JP7289676B2 - Curable resin composition for three-dimensional modeling - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition and a method for producing a three-dimensional object using the same.

As an example of the application of the liquid curable resin composition, the curable resin composition is cured layer by layer with light such as ultraviolet light, and the layers are sequentially laminated to produce a desired three-dimensional object. method (stereolithography method) has been earnestly studied. The use of stereolithography is not limited to the production of prototypes for shape confirmation (rapid prototyping), but is expanding to the production of working models and molds for functional verification (rapid tooling). In addition, the use of stereolithography is expanding to the modeling of actual products (rapid manufacturing).
Against this background, demands for curable resin compositions are becoming more sophisticated. Recently, there is a demand for a curable resin composition capable of forming a three-dimensional object having high slidability comparable to that of general-purpose engineering plastics and mechanical properties (strength, rigidity, toughness, etc.). As a method of lowering the friction coefficient of the cured product and improving the releasability and sliding properties, it is common to lower the surface free energy, add a solid lubricant, and incorporate a liquid lubricant such as oil. well known. In addition, mechanical properties such as thermal stability and toughness of the cured product largely depend on the chemical structure of the compounds contained in the resin composition. For example, it is generally well known that having a rigid structure gives a cured product with excellent heat resistance, and having a flexible structure gives a cured product with excellent toughness, and many studies have been made so far.
Patent Document 1 describes a resin composition using a urethane acrylate and an acrylic compound having a polycyclic substituent, and discloses that it can provide a highly durable protective coat with little warping after curing. Patent Document 2 describes a resin composition using an acrylic compound and polydimethylsiloxane having an acryloyl group, and discloses that a light sealing material having excellent transparency and heat resistance can be provided. Patent Document 3 describes a resin composition using an acrylic resin polymer and polydimethylsiloxane having an acryloyl group, and discloses that a topcoat layer having excellent wear resistance and adhesion can be provided. . Patent Document 4 describes a resin composition using a compound having two or more (meth)acryloyl groups and a silicon-modified poly(meth)acrylate compound, and exhibits high surface hardness and high surface hardness while suppressing curling. It is disclosed that a hard coat layer with scratch resistance can be provided.

Japanese Unexamined Patent Application Publication No. 2007-2144 JP 2011-225779 A JP 2011-16871 A WO2016/171024

When used as a curable resin composition for stereolithography, the cured product is desired to have high heat resistance, toughness and sliding properties. Furthermore, it is preferable from the viewpoint of modeling accuracy that the viscosity of the curable resin composition before curing is low. However, it is difficult to satisfy all of these physical properties, and the resin composition described in Patent Document 1 does not contain a component that improves the sliding property, so the sliding property was not sufficiently good. . The resin composition described in Patent Document 2 did not give a cured product with sufficiently good toughness. Since the resin composition described in Patent Document 3 uses an acrylic polymer, the resin composition has a high viscosity and is not suitable as a resin composition for stereolithography. Since the resin composition described in Patent Document 4 has a high acrylic value, the toughness of the resulting cured product was not sufficiently high.
Therefore, in the present invention, in order to solve the above-mentioned problems, a cured product for three-dimensional modeling that can obtain a cured product with low viscosity, excellent modeling accuracy, and high toughness, heat resistance, and sliding properties after curing. An object of the present invention is to provide a flexible resin composition.

The curable resin composition for three-dimensional modeling of the present invention is
(A) a (meth)acrylic compound represented by the following general formula (1) having a number average molecular weight of 2,100 or more and 3,900 or less;

（式（１）中、Ｒ₁は、水素原子またはメチル基を表す。
Ｌ₁、Ｌ₂は、置換基を有していてもよい直鎖状または環状の炭素原子数１から２０のアルキレン基または置換基を有していてもよい炭素原子数１から２０のアリーレン基を表し、前記アルキレン基およびアリーレン基を構成する炭素原子は、酸素原子、硫黄原子、窒素原子またはケイ素原子に置き換えられていても良い。
Ｌ₃は、エーテル構造、エステル構造またはカーボネート構造を含む、直鎖状または環状の２価の連結基である。
Ｑ₁、Ｑ₂、Ｑ₃は、二価の連結基－Ｏ－または－ＮＲ₂－（Ｒ₂は水素原子、置換基を有していてもよい直鎖状または環状の炭素数１から１０のアルキル基を表す）を表す。）
（Ｂ）数平均分子量が２８０以上１，０００以下である、下記一般式（２）に示される（メタ）アクリルオルガノシロキサン化合物と、

(In formula (1), R ₁ represents a hydrogen atom or a methyl group.
L ₁ and L ₂ are optionally substituted linear or cyclic C 1-20 alkylene groups or optionally substituted C 1-20 arylene groups and the carbon atoms constituting the alkylene group and the arylene group may be replaced with an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom.
L ₃ is a linear or cyclic divalent linking group containing an ether structure, an ester structure or a carbonate structure.
Q ₁ , Q ₂ and Q ₃ are divalent linking groups —O— or —NR ₂ — (R ₂ is a hydrogen atom, an optionally substituted linear or cyclic carbon number of 1 to 10 represents an alkyl group). )
(B) a (meth)acrylic organosiloxane compound represented by the following general formula (2) having a number average molecular weight of 280 or more and 1,000 or less;

（式（２）中、Ｒ₃は、水素原子またはメチル基を表す。
Ｒ₄は、炭素数１から６のアルキル基またはフェニル基を表し、異なる繰り返し構成単位のＲ₄同士は異なっていてもよい。
Ｌ₄は、単結合、置換基を有していてもよい直鎖状または環状の炭素原子数１から１０のアルキレン基を表し、前記アルキレン基を構成する炭素原子は、酸素原子、硫黄原子、窒素原子またはケイ素原子に置き換えられていても良い。
Ｑ₄は、単結合または二価の連結基－Ｏ－を表す。
ｍは、繰り返し構成単位の平均値を表し、（メタ）アクリルオルガノシロキサン化合物の数平均分子量が２８０以上１，０００以下になる値である。）
（Ｃ）硬化剤と、
を含有し、前記（メタ）アクリル化合物（Ａ）と前記（メタ）アクリルオルガノシロキサン化合物（Ｂ）との合計１００質量部に対して、前記（メタ）アクリル化合物（Ａ）と前記（メタ）アクリルオルガノシロキサン化合物（Ｂ）の質量比が、４０：６０乃至８５：１５であることを特徴とする。

(In Formula (2), R ₃ represents a hydrogen atom or a methyl group.
R ₄ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ₄ in different repeating structural units may be different.
L ₄ represents a single bond, an optionally substituted linear or cyclic alkylene group having 1 to 10 carbon atoms, and the carbon atoms constituting the alkylene group are an oxygen atom, a sulfur atom, It may be replaced with a nitrogen atom or a silicon atom.
Q ₄ represents a single bond or a divalent linking group -O-.
m represents the average value of repeating structural units, and is a value at which the number average molecular weight of the (meth)acrylorganosiloxane compound is 280 or more and 1,000 or less. )
(C) a curing agent;
containing, with respect to a total of 100 parts by mass of the (meth) acrylic compound (A) and the (meth) acrylic organosiloxane compound (B), the (meth) acrylic compound (A) and the (meth) acrylic The mass ratio of the organosiloxane compound (B) is from 40:60 to 85:15.

