KR20180113714A - A resin composition which is used for light radiation - Google Patents

Abstract

The present invention relates to a liquid resin composition for light shaping, intended to mold a molded article having high heat resistance and self-extinguishing properties. To this end, the resin composition for light shaping contains an acrylate-based resin and an additive. The acrylate-based resin contains 5-40 wt% of melamine acrylate, 10-40 wt% of dendrimer acrylate, and residual low-viscosity acrylate which has viscosity of 3-500 Cps at room temperature. According to the present invention, by using the resin composition, the molded article molded by using a three-dimensional (3D) printer secures high heat resistance and self-extinguishing properties, thereby being used for molding components suitable for high-temperature and high heat environment such as an automobile engine or a copier facsimile.

Description

[0001] The present invention relates to a resin composition,

The present invention relates to a resin composition for light-shaping used in a 3D printer.

A stereolithography type 3D printer for forming a molding by laminating a resin layer has been developed and commercialized. The stereolithography type 3D printer stores a liquid resin composition in a resin tank and irradiates light toward the bottom or surface of the resin tank to cure and laminate the liquid resin composition to form a three-dimensional object.

As the conventional resin composition, an acrylic resin, an epoxy resin, a hybrid resin obtained by mixing an acrylic resin and an epoxy resin, and the like are used. Such conventional epoxy-based, acryl-based or hybrid-based resin compositions usually exhibit heat resistance characteristics of 100 ° C or less.

However, in recent years, parts operating in a high-temperature environment such as automobiles are required to have high heat resistance of, for example, 200 DEG C or more, and in some cases, a relatively high level of flame retardancy or self-extinguishing property may be required. However, conventional resin materials for 3D forming do not satisfy such a high thermal requirement, and the utilization of 3D printing is limited.

An object of the present invention is to provide a photocuring resin composition having high heat resistance and self-extinguishing properties.

In order to achieve the above object, the present invention provides a resin composition for light-shaping comprising an acrylate resin and an additive, wherein the acrylate resin comprises 5 to 40% by weight of melamine acrylate, 10 to 40% by weight of a dendrimer acrylate, and a residual low-viscosity acrylate, wherein the low-viscosity acrylate has a viscosity of 3 to 500 Cps at room temperature.

The content of the melamine acrylate may be 20 to 40% by weight, and the content of the dendrimer acrylate may be 20 to 40% by weight.

The low viscosity acrylate may be selected from the group consisting of cyclic trimethylolpropane acrylate, isobornyl acrylate, trimethylcyclohexyl methacrylate, benzyl methacrylate, isobonyl acrylate, But are not limited to, methacrylate, isobornyl methacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane trimethacrylate, One or two or more selected from the group consisting of ethoxylated trimethylolpropane triacrylate (3EO-TMPTA) and ethoxylated pentaerythritol triacrylate (4EO-PETA) Can be used.

The resin composition for light-shaping of the present invention can obtain a sculpture having high heat resistance and self-extinguishing properties.

Although the present invention has been described in detail by way of examples, the present invention is not limited to the embodiments described herein but may be embodied in various forms.

The photocurable resin composition of the present invention is prepared by containing an acrylate resin and an additive. In particular, acrylate resins are excellent in self-extinguishing properties and high heat resistance.

The additives used in the photocurable resin composition of the present invention include photopolymerization initiators and other additives. The photopolymerization initiator is a photo-radical initiator. The photoradical polymerization initiator is a compound necessary to initiate a radical polymerization reaction caused by a radical generated by receiving light energy. 0.1 to 10% by weight of the total amount of the resin composition for light shaping is used.

Other additives are also used as additives to the resin composition for light modulation of the present invention. Other additives include additives used in usual light shaping resins such as a substrate absorbing agent, a leveling agent, a defoaming agent, a pigment dispersant, a light absorber, a polymerization inhibitor, a pigment, and a dye. Various additives are added as needed, and the content thereof is usually about 0.01 to 10% by weight.

The acrylate resin of the resin composition for light modulation of the present invention contains melamine acrylate and dendrimer acrylate to enhance flame retardancy and self-extinguishing properties. Melamine Acrylate has a viscosity of 3,000 to 5,000 Cps at room temperature (20 ° C) and Dendrimer Acrylate has a viscosity of 1,500 to tens of thousands of Cps at room temperature (20 ° C). These two functional acrylates are used with low viscosity acrylates because they have high viscosity and poor fluidity and moldability.

