JP7163958B2 - Polymerizable composition and method for producing three-dimensional shaped article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable composition and a method for producing a three-dimensional shaped article, and more particularly to a polymerizable composition and a method for producing a three-dimensional shaped article that enable production of a three-dimensional shaped article 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 molds. has become
Among stereolithography, the Continuous Liquid Interface Production (CLIP) method, in which light irradiation is performed while forming a hardening inhibition layer with oxygen, has a high molding speed and a high molding direction without forming a laminated structure. It has been attracting attention in recent years because of its high strength against stress (see, for example, Patent Documents 1 and 2). However, there are many electrical and electronic parts, automobile parts, and the like that require flame retardancy, and the method disclosed in the patent document has not yet yielded a three-dimensional molded article with sufficient flame resistance.

In stereolithography, it is known to add a flame retardant to the material (see, for example, Patent Document 3). As a result, the halogen-based and phosphorus-based flame retardants are decomposed, and the metal hydroxide-based flame retardants are oxidized.

In addition, by adding filler, it is possible to greatly improve the strength of the three-dimensional model, but since the addition of filler increases the viscosity of the polymerizable composition, the model that is being formed under the modeling stage It becomes very time consuming to fill the uncured polymerizable liquid between the bottom layer of the article and the substrate. This is not preferable in that the molding time becomes long. As a means of solving this problem, it is conceivable to increase the amount of oxygen supplied to increase the thickness of the polymerization inhibiting layer and secure a sufficiently thick fluidized bed. However, in order to harden the polymerizable liquid in the lowermost layer through the thicker polymerization inhibiting layer, it is necessary to irradiate ultraviolet light with a higher 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 is likely to become unable to exhibit its function due to decomposition or oxidative deterioration. There is such a problem.

Japanese Patent Publication No. 2016-509962 Japanese Patent Application Publication No. 2016-509964 Japanese Patent Application Laid-Open No. 2007-262401

The present invention has been made in view of the above problems and circumstances, and the problem to be solved is to provide a polymerizable composition and a method for producing a three-dimensional shaped article that can produce a three-dimensional shaped article having excellent flame retardancy. is.

In order to solve the above problems, the present inventors, in the process of studying the causes of the above problems, have found that flame retardancy is improved by containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent. The inventors have found that it is possible to provide a polymerizable composition and a method for producing a three-dimensional shaped article that are capable of producing a three-dimensional shaped article that is excellent in the above, resulting in the present invention.

That is, the above problems related to the present invention are solved by the following means.

1. A polymerizable composition used for manufacturing a three-dimensional object,
Containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent,
The flame retardant is at least one selected from halogen-based flame retardants, phosphorus-based flame retardants and nitrogen-based flame retardants,
The flame retardant protective agent is an amine light stabilizer,
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 protective 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, and the method for producing the three-dimensional object comprises: A polymerizable composition comprising the following steps (a) to (c).
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition.

2. A polymerizable composition used for manufacturing a three-dimensional object,
Containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent,
The flame retardant is a metal hydroxide flame retardant,
The flame retardant protective agent is at least one selected from phenolic antioxidants, phosphite antioxidants and thiol antioxidants,
The content of the flame retardant 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 content of the flame retardant protective 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, and
The polymerizable composition, wherein the method for producing the three-dimensional object includes the following steps (a) to (c).
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a base material that is permeable to oxygen and active energy rays;
(b) selectively irradiating active energy rays that have passed through the buffer region where the effect of the polymerizable composition is inhibited by the oxygen to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; and curing the polymerizable composition
(c) a step of continuously irradiating the active energy ray while moving the cured polymerizable composition to three-dimensionally and continuously form a shaped article obtained by curing the polymerizable composition;
3. 3. The polymerizable composition according to item 1 or 2 , wherein the photopolymerizable compound is a compound having a (meth)acryloyl group.

4 . 4. The polymerizable composition according to any one of items 1 to 3 , further comprising a liquid thermally polymerizable compound.

5 . 5. The polymerizable composition according to any one of items 1 to 4 , further comprising a filler.

6 . A method for producing a three-dimensional object using a polymerizable composition,
The polymerizable composition is the polymerizable composition according to any one of items 1 to 5 ,
including the following steps (a) to (c), and
A method for producing a three-dimensional object, wherein in the step (b), an active energy ray within a range of 1 to 200 mW/cm ² is applied.
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition.

7 . In the step of supplying oxygen, the 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 ). 6. The method for producing a three-dimensional model according to 6 above.

By the above-described means of the present invention, it is possible to provide a polymerizable composition and a method for producing a three-dimensional shaped article that enable production of a three-dimensional shaped article having excellent flame retardancy.

The expression mechanism and action mechanism of the effects of the present invention are speculated as follows.

The polymerizable composition of the present invention is characterized by containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protecting agent.
As described above, in the CLIP method, relatively high-intensity active energy rays (ultraviolet rays) are irradiated in the presence of oxygen. In such a case, if a flame retardant is added to the material to impart flame retardancy, the flame retardant will decompose or deteriorate due to oxidation by ultraviolet rays, and the function as a flame retardant cannot be fully exhibited. .
Therefore, in the present invention, by adding a flame retardant protective agent in addition to the flame retardant, the flame retardant is prevented from decomposing or oxidatively deteriorating even when exposed to relatively strong ultraviolet rays under the supply of oxygen. We believe that sufficient flame retardancy can be imparted to the formed three-dimensional object.

Schematic diagram as an example of a manufacturing apparatus applicable to the method for manufacturing a three-dimensional object of the present invention Schematic diagram showing the oxygen concentration distribution in the vicinity of the substrate 21

The polymerizable composition of the present invention is a polymerizable composition used in the production of a three-dimensional object, and contains a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, and the flame retardant is at least one selected from halogen-based flame retardants, phosphorus-based flame retardants and nitrogen-based flame retardants, the flame retardant protective agent is an amine-based light stabilizer, and the content of the flame retardant is It is within the range of 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition, and the content of the flame retardant protective agent is in the range of 100 parts by mass of the resin component in the polymerizable composition is in the range of 0.1 to 5 parts by mass, and the method for producing a three-dimensional object includes the following steps (a) to (c).
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition.
Alternatively, a polymerizable composition used for producing a three-dimensional object, comprising a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, wherein the flame retardant is a metal hydroxide-based A flame retardant, the flame retardant protective agent is at least one selected from phenolic antioxidants, phosphite antioxidants and thiol antioxidants, and the content of the flame retardant is the polymerization 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, and the content of the flame retardant protective agent is in the range of 100 parts by mass of the resin component in the polymerizable composition. , in the range of 0.1 to 5 parts by mass, and the method for producing the three-dimensionally shaped article includes the steps (a) to (c).
These features are technical features common to the inventions according to the following embodiments.

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.

Also, the flame retardant is preferably at least one selected from halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, and metal hydroxide-based flame retardants.

Moreover, the flame retardant protective agent is preferably at least one selected from phenol antioxidants, phosphite antioxidants, thiol antioxidants and amine light stabilizers.

