WO2019203134A1 - Polymerizable composition and method for producing three-dimensional modeled object - Google Patents

Abstract

The present invention addresses the problem of providing a polymerizable composition which enables the production of a three-dimensional modeled object having an excellent flame retardancy. The polymerizable composition (10) according to the present invention, which is to be used for producing a three-dimensional modeled object, comprises a photopolymerizable compound in a liquid state, a flame retardant and a flame retardant protector. The method for producing a three-dimensional modeled object is characterized by comprising steps (a) to (c): (a) a step for supplying oxygen into a modeling tank (20) in which the polymerizable composition (10) is contained through an oxygen-permeable and active energy ray-permeable base material (21); (b) a step for curing the polymerizable composition (10) by irradiating an active energy ray, said active energy ray having permeated through a buffer area (11) in which curing of the polymerizable composition (10) is inhibited by oxygen, selectively to a curing area (12) in which the oxygen concentration is lower and thus the polymerizable composition (10) can be cured; and (c) a step for continuously irradiating the active energy ray while moving the cured polymerizable composition (10) and thus three-dimensionally and continuously shaping a modeled object formed of the cured polymerizable composition.

Description

Polymerizable composition and method for producing three-dimensional structure

The present invention relates to a polymerizable composition and a method for producing a three-dimensional model, and more particularly to a polymerizable composition and a method for manufacturing a three-dimensional model that can produce a three-dimensional model having excellent flame retardancy.

Conventionally, stereolithography has been used as a method for producing prototypes at low cost and in a short period of time without the need for a mold, but in recent years, with the progress of materials and modeling technology, application to final products seems to be required It has become.
Among stereolithography, the continuous liquid interface production (CLIP) method, in which light irradiation is performed while forming a curing inhibition layer by oxygen, has a high modeling speed and does not form a laminated structure. In recent years, it has attracted attention because of its high strength. However, while there are many parts that are required to have flame retardancy in electrical and electronic parts, automobile parts, and the like, the method disclosed in the patent document has not yet yielded a three-dimensional molded article having sufficient flame retardancy.

In stereolithography, it is known to add a flame retardant to a material (for example, refer to Patent Document 3), but in the CLIP method, active energy rays (ultraviolet rays) with relatively high intensity are irradiated in the presence of oxygen. Therefore, it has been found that there is a problem that the halogen-based and phosphorus-based flame retardant decomposes and the metal hydroxide-based flame retardant is oxidized, so that it cannot perform a sufficient function as a flame retardant.

In addition, it is possible to greatly improve the strength of the three-dimensional modeled object by adding a filler, but since the viscosity of the polymerizable composition is increased by adding a filler, modeling that is being formed under the modeling stage It takes a lot of time to fill the uncured polymerizable liquid between the lowermost layer of the product and the substrate. This is not preferable in that the modeling time becomes long. As a means for solving this problem, it is conceivable to increase the amount of oxygen supply to increase the thickness of the polymerization-inhibiting layer and secure a fluidized bed having a sufficient thickness. However, in order to cure the polymerizable liquid in the lowermost layer through a thicker polymerization inhibiting layer, it is necessary to irradiate ultraviolet rays with stronger power. At this time, since the polymerizable liquid is irradiated with higher energy ultraviolet rays under a higher oxygen concentration, the flame retardant is exposed to a harsher environment and tends to be unable to exhibit its function due to decomposition or oxidative degradation. There is a problem.

Special table 2016-509962 gazette Special table 2016-509964 JP 2007-262401 A

This invention is made | formed in view of the said problem and the situation, The solution subject is providing the manufacturing method of the polymeric composition which can manufacture the three-dimensional molded item which is excellent in a flame retardance, and a three-dimensional molded item. It is.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, by containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, flame retardant The present inventors have found that it is possible to provide a polymerizable composition and a method for producing a three-dimensional modeled product that can produce a three-dimensional modeled product that is superior to the present invention.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. A polymerizable composition used for manufacturing a three-dimensional model,
A polymerization comprising a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, and the method for producing a three-dimensional structure includes the following steps (a) to (c): Sex composition.
(A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A step of continuously and three-dimensionally forming a shaped article formed by curing the polymerizable composition by continuously irradiating the active energy ray while moving the polymerizable composition

2. 2. The polymerizable composition according to item 1, wherein the photopolymerizable compound is a compound having a (meth) acryloyl group.

3. Item 3 or Item 2 is characterized in that the flame retardant is at least one selected from a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, and a metal hydroxide flame retardant. A polymerizable composition.

4. The flame retardant protecting agent is at least one selected from phenolic antioxidants, phosphite antioxidants, thiol antioxidants, and amine light stabilizers. The polymerizable composition according to any one of items 3 to 3.

5. The polymerizable composition according to any one of items 1 to 4, further comprising a liquid heat-polymerizable compound.

6). The flame retardant is at least one selected from a halogen flame retardant, a phosphorus flame retardant and a nitrogen flame retardant;
The polymerizable composition according to any one of Items 1 to 5, wherein the flame retardant protecting agent is an amine light stabilizer.

7). The flame retardant content is in the range of 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition,
The polymerizable property according to item 6, wherein the content of the flame retardant protecting agent is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition. Composition.

8). The flame retardant is a metal hydroxide flame retardant,
The flame retardant protecting agent is at least one selected from a phenol-based antioxidant, a phosphite-based antioxidant, and a thiol-based antioxidant. The polymerizable composition according to one item.

9. The flame retardant content is in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition,
The polymerization according to item 8, wherein the content of the flame retardant protecting agent is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition. Sex composition.

10. Furthermore, a filler is contained, The polymerizable composition as described in any one of 1st term | claim to 9th term | claim characterized by the above-mentioned.

11. A method for producing a three-dimensional structure using a polymerizable composition,
The polymerizable composition is the polymerizable composition according to any one of items 1 to 10,
Including the following steps (a) to (c), and
In the step (b), an active energy ray in the range of 1 to 200 mW / cm ² is irradiated.
(A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A step of continuously and three-dimensionally forming a shaped article formed by curing the polymerizable composition by continuously irradiating the active energy ray while moving the polymerizable composition

12 In the step of supplying oxygen, a permeation flux of oxygen into the modeling tank is set within a range of 3.4 × 10 ³ to 170 × 10 ³ kmol / (s · m ² ). The manufacturing method of the three-dimensional molded item of Item 11.

The above-mentioned means of the present invention can provide a polymerizable composition and a method for producing a three-dimensional structure that can produce a three-dimensional structure that is excellent in flame retardancy.

The expression mechanism / action mechanism of the effect of the present invention is presumed as follows.

The polymerizable composition of the present invention contains a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent.
As described above, in the CLIP method, active energy rays (ultraviolet rays) having relatively high intensity are irradiated in the presence of oxygen. In such a case, if a flame retardant is added to the material in order to impart flame retardancy, the flame retardant decomposes or deteriorates due to ultraviolet rays, and the function as a flame retardant cannot be fully exhibited. .
Therefore, in the present invention, by adding a flame retardant protecting agent in addition to the flame retardant, the flame retardant is prevented from being decomposed or oxidatively deteriorated even when irradiated with relatively strong ultraviolet rays under supply of oxygen. It is considered that sufficient flame retardancy can be imparted to the formed three-dimensional model.

Schematic as an example of a manufacturing apparatus applicable to the manufacturing method of the three-dimensional molded item of this invention Schematic showing the oxygen concentration distribution in the vicinity of the substrate 21

The polymerizable composition of the present invention is a polymerizable composition used for the production of a three-dimensional structure, and includes a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, and The method for producing a shaped article includes the following steps (a) to (c).
(A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A process of forming a three-dimensionally and continuously formed article formed by curing the polymerizable composition by continuously irradiating the active energy rays while moving the polymerizable composition. It is a technical feature common to the invention which concerns on a form.

As an embodiment of the present invention, the photopolymerizable compound is preferably a compound having a (meth) acryloyl group from the viewpoint of enabling curing with a small amount of light or a short time.

The flame retardant is preferably at least one selected from a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, and a metal hydroxide flame retardant.

The flame retardant protective agent is preferably at least one selected from a phenolic antioxidant, a phosphite antioxidant, a thiol antioxidant, and an amine light stabilizer.

Further, from the viewpoint of imparting heat resistance to the three-dimensional structure (improving the deflection temperature under load), it is preferable to further contain a liquid thermopolymerizable compound.

Further, it is preferable that the flame retardant is at least one selected from a halogen flame retardant, a phosphorus flame retardant, and a nitrogen flame retardant, and the flame retardant protecting agent is an amine light stabilizer. Since the organic flame retardant is mainly decomposed by light, the decomposition of the organic flame retardant can be suppressed by combining with the light stabilizer.
In this case, from the viewpoint of the expression of flame retardancy and suppression of deterioration of mechanical properties, the content of the flame retardant is in the range of 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition, The content of the flame retardant protecting agent is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition.