The curable resin composition for three-dimensional modeling of the present invention can provide a cured product having low viscosity, excellent modeling accuracy, and high toughness, heat resistance, and sliding properties after curing.

Embodiments of the present invention will be described below. The embodiment described below is merely one of the embodiments of the present invention, and the present invention is not limited to these embodiments.

<(Meth)acrylic compound (A) (component (A))>
The (meth)acrylic compound (A) used in the present invention has a number average molecular weight of 5,000 or less and is represented by the following general formula (1).

In general formula (1) above, R ₁ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

L ₁ and L ₂ are optionally substituted linear or cyclic C 1-20 alkylene groups or optionally substituted C 1-20 arylene groups represents Examples of L ₁ and L ₂ include linear alkylene groups such as a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene group, and cyclo Alicyclic alkylene groups such as propanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, phenylene group, tolylene group, biphenylene group, naphthalenediyl group, anthracenediyl group , a phenanthenediyl group, a fluorenediyl group, a diphenylmethanediyl group, a diphenylethanediyl group, and a diphenylpropanediyl group.

In addition, the carbon atoms constituting the alkylene group and arylene group may be replaced with an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, in which case the number of unsubstituted carbon atoms is 1 to 20. preferable. Examples thereof include dimethyletherdiyl group, diethylether group, dimethylsulfonediyl group, diethylsulfonediyl group, dimethylaminodiyl group, diethylaminodiyl group, pyridinediyl group and the like.

These may be unsubstituted or may have a substituent other than a (meth)acryloyl group. Substituents that may be present include, for example, linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Linear alkyl groups such as groups, cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, phenyl, tolyl, naphthyl, anthranyl, phenanthryl groups, etc. and alkoxy groups such as an aromatic hydrocarbon group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group.

L ₁ is preferably a methylene group, ethylene group, propylene group or butylene group. By using the (meth)acrylic compound (A) having these substituents, the viscosity of the curable resin composition of the present invention can be kept low, and the cured product obtained from the curable resin composition of the present invention. Heat resistance can be improved.

From the viewpoint of availability, L ₂ is preferably a diphenylmethanediyl group, a hexylene group, a phenylene group, a tolylene group, or an isophoronylene group. When a hexylene group or an isophoronylene group is used, the toughness of the cured product obtained from the curable resin composition of the present invention can be enhanced. Moreover, when using a diphenylmethanediyl group, a phenylene group, or a tolylene group, the heat resistance of the cured product obtained from the curable resin composition of the present invention can be enhanced.

L ₃ represents a linear or cyclic divalent linking group containing an ether structure, an ester structure or a carbonate structure. L ₃ preferably has, as a constituent unit, an alkylene unit such as methylene, a cycloalkylene unit such as cyclohexylene, or an arylene unit such as phenylene. When L ₃ contains an ether structure, it is preferable because the rotation of the molecule is not inhibited and the toughness of the cured product obtained from the curable resin composition of the present invention is excellent. In addition, when an ester structure or a carbonate structure is included, the rotation of molecules is suppressed to some extent, so that the cured product obtained from the curable resin composition of the present invention has an excellent balance between heat resistance and toughness, which is preferable.

Q ₁ , Q ₂ and Q ₃ each represent a divalent linking group —O— or —NR ₂ —, and R ₂ is a hydrogen atom or a direct group optionally having a substituent other than a (meth)acryloyl group. represents a chain or cyclic alkyl group having 1 to 10 carbon atoms; Examples of alkyl groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl cyclic alkyl groups such as groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups and cyclooctyl groups. From the viewpoint of reactivity, R ₂ is preferably a hydrogen atom. Q ₁ to Q ₃ are preferably -O- because of the availability of starting materials and the ability to select from a wide variety of starting materials.

The (meth)acrylic compound (A) of the present invention has a number average molecular weight of 5,000 or less. More preferably, the number average molecular weight is 1000 or more and 3200 or less. When the number average molecular weight of the (meth)acrylic compound (A) increases, the concentration of (meth)acryloyl groups tends to decrease and the heat resistance tends to decrease. It is preferable because the concentration of (meth)acryloyl groups achieves both toughness and heat resistance. Furthermore, it is preferable because the viscosity of the curable resin composition can be kept low.

(Meth) acrylic compounds (A) include, for example, UX-3204, UX-4101, UX-6100, UX-6101, UX-8101, UX-0937, UXF-4001-M35, UXF-4002 (above, Japan Kayaku), V-4221 (manufactured by DIC), U-2PPA, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P (manufactured by Shin-Nakamura Chemical) , Hitaloid 4861, Teslac 2300, Hitaloid 4863, Teslac 2311, Teslac 2304 (manufactured by Hitachi Chemical Co., Ltd.) AH-600, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UN-333, UN-2600, UN-2700 , and UN-9000PEP (manufactured by Negami Kogyo Co., Ltd.) can be suitably used.

As a specific example of the (meth)acrylic compound (A), a (meth)acrylic compound represented by the following structure is preferable from the viewpoint of achieving both toughness and heat resistance.

From the viewpoint of improving the toughness, heat resistance, and sliding properties of the cured product, the mass ratio of component (A) to component (B) ((A):(B)) is Taking the total mass value as 100, the ratio is 40:60 to 85:15, preferably 66:34 to 85:15. That is, the content of the (meth)acrylic compound (A) is 40 parts by mass or more and 85 parts by mass with respect to a total of 100 parts by mass of the (meth)acrylic compound (A) and the (meth)acrylic organosiloxane compound (B). Below, it is preferably 66 parts by mass or more and 85 parts by mass or less.

(Method for producing (meth)acrylic compound (A))
The method for producing the (meth)acrylic compound (A) is not particularly limited. ) to obtain a diisocyanate compound (A-iv) having isocyanate groups at both ends. Then, a diisocyanate compound (A-iv) having isocyanate groups at both ends and a (meth)acrylic compound (A-v) having a hydroxyl group or a (meth)acrylic compound (A-vi) having an amino group are reacted. to obtain the (meth)acrylic compound (A) of the present invention.

Examples of the diol compound (Ai) include compounds represented by the following general formula (3). L ₃ in general formula (3) corresponds to L ₃ in general formula (1), and the details are as explained in general formula (1). The diol compound (Ai) may be used alone or in combination of two or more.

Examples of the diamino compound (A-ii) include compounds represented by the following general formula (4). L ₃ and R ₂ in general formula (4) correspond to L ₃ and R ₂ in general formula (1), respectively, and the details are as explained in general formula (1). The diamino compound (A-ii) may be used alone or in combination of two or more.

Examples of the diisocyanate compound (A-iii) include aliphatic diisocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, Alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylenebis(cyclohexylisocyanate) or dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate, phenylene diisocyanate, tri Aromatic diisocyanates such as diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, and the like, but are not limited thereto. The diisocyanate compound (A-iii) may be used alone or in combination of two or more.

