The composition ratio of the component of the composition used in the present invention is 10
-80% by weight, preferably 10-60% by weight, more preferably 20-50% by weight.

When the composition ratio of the component (1) is less than 10% by weight, the effect of the present invention is not sufficiently exhibited, while when the composition ratio exceeds 80% by weight, the viscosity of the composition becomes too high.
Not only is it difficult to use, but the optically molded product is fragile and has problems in practice, so it is not preferable to use it. That is, the composition ratio effective in the present invention is limited to 10 to 80% by weight.

In the composition used in the present invention, the component (1) is a polymerizable vinyl compound, and either monofunctional or polyfunctional monomers and / or oligomers are used. These monofunctional and / or polyfunctional compounds are not particularly limited, and typical ones thereof include:

Monofunctional compounds: isobornyl acrylate, isobornyl methacrylate, zinc pentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, propylene glycol acrylate, vinylpyrrolidone, acrylamide. , Vinyl acetate, styrene, etc.

Polyfunctional compounds: trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, ethylene glycol diacrylate,
Examples include tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate and diallyl phthalate. To be

As such components, one or more monofunctional and / or polyfunctional compounds can be used in the form of a single mixture. The composition ratio of the component of 2 is based on the component of 2
0 to 90% by weight, preferably 90 to 40% by weight,
More preferably, it is 80 to 50% by weight.

When the composition ratio of the component (1) is less than 20% by weight, the content of the component (1) exceeds 80% by weight, so that the viscosity of the composition becomes too high, which not only causes difficulty in use but also optically. The formed product is brittle, which causes a problem in practical use. The composition ratio of the component is 90% by weight.
When it exceeds, the content of the component becomes less than 10% by weight, and therefore the effect of the present invention is not sufficiently exhibited.

The polymerization initiator used in the present invention includes
A photopolymerization initiator and a thermal polymerization initiator are used, and as the photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, Fluorene, anthraquinone, triphenylamine, carbazole, 3-
Typical examples thereof include methyl acetophenone and Michler's ketone, but the present invention is not limited thereto, and these initiators may be used alone or in combination of two or more. Further, if necessary, a sensitizer such as an amine compound may be used in combination.

As the thermal polymerization initiator, benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxide, azobisisobutyronitrile and the like are typical. It can be mentioned as a thing. The amount of the component of the polymerization initiator used in the present invention is 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the component +.

The resin composition of the present invention, if necessary,
A leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, an inorganic filler and the like may be added. The resin composition of the present invention is prepared by mixing the above-mentioned components and or, if necessary, mixing other components, but the mixing method of each component is not particularly limited. The light used in the optical three-dimensional molding of the resin composition of the present invention may be ultraviolet light, visible light, infrared light or the like depending on the purpose.

As a typical method of the optical three-dimensional molding method in which the resin composition of the present invention is used, the liquid composition is selectively irradiated with light so that a cured layer having a desired pattern can be obtained. To form a cured layer, then supply the uncured liquid composition to the cured layer, and similarly irradiate light to newly form a cured layer continuous with the above-mentioned cured layer. It is a method for obtaining a desired three-dimensional molded object.

[0027]

[Examples] Next, more detailed description will be given with reference to Examples.
The present invention is not limited to these.

Synthetic Example (Synthesis of Urethane Acrylate Oligomer) After stirring, isophorone diisocyanate was triplicated into a 5-liter three-necked flask equipped with a cooling tube and a dropping funnel with a side tube.
1023 g of PDI terpolymer (manufactured by Sumitomo Bayer Co .; Dismodule Z-4372) and 0.076 g of dibutyltin laurate are charged, and the internal temperature is brought to 65 ° C. in an oil bath. 420.1 g of polyneopentylene adipate (manufactured by Asahi Denka Co., Ltd .; ADEKA NEWACE Y9-10) is charged into a dropping funnel with a side tube which is preliminarily kept at 50 ° C.

The operation of depressurizing the entire system and returning to normal pressure with nitrogen gas is repeated to degas and replace nitrogen. The entire system is set to normal pressure, and the temperature of the flask contents is set to 6 in a nitrogen atmosphere.
While maintaining the content at 5 ° C., the polyneopentylene adipate is added dropwise over 1 hour from the dropping funnel while stirring the contents. After the dropping, the contents are kept at 65 ° C. for another hour and the reaction is continued with stirring.

After cooling the contents of the flask to 50 ° C., 2-hydroxyethyl acrylate 2 was added to the dropping funnel.
A liquid in which 0.90 g of methylhydroquinone was homogeneously dissolved and mixed in 54.5 g was charged, and the temperature of the flask contents was 55 ° C.
Quickly drop in a range not exceeding the value, and then with stirring for 2 hours,
Continue the reaction.

