JP2019104900A - Curable resin composition - Google Patents

Abstract

To provide a resin composition that can give a cured product having both hardness and toughness.SOLUTION: A curable resin composition contains (A) a curable resin represented by general formula (1) [X, Xeach represent a divalent linking group containing an aromatic ring. Xis a C4-18 alkylene group. Lto Leach represent a divalent linking group containing one or more bonds selected from the group consisting of -O-, -C-O-, -S-, -C-S-, ester bond, urethane bond, ether bond, thiourethane bond and thioether bond. Y, Yeach represent an epoxy group or the like. n is an average value and a real number of 0.1 to 10], (B) a polyhydric alcohol having 2 to 5 hydroxy groups, and (C) a curing agent. A content of the polyhydric alcohol (B) is 0.1 pts.mass or more and 20 pts.mass or less relative to the 100 pts.mass of the curable resin (A).SELECTED DRAWING: None

Description

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

An optical three-dimensional modeling method for obtaining a three-dimensional object is earnestly studied by curing a liquid curable resin layer by layer with energy active light such as ultraviolet light and laminating it. Optical three-dimensional objects are being developed not only as prototypes (rapid prototyping) for shape confirmation, but also as mold making (rapid tooling) and service parts (real products) (Rapid Manufacture Charing). Along with this, the demand for material properties (such as toughness and heat resistance) for a three-dimensional object has been further advanced, and recently, physical properties equivalent to engineering plastics are being sought.
The three-dimensional object made of a curable resin has been required to have a certain degree of hardness (elastic modulus) and toughness, particularly high fracture toughness. In patent document 1, the system which adds a polyhydric alcohol in a resin composition is examined in order to improve the toughness of three-dimensional model.

Unexamined-Japanese-Patent No. 2000-302964

However, since the modulus of elasticity and the toughness are in a contradictory relationship, the composition of Patent Document 1 lowers the modulus of elasticity, and the modulus of elasticity is insufficient for use in rapid prototyping or rapid manufacturing.
An object of the present invention is to provide a resin composition capable of giving a cured product having both hardness (elastic modulus) and toughness based on the above circumstances.

The curable resin composition of the present invention is
(A) A curable resin represented by the following general formula (1),

［Ｘ₁、Ｘ₂は、独立に、芳香環を含む２価の連結基である。
Ｘ₃は、炭素数４以上１８以下のアルキレン基であり、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よい。
Ｌ₁、Ｌ₂、Ｌ₃、Ｌ₄は、独立に、−Ｏ−、−Ｃ−Ｏ−、−Ｓ−、−Ｃ−Ｓ−、エステル結合、ウレタン結合、エーテル結合、チオウレタン結合及びチオエーテル結合からなる群から選ばれる結合を１つ以上含む２価の連結基である。
Ｙ₁、Ｙ₂は、独立に、エポキシ基、シクロアルケンオキシド基またはオキセタニル基である。
ｎは繰り返し構造単位の平均値であり、０．１以上１０以下の実数である。］
（Ｂ）２個以上５個以下の水酸基を有する多価アルコールと、
（Ｃ）硬化剤と、
を含有する硬化性樹脂組成物であって、前記硬化性樹脂（Ａ）１００質量部に対して、前記多価アルコール（Ｂ）を０．１質量部以上２０質量部以下で含有することを特徴とする。

[X ₁ and X ₂ are independently a divalent linking group containing an aromatic ring.
X ₃ is an alkylene group having 4 to 18 carbon atoms, and a carbon atom constituting the alkylene group may be replaced by an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom.
L ₁ , L ₂ , L ₃ and L ₄ are independently -O-, -C-O-, -S-, -C-S-, ester bond, urethane bond, ether bond, thiourethane bond and thioether It is a divalent linking group containing one or more bonds selected from the group consisting of bonds.
Y ₁ and Y ₂ are each independently an epoxy group, a cycloalkene oxide group or an oxetanyl group.
n is an average value of repeating structural units and is a real number of 0.1 or more and 10 or less. ]
(B) a polyhydric alcohol having 2 or more and 5 or less hydroxyl groups,
(C) a curing agent,
A curable resin composition containing at least 0.1 part by mass and at most 20 parts by mass of the polyhydric alcohol (B) with respect to 100 parts by mass of the curable resin (A) I assume.