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

Moreover, it is preferable that the flame retardant is at least one selected from a halogen-based flame retardant, a phosphorus-based flame retardant and a nitrogen-based flame retardant, and the flame retardant protective agent is an amine-based light stabilizer. Since organic flame retardants are mainly decomposed by light, the decomposition of organic flame retardants can be suppressed by combining them with light stabilizers.
In this case, 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, from the viewpoint of exhibiting flame retardancy and suppressing deterioration of mechanical properties, The content of the flame retardant protective 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 phenolic antioxidants, phosphite antioxidants and thiol antioxidants. is preferred. Inorganic (hydroxide) flame retardants are oxidatively deteriorated mainly by oxygen. Therefore, by combining them with antioxidants, the oxidative deterioration of inorganic flame retardants can be suppressed.
In this case, from the viewpoint of expressing flame retardancy and suppressing deterioration of mechanical properties, 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. The content of the flame retardant protective 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 object.

The present invention provides a method for producing a three-dimensional object using a polymerizable composition, wherein the polymerizable composition is the polymerizable composition of the present invention, comprises the following steps (a) to (c), and In the step (b), it is possible to provide a method for producing a three-dimensional object, characterized by irradiating with an active energy ray within the range of 1 to 200 mW/cm ² .
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition.

As an embodiment of the present invention, from the viewpoint of obtaining a sufficiently thick resin fluidized layer by ensuring an appropriate thickness of the polymerization inhibition layer, in the step of supplying oxygen, permeation of oxygen into the modeling tank It is preferable to set the flux within the range of 3.4×10 ³ to 170×10 ³ kmol/(s·m ² ).

DETAILED DESCRIPTION OF THE INVENTION The present invention, its constituent elements, and embodiments and modes for carrying out the present invention will be described in detail below. In addition, in the present application, "-" representing a numerical range is used in the sense that the numerical values described before and after it 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 in the production of a three-dimensional object, and contains a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, and the flame retardant is at least one selected from halogen-based flame retardants, phosphorus-based flame retardants and nitrogen-based flame retardants, the flame retardant protective agent is an amine-based light stabilizer, and the content of the flame retardant is It is within the range of 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition, and the content of the flame retardant protective agent is in the range of 100 parts by mass of the resin component in the polymerizable composition is in the range of 0.1 to 5 parts by mass, and the method for producing a three-dimensional object includes the following steps (a) to (c).

(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition.
Alternatively, a polymerizable composition used for producing a three-dimensional object, comprising a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent, wherein the flame retardant is a metal hydroxide-based A flame retardant, the flame retardant protective agent is at least one selected from phenolic antioxidants, phosphite antioxidants and thiol antioxidants, and the content of the flame retardant is the polymerization 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, and the content of the flame retardant protective agent is in the range of 100 parts by mass of the resin component in the polymerizable composition. , in the range of 0.1 to 5 parts by mass, and the method for producing the three-dimensionally shaped article includes the steps (a) to (c).

Various materials contained in the polymerizable composition of the present invention are described below.

<Photopolymerizable compound>
The photopolymerizable compound according to the present invention is not particularly limited as long as it is a compound that is liquid at room temperature (25° C.) and undergoes radical polymerization and cures upon irradiation 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 may contain two or more types.

The type of the photopolymerizable compound is not particularly limited as long as it has a radically polymerizable group upon irradiation with an active energy ray. Examples include ethylene group, propenyl group, butenyl group, vinylphenyl group and allyl ether group. , a vinyl ether group, a maleyl group, a maleimide group, a (meth)acrylamide group, an acetylvinyl group, a vinylamide group, a (meth)acryloyl group and the like in the molecule. Among these, unsaturated carboxylic acid esters containing one or more unsaturated carboxylic acid ester structures in the molecule are preferred, and (meth)acrylate compounds containing (meth)acryloyl groups are particularly preferred.
Incidentally, the description "(meth) acrylic" represents methacrylic and / or acrylic, the description "(meth) acryloyl" represents methacryloyl and / or acryloyl, the description "(meth) acrylate" , represents 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, and cyclohexyl allyl. Ether, Cyclohexanemethanol Monoallyl Ether, Phthalic Acid Diallyl Ether, Isophthalic Acid Diallyl Ether, Dimethanol Tricyclodecane Diallyl Ether, 1,4-Cyclohexanedimethanol Diallyl Ether, Alkylene (C2-5) Glycol Diallyl Ether, Polyethylene Glycol diallyl ether, glycerin diallyl ether, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, polyglycerin (degree of polymerization 2-5) diallyl ether, trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether and tetraallyl Oxyethane, pentaerythritol triallyl ether, diglycerin triallyl ether, sorbitol triallyl ether, polyglycerin (degree of polymerization 3 to 13) polyallyl ether and the like.

Examples of compounds 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, tricyclodecanedimethanol divinyl ether, EO adduct divinyl ether of bisphenol A, cyclohexanediol divinyl ether, cyclopentadiene vinyl ether, norbornyldimethanol divinyl ether , divinyl resorcin, 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-cyclohexanedivinyl ether, oxano Lubonane divinyl ether, neopentyl glycol 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 (addition of ethylene oxide number of moles 3), pentaerythritol trivinyl ether, ditrimethylolpropane hexavinyl ether and their oxyethylene adducts.

Compounds having a maleimide group include phenylmaleimide, cyclohexylmaleimide, n-hexylmaleimide and the like.

Compounds 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, isooctyl (meth)acrylate , isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, isomyrstyl (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)acryloyloxyethylhexa Hydrophthalic acid, methoxyethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxy ethyl (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-hydroxypropyl (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 succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalate acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, monofunctional (meth)acrylate monomers including 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) acrylates, 1,9-nonanediol di(meth)acrylate, cyclohexanedi(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecanediyldimethylene di(meth)acrylate, Dimethylol-tricyclodecane di(meth)acrylate, polyester di(meth)acrylate, PO adduct di(meth)acrylate of bisphenol A, neopentyl glycol hydroxypivalate di(meth)acrylate, polytetramethylene glycol di(meth) Bifunctional (meth)acrylate monomers including acrylates, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 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 ( Trifunctional or higher functional (meth)acrylate monomers including meth)acrylate, glycerin propoxytri(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate and the like, and oligomers and prepolymers thereof.

Further, the (meth)acrylate-based compound may be a (modified product) obtained by further modifying various (meth)acrylate monomers or oligomers thereof. 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 Propylene oxide-modified (meth)acrylate monomers such as glycerin tri(meth)acrylate, caprolactone-modified (meth)acrylate monomers such as caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactams such as caprolactam-modified dipentaerythritol hexa(meth)acrylate A modified (meth)acrylate monomer and the like are included.

The (meth)acrylate-based compound may also be a compound (hereinafter also referred to as a modified (meth)acrylate-based compound) in which various oligomers are (meth)acrylated. Examples of 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)acrylic oligomers, and the like. Among these, epoxy (meth)acrylate-based compounds, urethane (meth)acrylate-based compounds, and silicone (meth)acrylate-based compounds are particularly suitable for use.

The epoxy (meth)acrylate compound may be a compound containing one or more epoxy groups and one or more (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, and phenol novolac type epoxy (meth)acrylate etc.

A urethane (meth)acrylate compound is an aliphatic polyisocyanate compound having two or more isocyanate groups or an aromatic polyisocyanate compound having two or more isocyanate groups, and a (meth)acrylic acid derivative having a hydroxy group. It can be a compound having a urethane bond and a (meth)acryloyl group obtained by reacting.

Isocyanate compounds that are raw materials for urethane (meth)acrylate compounds include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 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 and the like.
In addition, chain-extended isocyanate compounds obtained by reacting polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diols, polyether diols, polyester diols, and polycaprolactone diols with excess isocyanate compounds. can be mentioned.