The urethane acrylate oligomer obtained is taken out of the flask while the contents are warm. The urethane acrylate oligomer obtained here was confirmed by IR and elemental analysis to have the following structural formula.

[0032]

[Chemical 7]

Example 1 (Preparation of composition for optical shaping) 1320 g of urethane acrylate synthesized in Synthesis Example and polyethylene glycol 200 diacrylate (in a 5 liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel with a side tube) 1080 g of Sartomer SR259) manufactured by Somar Co. and 480 g of ethoxy-modified trimethylolpropane triacrylate (Sartomer SR454 manufactured by Somar Co.) were charged and degassed with nitrogen under reduced pressure. The contents were heated to 50 ° C. and mixed with stirring for about 1 hour.

120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Kaiggy; Irgacure 651) is added in an environment where ultraviolet rays are cut, and mixed and stirred until completely dissolved. The degreasing composition obtained was a colorless and transparent viscous liquid containing 44.8% by weight of the compound according to the present invention (the urethane acrylate synthesized in Synthesis Example), and its viscosity was 1550 cps at 30 ° C. .

Focused Ar laser light (output 500 m
W, wavelength 368 mμ) perpendicular to the surface of the resin composition prepared as described above, 12.7 mm × 12.7 mm ×
Irradiation was performed so that a 125 mm rectangle was obtained. After removing the resin liquid adhering to the obtained cured product by washing with isopropyl alcohol, post-curing was performed with 3 KW of ultraviolet light for 10 minutes. The obtained test piece was measured for heat distortion temperature according to JIS K7207 and notched impact according to JIS K7110. Heat distortion temperature is 50.8 ℃
The notched impact was 3.7 kg / cm / cm.

COMPARATIVE EXAMPLE 1 Isophorone diisocyanate (manufactured by DIAHULS; polyisocyanate IPDIT-1890 / 100) was used in place of IPDI terpolymer (manufactured by Sumitomo Bayer; Dismodul Z-4372) in the synthesis example. Then, urethane acrylate was synthesized. A resin composition was prepared by using the urethane acrylate synthesized as described above in place of the urethane acrylate used in Example 1.

Further, as in Example 1, 12.7 mm × 12.
A 7 mm x 125 mm rectangular test piece was prepared and the heat distortion temperature was
As a result of measuring the notched impact, the heat distortion temperature of 40.
2 ° C., notched impact 3.2 kg · cm / cm. Comparing the mechanical properties and heat resistance of the three-dimensionally shaped rectangles obtained in Example 1 and Comparative Example 1, the invention of Example 1 is superior.

Example 2 A resin composition was prepared in the same manner as in Example 1, except that the amount of the urethane acrylate synthesized in the synthesis example was 660 g, and 660 g of the urethane acrylate synthesized in the comparative example was used. . The compound of the present invention is contained in the composition in an amount of 22.4% by weight. As a result of measuring the physical properties of the rectangle obtained in the same manner as in Example 1, the heat distortion temperature was 4
5.6 ℃, Notched impact is 4.5Kg · cm / c
It was confirmed that the heat resistance was improved.

Comparative Example 2 A resin composition was similarly prepared by using 165 g of the urethane acrylate synthesized in the synthesis example in Example 2 and 1155 g of the urethane acrylate synthesized in Comparative Example 1. The ratio of the compound according to the present invention contained in the composition was 5.6% by weight.

As a result of measuring the physical properties of the rectangle obtained in the same manner, the heat distortion temperature was 40.8 ° C., the notched impact was 3.3 Kg · cm / cm, and the compound ratio according to the present invention was 10% by weight. If less than%, no improvement effect was observed.

[0041]

INDUSTRIAL APPLICABILITY According to the present invention, an optical three-dimensional object obtained from a composition containing the compound represented by the general formula [I] in an amount of 10 to 80% by weight has remarkably improved heat resistance without impairing toughness. This makes it possible to develop a wide range of applications for dynamic three-dimensional objects.

Claims (1)

[Claims] 1. A compound of the formula [I] 10
80% by weight [Wherein R ₂ and R ₃ are a hydrogen atom or a lower alkyl group, n = 1 to 10, l = 2 to 10 and p = 0 to 15 are integers, and Z is represented by the general formula [II]. Substituents embedded image Here, R ₁ is a hydrogen atom or a lower alkyl group, and m = 2
Is an integer of 5 and X is (Here, R ₄ is a hydrogen atom or a lower alkyl group, and q =
0-10 and r = 0-4). Vinyl compound 20 to 90% by weight A photocurable liquid three-dimensional optical three-dimensional modeling resin composition mainly containing a polymerization initiator.