  According to the present invention, it is possible to form a cured product excellent in both hardness (elastic modulus) and toughness, and to provide a curable resin composition suitable for three-dimensional shaping.

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

<Curable resin (A) (component (A))>
The curable resin (A) used in the present invention is represented by the following general formula (1).

In the above general formula (1), X ₁ and X ₂ are independently a divalent linking group containing an aromatic ring. It is preferable that X ₁ and X ₂ contain two or less aromatic rings from the viewpoint of easy availability and solubility in a solvent. If the number of aromatic rings is 2 or less, problems in the synthesis reaction such as increased crystallinity and poor solubility in a solvent are less likely to occur. X ₁ and X _{2 each} represent a carbon atom constituting an aromatic ring and a linking group which is linked to an adjacent group (L ₁ , L ₂ , L ₃ , L ₄ ) or an atom other than a carbon atom constituting an aromatic ring The linking group may be a linking group, but a linking group linking to an adjacent group through a carbon atom constituting an aromatic ring is preferred.

As X ₁ and X ₂ , for example, a hydrocarbon group consisting of a structure having only one aromatic ring, a hydrocarbon group consisting of a structure having an aromatic ring bonded via a single bond, and an aromatic ring through an aliphatic carbon atom A hydrocarbon group having a structure bonded to each other, a hydrocarbon group having a structure having an aromatic ring bonded via an aliphatic cyclic hydrocarbon group, a hydrocarbon group having a structure having a plurality of benzene rings fused and polycondensed, and an aromatic ring And a hydrocarbon group having a structure in which an aromatic ring is bonded via an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, and the like. For example, specifically, a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a fluorenediyl group, a diphenylmethanediyl group, a diphenylethanediyl group, a diphenylpropanediyl group, a diphenyl ether diyl group, a diphenyl sulfone A diyl group etc. can be mentioned. These may be unsubstituted or may have a substituent. As a substituent which may be possessed, a C1-C6 linear or branched alkyl group etc. are mentioned, for example.

  In particular, diphenylmethanediyl group (general formula (1-I)), from the viewpoint of the balance between the flexibility and the toughness of the cured product obtained from the curable resin composition of the present invention and the light transmittance. Preferred are diphenyl propane diyl group (general formula (1-II)), biphenylene group (general formula (1-III)) and diphenyl ether diyl group (general formula (1-IV)), and these are unsubstituted or substituted. You may have. As a substituent which may be possessed, a C1-C6 linear or branched alkyl group etc. are mentioned, for example.

[* Represents a bond with L ₁ , L ₂ , L ₃ , L ₄ . ]

X ₃ is an alkylene group having 4 to 18 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. If the number of carbons is 3 or less, the flexibility is impaired and sufficient toughness can not be exhibited. Moreover, when carbon number is 19 or more, the hardness of hardened | cured material will fall and an elastic modulus will be impaired as a result. Specific examples of X ₃ include a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a nonenylene group, a dodecanylene group, a tridecanylene group, a tetradecanylene group, a pentadecanylene group, a hexadecanylene group, and a heptadecanylene group Group, acyclic alkylene group having a straight chain or branched structure such as octadecanylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, bicyclic, tricyclic And alkylene groups having a cyclic structure such as polycyclic, etc., and these may be unsubstituted or may have a substituent. As a substituent which may be possessed, a C1-C6 linear or branched alkyl group etc. are mentioned, for example. Among them, from the viewpoint of easy availability, preferred is a non-cyclic alkylene group having a linear or branched structure having 4 to 12 carbon atoms, and more preferably a linear chain having 4 to 10 carbon atoms. -Like noncyclic alkylene group.

In X ₃ , the carbon atom constituting the alkylene group may be replaced by an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, and has, for example, a repeating structure such as oxymethylene, oxyethylene, oxypropylene and the like Also good. In this case, the number of carbon atoms not replaced is preferably 4 or more and 10 or less.

As X ₃ , an alkylene group represented by the following general formula (1-VII) is preferable from the viewpoint of achieving both hydrophobicity and toughness and elastic modulus, and an alkylene group represented by the general formula (1-VIII) is improved in toughness It is more preferable from the viewpoint.