The flame retardant is a metal hydroxide flame retardant, and the flame retardant protective agent is at least one selected from a phenol antioxidant, a phosphite antioxidant, and a thiol antioxidant. Is preferred. Inorganic (hydroxide) flame retardants are oxidatively deteriorated mainly by oxygen. Therefore, when combined with an antioxidant, oxidative deterioration of inorganic flame retardants can be suppressed.
In this case, the content of the flame retardant is within the range of 5 to 50 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition, from the viewpoint of the expression of flame retardancy and the suppression of the deterioration of mechanical properties. The content of the flame retardant protecting agent is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition.

Moreover, it is preferable to further contain a filler from the viewpoint of improving the strength of the three-dimensional structure.

The present invention is a method for producing a three-dimensional structure using a polymerizable composition, wherein the polymerizable composition is the polymerizable composition of the present invention, and includes the following steps (a) to (c): In the step (b), it is possible to provide a method for producing a three-dimensional structure characterized by irradiating active energy rays within a range of 1 to 200 mW / cm ² .
(A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A step of continuously and three-dimensionally forming a shaped article formed by curing the polymerizable composition by continuously irradiating the active energy ray while moving the polymerizable composition

As an embodiment of the present invention, from the viewpoint of obtaining a resin fluidized bed having a sufficient thickness by ensuring an appropriate thickness of the polymerization-inhibiting layer, oxygen permeation into the modeling tank is performed in the step of supplying oxygen. The flux is preferably in the range of 3.4 × 10 ³ to 170 × 10 ³ kmol / (s · m ² ).

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.

<< Polymerizable composition >>
The polymerizable composition of the present invention is a polymerizable composition used for the production of a three-dimensional structure, and includes a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, and The method for producing a shaped article includes the following steps (a) to (c).

(A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A step of continuously and three-dimensionally forming a shaped article formed by curing the polymerizable composition by continuously irradiating the active energy ray while moving the polymerizable composition

Hereinafter, various materials included in the polymerizable composition of the present invention will be described.

<Photopolymerizable compound>
The photopolymerizable compound according to the present invention is not particularly limited as long as it is a liquid that is liquid at normal temperature (25 ° C.) and radically polymerizes and cures when irradiated with active energy rays. The photopolymerizable compound may be a monomer, an oligomer, a prepolymer, or a mixture thereof. The polymerizable composition may contain only one type of photopolymerizable compound or two or more types.

The type of the photopolymerizable compound is not particularly limited as long as it has a radical polymerizable group by irradiation with active energy rays. For example, an ethylene group, a propenyl group, a butenyl group, a vinylphenyl group, an allyl ether group. , Vinyl ether groups, maleyl groups, maleimide groups, (meth) acrylamide groups, acetyl vinyl groups, vinyl amide groups, (meth) acryloyl groups and the like in the molecule. Among these, an unsaturated carboxylic acid ester having at least one unsaturated carboxylic acid ester structure in the molecule is preferable, and a (meth) acrylate compound including a (meth) acryloyl group is particularly preferable.
In addition, description with "(meth) acryl" represents methacryl and / or acryl, description with "(meth) acryloyl" represents methacryloyl and / or acryloyl, and description with "(meth) acrylate" , Methacrylate and / or acrylate.

Compounds having an allyl ether group include phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl Ether, cyclohexanemethanol monoallyl ether, diallyl ether phthalate, diallyl ether isophthalate, dimethanol tricyclodecane diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, alkylene (2 to 5 carbon atoms) glycol diallyl ether, polyethylene glycol Diallyl ether, glycerol diallyl ether, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, polyglycerol (polymerization) 2-5) diallyl ether, trimethylolpropane triallyl ether, glyceryl triallyl ether, pentaerythritol tetraallyl ether and tetraallyloxyethane, pentaerythritol triallyl ether, diglyceryl triallyl ether, sorbitol triallyl ether, polyglycerin ( Polymerization degree 3 to 13) and polyallyl ether.

Examples of the compound having a vinyl ether group include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, 1,4-butanediol divinyl ether, ethylhexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, Cyclohexyl vinyl ether, tricyclodecane vinyl ether, adamantyl vinyl ether, cyclohexanedimethanol divinyl ether, tricyclodecane dimethanol divinyl ether, EO adduct divinyl ether of bisphenol A, cyclohexanediol divinyl ether, cyclopentadiene vinyl ether, norbornyl dimethanol divinyl ether Divinyl resorcinol, divinyl hydroquinone, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether, 4-cyclohexane divinyl ether, oxanorvo Nandivinyl ether, Neopentylglycol divinyl ether, Glycerin trivinyl ether, Oxetane divinyl ether, Glycerin ethylene oxide adduct trivinyl ether (addition mole number of ethylene oxide 6), Trimethylolpropane trivinyl ether, Trivinyl ether ethylene oxide adduct trivinyl ether (Ethylene ether) Sid addition mole number 3), pentaerythritol trivinyl ether, ditrimethylolpropane hexa ether and oxyethylene adducts thereof and the like.

Examples of the compound having a maleimide group include phenylmaleimide, cyclohexylmaleimide, n-hexylmaleimide and the like.

Examples of the compound having a (meth) acrylamide group include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide. , N-butyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, bismethylene acrylamide, di (ethyleneoxy) bispropylacrylamide, tri (ethyleneoxy) bispropylacrylamide, (meth) acryloylmorpholine Etc.

(Meth) acrylate compounds include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, and isooctyl (meth) acrylate. , Isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate 2-ethylhexyl-diglycol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, methoxyethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, benzyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2- Ethylhexyl carbitol (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalate Monofunctional (meth) acrylate monomers including phosphoric acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, t-butylcyclohexyl (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, cyclohexanedi (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, neopentylglycol di (meth) acrylate, Cyclodecanediyldimethylene di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, polyester di (meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) Bifunctional (meth) acrylate monomers including acrylate, polytetramethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, etc. , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol ethoxytetra (meth) Trifunctional or higher-functional (meth) acrylate monomers including acrylates, oligomers and prepolymers thereof, and the like can be given.

Further, the (meth) acrylate compound may be a product obtained by further modifying various (meth) acrylate monomers or oligomers thereof (modified product). Modified products include triethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified Ethylene oxide modified (meth) acrylate monomers such as nonylphenol (meth) acrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified Glycerin tri (meth) ac Propylene oxide modified (meth) acrylate monomers such as rate, caprolactone modified (meth) acrylate monomers such as caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactam modified (meth) acrylates such as caprolactam modified dipentaerythritol hexa (meth) acrylate And monomers.

The (meth) acrylate compound may be a compound (hereinafter also referred to as a modified (meth) acrylate compound) in which various oligomers are (meth) acrylated. Such modified (meth) acrylate compounds include polybutadiene (meth) acrylate oligomers, polyisoprene (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, urethane (meth) acrylate compounds, and silicone (meth) acrylate compounds. , Polyester (meth) acrylate oligomers, linear (meth) acryl oligomers, and the like. Among these, epoxy (meth) acrylate compounds, urethane (meth) acrylate compounds, and silicone (meth) acrylate compounds can be preferably used.

The epoxy (meth) acrylate compound may be a compound containing one or more epoxy groups and (meth) acrylate groups in one molecule. For example, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy ( Novolak type epoxy (meth) acrylates such as (meth) acrylate, bisphenyl type epoxy (meth) acrylate, triphenolmethane type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, phenol novolak type epoxy (meth) acrylate, etc. Etc.

Urethane (meth) acrylate compounds include aliphatic polyisocyanate compounds having two or more isocyanate groups or aromatic polyisocyanate compounds having two or more isocyanate groups, (meth) acrylic acid derivatives having hydroxy groups, and the like. It can be set as the compound which has a urethane bond and (meth) acryloyl group obtained by making this react.

Examples of the isocyanate compound used as a raw material for the urethane (meth) acrylate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4 ′. Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) ) Thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate Sulfonates, and the like.
In addition, chain-extended isocyanate compounds obtained by reaction of polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate compounds Can be mentioned.

Examples of (meth) acrylic acid derivatives having a hydroxy group that are raw materials for urethane (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 2, hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Mono (meth) acrylates of divalent alcohols, mono (meth) acrylates and di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, bisphenol A type epoxy acrylate Epoxy (meth) acrylate and the like.

Urethane (meth) acrylate compounds may be commercially available, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all manufactured by Daicel-Orunekusu Co., Ltd.), Art resin UN-330, Art resin SH-500B, Art Resin UN-1200TPK, A Toresin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Kogyo Co., Ltd.), U-2HA, U-2PHA, U-3HA, U -4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all of which are Shin-Nakamura Chemical Manufactured by Kogyo Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA- 06H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.).

The urethane (meth) acrylate compound may be a blocked isocyanate obtained by blocking the isocyanate group of polyisocyanate with a blocking agent having a (meth) acrylate group.