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

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（いずれもダイセル・オルネクス社製）、アートレジンＵＮ－３３０、アートレジンＳＨ－５００Ｂ、アートResin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin 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 manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.) etc.

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 used as a raw material for the urethane (meth)acrylate compound described above, and is a compound obtained by reacting these compounds with a polyol or a polyamine. good too.
Polyols 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 isocyanate or the like include compounds having at least two active hydrogen groups (specifically, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, ethylenediamine and alkanolamines such as ethanolamine and diethanolamine) and alkylene oxide (specifically, ethylene oxide, propylene oxide, etc.).
Methods for synthesizing polyether polyols are described, for example, in Gunter Oertel, "Polyurethane Handbook" (1985) Hanser Publishers (Germany), p. 42-53 can be referred to.

Polyester polyols include condensation reaction products of polyhydric carboxylic acids such as adipic acid and phthalic acid and polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and those used in nylon production. Waste, trimethylolpropane, waste of pentaerythrol, waste of phthalic acid polyester, polyester polyol derived from treated waste, etc. (for example, Keiji Iwata "Polyurethane Resin Handbook" (1987) Nikkan Kogyo Shimbun, p. .117).

Examples of polymer polyols include polymer polyols obtained by reacting polyether polyols with ethylenically unsaturated monomers (eg, butadiene, acrylonitrile, styrene, etc.) in the presence of radical polymerization catalysts. Polymer polyols having a molecular weight of about 5,000 to 12,000 are particularly preferred.

Vegetable oil polyols include hydroxy group-containing vegetable oils such as castor oil and coconut oil. Castor oil derivative polyols obtained from castor oil or hydrogenated castor oil can also be suitably used. Examples of castor oil derivative polyols include castor oil polyesters obtained by reacting castor oil, polyvalent carboxylic acids and short-chain diols, and alkylene oxide adducts of castor oils and castor oil polyesters.

Flame-retardant polyols include phosphorus-containing polyols obtained by adding alkylene oxide to a phosphoric acid compound, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, active hydrogen compounds having aromatic rings, and alkylene oxide and aromatic ester polyols obtained by the condensation reaction of a polyhydric carboxylic acid having an aromatic ring and a polyhydric alcohol.

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

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

As the blocking agent for blocking the isocyanate groups of the polyisocyanate, any agent may be used as long as it has a (meth)acryloyl group, reacts with the isocyanate group, and can be eliminated by heating.
Such blocking agents include t-butylaminoethyl methacrylate (TBAEMA), t-pentylaminoethyl methacrylate (TPAEMA), t-hexylaminoethyl methacrylate (THAEMA), t-butylaminopropyl methacrylate (TBAPMA), and the like. be done.

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

The blocking reaction between the polyisocyanate and the blocking agent can be carried out with or without the presence of solvent. When a solvent is used, it is preferable to use a solvent that is inert to isocyanate groups.
Moreover, a reaction catalyst can be used in the blocking reaction. Specific reaction catalysts include organic metal salts of tin, zinc, lead, etc., metal alkoxides, tertiary amines, and the like.

When the blocked isocyanate prepared as described above is used as the photopolymerizable compound, first, the acryloyl group portion is polymerized by light irradiation. After that, the blocking agent is removed by heating, and the generated isocyanate is newly polymerized with a polyol, polyamine, or the like to obtain a three-dimensional object containing polyurethane, polyurea, or a mixture thereof.

A silicone (meth)acrylate-based compound can be a compound having a polysiloxane bond in its main chain and having (meth)acrylic acid added to its terminals and/or side chains. The silicone, which is the raw material for the silicone (meth)acrylate compound, should be an organopolysiloxane obtained by polymerizing any combination of known monofunctional, difunctional, trifunctional or tetrafunctional silane compounds (e.g., alkoxysilane, etc.). can be done.

Specific examples of silicone acrylates include commercially available TEGORad2500 (trade name, manufactured by Tego Chemie Service GmbH), and organic modified products having a hydroxy group such as X-22-4015 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Acrylic acid is reacted with an organically modified silane compound such as epoxysilane such as KBM402 and KBM403 (trade names, both manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by esterifying silicone and acrylic acid in the presence of an acid catalyst. etc.

(Photoinitiator)
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.

Radical polymerization initiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (manufactured by BASF, IRGACURE 907 (“IRGACURE” is a registered trademark of the same company), etc.), 2 -hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF, IRGACURE 1173 ("IRGACURE" is a registered trademark of the same 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-diphenylethan-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(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzyl, methylphenylglyoxyester, benzophenone, o-benzoyl benzoin methyl acid-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butyl peroxycarbonyl)benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Michra-ketone, 4,4 ′-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,1 0-phenanthrenequinone, camphorquinone, 2,4-diethyloxanthen-9-one and the like.

The radical polymerization initiator is preferably contained within the range of 0.01 to 10% by mass, relative to the total mass (100% by mass) of the polymerizable composition, and within the range of 0.1 to 5% by mass. More preferably, it is contained within the range of 0.3 to 3% by mass. When the radical polymerization initiator is contained within this range, it becomes possible to efficiently polymerize the photopolymerizable compound.

<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 formed three-dimensional object, but for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, and metal hydroxide flame retardants. etc. These may be used individually by 1 type, or may use 2 or more types together.

Halogen-based flame retardants include bromine compounds and chlorine compounds, but chlorine compounds are not preferred due to toxicity problems. Bromine compounds include, for example, 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 (eg, SAYTEX BT-93 (manufactured by Albemarle), etc.), ethane-1,2-bis(penta Bromophenyl) (e.g., SAYTEX 8010 (manufactured by Albemarle), etc.), brominated epoxy oligomers (e.g., SR-T1000, SR-T2000 (manufactured by Sakamoto Chemical Industries), etc.), and commercially available products such as Firecut P -801 (manufactured by Suzuhiro Kagaku Co., Ltd.) and the like, but are not limited thereto.

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

In addition, when a halogen-based flame retardant is used as a flame retardant, flame retardant aids include, for example, antimony compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide; and tin compounds such as tin oxide and tin hydroxide. , molybdenum compounds such as molybdenum oxide and ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, boron compounds such as zinc borate and barium metaborate, silicone oils, silane coupling agents, high molecular weight silicones, etc. A silicon-based compound, chlorinated polyethylene, or the like may be used in combination.

Phosphorus-based flame retardants include polyphosphoric acid compounds such as melamine polyphosphate, aromatic phosphoric acid esters, aromatic condensed phosphoric acid esters, and the like. Specifically, phosphoric acids such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate Salt compounds, polyphosphate compounds, red phosphorus, organic phosphates, phosphazenes, phosphonic acids, phosphinic acids, phosphine oxides, phosphoranes, phosphoramides, and commercial products such as Hishiguard Select N-6ME (manufactured by Nippon Kagaku Kogyo Co., Ltd. ) etc. can be used.

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

Metal hydroxide flame retardants include aluminum hydroxide, magnesium hydroxide (eg, Kisuma 5E (manufactured by Kyowa Chemical Industry Co., Ltd.), etc.), basic magnesium carbonate, calcium hydroxide, hydrotalcites, and the like.