[L is an integer of 4 or more and 18 or less, preferably an integer of 4 or more and 10 or less.

R ₁ and R ₂ are hydrogen or a methyl group. m is an integer selected to have 4 to 18 carbon atoms, preferably 4 to 10 carbon atoms.

* Represents a bond with L ₁ and L ₂ . ]

L ₁ , L ₂ , L ₃ and L ₄ are independently -O-, -C-O-, -S-, -C-S-, ester bond, urethane bond, ether bond, thiourethane bond and thioether It is a divalent linking group containing one or more bonds selected from the group consisting of bonds. Hereinafter, "a bond selected from the group consisting of -O-, -C-O-, -S-, -C-S-, an ester bond, a urethane bond, an ether bond, a thiourethane bond and a thioether bond" Sometimes referred to as "combined". L _{1 to} L ₄ may be a linking group directly linked to an adjacent group (Y ₁ , Y ₂ , X ₁ , X ₂ , X ₃ ) at a specific bond, or between the specific bond and an adjacent group May be a linking group linked to one or more carbon atoms. When the specific bond is any of -O-, -C-O-, -S-, or -C-S-, the oxygen atom or sulfur atom of the specific bond is interposed between the specific bond and the adjacent group It is preferable to form an ether bond or a thioether bond by bonding with the carbon atom or the carbon atom of the adjacent group.

Curable when L _{1 to} L ₄ contain one or two bonds selected from the group consisting of -O-, -C-O-, -S-, -C-S-, an ether bond and a thioether bond It is preferable because the rotational movement of the molecular chain of the resin (A) becomes easy and the toughness improvement effect becomes large. If the number of bonds selected from the group consisting of -O-, -C-O-, -S-, -C-S-, an ether bond and a thioether bond is 2 or less, the mobility does not increase excessively; The elastic modulus of the cured product can be maintained.

Further, it is preferable that L _{1 to} L ₄ have a hydroxyl group, because they have the effect of accelerating the polymerization reaction of the curable resin (A). The number of hydroxyl groups is preferably 6 or less in one molecule of the curable resin (A). If the number of hydroxyl groups is 6 or less in one molecule, the water absorbency of the curable resin composition and the cured product obtained by curing the same will not decrease, and the stability over time will be obtained.

As L ₁ , L ₂ , L ₃ and L ₄ , specifically, for example, general formulas (1-a), (1-b), (1-c), (1-d), Groups represented by 1-e), (1-f) and (1-g) are preferred. In particular, the groups represented by the general formulas (1-a), (1-d), (1-e), (1-f) and (1-g) are from the viewpoint of the availability of materials and the efficiency of synthesis More preferable. Furthermore, groups represented by general formulas (1-d), (1-e), (1-f), and (1-g) are more preferable from the viewpoint of the toughness improvement effect. Moreover, the group represented by general formula (1-g) is preferable from the viewpoint of the polymerization reaction promotion of curable resin (A).

[A, b, c, d, e, f, g, h, i, j, k, o, p, q are independently integers of 0 to 5 and the flexibility and composition of the cured product of the composition From the viewpoint of viscosity of the material, an integer of 0 or more and 2 or less is preferable, and from the viewpoint of maintaining the elastic modulus, an integer of 0 or more and 1 or less is more preferable.

* Represents a bond with Y ₁ , Y ₂ , X ₁ , X ₂ , and X ₃ . ]

Y ₁ and Y ₂ are polymerizable groups, and independently, an epoxy group, a cycloalkene oxide group or an oxetanyl group. Examples of the cycloalkene oxide group include a cyclopropene oxide group, a cyclobutene oxide group, a cyclopentene oxide group, a cyclohexene oxide group, a cycloheptene oxide group and the like. Specifically, Y ₁ and Y ₂ are preferably those represented by the following general formulas (1-h), (1-i) and (1-j), respectively, from the viewpoint of synthesis and availability.