The polyisocyanate used to obtain the blocked isocyanate may be an isocyanate compound that is a raw material of the above-mentioned “urethane (meth) acrylate compound, and is a compound obtained by reacting these compounds with a polyol or polyamine. Also good.
Examples of the polyol include conventionally known polyether polyols, polyester polyols, polymer polyols, vegetable oil polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. One of these polyols may be contained in the blocked isocyanate, or two or more thereof may be contained.

Polyether polyols to be reacted with isocyanates and the like include compounds having at least two or more active hydrogen groups (specifically, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and pentaerythritol, ethylenediamine) And amine compounds such as ethanolamine and diethanolamine) and an alkylene oxide (specifically, ethylene oxide, propylene oxide, etc.).
A method for synthesizing a polyether polyol is described in, for example, Gunter Oertel, “Polyurethane Handbook” (1985) Hanser Publishers (Germany), p. Reference may be made to the methods described in 42-53.

Polyester polyols include condensation reaction products of polyvalent carboxylic acids such as adipic acid and phthalic acid with polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and at the time of nylon production. Examples include wastes, trimethylolpropane, pentaerythritol wastes, phthalic polyester wastes, polyester polyols obtained by treating and inducing wastes (for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. .117, see description).

Examples of the polymer polyol include a polymer polyol obtained by reacting a polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. As the polymer polyol, those having a molecular weight of about 5000 to 12000 are particularly preferred.

Examples of vegetable oil polyols include hydroxy group-containing vegetable oils such as castor oil and palm oil. A castor oil derivative polyol obtained using castor oil or hydrogenated castor oil as a raw material can also be suitably used. The castor oil derivative polyol includes castor oil polyester obtained by reaction of castor oil, polyvalent carboxylic acid and short chain diol, and an alkylene oxide adduct of castor oil and castor oil polyester.

Flame retardant polyols include phosphorus-containing polyols obtained by adding alkylene oxide to phosphoric acid compounds, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide, and alkylene oxides for active hydrogen compounds having aromatic rings. And aromatic ether polyols obtained by condensation reaction of polyvalent carboxylic acids having aromatic rings and polyhydric alcohols.

The hydroxy value (hydroxyl value) of the polyol to be reacted with isocyanate or the like is preferably within the range of 5 to 300 mgKOH / g, and more preferably within the range of 10 to 250 mgKOH / g. The hydroxy value can be measured by a method defined in JIS K 0070: 1992.

Polyamines to be reacted with isocyanate and the like include ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenepentamine, bisaminopropylpiperazine, tris (2-aminoethyl) amine, isophoronediamine, polyoxyalkylenepolyamine, diethanolamine, triethanolamine Examples include ethanolamine.

Any blocking agent for blocking the isocyanate group of the polyisocyanate may be used as long as it has a (meth) acryloyl group and can react with the isocyanate group and be removed by heating.
Examples of such blocking agents include t-butylaminoethyl methacrylate (TBAEMA), t-pentylaminoethyl methacrylate (TPAEMA), t-hexylaminoethyl methacrylate (THAEMA), t-butylaminopropyl methacrylate (TBAPMA) and the like. It is done.

The blocking reaction of polyisocyanate can be generally carried out at −20 to 150 ° C., preferably 0 to 100 ° C. If it is 150 ° C. or lower, side reactions can be prevented, while if it is −20 ° C. or higher, the reaction rate can be in an appropriate range.

The blocking reaction between the polyisocyanate and the blocking agent can be performed regardless of the presence or absence of a solvent. When using a solvent, it is preferable to use an inert solvent for the isocyanate group.
In the blocking reaction, a reaction catalyst can be used. Specific reaction catalysts include organic metal salts such as tin, zinc and lead, metal alkoxides, tertiary amines and the like.

When the blocked isocyanate prepared as described above is used as a photopolymerizable compound, first, the acryloyl group portion is polymerized by light irradiation. Thereafter, the block agent is removed by heating, and the generated isocyanate is newly polymerized with a polyol, polyamine, or the like, whereby a three-dimensional structure including polyurethane, polyurea, or a mixture thereof can be obtained.

The silicone (meth) acrylate compound can be a compound having a polysiloxane bond in the main chain and (meth) acrylic acid added to the terminal and / or side chain. The silicone used as a raw material for the silicone (meth) acrylate compound is an organopolysiloxane obtained by polymerizing a known monofunctional, bifunctional, trifunctional or tetrafunctional silane compound (for example, alkoxysilane) in any combination. Can do.

Specific examples of silicone acrylates include commercially available TEGORad 2500 (trade name, manufactured by Tego Chemie Service GmbH), and organic modification having a hydroxy group such as X-22-4015 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Reaction of acrylic acid with organically modified silane compounds such as epoxy silane such as KBM402 and KBM403 (trade names, both manufactured by Shin-Etsu Chemical Co., Ltd.) And the like.

(Photopolymerization initiator)
The polymerizable composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by irradiation with active energy rays and capable of polymerizing a photopolymerizable compound, and is a known radical polymerization initiator. be able to.

As the radical polymerization initiator, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, IRGACURE 907 (“IRGACURE” is a registered trademark of the company), etc.), 2 -Hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF, IRGACURE 1173 ("IRGACURE" is a registered trademark of the company), etc.), 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (manufactured by BASF, IRGACURE 127, etc.), 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propan-1-one (manufactured by BASF, IRGACURE 2959, etc.), 2 2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, IRGACURE 651, etc.), benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, benzoin, benzoin methyl ether, benzoin isopropyl ether, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,4) 6-Trimethylbenzoyl) -pheni Phosphine oxide, benzyl, methylphenylglyoxyester, benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylic Benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2,4-dichlorothioxanthone, mihira-ketone, 4,4'-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-fe Examples include nanthrenequinone, camphorquinone, and 2,4-diethyloxanthen-9-one.

The radical polymerization initiator is preferably contained within a range of 0.01 to 10% by mass, and within a range of 0.1 to 5% by mass with respect to the total mass (100% by mass) of the polymerizable composition. More preferably, it is contained in the range of 0.3 to 3% by mass. When the radical polymerization initiator is contained within the range, the photopolymerizable compound can be efficiently polymerized.

<Flame retardants>
The polymerizable composition of the present invention is characterized by containing a flame retardant.
The flame retardant is not particularly limited as long as it can impart flame retardancy to the three-dimensional structure to be formed. For example, halogen flame retardant, phosphorus flame retardant, nitrogen flame retardant, metal hydroxide flame retardant Etc. These may be used individually by 1 type, or may use 2 or more types together.

Examples of halogen flame retardants include bromine compounds and chlorine compounds, but chlorine compounds are not preferred due to toxicity problems. Examples of bromine compounds include p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetradecabromo-p-diphenoxybenzene, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, 2, 2'-ethylenebis (4,5,6,7-tetrabromoisoindoline-1,3-dione (for example, SAYTEX BT-93 (manufactured by Albemarle)), ethane-1,2-bis (penta Bromophenyl) (for example, SAYTEX 8010 (manufactured by Albemarle)), brominated epoxy oligomers (for example, SR-T1000, SR-T2000 (manufactured by Sakamoto Yakuhin Kogyo), etc.), and Fire Cut P as commercially available products -801 (Suzuhiro Chemical Co., Ltd. Etc. The, but not limited thereto.

The content of the halogen-based flame retardant is appropriately selected depending on the type of the halogen-based flame retardant, other components in the polymerizable composition, and the desired degree of flame retardancy. For example, the content of the polymerizable flame retardant It is preferable that the halogen content is contained in a range of 5 to 15% by mass with respect to 100% by mass of the total solid content (nonvolatile content).

Moreover, when using a halogen flame retardant as a flame retardant, as a flame retardant aid, for example, antimony compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide , Molybdenum compounds such as molybdenum oxide, ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, boron compounds such as zinc borate and barium metaborate, silicone oil, silane coupling agent, high molecular weight silicone, etc. These silicon compounds, chlorinated polyethylene, etc. may be used in combination.

Examples of phosphorus-based flame retardants include polyphosphate compounds such as melamine polyphosphate, aromatic phosphate esters, and aromatic condensed phosphate esters. Specifically, phosphoric acids such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate Salt-based compounds and polyphosphate-based compounds, red phosphorus, organophosphates, phosphazenes, phosphonic acids, phosphinic acids, phosphine oxides, phosphoranes, phosphoramides, and commercially available products such as Hishigard Select N-6ME (manufactured by Nippon Chemical Industry Co., Ltd.) ) Etc. can be used.

Nitrogen flame retardants include melamine compounds such as melamine cyanurate, triazine, guanidine and the like. Specifically, melamine compounds such as melamine, melam, melem, melon, melamine cyanurate (for example, melamine cyanurate MC-4000 (manufactured by Nissan Chemical Industries, Ltd.)), cyanuric acid, isocyanuric acid, triazole compound, Tetrazole, a diazo compound, urea, etc. can be used.