The content of melamine acrylate in the total acrylate resin is 5 to 40% by weight. This melamine acrylate has considerable flame retardancy and heat resistance, but is particularly excellent in self-extinguishing properties. Dendrimer acrylate has excellent thermal properties like melamine acrylate, but is superior in heat resistance to melamine acrylate. It is preferable that the dendrimer acrylate has a content of 10 to 40% by weight, though it is relatively depending on the content of the melamine acrylate.

The weight ratio of melamine acrylate and dendrimer acrylate combined is preferably 60% or less of the total acrylate resin. When the content thereof is 60% by weight or more, even if diluted with a low viscosity acrylate having a very low viscosity, it is difficult to ensure proper fluidity and proper molding workability is hardly guaranteed. Therefore, the lower viscosity acrylate and dendrimer acrylate are selected so that the higher the weight ratio is, the lower the viscosity is.

Of the total acrylate resin, the remaining amount except for melamine acrylate and dendrimer acrylate is occupied by low viscosity acrylate. The low viscosity acrylate has a low viscosity of 5 to 500 Cps at room temperature (20 degrees Celsius) and dilutes the melamine acrylate and dendrimer acrylate to increase the fluidity as a whole to facilitate molding and handling .

The acrylate-based resin has a viscosity of 100 to 3,000 Cps, preferably 100 to 1,000 Cps, more preferably 100 to 3,000 Celsius, and the viscosity of the acrylate-based resin mixed with melamine acrylate, dendrimer acrylate and low- More preferably 100 to 500 Cps.

The final viscosity may not sufficiently provide the fluidity necessary for molding. In this case, the resin material may be heated to increase the fluidity. The heating of the resin material may be performed by heating the resin tank containing the resin material, heating the resin material from the resin tank, heating the resin tank, and returning the resin material to the inside of the resin tank. A viscosity sensor and a temperature sensor are provided for viscosity and temperature control of the resin material, and on the basis thereof, the control unit appropriately controls the flow pumper and the heater of the resin material.

Examples of commercially available products of melamine acrylate are as follows. Miramer SC9610 from Miwon Specialty Chemical Co. Ltd, CN890 from Sartomer Company Inc, Bomer XMA-222F from Dymax Corporation, Bomer BMA-200, etc., have.

Examples of commercially available products of dendrimer acrylate are as follows. Bomer BTD-1015, Bomer BTD-1018 and Bomer BTD-4330 from Dymax Corporation and Miramer SP1106 from Miwon Specialty Chemical Co., Can be used.

Two or more types of low viscosity acrylates may be used in combination. In order to ensure heat resistance, the glass transition temperature (Tg) of the homopolymer is preferably relatively high.

The chemical names and commercial products of low viscosity acrylates are as follows, and one or more of these may be selected and used in combination. The low viscosity acrylate is Cyclic Trimethylolpropane Acrylate which is commercially available under the trade name Miramer M1110 from Miwon Specialty Chemical Co. Ltd and SR531 from Sartomer Company Inc Can be used. The low viscosity acrylate may be isobornyl acrylate, Miramer M1140 from Miwon Specialty Chemical Co. Ltd and SR508 from Sartomer Company Inc. may be used.

Another low viscosity acrylate is trimethylcyclohexyl methacrylate, and Sartomer Company Inc's CD421A is used. The low viscosity acrylate is benzyl methacrylate, and Miramer M1183 from Miwon Specialty Chemical Co. Ltd. is used. The low viscosity acrylate is isobornyl methacrylate, and SR423NS from Sartomer Company Inc may be used. The low viscosity acrylate may be tricyclodecane dimethanol diacrylate, Miramer M262 from Miwon Specialty Chemical Co. Ltd and SR833 from Sartomer Company Inc may be used .

The low viscosity acrylate is trimethylolpropane trimethacrylate, and Miramer M301 from Miwon Specialty Chemical Co. Ltd. is used. The low viscosity acrylate may be ethoxylated trimethylolpropane triacrylate (3EO-TMPTA), and NAM-TMP3EO of NAGASE & Co LTD may be used. Low viscosity acrylate is ethoxylated pentaerythritol triacrylate (4EO-PETA), and SR494NS from Sartomer Company Inc may be used.