[R ₃ and R ₄ independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of polymerizability and availability, hydrogen or an alkyl group having 1 to 2 carbon atoms] Is preferred, and hydrogen is more preferred.
* Is a bond with L ₃ and L ₄ . ]

  n represents an average value of repeating structural units, and is a real number of 0.1 or more and 10 or less. In order to suppress the increase in viscosity of the composition, n is preferably in the range of 0.2 to 5 and more preferably in the range of 0.5 to 3 from the viewpoint of the balance of the toughness and the elastic modulus of the cured product.

  As the curable resin (A), for example, commercially available products such as EPICLON EXA-4816 (manufactured by DIC), EPICLON EXA-4850-150 (manufactured by DIC), and EPICLON EXA-4850-1000 (manufactured by DIC) are preferable. It can be used for

  As a specific example of a curable resin (A), the curable resin represented by the following structure is preferable from the viewpoint of coexistence of toughness and an elastic modulus, and what is n = 1 is more preferable. Moreover, when it has a hydroxyl group, the point which has a hardening acceleration | stimulation effect of curable resin (A) is further more preferable.

(Method for producing curable resin (A))
The method for producing the curable resin (A) is not particularly limited. For example, the diglycidyl ether compound (A-1) is reacted with the aromatic dihydroxy compound (A-2) to obtain a dihydroxy compound. Obtain (A-3). Then, the halogen group of the cationically polymerizable compound having a halogen group can be reacted with the hydroxyl group of the dihydroxy compound (A-3) to obtain a curable resin (A).

As a diglycidyl ether compound (A-1), the compound represented, for example by following General formula (2) is mentioned. X ₃ corresponds to X ₃ in the general formula (1), the details of which are identical to those described for the general formula (1). The diglycidyl ether compounds (A-1) may be used alone or in combination of two or more.

  Examples of the compound represented by the general formula (2) include 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1, 7 -Heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decane Mention diol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,18-stearyl diol diglycidyl ether, etc. It can be.

As an aromatic dihydroxy compound (A-2), the compound represented by following General formula (3) is mentioned, for example. X ₇ corresponds to X ₁ and X ₂ in the general formula (1), and the details thereof are as described for the general formula (1).

  Examples of the compound represented by the general formula (3) include 1,4-dihydroxybenzene, catechol, 4,4′-dihydroxydiphenylmethane, 4,4′-methylenebis (2,6-dimethylphenol), 2,2 -Bis (4-hydroxyphenyl) propane, 2,2'-methylenebis (4-methylphenol), 4,4'-ethylidene bisphenol, 4,4'-dihydroxybenzophenone, 4,4 '-(1,3-dimethyl Butylidene) diphenol, 4,4 '-(α-methylbenzylidene) bisphenol, 4,4'-(α-methylbenzylidene) bisphenol, 4,4'-dihydroxytetraphenylmethane, 2,7-naphthalenediol, 2 And 3-naphthalenediol, 2, 6-anthracenediol etc. can be mentioned.

  The cationically polymerizable compound having a halogen group is a compound having an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and having a halogen group such as -I, -Br, or -Cl. Specifically, 2- (chloromethyl) -1,2-epoxypropane, 2- (chloromethyl) -1,2-epoxybutane and the like can be mentioned.

  In addition, as another production method, a difunctional phenol compound which is an aromatic dihydroxy compound is reacted with divinyl ether. Then, a cationically polymerizable compound having a halogen group can be reacted with the obtained bifunctional phenol resin to obtain a curable resin (A).

<Polyhydric alcohol (B) (component (B))>
Polyhydric alcohol (B) is useful for expressing toughness improvement of hardened | cured material. The polyhydric alcohol used as the component (B) is one having 2 or more and 5 or less hydroxyl groups, preferably 2 or more and 4 or less hydroxyl groups, and more preferably 2 hydroxyl groups in one molecule. When an alcohol having one hydroxyl group in one molecule is used, curing failure occurs. On the other hand, in the case where the number of hydroxyl groups in one molecule is 6 or more, when containing a polyhydric alcohol, the toughness of the resulting cured product tends to decrease.