Examples of the metal hydroxide flame retardant include aluminum hydroxide, magnesium hydroxide (for example, Kisuma 5E (manufactured by Kyowa Chemical Industry Co., Ltd.)), basic magnesium carbonate, calcium hydroxide, hydrotalcites and the like.

<Flame retardant protective agent>
The polymerizable composition of the present invention contains a flame retardant protecting agent for the purpose of protecting the flame retardant.
Examples of the flame retardant protecting agent include phenolic antioxidants, phosphite antioxidants, thiol antioxidants, and amine light stabilizers. In particular, when a halogen flame retardant, phosphorus flame retardant or nitrogen flame retardant is used as the flame retardant, the flame retardant protective agent is preferably an amine light stabilizer, When a physical flame retardant is used, the flame retardant protective agent is preferably a phenolic antioxidant, a phosphite antioxidant, or a thiol antioxidant.
A flame retardant protective agent may be used individually by 1 type, or may use 2 or more types together.

When a halogen-based flame retardant, a phosphorus-based flame retardant or a nitrogen-based flame retardant is used as the flame retardant, and an amine light stabilizer is used as the flame retardant protective agent, the content of the flame retardant is 100 mass of the resin component in the polymerizable composition. The content of the flame retardant protecting agent is preferably in the range of 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition. It is preferable to be within the range.
If the content of the flame retardant is 2 parts by mass or more, sufficient flame retardancy is exhibited, and if it is 20 parts by mass or less, a decrease in mechanical strength due to addition of the flame retardant can be sufficiently suppressed. In addition, if the content of the flame retardant protective agent is 0.1 parts by mass or more, the function of protecting the flame retardant is expressed, and if it is 5 parts by mass or less, the mechanical strength is sufficiently reduced by adding the flame retardant protective agent. Can be suppressed.

On the other hand, when using a metal hydroxide flame retardant as the flame retardant and a phenolic antioxidant, phosphite antioxidant or thiol antioxidant as the flame retardant protective agent, the flame retardant content is polymerized. The content of the flame retardant protecting agent is preferably in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition. The content is preferably in the range of 0.1 to 5 parts by mass.
If the content of the flame retardant is 5 parts by mass or more, sufficient flame retardancy is exhibited, and if it is 50 parts by mass or less, a decrease in mechanical strength due to addition of the flame retardant can be sufficiently suppressed. In addition, if the content of the flame retardant protective agent is 0.1 parts by mass or more, the function of protecting the flame retardant is expressed, and if it is 5 parts by mass or less, the mechanical strength is sufficiently reduced by adding the flame retardant protective agent. Can be suppressed.

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-t-butyl- 4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m) -Cresol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (6-t -Butyl-m-cresol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-t) Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t- Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3 5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, thio Ethylene glycol bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], Bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl) -5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1 -Dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetra Oxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], and commercially available products such as ADK STAB AO-20 (manufactured by ADEKA), etc. .

Examples of phosphite antioxidants include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite. , Tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t -Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol Diphosphite, bis (2,4-dicumylphenyl) Intererythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, tetrakis (2,4-di-t-butylphenyl) biphenylene diphosphonite, 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-t-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6 -T-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebi (4,6-di-t-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis-t-butyldibenzo [d, f] [1,3,2] dioxa Phosphopin-6-yl) oxy] ethyl) amine, 2,4,6-tri-t-butylphenol phosphite, tris (2,4-di-t-butylphenyl) phosphite, Examples include ADK STAB PEP-36 (manufactured by ADEKA).

Examples of thiol-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, pentaerythritol tetra (β-alkylthiopropionate), and commercially available Examples of the product include Sumilizer TPM (dimyristyl-3,3′-thiodipropionate) (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of amine light stabilizers include hindered amine light stabilizers. Examples of hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6. -Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis ( 1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxyl , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetra Lamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1 , 2,3,4-Butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-t-butyl-4- Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6, 6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) ) Hexane 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6 -Tetramethyl-4-piperidyl) amino) -sec-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N- Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -sec-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -sec-triazin-6-yl] aminoundecane, 1,6,11 Tris [2,4-bis (N-butyl-N- (1,2, 2,6,6-Pentamethyl-4-piperidyl) amino) -sec-triazin-6-yl] aminoundecane and commercially available products include ADK STAB LA-52 (manufactured by ADEKA).

<Thermal polymerizable compound>
The polymerizable composition according to the present invention preferably contains a thermally polymerizable compound.
The thermopolymerizable compound is not particularly limited as long as it is a liquid at room temperature (25 ° C.) and polymerizes by heat.
Examples of such a thermally polymerizable compound include a compound containing at least one group selected from the group consisting of a cyclic ether group, a cyanate group, an isocyanate group, and a hydrosilyl group.

Examples of the compound having a cyclic ether group include compounds containing epoxide, oxetane, tetrahydrofuran, tetrahydropyran and the like. Among these, from the viewpoint of polymerizability and the like, a compound having an epoxy group (hereinafter also referred to as an epoxy compound) is preferable.
Examples of the epoxy compound include an epoxy compound having one or two or more epoxy groups in the molecule. For example, biphenyl type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, stilbene type epoxy compound, crystalline epoxy compound such as hydroquinone type epoxy compound, cresol novolac type epoxy compound, phenol novolac type epoxy compound, naphthol novolak type Novolak epoxy compounds such as epoxy compounds, phenol aralkyl epoxy compounds containing phenylene skeleton, phenol aralkyl epoxy compounds containing biphenylene skeleton, phenol aralkyl epoxy compounds such as phenylene skeleton naphthol aralkyl epoxy compounds, triphenolmethane epoxy compounds, Alkyl-modified triphenol methane type epoxy compound, glycidylamine, tetrafunctional naphthalene type Polyfunctional epoxy compounds such as poxy compounds, dicyclopentadiene modified phenolic epoxy compounds, terpene modified phenolic epoxy compounds, modified phenolic epoxy compounds such as silicone modified epoxy compounds, and heterocyclic containing epoxy compounds such as triazine nucleus-containing epoxy compounds And naphthylene ether type epoxy.

The compound having a cyanate group may be a compound having one or more cyanate groups in the molecule. For example, 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (4 -Cyanatophenyl) propane, 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (3-dibromo-4-dicyanatophenyl) propane, bis (4-si Anatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, bi (3-chloro-4-cyanatophenyl) methane, 4-cyanatobiphenyl, 4-cumylcyanatobenzene, 2-t-butyl-1,4-dicyanatobenzene, 2,4-dimethyl-1,3- Dicyanatobenzene, 2,5-di-t-butyl-1,4-dicyanatobenzene, tetramethyl-1,4-dicyanatobenzene, 4-chloro-1,3-dicyanatobenzene, 3,3 ′, 5,5′-tetramethyl-4,4′-dicyanatodiphenylbis (3-chloro-4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1- Bis (4-cyanatophenyl) ethane, 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, Screw (p- Ano phenoxyphenoxy) benzene, di (4-cyanatophenyl) ketone, cyan oxide novolac include cyan oxide bisphenol polycarbonate oligomer. *

The compound having an isocyanate group is not particularly limited as long as it has one or two or more isocyanate groups in the molecule. For example, aromatic compounds such as tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, and diphenylmethane diisocyanate. Diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, alicyclic diisocyanate such as diisocyanate methylcyclohexane, aliphatic diisocyanate such as hexamethylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, trimethylolpropane and Hexamethylene diisocyanate 1: 3 adduct, hexamethylene diisocyanate Trifunctional or higher polyisocyanates such as cyclic trimers of socyanates, and blocking agents for isocyanate groups of these compounds (eg alcohols, phenols, lactams, oximes, acetoacetic acid alkyl esters, malonic acid alkyl esters) , Phthalimides, imidazoles, hydrogen chloride, hydrogen cyanide, sodium hydrogen sulfite and the like).

The compound having a hydrosilyl group may be a compound having one or more hydrosilyl groups in the molecule, and examples thereof include a methylhydrosiloxane-dimethylsiloxane copolymer.
A compound having a hydrosilyl group can be obtained by addition reaction with a polyorganosiloxane having a vinyl group at the terminal or side chain. Examples of the polysiloxane having a vinyl group include polydimethylsiloxane having a vinyl group substituted at each terminal silicon atom, a dimethylsiloxane-diphenylsiloxane copolymer having a vinyl group substituted at each terminal silicon atom, and a vinyl group at each terminal silicon atom. Examples thereof include substituted polyphenylmethylsiloxane, vinylmethylsiloxane-dimethylsiloxane copolymer having a trimethylsilyl group at each end, and the like.

(Curing agent, curing accelerator)
When the polymerizable composition contains a thermopolymerizable compound, it is preferable that a curing agent or a curing accelerator for curing the thermopolymerizable compound is further contained. The type of the curing agent and the curing accelerator is appropriately selected according to the type of the thermopolymerizable compound.