The photopolymerization initiator which is one of the additives of the resin composition for photo-shaping of the present invention is Photo-Radical Initiators. The photoradical polymerization initiator is a compound necessary to initiate a radical polymerization reaction caused by a radical generated by receiving light energy. The amount of the photopolymerization initiator to be used is 0.1 to 10% by weight of the resin composition for light shaping. When the photopolymerization initiator is used in an amount of 0.1% by weight or less, the polymerization reaction does not occur and the resin does not cure. If 10% or more of the photopolymerization initiator is used, it is economically disadvantageous.

As a specific example of the chemical name of the photopolymerization initiator and a commercially available product, IRGACURE (trade name, manufactured by BASF) as 2,2-dimethoxy-1,2-diphenylethan-1- 651 can be used. Alternatively, IRGACURE 184 from BASF may be used as 1-Hydroxy-cyclohexyl-phenyl-ketone, or 2-hydroxy-2-methyl- IRGACURE 1173 available from BASF can be used as 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

As another specific example, a method for preparing 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- morpholinopropan-1-one), IRGACURE 907 from BASF can be used.

As another specific example, LUCIRIN TPO manufactured by BASF Corp. may be used as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) IRGACURE 819 from BASF can be used as phosphine oxide (Bis (2,4,6-trimethylbenzoyl) phosphine oxide). These compounds may be used singly or in combination of two or more.

The photopolymerization initiator may be combined with a photosensitizer. An example of the photosensitizer may be Anthracure UVS-1331 manufactured by KAWASAKI KASEI CHEMICALS LTD as 9,10-dibutoxyanthracene. Another example of a photosensitizer is an anthracene derivative such as 9,10-Diethoxyanthracene, such as Anthracure UVS-1221 from KAWASAKI KASEI CHEMICALS LTD. (Antracene derivative) can be used. In another embodiment, SPEEDCURE DETX from LAMBSON is used as 2,4-Diethylthioxanthone or 2-isopropylthioxanthone is used as 2,4- A thioxanthone derivative such as SPEEDECURE ITX manufactured by LAMBSON may be used.

 Another additive of the resin composition for light-shaping of the present invention is other additive. The other additives may be those used in conventional light modifying resins such as a substrate absorbing agent, a leveling agent, a defoaming agent, a pigment dispersant, a light absorbent, a polymerization inhibitor, a pigment, and a dye.

Specific examples of commercial products of other additives are as follows. As the base wetting agent, Polyflow KL-100 and Polyflow KL-700 of Oligomer including silicone are used, and nonionic TEGO WET 500 from Evonik Industries AG is available as a non-ionic organic surfactant.

The leveling agent is Polyflow No. 75 and Polyflow No. 77 of Acrylic Polymer, which are available from Kyowa Chemical Industry Co., Ltd., Polfllo KL-401, KL-402 and Evonik Industries AG TEGO Rad 2100 and TEGO Rad 2250 available from the same company are available as Slicone compounds. Megaface F-444, Megaface F-554 and Sumitomo 3M Limited of DIC Corporation were used as a fluoro surfactant. FC-4430 and FC-4432 are also used.

Pigment dispersants were obtained from Ajinomoto Fine-Techno Co., Inc., AJISPER PB-711 (AJISPER PB-711), PB-821, PB-822 and Ajinomoto Fine-Techno Co., G-700 (FLOWLEN G-700), Ebonic's TEGO Dispers 685 and the like.

The light absorber is Kayaset Red B, Kayaset Yellow 2G, Kayaset Blue N, and LANXESS, manufactured by NIPPON KAYAKU Co., Ltd., MACROLEX Yellow 6G Gran Co., Ltd.) is used.

As the polymerization inhibitor, MEHQ, TBC of Kawasaki Kasei Kogyo Co., FLORSTAB UV12 of Kromachen Co., and Q-1301 of WAKO Pure Chemical Industries, Ltd. can be used.

On the other hand, the resin composition for stereolithography of the present invention can be used in combination with inorganic and organic powders used in conventional stereolithography. Specific examples of the inorganic powders include ceramic powders such as alumina ceramics and zirconia ceramics; inorganic powders such as calcium phosphate powders such as apatite and tricalcium phosphate; silica; hollow glass; glass fibers; carbon nanofibers; and cellulose nanofibers. Specific organic powders include polystyrene, polymethacrylate polymer particles, polybutadiene, and rubber powders such as SBR (styrene butadiene rubber) and NBR (acrylonitrile butadiene rubber). The amount of the organic powder and the inorganic powder used is 0 to 85% by weight. And more preferably 0 to 40% by weight. Inorganic powders and organic powders are used to reinforce strength.