<Flame retardant protective agent>
The polymerizable composition of the present invention contains a flame retardant protective agent for the purpose of protecting the flame retardant.
Examples of flame retardant protective agents include phenol antioxidants, phosphite antioxidants, thiol antioxidants, amine light stabilizers, and the like. In particular, when a halogen-based flame retardant, a phosphorus-based flame retardant, or a nitrogen-based flame retardant is used as the flame retardant, the flame retardant protective agent is preferably an amine-based 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.
The flame retardant protective agent may be used singly or in combination of two or more.

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-based 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. part, and the content of the flame retardant protective 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. is within .
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, the decrease in mechanical strength due to the addition of the flame retardant can be sufficiently suppressed. Further, 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 exhibited, and if it is 5 parts by mass or less, the mechanical strength is sufficiently reduced due to the addition of the flame retardant protective agent. can be suppressed to

On the other hand, when using a metal hydroxide flame retardant as a flame retardant and a phenol antioxidant, phosphite antioxidant or thiol antioxidant as a flame retardant protective agent, the content of the flame retardant is 5 to 50 parts by mass with respect to 100 parts by mass of the resin component in the polymerizable composition, and the content of the flame retardant protective agent is in the range of 100 parts by mass of the resin component in the polymerizable composition, It is within 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, the decrease in mechanical strength due to the addition of the flame retardant can be sufficiently suppressed. Further, 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 exhibited, and if it is 5 parts by mass or less, the mechanical strength is sufficiently reduced due to the addition of the flame retardant protective agent. can be suppressed to

Phenolic antioxidants include, for example, 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-t-butyl-4-hydroxyphenyl)propionamide], 4,4′-thiobis(6-t-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-t-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate , 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, stearyl (3,5-di-t -butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)methylpropionate]methane, thiodiethylene glycol bis[(3,5-di-t-butyl -4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(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-t-butyl-4 -hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetrao Xaspiro[5,5]undecane, triethylene glycol bis[(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], and commercial products such as ADEKA STAB AO-20 (manufactured by ADEKA). .

Phosphite antioxidants include trisnonylphenyl phosphite, tris[2-t-butyl-4-(3-t-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite , tridecylphosphite, octyldiphenylphosphite, di(decyl)monophenylphosphite, 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) pentaerythritol diphosphite, tetra(tridecyl)isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4′-n-butylidene bis(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)biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis(4,6-t-butylphenyl)-2- Ethylhexylphosphite, 2,2'-methylenebis(4,6-t-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite, tris( 2-[(2,4,8,10-tetrakis-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 2,4, Phosphite of 6-tri-t-butylphenol, tris(2,4-di-t-butylphenyl)phosphite, and commercially available products such as ADEKA STAB PEP-36 (manufactured by ADEKA).

Thiol-based antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, dialkylthiodipropionates such as distearyl thiodipropionate, pentaerythritol tetra (β-alkylthiopropionate), and commercially available Products include Sumilizer TPM (dimyristyl-3,3'-thiodipropionate) (manufactured by Sumitomo Chemical Co., Ltd.).

Amine light stabilizers include hindered amine light stabilizers. 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-piperidyl benzoate, 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-butanetetracarboxy tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) )・di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)・di(tridecyl)-1,2,3, 4-butane tetracarboxylate, 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-tetra methyl-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 such as ADEKA STAB LA-52 (manufactured by ADEKA).

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

Compounds having a cyclic ether group include compounds containing epoxides, oxetanes, tetrahydrofuran, tetrahydropyran, and the like. Among these, compounds having an epoxy group (hereinafter also referred to as epoxy-based compounds) are preferred from the viewpoint of polymerizability and the like.
Epoxy-based compounds include epoxy-based compounds having one or more epoxy groups in the molecule. For example, crystalline epoxy compounds such as biphenyl-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, stilbene-type epoxy compounds, hydroquinone-type epoxy compounds, cresol novolac-type epoxy compounds, phenol novolak-type epoxy compounds, naphthol novolac-type Novolak type epoxy compounds such as epoxy compounds, phenol aralkyl type epoxy compounds containing a phenylene skeleton, phenol aralkyl type epoxy compounds containing a biphenylene skeleton, phenol aralkyl type epoxy compounds such as naphthol aralkyl type epoxy compounds containing a phenylene skeleton, triphenol methane type epoxy compounds, Polyfunctional epoxy compounds such as alkyl-modified triphenolmethane-type epoxy compounds, glycidylamine, and tetrafunctional naphthalene-type epoxy compounds, modified phenols such as dicyclopentadiene-modified phenol-type epoxy compounds, terpene-modified phenol-type epoxy compounds, and silicone-modified epoxy compounds. type epoxy compounds, heterocyclic ring-containing epoxy compounds such as triazine nucleus-containing epoxy compounds, and naphthylene ether type epoxies.

The compound having a cyanate group may be a compound having one or two 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- or 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-cyanatophenyl)propane, anatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)phosphate, bis(3 -chloro-4-cyanatophenyl)methane, 4-cyanatobiphenyl, 4-cumylcyanatobenzene, 2-t-butyl-1,4-dicyanatobenzene, 2,4-dimethyl-1,3-dicyanato Benzene, 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, bis( p-cyanophenoxyphenoxy)benzene, di(4-cyanatophenyl)ketone, novolac cyanide, bisphenol cyanide polycarbonate oligomer and the like.

The compound having an isocyanate group is not particularly limited as long as it is a compound having one or two or more isocyanate groups in the molecule. Diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, alicyclic diisocyanate such as diisocyanatemethylcyclohexane, aliphatic diisocyanate such as hexamethylene diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, trimethylolpropane and Trifunctional or higher polyisocyanates such as 1:3 adducts of hexamethylene diisocyanate and cyclic trimers of hexamethylene diisocyanate, blocking agents for the isocyanate groups of these compounds (e.g., alcohols, phenols, lactams, oximes , acetoacetic acid alkyl esters, malonic acid alkyl esters, phthalimides, imidazoles, hydrogen chloride, hydrogen cyanide, sodium hydrogen sulfite, etc.).

The compound having a hydrosilyl group may be any compound having one or more hydrosilyl groups in the molecule, and examples thereof include methylhydrosiloxane-dimethylsiloxane copolymers.
A compound having a hydrosilyl group can be obtained by an addition reaction with a polyorganosiloxane having a terminal or side chain vinyl group. Polysiloxane having a vinyl group includes polydimethylsiloxane in which each terminal silicon atom is substituted with a vinyl group, dimethylsiloxane-diphenylsiloxane copolymer in which each terminal silicon atom is substituted with a vinyl group, and vinyl group at each terminal silicon atom. Substituted polyphenylmethylsiloxanes, vinylmethylsiloxane-dimethylsiloxane copolymers having trimethylsilyl groups at each end, and the like.

(Curing agent, curing accelerator)
When the polymerizable composition contains a thermally polymerizable compound, it preferably further contains a curing agent and a curing accelerator for curing the thermally polymerizable compound. The types of curing agent and curing accelerator are appropriately selected according to the type of the thermally polymerizable compound.