Curing agents and accelerators include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, N, N-dimethyl-n-octylamine, dicyanodiamide and other amino acids, aniline modified resole resin Resol type phenol resins such as dimethyl ether resol resin, phenol novolac resin, cresol novolak resin, t-butylphenol novolak resin, novolac type phenol resin such as nonylphenol novolak resin, phenol such as phenylene skeleton-containing phenol aralkyl resin, phenol aralkyl resin containing biphenylene skeleton Aralkyl resins, phenol resins having a condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton, polyoxystyrene such as polyparaoxystyrene, alicyclic such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Aromatics such as acid anhydride, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA) Acid anhydrides including anhydrides, polymercaptan compounds such as polysulfides, thioesters, thioethers, isocyanate prepolymers, isocyanate compounds such as blocked isocyanates, organic acids such as carboxylic acid-containing polyester resins, zinc naphthenates, cobalt naphthenates And organic metal salts such as tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), and zinc acetylacetonate.
Only 1 type of these hardening | curing agents and hardening accelerators may be contained in polymeric composition, and 2 or more types may be contained.
The amount of the curing agent and the curing accelerator is appropriately selected according to the type and amount of the thermally polymerizable compound.

<Filler>
The polymerizable composition of the present invention preferably contains a filler. The filler contained in the polymerizable composition is not particularly limited, and may be an organic filler or an inorganic filler.
Only 1 type of filler may be contained and 2 or more types may be contained.

As filler, glass filler made of soda-lime glass, silicate glass, borosilicate glass, aluminosilicate glass, quartz glass, etc., alumina, zirconium oxide, titanium oxide, lead zirconate titanate, silicon carbide, silicon nitride, aluminum nitride , Ceramic fillers made of tin oxide, etc., metal fillers made of simple metals such as iron, titanium, gold, silver, copper, tin, lead, bismuth, cobalt, antimony, cadmium, or alloys thereof, graphite, graphene, carbon Carbon filler made of nanotubes, polyester, polyamide, polyaramid, polyparaphenylene benzobisoxazole, organic polymer fiber made of polysaccharides, potassium titanate whisker, silicone carbide whisker, silicon night trial Whisker-like inorganic compound comprising whisker, α-alumina whisker, zinc oxide whisker, aluminum borate whisker, calcium carbonate whisker, magnesium hydroxide whisker, basic magnesium sulfate whisker, calcium silicate whisker, etc. Including single crystals.), Talc, mica, clay, wollastonite, hectorite, saponite, stevensite, hydelite, montmorillonite, nontrinite, bentonite, Na-type tetrasilicic fluorine mica, Li-type tetralithic fluorine mica, Na And clay minerals such as swellable mica, vermiculite, and the like of type fluorine teniolite and Li type fluorine teniolite. As the filler, polyolefin filler made of polyethylene, polypropylene, etc., FEP (tetrafluoroethylene-hexafluoropropylene copolymer), PFA (tetrafluoroethylene-perfluoroalkoxyethylene copolymer), ETFE (four And fluororesin filler made of ethylene fluoride (ethylene fluoride).

Among these, organic polymer fibers are preferable, and nanofibers made of polysaccharides are particularly preferable. Examples of the polysaccharide include cellulose, hemicellulose, lignocellulose, chitin, chitosan and the like. Among these, cellulose and chitin are preferable, and cellulose is more preferable from the viewpoint of further increasing the strength of the three-dimensional structure to be obtained.

A fibrous filler composed of cellulose, ie, cellulose nanofiber (hereinafter also simply referred to as “nanocellulose”), is a plant-derived fiber or mechanical defibrillation of plant cell walls, biosynthesis by acetic acid bacteria, 2, 2 , 6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) and other cellulose nanofibers mainly composed of fibrous nanofibrils obtained by oxidation or electrospinning with N-oxyl compounds. Nanocellulose is cellulose mainly composed of nanofibrils crystallized in a whisker shape (needle shape), which is obtained by mechanically defibrating plant-derived fibers or plant cell walls. It may be a nanocrystal or any other shape. Nanocellulose should just have cellulose as a main component and may contain lignin, hemicellulose, etc.

The shape of the filler is not particularly limited, and may be, for example, a fibrous shape (including a whisker shape) or a particulate shape, but is preferably a fibrous shape from the viewpoint of improving the strength of the three-dimensional structure. .
When the filler is particulate, the average particle size is preferably in the range of 0.005 to 200 μm, more preferably in the range of 0.01 to 100 μm, and in the range of 0.1 to 50 μm. More preferably. When the average particle size of the particulate filler is 0.1 μm or more, the strength of the three-dimensional structure is easily increased. On the other hand, when the average particle size is 50 μm or less, it becomes easy to form a three-dimensional modeled object with high definition. The average particle size can be measured by analyzing an image obtained by imaging the polymerizable composition with a transmission electron microscope (TEM).

On the other hand, when the filler is fibrous, the average fiber diameter is preferably in the range of 0.002 to 20 μm. When the average fiber diameter is 0.002 μm or more, the strength of the three-dimensional structure is easily increased. When the average fiber diameter is 20 μm or less, the filler does not excessively increase the viscosity of the polymerizable composition, and the accuracy of the three-dimensional structure tends to be good. The average fiber diameter of the filler is more preferably within a range of 0.005 to 10 μm, further preferably within a range of 0.01 to 8 μm, and particularly preferably within a range of 0.02 to 5 μm. preferable.

The average fiber length of the filler is preferably in the range of 0.2 to 200 μm. When the average fiber length is 0.2 μm or more, the strength of the three-dimensional model is easily increased. When the average fiber length is 200 μm or less, the filler is less likely to settle due to the entanglement of the fillers. The average fiber length of the filler is more preferably in the range of 0.5 to 100 μm, still more preferably in the range of 1 to 60 μm, and particularly preferably in the range of 1 to 40 μm.

The aspect ratio of the filler is preferably in the range of 10 to 10,000. If the aspect ratio is 10 or more, the strength of the three-dimensional structure tends to be higher. When the aspect ratio is 10,000 or less, the filler is hardly precipitated due to the entanglement between the fillers. The aspect ratio of the filler is more preferably in the range of 12 to 8000, further preferably in the range of 15 to 2000, and particularly preferably in the range of 18 to 800.

The average fiber diameter, average fiber length, and aspect ratio of the filler can be measured by analyzing an image obtained by imaging the polymerizable composition with a transmission electron microscope (TEM).

The amount of the filler contained in the polymerizable composition is preferably in the range of 1 to 50% by mass with respect to the total mass (100% by mass) of the polymerizable composition, and in the range of 5 to 40% by mass. It is more preferable that When the amount of the filler is within the above range, a three-dimensional model with high strength is easily obtained.

The filler may be surface-modified with a surface modifier having a functional group capable of reacting with a photopolymerizable compound or a thermopolymerizable compound. When the surface of the filler is modified, the adhesion between the filler and the photopolymerizable compound or between the filler and the thermopolymerizable compound is increased, and a three-dimensional model with higher strength is easily obtained. The surface modifier is not particularly limited as long as it has a group capable of reacting with a photopolymerizable compound or a thermopolymerizable compound and a group capable of binding to or adsorbing to a filler.

The groups and structures contained in the surface modifier that can be bonded to or adsorbed to the filler include Si atom, Ti atom, Zr atom, carboxy group, amino group, imino group, cyano group, azo group, azide group, Examples include thiol groups, sulfo groups, (meth) acryloyl groups, epoxy groups, and isocyanate groups. Of these, Si atoms, Ti atoms, and Zr atoms are preferable, and Si atoms are particularly preferable from the viewpoint of reactivity to the filler.
In addition, as a group capable of reacting with the photopolymerizable compound or the thermopolymerizable compound contained in the surface modifier, (meth) acryloyl group, amino group, imino group, epoxy group, glycidyl group, oxetanyl group, isocyanate group, Examples include a cyanate group, a vinyl group, a styryl group, a hydrosilyl group, a mercapto group, and a ureido group.

From the above, the surface modifier is preferably a silane coupling agent, a titanium coupling agent or a zirconium-based coupling agent, and particularly preferably a silane coupling agent.

Silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Compounds having reactive functional groups such as 3-isocyanatopropyltriethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrib Xysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dihexyldimethoxysilane, trihexylmethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane N-propyltriacetoxysilane, n-propyltrichlorosilane, 1-propyn-3-yltrimethoxysilane, 1-propyne-3-yltriethoxysilane, 1-propyn-3-yltributoxysilane, 2-cyclohexene Compounds having an aliphatic hydrocarbon group such as -1-yltriethoxysilane, 1,3-hexadiin-5-yltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Lan, naphthyltrimethoxysilane, naphthyltriethoxysilane, anthryltrimethoxysilane, phenanthryltrimethoxysilane, biphenyltrimethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, methylphenyldimethoxysilane, 2-methylbenzyltrimethoxy Examples thereof include compounds having an aromatic hydrocarbon group such as silane, 3-methylbenzyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, and silazane compounds such as hexamethyldisilazane.