(Meth)acrylic compounds (A-v) having a hydroxyl group include, for example, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, N-( hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxypropyl)acrylamide, N-(3-hydroxypropyl)acrylamide, N-(4-hydroxybutyl)acrylamide, hydroxymethyl methacrylate, 2 - hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, N-(hydroxymethyl) methacrylamide, N-(2-hydroxyethyl) methacrylamide, N-(2-hydroxypropyl) ) methacrylamide, N-(3-hydroxypropyl)methacrylamide, N-(4-hydroxybutyl)methacrylamide, and the like, but are not limited thereto. The (meth)acrylic compounds (Av) having a hydroxyl group may be used alone or in combination of two or more.

(Meth)acrylic compounds (A-vi) having an amino group include, for example, aminomethyl acrylate, 2-aminoethyl acrylate, 2-aminopropyl acrylate, 3-aminopropyl acrylate, 4-aminobutyl acrylate, N-( aminomethyl)acrylamide, N-(2-aminoethyl)acrylamide, N-(2-aminopropyl)acrylamide, N-(3-aminopropyl)acrylamide, N-(4-aminobutyl)acrylamide, aminomethyl methacrylate, 2 -aminoethyl methacrylate, 2-aminopropyl methacrylate, 3-aminopropyl methacrylate, 4-aminobutyl methacrylate, N-(aminomethyl) methacrylamide, N-(2-aminoethyl) methacrylamide, N-(2-aminopropyl) ) methacrylamide, N-(3-aminopropyl)methacrylamide, N-(4-aminobutyl)methacrylamide, and the like, but are not limited thereto. The (meth)acrylic compound (A-vi) having an amino group may be used alone or in combination of two or more.

Further, as another production method, a (meth)acrylic compound (A-v) having a hydroxyl group or a (meth)acrylic compound (A-vi) having an amino group and an excess diisocyanate compound (A-iii) A (meth)acrylic compound (A-vii) having an isocyanate group at the end is obtained by reaction. Next, by reacting the (meth)acrylic compound (A-vii) having an isocyanate group at the end with the diol compound (Ai) or the diamino compound (A-ii), the (meth)acrylic compound (A ) can also be obtained.

<(Meth)acrylic organosiloxane compound (B) (component (B))>
The (meth)acrylorganosiloxane compound (B) used in the present invention has a number average molecular weight of 1,000 or less and is represented by the following general formula (2).

In formula (2), _R3 represents a hydrogen atom or a methyl group.

R ₄ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ₄ in different repeating structural units may be different. Examples of alkyl groups for _R4 include methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. When R ₄ is a methyl group, it is preferable because the coefficient of friction of the cured product obtained from the curable resin composition of the present invention can be kept low. It is preferable because the heat resistance of the cured product obtained can be increased.

L ₄ represents a linear or cyclic alkylene group having 1 to 20 carbon atoms which may have a substituent other than a single bond and a (meth)acryloyl group. The carbon atoms constituting the alkylene group may be replaced by an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, and in this case, the number of unsubstituted carbon atoms is preferably 1 to 20.

Examples of L ₄ include the same alkylene groups as L ₁ and L ₂ in general formula (1) described above. _L4 is preferably a single bond, a methylene group, an ethylene group, a propylene group or a butylene group. In this case, the viscosity of the curable resin composition can be kept low, and the heat resistance of the cured product obtained from the curable resin composition of the present invention increases.

Q ₄ represents a single bond or a divalent linking group -O-. Q ₄ is preferably -O- because of the availability of starting materials and the ability to select from a wide variety of starting materials.

m represents the average value of repeating structural units, and is the value at which the number average molecular weight of the (meth)acrylorganosiloxane compound is 1,000 or less. In order to achieve both toughness and heat resistance, which are important physical properties of a cured product for three-dimensional modeling, it is important to keep the (meth)acryloyl concentration of the entire curable resin composition neither too high nor too low. be. Since the (meth)acrylorganosiloxane compound (B) of the present invention has two (meth)acryloyl groups, when the number average molecular weight is determined by m of the repeating structural unit, the concentration of the (meth)acryloyl groups is uniquely Determined. It is preferable to select m such that the number average molecular weight of the (meth)acrylic organosiloxane compound (B) is 1,000 or less, more preferably 200 or more and 500 or less. By selecting such m, it is possible to achieve a concentration of (meth)acrylic groups that satisfies both toughness and heat resistance of the resulting cured product. Furthermore, it is preferable because the viscosity of the curable resin composition can be kept low.

Commercially available products such as X-22-164 and X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd.) can be suitably used as the (meth)acrylic organosiloxane compound (B).

As a specific example of the (meth)acrylorganosiloxane compound (B), a (meth)acrylorganosiloxane compound represented by the following structure is preferable from the viewpoint of achieving both toughness and heat resistance.

From the viewpoint of improving the toughness, heat resistance, and sliding properties of the cured product, the mass ratio of component (A) to component (B) ((A):(B)) is Taking the total mass value as 100, the ratio is 40:60 to 85:15, preferably 66:34 to 85:15. That is, the content of the (meth)acrylorganosiloxane compound (B) is 15 parts by mass or more and 60 Parts by mass or less, preferably 15 parts by mass or more and 34 parts by mass or less.

(Method for producing (meth)acrylic organosiloxane compound (B))
The method for producing the (meth)acrylorganosiloxane compound (B) is not particularly limited. ) acrylic organosiloxane compound (B) can be obtained.

Examples of the organosiloxane diol compound (Bi) include compounds represented by the following general formula (5). Q ₄ , L ₄ , R ₄ and m in general formula (5) correspond to Q ₄ , L ₄ , R ₄ and m in general formula (2), the details of which are explained in general formula (2). As I said.

Further, as another production method, (meth)acrylicorganosiloxane can also be produced by reacting the diol compound (Bi) of (meth)acrylicorganosiloxane and (meth)acrylic acid in the presence of a condensing agent such as carbodiimide. Compound (B) can also be obtained.

<Curing Agent (C) (Component (C))>
As the curing agent (C), a photopolymerization initiator is preferably used, and a photoradical polymerization initiator is more preferably used. These may be used singly or in combination as long as the effects of the present invention are not impaired. In addition to the photopolymerization initiator, other curing agents such as thermal radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, and thermal latent curing agents may be contained.

[Radical photopolymerization initiator]
Photoradical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type. In the intramolecular cleavage type, by absorbing light of a specific wavelength, a bond at a specific site is cleaved, and a radical is generated at the cleaved site, which acts as a polymerization initiator and acts as a (meth)acrylic compound (A). and polymerization of the (meth)acrylorganosiloxane compound (B) begins. In the hydrogen abstraction type, it absorbs light of a specific wavelength and becomes an excited state, and the excited species causes a hydrogen abstraction reaction from the surrounding hydrogen donor, generating radicals, which act as polymerization initiators and become (meth)acrylic compounds. Polymerization of (A) and (meth)acrylic organosiloxane compound (B) begins.