Curing agents and curing 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'-diaminodiphenyl sulfone, 4,4'-diaminodicyclohexane, bis(4-aminophenyl)phenylmethane , 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis(4-aminophenyl)cyclohexane, N,N-dimethyl-n-octylamine, aminos such as dicyanodiamide, aniline-modified resol Resins, resol-type phenolic resins such as dimethyl ether resol resins, phenolic novolac resins, cresol novolac resins, t-butylphenol novolac resins, novolac-type phenolic resins such as nonylphenol novolak resins, phenylene skeleton-containing phenol aralkyl resins, biphenylene skeleton-containing phenol aralkyl resins, etc. phenolic aralkyl resins, phenolic resins having a condensed polycyclic structure such as a naphthalene skeleton or anthracene skeleton, polyoxystyrenes such as polyparaoxystyrene, hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), etc. Cyclic acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), acid anhydrides including aromatic acid anhydrides such as benzophenonetetracarboxylic acid (BTDA), polysulfides, thioesters, thioethers, etc. Isocyanate compounds such as polymercaptan compounds, isocyanate prepolymers, blocked isocyanates, organic acids such as carboxylic acid-containing polyester resins, etc., zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt bisacetylacetonate (II ), trisacetylacetonate cobalt (III), and acetylacetonate zinc.
The polymerizable composition may contain only one type of these curing agents and curing accelerators, or may contain two or more types thereof.
The amounts of the curing agent and curing accelerator are appropriately selected according to the type and amount of the thermally polymerizable compound.

<Filler>
The polymerizable composition of the 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 one filler may be contained, or two or more fillers may be contained.

Fillers include glass fillers such as soda lime glass, silicate glass, borosilicate glass, aluminosilicate glass, quartz glass, alumina, zirconium oxide, titanium oxide, lead zirconate titanate, silicon carbide, silicon nitride, and aluminum nitride. , ceramic fillers made of tin oxide, etc., simple metals such as iron, titanium, gold, silver, copper, tin, lead, bismuth, cobalt, antimony, cadmium, etc., or metal fillers made of alloys thereof, graphite, graphene, carbon Carbon fillers such as nanotubes, polyester, polyamide, polyaramid, polyparaphenylenebenzobisoxazole, organic polymer fibers such as polysaccharides, potassium titanate whiskers, silicone carbide whiskers, silicon nitride whiskers, α-alumina whiskers, whisker-like inorganic compounds comprising zinc oxide whiskers, aluminum borate whiskers, calcium carbonate whiskers, magnesium hydroxide whiskers, basic magnesium sulfate whiskers, calcium silicate whiskers, etc. (including needle-like single crystals of the above ceramic fillers); Talc, mica, clay, wollastonite, hectorite, saponite, stevensite, hydrite, montmorillonite, nonthrite, bentonite, Na-type tetrasilicic fluoromica, Li-type tetrasilicic fluoromica, Na-type fluorine teniolite, Li-type fluorine Examples include swelling mica such as teniolite, and clay minerals such as vermicularite. Examples of fillers include polyolefin fillers made of polyethylene, polypropylene, etc., FEP (tetrafluoroethylene-hexafluoropropylene copolymer), PFA (tetrafluoroethylene-perfluoroalkoxyethylene copolymer), ETFE (tetrafluoroethylene-perfluoroalkoxyethylene copolymer), fluororesin fillers such as fluoroethylene-ethylene copolymer).

Among the above, organic polymer fibers are preferable, and nanofibers made of polysaccharides are particularly preferable. Polysaccharides 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 molded article obtained.

A fibrous filler made of cellulose, that is, cellulose nanofiber (hereinafter also simply referred to as nanocellulose) is produced by mechanical defibration of plant-derived fibers or plant cell walls, biosynthesis by acetic acid bacteria, 2, 2. , 6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) or the like, or cellulose nanofibers composed mainly of fibrous nanofibrils obtained by electrospinning or the like. In addition, nanocellulose is cellulose whose main component is whisker-like (needle-like) crystallized nanofibrils obtained by mechanically defibrating plant-derived fibers or plant cell walls and then subjecting them to acid treatment, etc. It may be nanocrystals or other shapes. Nanocellulose may contain cellulose as a main component, and may contain lignin, hemicellulose, and the like.

The shape of the filler is not particularly limited, and may be, for example, fibrous (including whisker-like) or particulate, but from the viewpoint of improving the strength of the three-dimensional object, fibrous is preferred. .
When the filler is particulate, its 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 more preferably in the range of 0.1 to 50 μm. is more preferable. When the average particle size of the particulate filler is 0.1 μm or more, the strength of the three-dimensionally shaped article tends to increase. On the other hand, when the average particle size is 50 µm or less, it becomes easier to form a three-dimensional 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 within 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 object tends to increase. 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-dimensionally shaped article tends to be good. The average fiber diameter of the filler is more preferably in the range of 0.005 to 10 μm, still more preferably in the range of 0.01 to 8 μm, and particularly in the range of 0.02 to 5 μm. preferable.

The average fiber length of the filler is preferably within the range of 0.2-200 μm. When the average fiber length is 0.2 μm or more, the strength of the three-dimensional object tends to increase. When the average fiber length is 200 μm or less, sedimentation of the filler due to entanglement of the filler with each other is less likely to occur. The average fiber length of the filler is more preferably in the range of 0.5-100 μm, still more preferably in the range of 1-60 μm, and particularly preferably in the range of 1-40 μm.

The aspect ratio of the filler is preferably within the range of 10-10,000. When the aspect ratio is 10 or more, the strength of the three-dimensional object tends to be higher. If the aspect ratio is 10,000 or less, the fillers are less likely to sediment due to entanglement of the fillers. The aspect ratio of the filler is more preferably within the range of 12-8000, more preferably within the range of 15-2000, and particularly preferably within the range of 18-800.

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

The amount of filler contained in the polymerizable composition is preferably in the range of 1 to 50% by mass, and in the range of 5 to 40% by mass, relative to the total mass (100% by mass) of the polymerizable composition. is more preferable. When the amount of the filler is within this range, it becomes easier to obtain a three-dimensionally shaped article with high strength.

The filler may be surface-modified with a surface-modifying agent having a functional group capable of reacting with a photopolymerizable compound or a thermally polymerizable compound. When the surface of the filler is modified, the adhesion between the filler and the photopolymerizable compound or between the filler and the thermally polymerizable compound is enhanced, making it easier to obtain a three-dimensional object with higher strength. The surface modifier is not particularly limited as long as it has a group capable of reacting with a photopolymerizable compound or a thermally polymerizable compound and a group capable of binding to or adsorbing to the filler.

Groups and structures that can be bonded to or adsorbed on fillers contained in the surface modifier include Si atoms, Ti atoms, Zr atoms, carboxy groups, amino groups, imino groups, cyano groups, azo groups, azide groups, Thiol group, sulfo group, (meth)acryloyl group, epoxy group, isocyanate group and the like. Among these, Si atoms, Ti atoms, and Zr atoms are preferred, and Si atoms are particularly preferred, from the viewpoint of reactivity with fillers and the like.
In addition, the group capable of reacting with the photopolymerizable compound or thermally polymerizable compound contained in the surface modifier includes a (meth)acryloyl group, an amino group, an imino group, an epoxy group, a glycidyl group, an oxetanyl group, an isocyanate group, cyanate group, vinyl group, styryl group, hydrosilyl group, mercapto group, ureido group and the like.