Titanium coupling agents include methyl trimethoxy titanium, ethyl triethoxy titanium, n-propyl trimethoxy titanium, i-propyl triethoxy titanium, n-hexyl trimethoxy titanium, cyclohexyl triethoxy titanium, phenyl trimethoxy titanium, 3- Chloropropyltriethoxytitanium, 3-aminopropyltrimethoxytitanium, 3-aminopropyltriethoxytitanium, 3- (2-aminoethyl) -aminopropyltrimethoxytitanium, 3- (2-aminoethyl) -aminopropyltriethoxy Titanium, 3- (2-aminoethyl) -aminopropylmethyldimethoxytitanium, 3-anilinopropyltrimethoxytitanium, 3-mercaptopropyltriethoxytitanium, 3-isocyanatopropyltrimethoxytitanium Trialkoxytitaniums such as 3-glycidoxypropyltriethoxytitanium and 3-ureidopropyltrimethoxytitanium, dimethyldiethoxytitanium, diethyldiethoxytitanium, di-n-propyldimethoxytitanium, di-i-propyldiethoxytitanium Di-n-pentyldimethoxytitanium, di-n-octyldiethoxytitanium, di-n-cyclohexyldimethoxytitanium, diphenyldimethoxytitanium and the like.

Zirconium-based coupling agents include tri-n-butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl) Acetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, di-n-butoxy bis (acetylacetonate) zirconium and the like.

Among the above, a silane coupling agent having a reactive functional group is particularly preferable. The method for modifying the surface of the filler with the surface modifier is not particularly limited. For example, the filler is dispersed in an arbitrary solvent, the surface modifier is added to the dispersion, and the solvent is removed by filtration after stirring. And a method of heating and drying. When the surface of the filler is modified with the surface modifier, it is preferable to add about 0.1 to 5 parts by mass of the surface modifier to 100 parts by mass of the filler.

<Other ingredients>
In the polymerizable composition, a photosensitizer, a polymerization inhibitor, an ultraviolet ray can be used as long as it enables formation of a three-dimensional structure by irradiation with active energy rays and does not cause significant unevenness in strength in the resulting three-dimensional structure. Arbitrary additives, such as an absorber, antioxidant, coloring materials, such as dye and a pigment, an antifoamer, and surfactant, may further be contained.

<Method for preparing polymerizable composition>
The polymerizable composition is a mixture of a photopolymerizable compound, a flame retardant and a flame retardant protective agent, and a thermal polymerizable compound, a filler, a photopolymerization initiator, a curing agent, a curing accelerator, etc. in any order as necessary. Can be prepared.

A well-known apparatus can be used as an apparatus used for mixing the polymerizable composition. For example, Ultra Tarrax (manufactured by IKA Japan), TK homomixer (manufactured by Primix), TK pipeline homomixer (manufactured by Primics), TK Philmix (manufactured by Primix), Claremix (manufactured by M Technique), Medialess stirrers such as Claire SS5 (manufactured by M Technique), Cavitron (manufactured by Eurotech), Fine Flow Mill (manufactured by Taiheiyo Kiko), Viscomill (manufactured by IMEX), Apex Mill (manufactured by Kotobuki Industries), Star mill (Ashizawa, manufactured by Finetech), DCP Super Flow (manufactured by Nihon Eirich), MP Mill (manufactured by Inoue Mfg.), Spike mill (manufactured by Inoue Mfg.), Mighty mill (manufactured by Inoue Mfg.), SC mill (Mitsui) Media stirrers such as mining) and optimizers ( Ginomashin Inc.), manufactured by Starburst (Sugino Machine Limited), Nanomizer (manufactured by Yoshida Kikai), and a high-pressure impact type dispersing device such as NANO 3000 (manufactured by Bitsubusha).
Also, revolving mixers such as Awatori Nerita (Shinky) and Kaku Hunter (Photochemical), planetary mixers such as Hibismix (Primics) and Hibis Disper (Primics), Nanouptor An ultrasonic dispersion apparatus such as (manufactured by Sonic Bio) can also be suitably used.

<Method for manufacturing a three-dimensional model>
As a manufacturing method of the three-dimensional molded item of this invention, the method which has at least the following process is mentioned.

Step (a): Step of supplying oxygen into a modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays Step (b): The effect of the polymerizable composition is inhibited by oxygen A step of selectively irradiating a curing region where the polymerizable composition can be cured with a lower concentration of oxygen through the active energy ray transmitted through the buffer region to cure the polymerizable composition Step (c): Cured A process of forming a three-dimensionally and continuously formed article formed by curing the polymerizable composition by continuously irradiating active energy rays while moving the polymerizable composition.

In addition, you may have the process of irradiating an active energy ray further after a process (c). In addition, when the polymerizable composition contains a thermopolymerizable compound, following the step (c), after removing unnecessary resins and the like by washing or the like, heating is performed to heat the thermopolymerizable compound. You may have the process to harden.

Hereinafter, a manufacturing apparatus for a three-dimensional structure that can be used in the method for manufacturing a three-dimensional structure according to the present invention will be described.

(Manufacturing equipment)
As shown in FIG. 1, the manufacturing apparatus 1 of a three-dimensional model | molding object is the modeling tank 20 which can store the liquid polymerizable composition 10, the modeling stage 30 which can be reciprocated to an up-down direction (depth direction), and activity. And a light source 40 for irradiating energy rays.

A base material 21 that does not transmit the polymerizable composition 10 but transmits the active energy ray and oxygen is provided at the bottom of the modeling tank 20.
The base material 21 is not particularly limited as long as it has a property of transmitting the active energy ray and oxygen without transmitting the polymerizable composition 10 as described above. For example, TEFLON (registered trademark) AF 1600 Fluoropolymer films, fluoropolymer films such as amorphous thermoplastic fluoropolymers such as TEFLON® AF 2400 fluoropolymer film, perfluoropolyether (PFPE), especially crosslinked PFPE films, crosslinked silicone polymer films, etc. Can be mentioned.
The material of the modeling tank 20 is not particularly limited as long as the modeling tank 20 has a width wider than that of the three-dimensional model to be manufactured and can be accommodated and does not interact with the polymerizable composition.

A known light source 40 can be used. Examples of the active energy rays irradiated from the light source 40 for polymerizing the photopolymerizable compound include ultraviolet rays, X-rays, electron beams, γ rays, and visible rays.
The irradiation intensity of the active energy ray irradiated from the light source 40 is in the range of 1 to 200 mW / cm ² from the viewpoint of curing of the photopolymerizable component, the thickness of the polymerization inhibiting layer, the fluidity of the resin, and the like. preferable.
Further, an SLM projection optical system having a spatial light modulator (SLM) 41 such as a liquid crystal panel or a digital mirror device (DMD) as the light source 40 may be used. Thereby, an active energy ray can be surface-irradiated to a desired area.

In the manufacturing apparatus 1 of the three-dimensional modeled object mentioned above, a three-dimensional modeled object is manufactured as follows.
First, the molding composition 20 is filled with the polymerizable composition 10. And oxygen is introduce | transduced into the polymeric composition 10 side in the modeling tank 20 through the base material 21 provided in the bottom part of the modeling tank 20. FIG. As a result, the oxygen concentration of the introduced oxygen decreases in the direction of the upward arrow 14, and the region where the oxygen concentration is equal to or higher than the predetermined concentration becomes the buffer region 11, and the oxygen concentration is the predetermined concentration. The area less than this becomes the cured area 12.

The method for introducing oxygen is not particularly limited as long as the oxygen concentration gradient as described above can be formed in the molding tank 20 containing the polymerizable composition 10. For example, as shown in FIG. 2, oxygen is supplied to the oxygen flow path 13 below the base material 21, and the outside (the flow path 13 side) of the base material 21 is set to an atmosphere having a high oxygen concentration, and pressure is applied to the atmosphere. It can be a method of applying. Thereby, oxygen supplied to the oxygen flow path 13 below the base material 21 diffuses from the flow path 13 through the base material 21 to the polymerizable composition 10 side. In the modeling tank 20 in which the object 10 is accommodated, an oxygen concentration gradient is formed as shown in FIG.
At this time, it is preferable to set the oxygen permeation flux into the modeling tank 20 within the range of 3.4 × 10 ³ to 170 × 10 ³ kmol / (s · m ² ). If the permeation flux of oxygen ^{3.4 × 10 3 kmol / (s} · m 2) or more, it is possible to obtain a curing inhibition layer made of the resin in the fluidized ^{bed, 170 × 10 3 kmol / (} s · m ² ) If it is below, the resin can be sufficiently cured through the curing inhibition layer.
Note that the oxygen permeation flux into the modeling tank 20 can be obtained by the following equation.