As the intramolecular cleavage type photoradical polymerization initiator, an alkylphenone photoradical polymerization initiator, an acylphosphine oxide photoradical polymerization initiator, and an oxime ester photoradical polymerization initiator are known. These are of the type in which the bond adjacent to the carbonyl group undergoes α-cleavage to generate a radical species. Examples of the alkylphenone-based radical photopolymerization initiator include benzylmethylketal-based radical photopolymerization initiators, α-hydroxyalkylphenone-based radical photopolymerization initiators, and aminoalkylphenone-based radical photopolymerization initiators. Specific compounds include, for example, benzyl methyl ketal photoradical polymerization initiators such as 2,2′-dimethoxy-1,2-diphenylethan-1-one (Irgacure (R) 651, manufactured by BASF). 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure (R) 1173, manufactured by BASF) and 1-hydroxycyclohexylphenyl ketone as α-hydroxyalkylphenone photoradical polymerization initiators. (Irgacure (R) 184, manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure (R) 2959, manufactured by BASF) ), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Irgacure (R) 127, manufactured by BASF), etc. , and the aminoalkylphenone photoradical polymerization initiator includes 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure (R) 907, manufactured by BASF) or 2 -benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (Irgacure (R) 369, manufactured by BASF) and the like, but are not limited thereto. Acylphosphine oxide-based photoradical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (lucirin (R) TPO, manufactured by BASF) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. (Irgacure (R) 819, manufactured by BASF) and the like, but are not limited to these. As the oxime ester photoradical polymerization initiator, (2E)-2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (Irgacure (R) OXE-01, manufactured by BASF Corporation ), etc., but not limited to these.

Hydrogen abstraction photoradical polymerization initiators include anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-t-butyl-9,10-anthraquinone, thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone. but not limited thereto.

In the present invention, two or more photoradical polymerization initiators may be used in combination, or may be used alone. In addition, a thermal radical polymerization initiator may be contained in order to advance the polymerization reaction by heat treatment after modeling.

The amount of the radical photopolymerization initiator to be added is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass, with respect to 100 parts by mass of all the radically polymerizable compounds in the curable resin composition. It is more than 10 parts by mass and less than 10 parts by mass. If the amount of photoradical polymerization initiator is small, polymerization tends to be insufficient. If the amount of the radical photopolymerization initiator is large, the light transmittance may be lowered and the polymerization may become uneven.

[Thermal radical polymerization initiator]
The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides and persulfates are preferred. can be exemplified. Azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- and azobis(1-acetoxy-1-phenylethane). Examples of peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate and di(4-t-butylcyclohexyl)peroxydicarbonate. Persulfates include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

The amount of the thermal radical polymerization initiator to be added is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.1 part by mass, with respect to 100 parts by mass of all the radically polymerizable compounds in the curable resin composition. It is more than 10 parts by mass and less than 10 parts by mass. If the thermal radical polymerization initiator is excessively added, the molecular weight cannot be increased and the physical properties may deteriorate.

[Cationic polymerization initiator]
When adding a cationic polymerizable compound as a reactive diluent (D) described later to the curable resin composition of the present invention, a cationic polymerization initiator can be used. Cationic polymerization initiators are classified into photoacid generators and thermal acid generators.

(Photoacid generator)
The photoacid generator is a photocationically polymerizable initiator that generates an acid capable of initiating cationic polymerization by irradiation with energy rays such as ultraviolet rays.

Examples of photocationically polymerizable initiators include, for example, cationic moieties such as aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxanthonium, (2,4-cyclopentadien-1-yl ) [(1-methylethylbenzene]-Fe cation, and the anion moiety is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , [BX ₄ ] ^{- ,} where X is at least two fluorines or trifluoromethyl An onium salt composed of a phenyl group substituted with a group) can be used alone or in combination of two or more.

Examples of aromatic sulfonium salts include bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenylsulfonio) nio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio) Phenylsulfonium hexafluoroantimonate, Diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, Diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, Triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroantimonate triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[ 4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide Bis-tetrafluoroborate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate and the like can be used.

Examples of aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis (dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa fluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-( 1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate and the like can be used.

As aromatic diazonium salts, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis(pentafluorophenyl)borate, etc. can be used.

Further, aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl- 2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)- 2-Cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate and the like can be used.

Thianthrenium salts include 5-methylthianthrenium hexafluorophosphate, 5-methyl-10-oxothianthenium tetrafluoroborate, 5-methyl-10,10-dioxothianthrenium hexafluorophosphate, and the like. can be used.

As the thioxanthonium salt, S-biphenyl 2-isopropylthioxanthonium hexafluorophosphate and the like can be used.

Further, as the (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe salt, (2,4-cyclopentadien-1-yl)[(1-methylethylbenzene]-Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)[(1-methylethylbenzene]-Fe(II) hexafluoroantimonate, (2,4-cyclopentadien-1-yl)[( 1-methylethylbenzene]-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)[(1-methylethylbenzene]-Fe(II) tetrakis(pentafluorophenyl)borate, etc. can be done.

Examples of photocationic polymerization initiators include CPI (R)-100P, CPI (R)-110P, CPI (R)-101A, CPI (R)-200K, and CPI (R)-210S (San-Apro Co., Ltd. ), Cyracure (R) photo-curing initiator UVI-6990, Cyracure (R) photo-curing initiator UVI-6992, Cyracure (R) photo-curing initiator UVI-6976 (manufactured by Dow Chemical Japan), Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300 (manufactured by ADEKA Co., Ltd.), CI-5102, CI-2855 (Above, manufactured by Nippon Soda Co., Ltd.), San-Aid (R) SI-60L, San-Aid (R) SI-80L, San-Aid (R) SI-100L, San-Aid (R) SI-110L, San-Aid (R) SI-180L , San-Aid (R) SI-110, San-Aid (R) SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure (R) 1064, Esacure (R) 1187 (manufactured by Lamberti), Omnicat 550 (manufactured by IGM Resin), Irgacure (R) 250 (manufactured by BASF), Rhodosyl Photoinitiator 2074 (RHODORSILPOTOINITIATOR 2074 (manufactured by Rhodia Japan), etc. are commercially available.

In the present invention, two or more photocationic polymerization initiators may be used in combination, or may be used alone. In addition, other curing agents such as a thermal cationic polymerization initiator may be contained at the same time in order to advance the polymerization reaction by heat treatment after modeling.

The amount of the photoacid generator to be added is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of the cationic polymerizable compound. be. If the amount of the photoacid generator is small, the polymerization tends to be insufficient. If the amount of the photoacid generator is large, the light transmittance may be lowered and the polymerization may become non-uniform.

(Thermal acid generator)
A thermal acid generator is also called a thermal cationic polymerization initiator. A compound containing a cationic species is excited by heating, a thermal decomposition reaction occurs, and it exhibits a substantial function as a curing agent that advances thermal curing. Thermal cationic polymerization initiators, unlike acid anhydrides, amines, phenolic resins, etc., which are generally used as curing agents, even if they are contained in the resin composition, It does not cause viscosity increase or gelling. Therefore, it is possible to provide a one-liquid resin composition excellent in handleability.

Thermal cationic polymerization initiators include, for example, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, triphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenyl sulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-p-toluenesulfonate, diphenyl-p-phenylthiophenylsulfonium hexafluorophosphate and the like.