For the above reasons, the surface modifier is preferably a silane coupling agent, a titanium coupling agent or a zirconium 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, 3-isocyanatopropyltriethoxysilane compounds having reactive functional groups such as trimethylmethoxysilane, trimethylethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltributoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyl trimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dihexyldimethoxysilane, trihexylmethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane , 1-propyn-3-yltrimethoxysilane, 1-propyn-3-yltriethoxysilane, 1-propyn-3-yltributoxysilane, 2-cyclohexene-1-yltriethoxysilane, 1,3-hexadiyne Compounds having an aliphatic hydrocarbon group such as -5-yltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane n, naphthyltrimethoxysilane, naphthyltriethoxysilane, anthryltrimethoxysilane, phenanthryltrimethoxysilane, biphenyltrimethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, methylphenyldimethoxysilane, 2-methylbenzyltrimethoxysilane Compounds having an aromatic hydrocarbon group such as silane, 3-methylbenzyltrimethoxysilane and 4-methylbenzyltrimethoxysilane, silazane compounds such as hexamethyldisilazane, and the like can be mentioned.

Titanium coupling agents include methyltrimethoxytitanium, ethyltriethoxytitanium, n-propyltrimethoxytitanium, i-propyltriethoxytitanium, n-hexyltrimethoxytitanium, cyclohexyltriethoxytitanium, phenyltrimethoxytitanium, 3- Chloropropyltriethoxytitanium, 3-aminopropyltrimethoxytitanium, 3-aminopropyltriethoxytitanium, 3-(2-aminoethyl)-aminopropyltrimethoxytitanium, 3-(2-aminoethyl)-aminopropyltriethoxytitanium Titanium, 3-(2-aminoethyl)-aminopropylmethyldimethoxytitanium, 3-anilinopropyltrimethoxytitanium, 3-mercaptopropyltriethoxytitanium, 3-isocyanatopropyltrimethoxytitanium, 3-glycidoxypropyltriethoxy titanium, trialkoxytitaniums such as 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-ethylacetoacetate zirconium, di-n-butoxy-bis(ethylacetoacetate) zirconium, n-butoxy-tris(ethylacetoacetate) zirconium, tetrakis(n-propyl acetoacetate)zirconium, tetrakis(acetylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, di-n-butoxy bis(acetylacetoacetate)zirconium and the like.

Among the above, a silane coupling agent having a particularly reactive functional group is preferred. The method of surface-modifying the filler with a surface-modifying agent is not particularly limited. For example, the filler is dispersed in an arbitrary solvent, the surface-modifying agent is added to the dispersion, and the solvent is removed by filtration or the like after stirring. Then, a method of heat drying can be used. When the filler is surface-modified with a 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>
The polymerizable composition contains photosensitizers, polymerization inhibitors, ultraviolet rays, as long as it enables the formation of a three-dimensional object by irradiation with active energy rays and does not significantly cause unevenness in the intensity of the three-dimensional object obtained. Optional additives such as absorbents, antioxidants, colorants such as dyes and pigments, antifoaming agents, and surfactants may be further included.

<Method for preparing polymerizable composition>
The polymerizable composition includes a photopolymerizable compound, a flame retardant, a flame retardant protective agent, and, if necessary, a thermally polymerizable compound, a filler, a photopolymerization initiator, a curing agent, a curing accelerator, etc., mixed in any order. It can be prepared by

A known device can be used for mixing the polymerizable composition. For example, Ultra Turrax (manufactured by IKA Japan), TK Homomixer (manufactured by Primix), TK Pipeline Homomixer (manufactured by Primix), TK Filmix (manufactured by Primix), Clearmix (manufactured by M Technic), Clea SS5 (manufactured by M Technic Co., Ltd.), Cavitron (manufactured by Eurotech Co., Ltd.), Medialess stirrer such as Fine Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.), Visco Mill (manufactured by Aimex), Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.), Star Mill (Ashizawa, manufactured by Fine Tech), DCP Super Flow (manufactured by Nihon Eirich Co., Ltd.), MP Mill (manufactured by Inoue Seisakusho), Spike Mill (manufactured by Inoue Seisakusho), Mighty Mill (manufactured by Inoue Seisakusho), SC Mill (Mitsui Mining Co., Ltd.) and other media agitators, Ultimizer (Sugino Machine Co., Ltd.), Starburst (Sugino Machine Co., Ltd.), Nanomizer (Yoshida Kikai Co., Ltd.), NANO 3000 (Miryu Co., Ltd.), etc. apparatus.
In addition, a rotation and revolution mixer such as Awatori Mixer (manufactured by Thinky) and Kakuhunter (manufactured by Shashin Kagaku), planetary mixers such as Hivis Mix (manufactured by Primix) and Hivis Disper (manufactured by Primix), Nanoruptor (manufactured by Sonic Bio), etc., can also be suitably used.

<Method for manufacturing three-dimensional object>
Examples of the method for producing a three-dimensional object of the present invention include a method having at least the following steps.

Step (a): A step of supplying oxygen into a modeling tank containing a 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 concentration of oxygen is lower and in which the polymerizable composition can be cured is irradiated with an active energy ray that has passed through the buffer region, thereby curing the polymerizable composition Step (c): Cured A step of continuously irradiating the active energy ray while moving the polymerizable composition to three-dimensionally and continuously form a modeled article obtained by curing the polymerizable composition.

In addition, you may have the process of irradiating an active energy ray further following a process (c). Further, when a thermally polymerizable compound is contained in the polymerizable composition, following the step (c), after removing unnecessary resin etc. by washing etc., heating is performed to heat the thermally polymerizable compound. It may have a step of curing.

A three-dimensional object manufacturing apparatus that can be used in the three-dimensional object manufacturing method of the present invention will be described below.

(manufacturing device)
As shown in FIG. 1, a three-dimensional object manufacturing apparatus 1 includes a modeling tank 20 capable of storing a liquid polymerizable composition 10, a modeling stage 30 capable of reciprocating in the vertical direction (depth direction), and an active and a light source 40 for irradiating energy rays.

At the bottom of the modeling tank 20, a base material 21 is provided that is impermeable to the polymerizable composition 10 and permeable to active energy rays and oxygen.
The base material 21 is not particularly limited as long as it does not allow the polymerizable composition 10 to pass therethrough as described above, but allows active energy rays and oxygen to pass therethrough. Fluoropolymer films, such as amorphous thermoplastic fluoropolymers such as TEFLON® AF 2400 fluoropolymer films, perfluoropolyethers (PFPE), especially crosslinked PFPE films, crosslinked silicone polymer films, and the like. mentioned.
The material of the modeling bath 20 is not particularly limited as long as it has a wider width than the three-dimensional model to be manufactured, can be accommodated, and does not interact with the polymerizable composition.

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

In the three-dimensional object manufacturing apparatus 1 described above, a three-dimensional object is manufactured as follows.
First, the modeling tank 20 is filled with the polymerizable composition 10 . Then, oxygen is introduced into the modeling bath 20 on the side of the polymerizable composition 10 through the base material 21 provided at the bottom of the modeling bath 20 . As a result, the introduced oxygen decreases in oxygen concentration in the direction of the upward arrow 14, and the region where the oxygen concentration is equal to or higher than a predetermined concentration becomes the buffer region 11, and the oxygen concentration reaches the predetermined concentration. The area below is the hardened area 12 .