The stereolithography apparatus used in the present invention uses a surface exposure method and uses a visible light as a regulating liquid surface method as an embodiment. The surface exposure apparatus used in the present invention uses a digital mirror device (DMD) to project a cross-sectional shape from the lower side of a transparent substrate by using an LED lamp having a wavelength of 405 nm to cure the light modulation resin composition disposed on the transparent substrate . The present invention is not limited to a continuous layer method or a general molding method in which a shaping plate is continuously raised or lowered at a constant speed. Therefore, the detailed operation of the 3D printer forming method and apparatus will be omitted.

Example

An acrylate resin in the resin composition was prepared in the proportions shown in Table 1 below.

                                                        (Unit: wt%)    division Example 1 Example 1 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Melamine Acrylate 12 22 34 12 22 32 5 40 40 30 15 30    Miramer SC9610 12 22 34 5 40 30 30    CN890 12 22 32 40 15 Dendrimer Acrylate 32 34 22 22 34 22 36 24 10 40 15 40    Bomer T-1006 32 34 22 12 36 24 40    Bomer BDT-4330 22 10 40    Miramer SP1106 34 10 15 Low viscosity Acrylate 56 44 44 66 44 46 59 36 50 30 70 60 70 100    Miramer M1140 12 12 10 22 12 22 12 12 14 10 20 20 20 30    SR833 12 10 12 22 10 12 13 12 12 10 20 20 30 30    NAM-TMP3EO 32 22 22 10 12 34 12 12 10 20 20 20 40    SR494NS 22 12 12 10 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100

Each component was compounded in the ratio shown in Table 1 to prepare an acrylate resin in the resin composition. In the mixing method, melamine-formaldehyde, dendrimer acrylate and low-viscosity acrylate are placed in a container, heated to 60 ° C. with stirring, and stirred for about 2 hours. The temperature is then lowered to room temperature while stirring.

Hereinafter, for convenience of the experiment, only 10% by weight of the total amount of additives is used, among which 7% of photopolymerization initiator and 3% of other additives are used. The mixing ratio of the base resin and the additive and the composition method for completing the light-shaping resin are not known in detail because they are generally known.

Example  1 to 3, 7, 8, and 10

The melamine acrylate uses Miramer SC9610. Dendrimer acrylate uses Bomer T-1006. The low viscosity acrylate is used in combination with three components: Miramer M1140, SR833, and NAM-TMP3EO. Melamine acrylate, dendrimer acrylate and low-viscosity acrylate are 100% by weight in total, and the blending ratios of the respective components are in accordance with Examples 1 to 3, 7, 8 and 10 of Table 1.

Example  4

The melamine acrylate uses CN890. The dendrimer acrylate uses Bomer BDT-4330. Low viscosity acrylates are used in combination with Miramer M1140, SR833, SR494NS. The blending ratio of melamine acrylate, dendrimer acrylate and low-viscosity acrylate is 100% by weight in total.

Example  5, 9, and 11

The melamine acrylate uses CN890. The dendrimer acrylate is Miramer SP1106. Low viscosity acrylate is used in combination with M1140, SR833, NAM-TMP3EO and SR494NS. Melamine acrylate, dendrimer acrylate and low-viscosity acrylate are 100% by weight in total, and the blending ratios of the components are as shown in Table 5 Example 5.

Example  6

The melamine acrylate uses CN890. The dendrimer acrylate is used in combination of two components, Bomer T-1006 and Bomer BDT-4330. The low viscosity acrylate is used in combination with three components: Miramer M1140, SR833, and NAM-TMP3EO. Melamine acrylate, dendrimer acrylate and low-viscosity acrylate are 100% by weight in total, and the blending ratios of the components are as shown in Table 6 Example 6.

Comparative Example  One

Melamine acrylate is not used. The dendrimer acrylate uses Bomer BDT-4330. The low viscosity acrylate is used in combination with three components: Miramer M1140, SR833, and NAM-TMP3EO. The blending ratio of melamine acrylate, dendrimer acrylate and low viscosity acrylate is 100% by weight in total, and the blending ratios of the components are as shown in Table 1, Comparative Example 1.

Comparative Example  2

The melamine acrylate uses Miramer SC9610. Dendrimer acrylate is not used. The low viscosity acrylate is used in combination with three components: Miramer M1140, SR833, and NAM-TMP3EO. The blend ratio of melamine acrylate, dendrimer acrylate and low viscosity acrylate is 100% by weight in total, and the blending ratios of the respective components are as shown in Table 1, Comparative Example 2.