  Examples of dihydric alcohols include salicyl alcohol, catechol, resorcinol, hydroquinone, 1,4-benzenedimethanol, bisphenol A, bisphenol F, neopentyl glycol, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol and the like. It can be used. As the trihydric alcohol, for example, glycerin, phloroglucinol, trimethylolpropane and the like can be used. As the tetrahydric alcohol, for example, erythritol, threitol, pentaerythritol or the like can be used. As the pentahydric alcohol, for example, xylitol, arabitol, fusitol, glucose, galactose, fructose and the like can be used. The polyhydric alcohol (B) is not limited to these. The polyhydric alcohol (B) can be used alone or in combination of two or more.

  The molecular weight of the polyhydric alcohol (B) is preferably 1,000 or less, more preferably 800 or less. When the molecular weight exceeds 1,000, the local reduction of the crosslink density may occur and the elastic modulus may decrease.

  The content of the polyhydric alcohol (B) is 0.1 parts by mass or more per 100 parts by mass of the component (A) (the total of the component (A) and the component (D) when the component (D) is contained) It is 20 parts by mass or less, preferably 0.2 parts by mass or more and 15 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less. If the content of the polyhydric alcohol (B) is less than 0.1 parts by mass, the effect of the polyhydric alcohol (B) does not appear, and a cured product having a sufficient elastic modulus can not be obtained. When the content of the polyhydric alcohol (B) exceeds 20 parts by mass, the polyhydric alcohol (B) polymerizes the component (A), and when the component (D) contains the polymer (A) and the component (D) Sufficient toughness can not be obtained.

(Function of polyhydric alcohol (B))
The mechanism showing the improvement of the toughness of the curable composition of the present embodiment will be described taking the case where the component (A) is an epoxy resin, the component (C) is a cationic polymerization initiator, and the component (D) is contained. Do. When a cationic polymerization initiator absorbs an active energy ray or thermal energy, a cation is generated, and this cation initiates cationic polymerization of the epoxy group of component (A) or the oxetanyl group of component (D). The epoxy group and the oxetanyl group are cationically polymerized with each other or respectively to increase the molecular weight, but since the activated epoxy group and oxetanyl group are unstable, the polymerization tends to be terminated. Therefore, a low molecular weight polymer chain having an unreacted epoxy group or oxetanyl group at the end of the polymer is formed. The component (B) of the present embodiment is made to have a high molecular weight by reacting the low molecular weight polymer chains with a hydroxyl group, for example, as shown in the following formula, and the toughness is improved. In addition, it is assumed that the toughness is improved more efficiently by the formation of hydrogen bonds by the polyhydric alcohol incorporated into the polymer chain.

<Hardener (C) (Component (C))>
As the curing agent (C), a cationically polymerizable initiator such as a photoacid generator, a photobase generator, or a thermal acid generator can be used. These may be used alone or in combination as long as the effects of the present invention are not impaired. In the case of forming a three-dimensional object by photocuring, it is preferable to use a photoacid generator or a photobase generator due to the stability of the curable resin composition of the present invention with time and the three-dimensional modeling method. It is particularly preferable to use a photoacid generator. Further, as the curing agent (C), a radical polymerization initiator, for example, another curing agent such as a heat latent curing agent may be contained.

[Cationic polymerization initiator]
(Photo acid generator)
The photoacid generator is, for example, a cationic photopolymerization initiator that generates an acid capable of initiating cationic polymerization by irradiation of energy rays such as ultraviolet light. When using as a curable resin for three-dimensional modeling, it is preferable to use a photocationic polymerization initiator.

As a photocationic polymerization initiator, for example, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thiancerenium, thioxanthonium, (2,4-cyclopentadien-1-yl ) [(1-methylethylbenzene] -Fe cation, and the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (wherein X is at least two or more fluorine or trifluoromethyl) The onium salt composed of a group-substituted phenyl group can be used alone or in combination of two or more.

  Examples of the aromatic sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfone) Nio) phenyl] sulfide bis tetrafluoroborate, bis [4- (diphenyl sulfo nio) phenyl] sulfide tetrakis (pentafluoro phenyl) borate, diphenyl -4- (phenyl thio) phenyl sulfonium hexa fluoro phosphate, diphenyl -4- (phenyl thio) Phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) fe Trisulfone 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- ( - hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) can be used borate.

  Also, as the aromatic iodonium salt, for example, 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 hexame Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Henyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, etc. It can be used.

  Further, as the aromatic diazonium salt, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate and the like can be used.