In the present invention, as a thermal cationic polymerization initiator, for example, diazonium salt compounds AMERICURE series (manufactured by American Scan), ULTRASET series (manufactured by ADEKA), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), iodonium salt-based Compounds UVE series (manufactured by General Electric Co.), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), WPI series (manufactured by Wako Pure Chemical Industries), CYRACURE series of sulfonium salt compounds (Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Sartomer), Optomer SP series, Optomer CP series (manufactured by Adeka), San-Aid SI series (Sanshin) Chemical Industry Co., Ltd.), CI series (Nippon Soda Co., Ltd.), WPAG series (Wako Pure Chemical Industries, Ltd.), CPI series (San-Apro Co., Ltd.), and other commercially available products can be used.

In the present invention, two or more thermal cationic polymerization initiators may be used in combination, or may be used alone. A thermal cationic polymerization initiator that decomposes at a high temperature may also be used in order to advance the polymerization reaction by heat treatment after modeling.

The amount of the thermal acid generator to be added is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to a total of 100 parts by mass of the cationic polymerizable compound. be. If the amount of the thermal acid generator is too small, the polymerization tends to be insufficient.

[Anionic polymerization initiator]
When adding an anionically polymerizable compound as a reactive diluent (D) described later to the curable resin composition of the present invention, an anionic polymerization initiator can be used. A photo-salt generator can be used as an anionic polymerization initiator.

(Photobase generator)
A photobase generator refers to a compound that generates a base upon irradiation with energy rays such as ultraviolet rays and visible light. In particular, a salt containing a borate anion is preferred because of its good sensitivity to light. Specific products include U-CAT5002 manufactured by San-Apro Co., Ltd., and P3B, BP3B, N3B, and MN3B manufactured by Showa Denko K.K., but are not limited to these.

The amount of the anionic polymerization initiator to be added is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to the total of 100 parts by mass of the anionically polymerizable compounds. be. When the amount of the anionic polymerization initiator is small, the polymerization tends to be insufficient.

[Other curing agents]
The following thermal latent curing agents can be used in the curable resin composition of the present invention. A heat-latent curing agent refers to a curing agent that advances thermal curing by heating.

As the acid anhydride (acid anhydride-based curing agent), a known or commonly used acid anhydride-based curing agent can be used, and is not particularly limited. 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, Phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, methyl nadic anhydride , hydrogenated methylnadic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexenetetracarboxylic anhydride, vinyl ether-maleic anhydride copolymers, alkylstyrene-maleic anhydride copolymers, and the like. Among them, acid anhydrides that are liquid at 25° C. [eg, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] are preferable from the viewpoint of handling. On the other hand, for an acid anhydride that is solid at 25°C, for example, by dissolving it in an acid anhydride that is liquid at 25°C to form a liquid mixture, the curable resin composition of the present invention can be handled more easily. Tend. As the acid anhydride-based curing agent, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including an anhydride having a substituent such as an alkyl group bonded to the ring) is preferable from the viewpoint of heat resistance and transparency of the cured product.

As amines (amine-based curing agents), known or commonly used amine-based curing agents can be used without particular limitation. Examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, and diethylaminopropylamine. , aliphatic polyamines such as polypropylenetriamine; alicyclic polyamines such as bis(3-aminopropyl)-3,4,8,10-tetraoxaspiro[5,5]undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, Mononuclear polyamines such as tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6-diamine, biphenylene Aromatic polyamines such as diamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine, and the like are included.

Phenols (phenol-based curing agents) can be known or commonly used phenol-based curing agents, and are not particularly limited. Aralkyl resins such as resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, triphenol propane and the like can be mentioned.

Polyamide resins include, for example, polyamide resins having either or both of a primary amino group and a secondary amino group in the molecule.

As imidazoles (imidazole-based curing agents), known or commonly used imidazole-based curing agents can be used without particular limitation. Examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino -6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine and the like mentioned.

Examples of polymercaptans (polymercaptan-based curing agents) include liquid polymercaptans and polysulfide resins.

Examples of polycarboxylic acids include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxy group-containing polyesters.

The amount of the other curing agent added is preferably 0.1 parts by mass or more and 75 parts by mass or less with respect to a total of 100 parts by mass of the (meth)acrylic compound (A) and the (meth)acrylic organosiloxane compound (B). More preferably, it is 5 parts by mass or more and 30 parts by mass or less. If the amount of the other curing agent added is too small, the polymerization tends to be insufficient.

<Reactive Diluent (D) (Component (D))>
The curable resin composition according to the present invention may contain a reactive diluent (D) in addition to the (meth)acrylic compound (A) and the (meth)acrylic organosiloxane compound (B). By including the reactive diluent (D) in the curable composition, the viscosity of the curable composition can be reduced. Moreover, the mechanical properties and thermal properties of the cured product obtained by curing the curable composition can be adjusted. The reactive diluent (D) can be added with radically polymerizable, cationically polymerizable, or anionically polymerizable monomers.

Examples of radically polymerizable monomers include (meth)acrylate-based monomers, styrene-based monomers, acrylonitrile compounds, vinyl ester-based monomers, N-vinylpyrrolidone, acrylamide-based monomers, conjugated diene-based monomers, vinyl ketone-based monomers, vinyl halides, vinylidene halide-based monomers, and the like. Examples of cationic polymerizable monomers include epoxy-based monomers, oxetane-based monomers, and vinyl ether-based monomers. Monomers having anionic polymerizability include, but are not limited to, (meth)acrylate monomers. Among them, (meth)acrylate-based monomers are particularly preferred from the viewpoint of reaction rate and solubility because they have the same reactive groups as the (meth)acrylic compound (A) and (meth)acrylic organosiloxane compound (B).

Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, n-octyl (meth)acrylate, i-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 2- Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenylglycidyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, phenyl cellosolve (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, biphenyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acryloyl phosphate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, monofunctional (meth) acrylate monomers such as benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4 butanediol Di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexamethylene di(meth)acrylate, hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Polyfunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate and tris(meth)acryloxyethyl isocyanurate can be mentioned.

One or more reactive diluents (D) can be optionally mixed and used. The content of the reactive diluent (D) is 10 parts by mass or more and 75 parts by mass or less with respect to a total of 100 parts by mass of the (meth) acrylic compound (A) and the (meth) acrylic organosiloxane compound (B). It is preferably 22 parts by mass or more and 46 parts by mass or less. If the amount of the reactive diluent (D) exceeds 75 parts by mass, the effects of the present invention may be impaired. Moreover, if the amount of the reactive diluent (D) is less than 10 parts by mass, there is a possibility that the mechanical properties and thermal properties cannot be adjusted within the desired ranges.