Comparative Example  3

Melamine acrylate is not used. Dendrimer acrylate is not used. The component (C) is a combination of three components: Miramer M1140, SR833, and NAM-TMP3EO. The blending ratio of melamine acrylate, dendrimer acrylate and low viscosity acrylate is 100% by weight in total, and the blending ratios of the components are as shown in Table 1, Comparative Example 3.

The acrylate resins of the resin compositions were prepared in the blending ratios of Examples 1 to 11 and Comparative Examples 1 to 3, respectively, and the additives (photopolymerization initiator and other additives) were added to the respective acrylate resins in such a manner that the acrylate- Can be compounded at a ratio of 8: 2 to 99: 1. However, in the specimen for the embodiment of the present invention, 7% by weight of a photopolymerization agent and 3% by weight of other additives were added to prepare a resin composition. This has the advantage of simplifying the experiment.

Each of the resin compositions thus prepared was used to mold a test piece for testing heat resistance and self-extinguishing ability using a 3D printer molding machine. Test pieces for testing heat resistance are formed so that the width X length X height is 80 mm X 10 mm X 4 mm. Test pieces for testing the self-extinguishing properties are formed so that the width X length X height is 127 mm X 12.7 mm X 12.7 mm.

First, heat resistance test is performed. Using a test piece for each of the examples and comparative examples, an in-degradation test method of ASTM D648 is used using an HDT tester of Toyoseiki Seisaku, Ltd. If the specimen is not deformed at 180 degrees Celsius according to this test method, it is indicated as satisfying a predetermined criterion and is marked as " o ". If the degree of deformation is very good, X ".

The self-extinguishing property was evaluated as "○" when the burning length of the test piece was not less than 25 mm and not more than 100 mm and the burning length was very good Quot; and "X" if the combustion length is 100 mm or more.

   division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Self-extinguishing ○ ◎ ◎ ○ ◎ ◎ ○ ◎ ◎ ◎ ○ X ○ X Heat resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ○ X X Overall assessment ○ ◎ ◎ ○ ◎ ◎ ○ ◎ ○ ◎ ○ X X X

As shown in Table 2, Examples 1 to 11 exhibited performance satisfying all predetermined criteria in heat resistance and self-extinguishing test. On the other hand, it was confirmed that Examples 2, 3, 5, 6, 8, and 10 are superior in terms of self-extinguishing properties and heat resistance. As a result, the self-extinguishing property and the high heat resistance were even better when 22 to 40% by weight of melamine acrylate, 22 to 40% by weight of (B) dendrimer acrylate and the remaining amount of low viscosity acrylate were used.

However, Comparative Examples 1 to 3 do not satisfy all the conditions as shown in Table 2. In Comparative Example 1, although the heat resistance satisfies predetermined criteria, it does not satisfy the criterion for self-extinguishing property. Comparative Example 2 does not satisfy predetermined criteria for heat resistance, and satisfies the criteria for self-extinguishing properties. In Comparative Example 3, neither the heat resistance nor the self-extinguishing property satisfied the predetermined criteria.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, You will know the point. Modifications may be made by those skilled in the art without departing from the scope of the claims.

Claims (3)

1. A resin composition for light control molding comprising an acrylate resin and an additive, the resin composition comprising:
The acrylate-based resin comprises 5 to 40% by weight of melamine acrylate, 10 to 40% by weight of dendrimer acrylate, and a residual low-viscosity acrylate,
Wherein the low viscosity acrylate has a viscosity of 3 to 500 Cps at room temperature.
The method according to claim 1,
Wherein the melamine acrylate (Methacrylate) contains 22 to 40% by weight and the dendrimer acrylate (Dendrimer Acrylate) contains 22 to 40% by weight.
4. The method according to any one of claims 1 to 3,
The low viscosity acrylate may be selected from the group consisting of cyclic trimethylolpropane acrylate, isobornyl acrylate, trimethylcyclohexyl methacrylate, benzyl methacrylate, , Isobornyl methacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropan trimethacrylate, ethoxylated trimethylolpropane triacrylate (3EO), trimethylolpropane trimethacrylate, -TMPTA, Ethoxylated Trimethylolpropane Triacrylate), and Ethoxylated Pentaerythritol Triacrylate (4EO-PETA).