Permeation flux (kmol / (s · m ² ))
= Permeation coefficient (kmol · m / (s · m ² · kPa)) x Pressure difference (kPa) / Thickness (m)

Thus, even if oxygen concentration rises and the active energy ray is irradiated to the area | region by the side of the base material 21 of the polymeric composition 10 by supplying oxygen in the modeling tank 20 through the base material 21. It becomes the buffer region 11 where the photopolymerizable compound is not cured. On the other hand, in the region above the buffer region 11, oxygen diffuses into the polymerizable composition 10, so that the oxygen concentration is sufficiently lower than that of the buffer region 11, and the photopolymerizable compound is cured by irradiation with active energy rays. A possible cure region 12 results.

Subsequently, the active energy ray irradiated from the light source 40 is selectively irradiated onto the curing region 12 from below the modeling tank 20 to cure the polymerizable composition 10 (photopolymerizable compound). More specifically, the modeling stage 30 is arranged in the vicinity of the interface between the curing region 12 and the buffer region 11, and selectively from the light source 40 arranged on the buffer region 11 side toward the bottom surface side of the modeling stage 30. Irradiate active energy rays. Thereby, the photopolymerizable compound in the vicinity of the bottom surface of the modeling stage 30 (cured region 12) is cured, and the uppermost part of the three-dimensional modeled object is formed.

Thereafter, the modeling stage 30 is raised (moved away from the buffer area 11). Thereby, the uncured polymerizable composition 10 is newly supplied to the cured region 12 on the bottom side of the modeling tank 20. Then, while continuously raising the modeling stage 30 and the cured product 50, the active energy ray is continuously and selectively irradiated (cured region) from the light source 40. Thereby, hardened | cured material is continuously formed from the modeling stage 30 bottom face to the bottom part side of the modeling tank 20, and there is no seam and a solid modeling thing with high intensity | strength is manufactured.

Then, you may further irradiate an active energy ray with respect to a three-dimensional molded item as needed. Irradiation of active energy rays may be performed only in a desired range, or may be performed on the entire three-dimensional structure. Thus, when irradiation of an active energy ray is performed, the polymerizability of the photopolymerizable compound inside the three-dimensional structure increases, and the warping of the three-dimensional structure obtained is easily suppressed.
When the modeling stage 30 is moved in a direction other than the vertical direction (depth direction) during modeling, the lower part of the three-dimensional model that is immersed in the polymerizable composition in the modeling tank 20 reduces the resistance of the liquid. Therefore, it is preferable to move the modeling stage 30 only in the vertical direction (depth direction). However, when the accuracy of the three-dimensional object is allowed to be lowered or when the accuracy of the three-dimensional object can be ensured by using in combination with other means, the modeling stage 30 in a direction other than the vertical direction (depth). It is also possible to perform three-dimensional modeling while moving. For example, it is possible to move the modeling stage 30 not only in the vertical direction (depth) direction but also in a plane perpendicular to the vertical direction (depth) (a plane parallel to the base material 21).

In addition, when a thermopolymerizable compound is contained in the polymerizable composition, the three-dimensional object is heated and cured by a known method. When heating, it is preferable to set it as the temperature which a three-dimensional molded item does not deform | transform, for example, it is preferable to set it as temperature lower than the glass transition temperature (Tg) of a photopolymerizable compound.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

<< Preparation of polymerizable composition >>
A photopolymerizable liquid containing a photopolymerizable compound, a flame retardant, a flame retardant protecting agent, a thermopolymerizable liquid containing a thermopolymerizable compound and a filler are mixed so as to have the composition shown in Table I, and the mixture is a planetary system. Polymerizable compositions 1 to 19 were prepared by kneading for 5 minutes at a revolution speed of 60 rpm and a rotation speed of 180 rpm using a kneading machine (Hibismix 2P-1 manufactured by Primics).
In Table I, photopolymerizable liquids A to C, flame retardants A to D, flame retardant protective agents A to D, thermal polymerizable liquids A to D and fillers are as shown below.

(Photopolymerizable liquid)
A: Mixture of 100 parts by mass of urethane diacrylate (Sartomer, CN983) as a photopolymerizable compound and 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRSFACURE 184) as a polymerization initiator B: Mixture of 100 parts by mass of trimethylpropanetriacrylate as a photopolymerizable compound and 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE 184) as a polymerization initiator C: photopolymerizable compound 100 parts by mass of a silicone acrylate (manufactured by Bluestar Silicones, UV RCA170) as a polymerization initiator and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, as a polymerization initiator) IR GACURE907) Mixture with 1 part by weight

(Flame retardants)
A: Fire-cut P-801, a halogen-based flame retardant (manufactured by Suzuhiro Chemical)
B: Hishiguard Select N-6ME (manufactured by Nippon Chemical Industry Co., Ltd.), a phosphorus flame retardant
C: Melamine cyanurate MC-4000 (Nissan Chemical Industry Co., Ltd.), a nitrogen flame retardant
D: Magnesium hydroxide Kisuma 5E (manufactured by Kyowa Chemical Industry Co., Ltd.) as a metal hydroxide flame retardant

(Flame retardant protective agent)
A: Adekastab AO-20 (manufactured by ADEKA) which is a phenolic antioxidant
B: Adekastab PEP-36 (manufactured by ADEKA) which is a phosphite antioxidant
C: Sumilizer TPM (manufactured by Sumitomo Chemical Co., Ltd.), a thiol-based antioxidant
D: Adekastab LA-52 (manufactured by ADEKA), which is an amine light stabilizer

(Thermally polymerizable liquid)
A (epoxy): poly [2- (chloromethyl) oxirane-alt-4,4 ′-(propane-2,2-diyl) diphenol] as a thermally polymerizable compound (manufactured by Huntsman, Araldite 506) 55 mass And 45 parts by mass of 4,4′-methylenebis (2,6-dimethylaniline) as a curing agent B (urethane): poly (propylene glycol) bis (2-aminopropyl ether) as a thermopolymerizable compound ) A mixture of 50 parts by mass and 50 parts by mass of 2,2′-dimethyl-4,4′-methylenebis (cyclohexane-1-ylamine) as a curing agent C (silicone): addition-curing silicone KE-1056 (Shin-Etsu) (Made by Chemical Industries)
D (cyanate ester): Isoform containing 100 parts by mass of 1,1-bis (4-cyanatophenyl) ethane as a thermopolymerizable compound and 1500 ppm of zinc (II) acetylacetonate monohydrate as a curing agent Mixture with 5 parts by weight of bornyl acrylate solution

(Filler)
The following polysaccharide nanofibers were used as fillers.
While stirring 1000 g of BiNFi-s, a 2% by weight cellulose nanofiber dispersion manufactured by Sugino Machine, with a stirrer, 0.3 g of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) was added. . Thereafter, stirring was continued for 20 minutes, and solvent substitution with ethanol was performed to obtain polysaccharide nanofibers.

<Production of test piece>
Test pieces (three-dimensional modeled objects) 1 to 19 were produced using the prepared polymerizable compositions 1 to 19.

For manufacturing the test piece, the manufacturing apparatus 1 shown in FIG. 1 was used. A Teflon (registered trademark) AF2400 film with a thickness of 64 μm manufactured by Biogeneral, which is capable of transmitting oxygen as a polymerization inhibitor, was disposed as a base material 21 at the bottom of the modeling tank 20.
The oxygen permeability of this 64 μm thick AF2400 film was measured with Gasperm-100 manufactured by Hitachi Spectroscopic Co., Ltd., and the oxygen permeability coefficient was calculated to be 0.005 kmol · m / (s · m ² · kPa).

Then, by supplying oxygen from the bottom of the modeling tank 20 under a pressure of 44 kPa, the buffer region 11 containing the polymerizable composition 10 and oxygen is formed on the base material 21, and the buffer region 11 is provided above the buffer region 11. A cured region 12 having an oxygen concentration lower than that of region 11 was formed.
The oxygen permeation flux is 3.4 × 10 ³ kmol / (s · m ² ).

Then, an ultraviolet ray source: LED projector (DLP (VISITECH LE4910H UV-388 manufactured by Texas Instruments)) is used as the light source 40 to raise the modeling stage 30 while irradiating light in a plane, thereby causing a test piece for a combustion test, a tension A test piece for testing and a test piece for measuring deflection temperature under load were prepared. At this time, the irradiation intensity of ultraviolet rays was 1 mW / cm ² . The lifting speed of the modeling stage 30 was 50 mm / hr.

In the production of the test piece 16, the pressure condition was 2150 kPa, and the ultraviolet irradiation intensity was 200 mWcm ² . At this time, the permeation flux of oxygen is 168 × 10 ³ kmol / (s · m ² ).