<Other ingredients>
The curable resin composition of the present invention may contain various additives as other optional components within a range that does not impair the object and effect of the present invention. Examples of such additives include resins such as epoxy resins, polyurethanes, polybutadiene, polychloroprene, polyesters, styrene-butadiene block copolymers, polysiloxanes, petroleum resins, xylene resins, ketone resins, cellulose resins, polycarbonates, and modified polyphenylene ethers. , polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, ultra-high molecular weight polyethylene, polyphenylsulfone, polysulfone, polyarylate, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyethersulfone, polyamideimide, liquid crystal polymer, polytra Engineering plastics such as fluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, reactive monomers such as fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, fluorine-containing monomers, and siloxane structure-containing monomers, and soft materials such as gold, silver, and lead Layered crystal structure substances such as metals, graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, molybdenum selenide, phenothiazine, 2,6- Polymerization inhibitors such as di-t-butyl-4-methylphenol, photosensitizers such as benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds, polymerization Initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, antifoaming agents etc. can be mentioned.

<Curable resin composition>
The curable resin composition of the present invention is prepared by charging appropriate amounts of the essential components (A), (B) and (C) and, if necessary, other optional components into a stirring vessel, and the temperature is usually 30° C. or higher and 120° C. or lower. Preferably, it can be produced by stirring at 50°C or higher and 100°C or lower. The stirring time at that time is usually 1 minute or more and 6 hours or less, preferably 10 minutes or more and 2 hours or less. The total content of component (A) and component (B) (when component (D) is included, the total of component (A), component (B), and component (D)) is With respect to 100 parts by mass of the curable resin composition, it is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 25 parts by mass or more and 100 parts by mass or less, still more preferably 75 parts by mass or more and 100 parts by mass or less. , the effect of the present invention can be sufficiently obtained.

The viscosity at 25° C. of the curable resin composition of the present invention is preferably from 50 mPa·s to 10,000 mPa·s, more preferably from 70 mPa·s to 5,000 mPa·s.

The curable resin composition of the present invention obtained as described above is suitably used as a photocurable resin composition in optical stereolithography. That is, by selectively irradiating the curable resin composition of the present invention with active energy rays such as ultraviolet rays, electron beams, X-rays, and radiation to supply the energy necessary for curing, A three-dimensional object having a desired shape can be manufactured.

<Cured product>
The curable resin composition of the present invention comprises a (meth)acrylic compound (A), a (meth)acrylic organosiloxane compound (B), and a curing agent (C) as essential components. Obtainable. Curing can be performed using any known method such as active energy ray curing or heat curing depending on the curing agent to be contained. A plurality of curing methods may be combined.

<Function of curable resin composition>
The curable resin composition of the present invention can be cured by applying external energy to form a cured product. At this time, the radical polymerization reaction of the (meth)acrylic compound (A) and the (meth)acrylic organosiloxane compound (B) is initiated by radicals generated by the curing agent (C), and curing of the curable resin composition proceeds. do. In order to increase the curability and heat resistance of the cured product, it is preferable that the crosslink density in the cured product is high. The toughness is remarkably lowered and the steel becomes brittle.

On the other hand, in the curable resin composition of the present invention, the (meth)acrylic compound (A) and the (meth)acrylorganosiloxane compound (B) each have their own number average molecular weights. As a result, the concentration of (meth)acryloyl groups in the entire curable resin composition, ie, the crosslink density, can be adjusted to a concentration suitable for a cured product for three-dimensional modeling. As a result, it is possible to obtain a cured product having a better balance between toughness and heat resistance than conventional ones.

Furthermore, the curable resin composition according to the present invention is a curable resin composition by defining the number average molecular weights of the (meth)acrylic compound (A) and the (meth)acrylic organosiloxane compound (B). can be kept low. As a result, when a pull-down type three-dimensional shaping machine is used, the stability of the liquid surface of the curable resin composition is improved, and the molding accuracy of the cured product is improved as compared with the conventional one. In addition, when using a pull-up type three-dimensional modeling machine, it is possible to suppress the adhesion of the curable resin composition before curing to the cured product after curing, and the molding accuracy of the cured product is improved. .

<Manufacturing method of three-dimensional object>
The curable resin composition of the present invention contains a photopolymerization initiator such as a photoradical polymerization initiator as the curing agent (C), so that it can be suitably used for an optical stereolithography method. A cured product of the curable resin composition may be produced using any conventionally known optical stereolithography method and apparatus. A representative example of a preferred optical stereolithography method is a method having a step of curing a curable resin composition layer by layer based on slice data to form a modeled object. Specifically, a cured layer is formed by selectively irradiating an active energy ray based on slice data so that a cured layer having a desired pattern is obtained in a liquid curable resin composition. Next, an uncured curable resin composition is supplied to this cured layer, and an active energy ray is similarly irradiated based on the slice data to form a new cured layer continuous with the cured layer. A method of finally obtaining a desired three-dimensional object by repeating this stacking operation can be mentioned.

Examples of active energy rays used in this case include ultraviolet rays, electron beams, X-rays, and radiation. Among them, ultraviolet light having a wavelength of 300 nm or more and 450 nm or less is preferably used from an economical point of view. As a light source at that time, an ultraviolet laser (for example, Ar laser, He--Cd laser, etc.), a mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, or the like can be used. Among them, a laser light source is preferably employed because it can increase the energy level to shorten the modeling time, and has excellent light-gathering properties to obtain high modeling accuracy.

When forming each cured resin layer having a predetermined shape pattern by irradiating an active energy ray onto a molding surface made of a curable resin composition, an active energy ray focused into dots such as a laser beam is used. The cured resin layer may be formed by stippling or line drawing. In addition, there is a molding method in which active energy rays are applied to the molding surface through a planar drawing mask formed by arranging a plurality of minute light shutters such as liquid crystal shutters or digital micromirror shutters to form a cured resin layer. may be adopted.

A representative example of the optical stereolithography method is as follows. First, the curable resin composition is supplied onto the support stage by lowering (sedimenting) a small amount (sedimentation) from the liquid surface of the curable resin composition on the support stage which is provided to be able to move up and down in the container, and the thin film of the curable resin composition is supplied. Form layer (1). Next, by selectively irradiating the thin layer (1) with light, a solid cured resin layer (1) is formed. Next, a curable resin composition is supplied onto the cured resin layer (1) to form the thin layer (2), and the thin layer (2) is selectively irradiated with light to obtain a cured resin. A new cured resin layer (2) is formed on layer (1) so that it is continuously and integrally laminated therewith. By repeating this process a predetermined number of times while changing or not changing the light irradiation pattern, a three-dimensional structure in which a plurality of cured resin layers (1, 2, . . . n) are integrally laminated. A molded object is molded.

The three-dimensional object thus obtained is removed from the container, and after removing the unreacted curable resin composition remaining on the surface thereof, the object is washed as necessary. Examples of detergents include alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, and methyl ethyl ketone; and aliphatic solvents typified by terpenes. system organic solvents. In addition, after cleaning with a cleaning agent, post-curing by light irradiation or heat irradiation may be performed as necessary. Post-cure can cure the unreacted curable resin composition that may remain on the surface and inside of the three-dimensional object, and in addition to suppressing the stickiness of the surface of the three-dimensional object, the initial strength of the object can be improved.

<Application>
Applications of the curable resin composition according to the present invention and its cured product are not particularly limited. For example, it can be used for various applications such as resins for stereolithography 3D printers, sporting goods, medical and nursing care products, industrial machinery and equipment, precision equipment, electrical and electronic equipment, electrical and electronic parts, and building materials. be.