A method for introducing oxygen is not particularly limited as long as the oxygen concentration gradient as described above can be formed in the modeling tank 20 containing the polymerizable composition 10 . For example, as shown in FIG. 2, oxygen is supplied to the oxygen channel 13 under the base material 21, and the outside of the base material 21 (channel 13 side) is made into an atmosphere with a high oxygen concentration, and the atmosphere is pressurized. can be used as a method of applying As a result, the oxygen supplied to the oxygen channel 13 below the base material 21 diffuses from the channel 13 to the polymerizable composition 10 side through the base material 21, so that the polymerizable composition In the modeling tank 20 containing the object 10, an oxygen concentration gradient is formed as shown in FIG.
At this time, it is preferable that the permeation flux of oxygen into the modeling tank 20 is within the range of 3.4×10 ³ to 170×10 ³ kmol/(s·m ² ). If the permeation flux of oxygen is ^3.4 ×10 ³ kmol/(s·m ² ) or more, it is possible to obtain a hardening inhibition layer that becomes a fluidized layer of the resin, ² ) If it is below, the resin can be sufficiently cured through the curing inhibition layer.
The permeation flux of oxygen into the modeling tank 20 can be obtained by the following formula.

Permeation flux (kmol/(s·m ² ))
= Permeability coefficient (kmol m/(s ^m2 kPa)) x pressure difference (kPa)/thickness (m)

By supplying oxygen into the modeling tank 20 through the base material 21 in this way, the oxygen concentration in the region of the polymerizable composition 10 on the side of the base material 21 increases, and even if the active energy ray is irradiated, The photopolymerizable compound becomes a buffer region 11 that 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 becomes sufficiently lower than the buffer region 11, and the photopolymerizable compound is cured by irradiation with active energy rays. A possible cure area 12 results.

Subsequently, active energy rays emitted from the light source 40 are selectively applied to 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 near the interface between the curing region 12 and the buffer region 11, and the light source 40 arranged on the buffer region 11 side is selectively directed toward the bottom surface of the modeling stage 30. Irradiate with active energy rays. As a result, the photopolymerizable compound near the bottom surface (curing region 12) of the modeling stage 30 is cured to form the top of the three-dimensional object.

After that, the modeling stage 30 is raised (moved in a direction away from the buffer area 11). As a result, the uncured polymerizable composition 10 is newly supplied to the curing region 12 on the bottom side of the modeling bath 20 . Then, while the modeling stage 30 and the cured product 50 are continuously raised, the light source 40 continuously and selectively irradiates the active energy ray (area to be cured). As a result, the cured product is continuously formed from the bottom surface of the modeling stage 30 to the bottom side of the modeling tank 20, and a seamless and high-strength three-dimensional modeled object is manufactured.

After that, the three-dimensional object may be further irradiated with active energy rays, if necessary. Irradiation of the active energy ray may be performed only on a desired range, or may be performed on the entire three-dimensional molded article. By irradiating the active energy ray in this way, the polymerizability of the photopolymerizable compound inside the three-dimensional object is increased, and the resulting three-dimensional object is likely to be prevented from warping.
In addition, 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 immersed in the polymerizable composition in the modeling tank 20 will reduce the resistance of the liquid. It is preferable to move the modeling stage 30 only in the vertical direction (depth direction), since there is a possibility that it may be shifted from the original position. However, if it is possible to reduce the accuracy of the three-dimensional object, or if it is possible to secure the accuracy of the three-dimensional object by using it in combination with other means, the modeling stage 30 It is also possible to perform three-dimensional modeling while moving the . For example, it is possible to move the modeling stage 30 not only in the vertical direction (depth) but also in a plane perpendicular to the vertical direction (depth) (a plane parallel to the substrate 21).

Moreover, when a thermally polymerizable compound is contained in the polymerizable composition, the three-dimensionally shaped article is heated by a known method to be cured. When heating, it is preferable to set the temperature to a temperature at which the three-dimensional object is not deformed. For example, it is preferable to set the temperature to a temperature lower than the glass transition temperature (Tg) of the photopolymerizable compound.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these.

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

(Photopolymerizable liquid)
A: A mixture of 100 parts by mass of urethane diacrylate (CN983, manufactured by Sartomer) as a photopolymerizable compound and 1 part by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE184, manufactured by BASF) as a polymerization initiator. B: 100 parts by weight of trimethylpropane triacrylate as a photopolymerizable compound and 1-hydroxy-cyclohexyl-phenyl-ketone as a polymerization initiator (manufactured by BASF, IRGACURE 184) 1 part by weight mixture C: photopolymerizable compound 100 parts by mass of silicone acrylate (manufactured by Bluestar Silicones, UV RCA170) as a polymerization initiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (manufactured by BASF, IRGACURE907) A mixture with 1 part by mass

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

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

(Thermal polymerizable liquid)
A (epoxy): Poly[2-(chloromethyl)oxirane-alt-4,4′-(propane-2,2-diyl)diphenol] (Araldite 506, manufactured by Huntsman) as a thermally polymerizable compound 55 mass part 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 thermally polymerizable compound ) and 50 parts by mass of 2,2′-dimethyl-4,4′-methylenebis(cyclohexan-1-ylamine) as a curing agent C (silicone): addition curing silicone KE-1056 (Shin-Etsu manufactured by Kagaku Kogyo Co., Ltd.)
D (cyanate ester): 100 parts by mass of 1,1-bis(4-cyanatophenyl)ethane as a thermally polymerizable compound and 1500 ppm of zinc (II) acetylacetonate monohydrate as a curing agent. Mixture with 5 parts by mass of bornyl acrylate solution

(filler)
The following polysaccharide nanofibers were used as fillers.
0.3 g of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) was added while stirring 1000 g of BiNFi-s, a 2% by mass dispersion of cellulose nanofibers manufactured by Sugino Machine, with a stirrer. . After that, stirring was continued for 20 minutes, and the solvent was replaced with ethanol to obtain polysaccharide nanofibers.

《Preparation of test piece》
Test pieces (three-dimensional objects) 1 to 19 were produced using the prepared polymerizable compositions 1 to 19.

A manufacturing apparatus 1 shown in FIG. 1 was used for manufacturing the test piece. A 64 μm thick Teflon (registered trademark) AF2400 film manufactured by Biogeneral, which is permeable to oxygen, which is a polymerization inhibitor, was placed as a base material 21 at the bottom of the modeling tank 20 .
The oxygen transmission rate of this AF2400 film with a thickness of 64 μm was measured with a Gasperm-100 manufactured by Hitachi Spectroscopy Co., Ltd., and the oxygen transmission 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, a buffer region 11 containing the polymerizable composition 10 and oxygen is formed on the base material 21, and a buffer region 11 is formed above the buffer region 11. A cured region 12 having a lower oxygen concentration than region 11 was formed.
The permeation flux of oxygen is 3.4×10 ³ kmol/(s·m ² ).

Then, as the light source 40, an ultraviolet light source: an LED projector (Texas Instruments DLP (VISITECH LE4910H UV-388)) is used to irradiate light from a surface, while the modeling stage 30 is raised while a test piece for a combustion test, a tensile A test piece for testing and a test piece for measurement of deflection temperature under load were produced. At this time, the irradiation intensity of the ultraviolet rays was set to 1 mW/cm ² . Moreover, the lifting speed of the modeling stage 30 was set to 50 mm/hr.

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

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

Also, as the test piece for the combustion test, a strip-shaped test piece of 125 mm×13 mm×1.5 mm was subjected to stereolithography so that the longitudinal direction was the molding direction (lifting direction of the molding stage 30).
As a test piece for tensile test, a JIS K 7161-2 (ISO 527-2) type 1A test piece for tensile test was subjected to stereolithography so that the longitudinal direction was the molding direction.
As the test piece for measuring deflection temperature under load, a test piece of 80 mm x 10 mm x 4 mm was subjected to stereolithography so that the longitudinal direction was the molding direction.