In the production of test pieces 9 to 16, the obtained test pieces were washed with isopropyl alcohol, then heated in an oven at 120 ° C. for 4 hours, further at 150 ° C. for 4 hours, and further at 180 ° C. for 4 hours. Heat treatment for hours was performed.
In the production of the test pieces 17 and 18, the obtained test pieces were washed with isopropyl alcohol and then heat-treated at 120 ° C. for 8 hours in an oven.
In the production of the test piece 19, the obtained test piece was washed with isopropyl alcohol, heated in an oven at 120 ° C. for 4 hours, further at 150 ° C. for 4 hours, further at 180 ° C. for 4 hours, and further Heat treatment was performed at 220 ° C. for 4 hours.

Moreover, the test piece for a combustion test performed the optical modeling of the strip-shaped test piece of 125 mm × 13 mm × 1.5 mm so that the longitudinal direction is the modeling direction (the lifting direction of the modeling stage 30).
As the test piece for tensile test, JIS K 7161-2 (ISO 527-2) 1A type test piece for tensile test was subjected to optical modeling so that the longitudinal direction was the modeling direction.
The test piece for measuring the deflection temperature under load was optically modeled so that the longitudinal direction of the test piece of 80 mm × 10 mm × 4 mm was the modeling direction.

<Evaluation>
The obtained test pieces 1 to 19 were evaluated as follows.
The evaluation results are shown in Table I.

<Evaluation of flammability>
Using a test piece for a combustion test, a combustion test was performed by the UL-94 test method, and the combustibility was evaluated according to the following evaluation criteria.

○: V-0 was achieved. Δ: HB was achieved but V-0 was not achieved. ×: HB was not achieved.

<Evaluation of tensile strength>
The tensile strength of the test piece for tensile test was evaluated according to JIS K 7161-1 according to the following evaluation criteria. At this time, the distance between the gripping tools was 115 mm, and the test speed was 5 mm / min. And the value which divided the stress at the time of a fracture | rupture by the cross-sectional area of the test piece was computed as tensile strength.

A: 150 MPa ≦ tensile strength ○: 40 MPa ≦ tensile strength <150 MPa
Δ: 10 MPa ≦ tensile strength <40 MPa

<Measurement of deflection temperature under load>
For test pieces for measuring deflection temperature under load, in accordance with ISO75-1 and 2, using a thermal strain measuring device manufactured by Toyo Seiki Seisakusho, the deflection temperature under load with a distance between fulcrums of 64 mm and a bending stress of 0.45 MPa using a flat-wise method. Was measured and evaluated according to the following evaluation criteria.

A: 150 ° C. or higher ○: 50 ° C. or higher, lower than 150 ° C.

As is apparent from Table I, the test piece using the polymerizable composition of the present invention has excellent tensile strength and deflection temperature under load as compared with the test piece of the comparative example, and is excellent in combustibility. I understand that.
Specifically, compared with the test piece 1 produced using the polymerizable composition 1 not containing the flame retardant protective material and the test piece 2 produced using the polymerizable composition 2 containing no flame retardant, The test pieces 3 to 19 produced using the polymerizable compositions 3 to 19 including both the flame retardant and the flame retardant protective material have improved flame retardancy. When the flame retardant protective material is present, the decomposition or oxidation of the flame retardant is suppressed even when the polymerizable composition is irradiated with active energy rays (ultraviolet rays) having a relatively high intensity in the presence of oxygen. The function can be sufficiently performed.

In particular, as can be seen from test pieces 3 to 8, when the flame retardant is a halogen flame retardant, a phosphorus flame retardant, or a nitrogen flame retardant, and the flame retardant protective agent is an amine light stabilizer, it is polymerizable. Containing 2 to 20 parts by mass of a flame retardant and 0.1 to 5 parts by mass of a flame retardant protecting agent for 100 parts by mass of the resin component (photopolymerizable compound, thermopolymerizable compound) in the composition (Test pieces 4, 5, 7, and 8) can simultaneously realize the prevention of decomposition or oxidation of the flame retardant and the reduction of the mechanical strength due to the addition of the flame retardant or the flame retardant protective material. . The same applies to the test piece 17.

In addition, the test pieces 9 to 19 prepared using the polymerizable compositions 9 to 19 further containing a thermopolymerizable compound form a polymer having higher heat resistance by the thermal polymerization of the thermopolymerizable compound. Therefore, the heat resistance of the three-dimensional model was further improved.
In particular, as can be seen from test pieces 9 to 14, the flame retardant is a metal hydroxide flame retardant, and the flame retardant protective agent is a phenol antioxidant, phosphite antioxidant or thiol antioxidant. In some cases, the flame retardant is contained in an amount of 5 to 50 parts by mass and the flame retardant protecting agent is added in an amount of 0.1 to 5 with respect to 100 parts by mass of the resin component (photopolymerizable compound, thermopolymerizable compound) in the polymerizable composition. Those containing parts by mass ( test pieces 10, 11, 13, and 14) simultaneously prevent the decomposition or oxidation of the flame retardant and prevent the mechanical strength from decreasing due to the addition of the flame retardant or the flame retardant protective material. Can be realized. The same applies to the test pieces 17 and 18.
Moreover, as can be seen from the test pieces 15 and 16, the test piece 16 produced using the polymerizable composition 16 further containing a filler has further improved the mechanical strength of the three-dimensional structure by the reinforcing effect of the filler.

From the above, it is possible to produce a three-dimensionally shaped article having a liquid photopolymerizable compound, a flame retardant, and a flame retardant protecting agent, which makes it possible to produce a three-dimensionally shaped article excellent in flame retardancy. It was confirmed that it was useful for providing a manufacturing method.

The polymerizable composition of the present invention is a polymerizable composition that enables the production of a three-dimensional structure excellent in flame retardancy, and can produce a three-dimensional structure that has no joints and high strength.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 10 Polymerizable composition 11 Buffer area | region 12 Curing area | region 13 Oxygen flow path 14 The arrow 15 which shows the density | concentration change direction of oxygen in the modeling tank which accommodated the polymerizable composition The oxygen moving direction in the oxygen flow path Shown arrow 20 Modeling tank 21 Base material 30 Modeling stage 40 Light source 41 Spatial light modulator 50 Cured product

Claims (12)

1. A polymerizable composition used for manufacturing a three-dimensional model,
   A polymerization comprising a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, and the method for producing a three-dimensional structure includes the following steps (a) to (c): Sex composition.
   (A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A step of continuously and three-dimensionally forming a shaped article formed by curing the polymerizable composition by continuously irradiating the active energy ray while moving the polymerizable composition
2. The polymerizable composition according to claim 1, wherein the photopolymerizable compound is a compound having a (meth) acryloyl group.
3. 3. The flame retardant according to claim 1, wherein the flame retardant is at least one selected from a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, and a metal hydroxide flame retardant. A polymerizable composition.
4. The said flame retardant protective agent is at least one selected from a phenolic antioxidant, a phosphite antioxidant, a thiol antioxidant, and an amine light stabilizer. Item 5. The polymerizable composition according to any one of Items 3 to 3.
5. The polymerizable composition according to any one of claims 1 to 4, further comprising a liquid thermopolymerizable compound.
6. The flame retardant is at least one selected from a halogen flame retardant, a phosphorus flame retardant and a nitrogen flame retardant;
   The polymerizable composition according to any one of claims 1 to 5, wherein the flame retardant protecting agent is an amine light stabilizer.
7. The flame retardant content is in the range of 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition,
   The polymerizable property according to claim 6, wherein the content of the flame retardant protecting agent is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition. Composition.
8. The flame retardant is a metal hydroxide flame retardant,
   The said flame retardant protective agent is at least one selected from a phenolic antioxidant, a phosphite antioxidant, and a thiol antioxidant, Any one of Claim 1-5 The polymerizable composition according to one item.
9. The flame retardant content is in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition,
   The polymerization according to claim 8, wherein the content of the flame retardant protecting agent is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition. Sex composition.
10. The polymerizable composition according to any one of claims 1 to 9, further comprising a filler.
11. A method for producing a three-dimensional structure using a polymerizable composition,
    The polymerizable composition is the polymerizable composition according to any one of claims 1 to 10,
    Including the following steps (a) to (c), and
    In the step (b), an active energy ray in the range of 1 to 200 mW / cm ² is irradiated.
    (A) Supplying oxygen into the modeling tank containing the polymerizable composition through a base material that transmits oxygen and active energy rays (b) The effect of the polymerizable composition is inhibited by the oxygen A step of selectively irradiating the curing region where the polymerizable composition can be cured with the active energy ray that has passed through the buffer region to cure the polymerizable composition; and (c) the curing. A step of continuously and three-dimensionally forming a shaped article formed by curing the polymerizable composition by continuously irradiating the active energy ray while moving the polymerizable composition
12. The step (a) is characterized in that the oxygen permeation flux into the modeling tank is in the range of 3.4 × 10 ³ to 170 × 10 ³ kmol / (s · m ² ). The manufacturing method of the three-dimensional molded item of 11.

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