Examples are given below to describe the present invention in detail, but the present invention is not limited to these examples.

<Example 1>
Each component was blended according to the following recipe, heated to 75° C. and stirred for 2 hours with a stirrer to prepare a curable resin composition.

[(Meth) acrylic compound (A)]
Compound A-30: Nippon Kayaku "UX-6101" 66 parts by mass Compound A-30 has the structure shown below, L ₃ has a repeating structure of ether, and the number average molecular weight is 2,700 ± 500. be.

[(Meth) acrylic organosiloxane compound (B)]
Compound B-20: Shin-Etsu Chemical Co., Ltd. "X-22-164" 34 parts by mass Compound B-20 has the structure shown below, L ₄ corresponds to L ₄ in general formula (2), and its details is as described in general formula (2). m represents the number of repeating units and is a value at which the number average molecular weight is 380±100.

[Reactive diluent (D)]
Compound D-1: isobornyl methacrylate 36 parts by mass [curing agent (C)]
Compound C-1: Photoradical polymerization initiator (1-hydroxycyclohexylphenyl ketone (Irgacure (R) 184) manufactured by BASF) 3 parts by mass

[Preparation of test piece]
A test piece was prepared from the prepared curable resin composition by the following method. First, a mold having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was sandwiched between two sheets of quartz glass, and a curable resin composition was poured into the mold. The poured curable resin composition is irradiated with UV rays of 5 mW/cm ² from both sides of the mold for 120 seconds each with an UV irradiation machine (manufactured by HOYA CANDEO OPTRONICS, trade name “LIGHT SOURCE EXECURE 3000”) for temporary curing. did After that, UV rays were applied again from both sides for 600 seconds each for final curing to obtain a cured product (total energy: 7200 mJ/cm ² ). The resulting cured product was placed in a heating oven at 50°C for 1 hour and then placed in a heating oven at 100°C for 2 hours to obtain a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. rice field.

[Preparation of test film]
A test film was produced from the prepared curable resin composition by the following method. First, several drops of the curable resin composition were put on the center of a slide glass having a width of 26 mm, a length of 76 mm, and a thickness of about 1 mm, and spacers having a thickness of 300 μm were placed at both ends of the slide glass. Next, a PET film was placed on the dropped curable resin composition, and a slide glass was placed thereon. Thereafter, the dropped curable resin composition was irradiated with ultraviolet rays of 5 mW/cm ² for 300 seconds using an ultraviolet irradiator (manufactured by HOYA-SCHOTT, trade name “UV LIGHT SOURCE EX250”) (total energy of 1500 mJ/cm ² ). )bottom. Next, the PET film was peeled off, and the obtained cured product was placed in a heating oven at 50 ° C. for 1 hour and placed in a heating oven at 100 ° C. for 2 hours to obtain a thickness of 300 μmm and a diameter of about 300 μm. A test film adhered to a 2 cm glass slide was obtained.

[evaluation]
(Charpy impact strength)
According to JIS K 7111, a 45° notch with a depth of 2 mm was made in the center of the test piece with a notch forming machine (manufactured by Toyo Seiki Seisakusho, trade name "Notching Tool A-4"). Using an impact tester (manufactured by Toyo Seiki Seisakusho, trade name "IMPACT TESTER IT"), the test piece is destroyed with an energy of 2J from the back of the notch. The energy required for breaking was calculated from the angle at which the hammer raised to 150° was swung up after breaking the test piece, and this was defined as Charpy impact strength and used as an index of toughness. The toughness evaluation criteria are shown below. Table 1 shows the results obtained.
A: 7.0 kJ/m ² or more B: Less than 7.0 kJ/m ² 5.0 kJ/m ² or more C: Less than 5.0 kJ/m ²

(Load deflection temperature)
According to JIS K 7191-2 for the test piece, using a load deflection temperature tester (manufactured by Toyo Seiki Seisakusho, trade name "No. 533 HDT test device 3M-2"), bending stress 1.80 MPa, room temperature to 2 C. per minute. The temperature at which the amount of deflection of the test piece reached 0.34 mm was defined as the deflection temperature under load, and was used as an index of heat resistance. The evaluation criteria for heat resistance are shown below. Table 1 shows the results obtained.
A: 70°C or higher B: Lower than 70°C 50°C or higher C: Lower than 50°C

(Coefficient of friction)
The dynamic friction coefficient was measured using an abrasion friction tester (trade name: HEIDON Type 20, manufactured by Shinto Kagaku Co., Ltd.). The test film was fixed on a rotating stage, and a ball made of SUS304 with a diameter of 10 mm was brought into contact with it so that the sliding radius was 5 mm. A vertical load of 100 g was applied to the ball, the stage was rotated at a speed of 10 cm/sec, and the force applied between the test film and the SUS304 ball was measured. The coefficient of friction was calculated by dividing the applied force by the load. The average value excluding the initial 5 minutes of the measurement for a total of 3 hours was taken as the coefficient of dynamic friction and used as an index of slidability. The criteria for slidability are shown below. Table 1 shows the results obtained.
A: less than 0.4 B: 0.4 or more and less than 0.5 C: 0.5 or more

(viscosity)
The obtained curable resin composition was measured as follows using a viscoelasticity measuring device (MCR302 manufactured by Anton Paar). About 0.5 mL of the sample was filled in a measuring device equipped with a cone plate type measuring jig (25 mm diameter, 2°) and adjusted to 25°C. The value at a shear rate of 50 s ^-1 was taken as the viscosity. Evaluation criteria for viscosity are shown below. Table 1 shows the results obtained.
A: Less than 5.0 Pa s B: 5.0 Pa s or more and less than 10 Pa s C: 10 Pa s or more

<Examples 2 to 8, Comparative Examples 1 to 5>
A curable composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1, except that the type and content of each component were changed as shown in Table 1. Table 1 shows the results. The compounds used in Examples and Comparative Examples are as follows.

[(Meth) acrylic compound (A)]
Compound A-31: A diacrylate compound having no urethane structure, which is obtained by introducing methacrylate into "NL300B" manufactured by Ube Industries, Ltd. Compound A-32: "UX-5103D" manufactured by Nippon Kayaku (6 acryloyl groups per molecule)
Compound A-33: A urethane dimethacrylate compound having a number average molecular weight of 15,000 Compound A-34: _" KUA-PC21" manufactured by KSM (Compound A-34 has the same structure as the above [Chemical 13], L has a repeating structure containing a carbonate structure, has 2 acryloyl groups per molecule, and has a number average molecular weight of 3,400±500.)
Compound A-35: "UX-3204" manufactured by Nippon Kayaku Co., Ltd. (Compound A-35 has the structure shown in [Chemical 15] below, L ₃ has a repeating structure containing an ester structure, and has a number average molecular weight of 2, 600±500.)