"evaluation"
The obtained test pieces 1 to 19 were subjected to the following evaluations.
The evaluation results are shown in Table I.

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

○: Achieved V-0 △: Achieved HB, but could not achieve V-0 ×: Could not achieve HB

<Evaluation of tensile strength>
The tensile strength of the test piece for tensile test was evaluated according to the following evaluation criteria in accordance with JIS K 7161-1. At this time, the distance between the grips was 115 mm, and the test speed was 5 mm/min. Then, the value obtained by dividing the stress at break by the cross-sectional area of the test piece was calculated as the tensile strength.

◎: 150 MPa ≤ tensile strength ○: 40 MPa ≤ tensile strength < 150 MPa
△: 10 MPa ≤ tensile strength < 40 MPa

<Measurement of deflection temperature under load>
Regarding the test piece for measuring the deflection temperature under load, in accordance with ISO 75-1 and 2, using a thermal strain measuring device manufactured by Toyo Seiki Seisakusho, the deflection temperature under load is measured at a flatwise method with a distance between fulcrums of 64 mm and a bending stress of 0.45 MPa. was measured and evaluated according to the following evaluation criteria.

◎: 150 ° C. or higher ○: 50 ° C. or higher and less than 150 ° C.

As is clear from Table I, the test pieces using the polymerizable composition of the present invention have excellent tensile strength and deflection temperature under load and excellent combustibility compared to the test pieces of the comparative examples. I understand.
Specifically, compared to the test piece 1 produced using the polymerizable composition 1 containing no flame retardant protective material and the test piece 2 produced using the polymerizable composition 2 containing no flame retardant, Test pieces 3 to 19 prepared using polymerizable compositions 3 to 19 containing both a flame retardant and a flame retardant protective material exhibited improved flame retardancy. When the flame retardant protective material is present, even if the polymerizable composition is irradiated with relatively high intensity active energy rays (ultraviolet rays) in the presence of oxygen, decomposition or oxidation of the flame retardant is suppressed, and the flame retardant is It becomes possible to perform the function sufficiently.

In particular, as can be seen from test pieces 3 to 8, when the flame retardant is a halogen-based flame retardant, a phosphorus-based flame retardant, or a nitrogen-based flame retardant, and the flame retardant protective agent is an amine-based light stabilizer, polymerizable A composition containing 2 to 20 parts by mass of a flame retardant and 0.1 to 5 parts by mass of a flame retardant protective agent per 100 parts by mass of the resin component (photopolymerizable compound, thermally polymerizable compound) in the composition. (Test pieces 4, 5, 7 and 8) can simultaneously prevent the decomposition or oxidation of the flame retardant and prevent the decrease in mechanical strength due to the addition of the flame retardant or flame retardant protective material. . Incidentally, the same applies to the test piece 17 as well.

In addition, in test pieces 9 to 19 produced using polymerizable compositions 9 to 19 further containing a thermally polymerizable compound, a polymer having higher heat resistance is formed by thermal polymerization of the thermally polymerizable compound. Therefore, the heat resistance of the three-dimensional object 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, a phosphite antioxidant, or a thiol antioxidant. In some cases, the resin component (photopolymerizable compound, thermally polymerizable compound) in the polymerizable composition contains 5 to 50 parts by mass of the flame retardant and 0.1 to 5 parts by mass of the flame retardant protective agent. 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 decrease in mechanical strength due to the addition of the flame retardant or flame retardant protective material. can be realized. The same applies to the test pieces 1-8 and 1-9 .
In addition, as can be seen from test pieces 15 and 16, test piece 16 produced using polymerizable composition 16 further containing filler further improved the mechanical strength of the three-dimensional object due to the reinforcing effect of the filler.

From the above, the polymerizable composition and the three-dimensional shaped article that contain a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent can produce a three-dimensional shaped article with excellent flame retardancy. It has been confirmed that it is useful for providing a manufacturing method.

INDUSTRIAL APPLICABILITY The polymerizable composition of the present invention is a polymerizable composition that enables production of a three-dimensional shaped article having excellent flame retardancy, and enables production of a seamless three-dimensional shaped article with high strength.

1 Manufacturing apparatus 10 Polymerizable composition 11 Buffer region 12 Curing region 13 Oxygen channel 14 Arrow 15 showing the direction of oxygen concentration change in the modeling tank containing the polymerizable composition The direction of movement of oxygen in the oxygen channel Indicated arrow 20 modeling tank 21 substrate 30 modeling stage 40 light source 41 spatial light modulator 50 cured product

Claims (7)

A polymerizable composition used for manufacturing a three-dimensional object,
Containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent,
The flame retardant is at least one selected from halogen-based flame retardants, phosphorus-based flame retardants and nitrogen-based flame retardants,
The flame retardant protective agent is an amine light stabilizer,
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 protective 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, and
The polymerizable composition, wherein the method for producing the three-dimensional object includes the following steps (a) to (c).
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition. A polymerizable composition used for manufacturing a three-dimensional object,
Containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent,
The flame retardant is a metal hydroxide flame retardant,
The flame retardant protective agent is at least one selected from phenolic antioxidants, phosphite antioxidants and thiol antioxidants,
The content of the flame retardant 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 content of the flame retardant protective 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, and
The polymerizable composition, wherein the method for producing the three-dimensional object includes the following steps (a) to (c).
(a) a structure containing the polymerizable composition through a substrate that transmits oxygen and active energy rays;
Process of supplying oxygen into the shape tank
(b) selectively irradiating active energy rays that have passed through the buffer region where the effect of the polymerizable composition is inhibited by the oxygen to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; and curing the polymerizable composition
(c) a step of continuously irradiating the active energy ray while moving the cured polymerizable composition to three-dimensionally and continuously form a shaped article obtained by curing the polymerizable composition; 3. The polymerizable composition according to claim 1, wherein the photopolymerizable compound is a compound having a (meth)acryloyl group. 4. The polymerizable composition according to any one of claims 1 to 3 , further comprising a liquid thermally polymerizable compound. 5. The polymerizable composition according to any one of claims 1 to 4 , further comprising a filler. A method for producing a three-dimensional object using a polymerizable composition,
The polymerizable composition is the polymerizable composition according to any one of claims 1 to 5 ,
including the following steps (a) to (c), and
A method for producing a three-dimensional object, wherein in the step (b), an active energy ray within a range of 1 to 200 mW/cm ² is applied.
(a) a step of supplying oxygen into a modeling tank containing the polymerizable composition through a substrate that transmits oxygen and active energy rays; (b) the oxygen inhibits the effect of the polymerizable composition; (c) curing the polymerizable composition by selectively irradiating the active energy ray that has passed through the buffer region to the curing region where the oxygen concentration is lower and the polymerizable composition can be cured; A step of continuously irradiating the active energy ray while moving the polymerizable composition to form three-dimensionally and continuously a modeled object obtained by curing the polymerizable composition. 3. The method according to claim 1, wherein in the step (a), the permeation flux of oxygen into the modeling tank is within the range of 3.4×10 ³ to 170×10 ³ kmol/(s·m ² ). 7. The method for manufacturing a three-dimensional model according to 6 .

Images