[(Meth) acrylic organosiloxane compound (B)]
Compound B-21: A non-reactive polydimethylsiloxane compound having no (meth) acryloyl group B-22: A (meth) acrylic organosiloxane compound having a number average molecular weight of 3,600 (manufactured by Ube Industries, Ltd. “X-22- 164B")
Compound B-23: "X-22-164AS" manufactured by Shin-Etsu Chemical Co., Ltd. (Compound B-23 has the same structure as the above [Chemical 14], the number of acryloyl groups in one molecule is 2, the number average molecular weight is 900 ± 100 is.)

Compound D-2: isobornyl acrylate

As shown in Table 1, all of Examples 1 to 8 according to the present invention had a Charpy impact strength of 5.0 KJ/m ² or more, a deflection temperature under load of 50°C or more, and a friction coefficient of less than 0.5. It was possible to obtain a cured product having both good toughness and heat resistance and high slidability. Moreover, since the viscosity of the curable resin composition is less than 10 Pa·sec, it is possible to provide a curable resin composition with excellent modeling accuracy.

In addition, there is a suitable range for the ratio of the (meth)acrylic compound (A) to the (meth)acrylic organosiloxane compound (B), and Comparative Examples 1 and 2, which are outside the preferred range, exceed the evaluation target values. There was an item that I couldn't do. These results suggest that the (meth)acrylorganosiloxane compound (B) is highly effective in reducing the coefficient of friction and viscosity, but that if the amount added is too large, the toughness and heat resistance deteriorate.

On the other hand, in Comparative Examples 3 to 5, in which component (A) does not belong to the scope of the present invention, the target value for evaluation is There were items that could not be surpassed. These results suggest that the (meth)acrylic compound (A) preferably has two (meth)acryloyl groups, has a urethane or urea structure in the molecule, and has a number average molecular weight of 5000 or less. .

Furthermore, in Comparative Examples 6 and 7 where the component (B) does not belong to the scope of the present invention, the target value of the evaluation is There were items that could not be surpassed. These results suggest that the (meth)acrylorganosiloxane compound (B) preferably has two (meth)acryloyl groups and a number average molecular weight of 1,000 or less.

Claims (20)

(A) a (meth)acrylic compound represented by the following general formula (1) having a number average molecular weight of 2,100 or more and 3,900 or less;

(In formula (1), R ₁ represents a hydrogen atom or a methyl group.
L ₁ and L ₂ are optionally substituted linear or cyclic C 1-20 alkylene groups or optionally substituted C 1-20 arylene groups and the carbon atoms constituting the alkylene group and the arylene group may be replaced with an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom.
L ₃ is a linear or cyclic divalent linking group containing an ether structure, an ester structure or a carbonate structure.
Q ₁ , Q ₂ and Q ₃ are divalent linking groups —O— or —NR ₂ — (R ₂ is a hydrogen atom, an optionally substituted linear or cyclic carbon number of 1 to 10 represents an alkyl group). )
(B) a (meth)acrylic organosiloxane compound represented by the following general formula (2) having a number average molecular weight of 280 or more and 1,000 or less;

(In Formula (2), R ₃ represents a hydrogen atom or a methyl group.
R ₄ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ₄ in different repeating structural units may be different.
L ₄ represents a single bond, an optionally substituted linear or cyclic alkylene group having 1 to 10 carbon atoms, and the carbon atoms constituting the alkylene group are an oxygen atom, a sulfur atom, It may be replaced with a nitrogen atom or a silicon atom.
Q ₄ represents a single bond or a divalent linking group -O-.
m represents the average value of repeating structural units, and is a value at which the number average molecular weight of the (meth)acrylorganosiloxane compound is 280 or more and 1,000 or less. )
(C) a curing agent;
containing, with respect to a total of 100 parts by mass of the (meth) acrylic compound (A) and the (meth) acrylic organosiloxane compound (B), the (meth) acrylic compound (A) and the (meth) acrylic A curable resin composition for stereolithography, wherein the mass ratio of the organosiloxane compound (B) is from 40:60 to 85:15. The curable resin composition for stereolithography according to claim 1, wherein the (meth)acrylic compound (A) has a number average molecular weight of 2,100 or more and 3,200 or less. The curable resin composition for stereolithography according to claim 1 or 2, wherein _R1 in the (meth)acrylic compound (A) is hydrogen. 4. The stereo according to any one of claims 1 to 3, wherein Q ₁ , Q ₂ and Q ₃ in the (meth)acrylic compound (A) are divalent linking groups -O-. A curable resin composition for modeling. The curable resin composition for stereolithography according to any one of claims 1 to 4, wherein the (meth)acrylorganosiloxane compound (B) has a number average molecular weight of 280 or more and 500 or less. The curable resin composition for stereolithography according to any one of claims 1 to 5, wherein _R3 in the (meth)acrylorganosiloxane compound (B) is a methyl group. The curable resin composition for stereolithography according to any one of claims 1 to 6, wherein _R4 in the (meth)acrylorganosiloxane compound (B) is a methyl group. The curable resin composition for stereolithography according to any one of claims 1 to 7, wherein the (C) curing agent is a photopolymerization initiator. The curable resin composition for stereolithography according to claim 8, wherein the photopolymerization initiator is a photoradical polymerization initiator. The curable resin composition for stereolithography according to any one of claims 1 to 9, further comprising a reactive diluent (D). The content of the reactive diluent (D) is 10 parts by mass or more and 75 parts by mass with respect to a total of 100 parts by mass of the (meth)acrylic compound (A) and the (meth)acrylic organosiloxane compound (B). 11. The curable resin composition for three-dimensional modeling according to claim 10, wherein the composition is less than or equal to parts. The curable resin composition for three-dimensional modeling according to any one of claims 1 to 11, wherein the viscosity at 25°C is 70 mPa·s or more and 5,000 mPa ·s or less. A cured product of a curable resin composition, wherein the curable resin composition is the curable resin composition according to any one of claims 1 to 12. A three-dimensional object, wherein the cured product of the curable resin composition according to any one of claims 1 to 12 is laminated in layers and integrated. A method for producing a three-dimensional object, comprising a step of photocuring a curable resin composition layer by layer based on slice data to form a laminate of cured resin layers, wherein the curable resin composition is 13. A method for producing a three-dimensional object, wherein the curable resin composition is the curable resin composition according to any one of items 1 to 12. forming a layer of the curable resin composition;
A step of selectively irradiating the layer of the curable resin composition with light according to the cross section of the three-dimensional object to form the curable resin layer;
is repeated to form a laminate of the cured resin layers. 17. The method of manufacturing a three-dimensional object according to claim 15 or 16, wherein in the step of forming the cured resin layer, the layer of the cured resin composition is irradiated with an ultraviolet laser in a stippling or line drawing manner. 17. The method of manufacturing a three-dimensional object according to claim 15, wherein in the step of forming the cured resin layer, the layer of the curable resin composition is planarly irradiated with light through a drawing mask. The method further comprises a step of washing the laminate of the cured resin layers with a solvent selected from the group consisting of an alcohol-based organic solvent, a ketone-based organic solvent, and an aliphatic-based organic solvent. Item 19. The method for producing a three-dimensional object according to any one of Items 15 to 18. 20. The method of manufacturing a three-dimensional object according to any one of claims 15 to 19, further comprising a post-curing step of irradiating the laminate of the cured resin layers with light or heat.