  Also, as the aromatic ammonium salt, 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.

  In addition, as thiansurenium salt, 5-methylthianthrenium hexafluorophosphate, 5-methyl-10-oxothianthrenium tetrafluoroborate, 5-methyl-10,10-dioxothianthrenium hexafluorophosphate, etc. Can be used.

  Moreover, as a thioxanthonium salt, S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate etc. can be used.

  Further, as (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt, (2,4-cyclopentadien-1-yl) [(1-methylethylbenzene) -Fe is exemplified. (II) Hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethylbenzene] -Fe (II) hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [( Using 1-methylethylbenzene] -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) [(1-methylethylbenzene) -Fe (II) tetrakis (pentafluorophenyl) borate, etc. Can.

  As a cationic photopolymerization initiator, for example, CPI (R)-100 P, CPI (R)-110 P, CPI (R)-101 A, CPI (R)-200 K, CPI (R)-210 S (all, San-Apro Corporation) Made, CYRA CURE (R) photo-curing initiator UVI-6990, CYRA CURE (R) photo-curing initiator UVI-6992, CYRA CURE (R) photo-curing initiator UVI-6976 (above, Dow Chemical Japan), Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300 (all manufactured by ADEKA), CI-5102, CI-2855 (The above, Nippon Soda Co., Ltd. product), San Aid (R) SI-60L, San Aid (R) SI-80 L, San Aid R) SI-100L, SanAid (R) SI-110L, SanAid (R) SI-180L, SanAid (R) SI-110, SanAid (R) SI-180 (all, manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure R) 1064, Esacure (R) 1187 (all, made by Lamberti), Omnicat 550 (made by IG Resin Co., Ltd.), Irgacure (R) 250 (made by BASF), Rhodosil Photoinitiator 2074 (RHODORSILPHOTOINITIATOR 2074 (Lodya) -Japan (manufactured by Japan Co., Ltd.) and the like are commercially available.

  In the present invention, two or more types of photo cationic polymerization initiators may be used in combination, or may be used alone. Moreover, in order to advance a polymerization reaction by heat treatment after shaping, other curing agents such as a thermal cationic polymerization initiator may be simultaneously contained.

(Photo base generator)
The photobase generator refers to a compound that generates a base by irradiation of energy rays such as ultraviolet light and visible light. In particular, a salt containing a borate anion is preferred because of its good sensitivity to light. Specific products include U-CAT (R) 5002 manufactured by San-Apro Co., Ltd. and P3B, BP3B, N3B, MN3B manufactured by Showa Denko Co., Ltd., but not limited thereto.

(Thermal acid generator)
The thermal acid generator is also called a thermal cationic polymerization initiator. By heating, a compound containing a cationic species is excited, and a thermal decomposition reaction occurs to exhibit a substantial function as a curing agent for promoting thermal curing. The thermal cationic polymerization initiator is different from acid anhydrides, amines, phenol resin and the like generally used as a curing agent, and even if it is contained in the resin composition, the resin composition is aged over time at ordinary temperature. It does not cause viscosity rise or gelation. Therefore, it becomes possible to provide a one-component resin composition excellent in handling properties.

  As a thermal cationic polymerization initiator, 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-trimethylphenyl Sulfonium -p- toluenesulfonate, diphenyl -p- phenylthiophenylsulfonium hexafluorophosphate and the like.

  In the present invention, as a thermal cationic polymerization initiator, for example, AMERICURE series (made by American Can), ULTRASET series (made by Adeka), WPAG series (made by Wako Pure Chemical Industries, Ltd.), which are diazonium salt based compounds, iodonium salt based Compounds are UVE series (made by General Electric Co., Ltd.), FC series (made by 3M company), UV9310C (made by GE Toshiba Silicone Co., Ltd.), WPI series (made by Wako Pure Chemical Industries, Ltd.), CYRACURE series (sulfone salt compounds) Carbide company), UVI series (General Electric company), FC series (3M company), CD series (Sartmar company), Optomer SP series, Optomer CP series (Adeka company), Sun Aid SI series (3 Shin Shin) Chemical industry company ), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), a commercially available product can be used, such as CPI series (manufactured by San-Apro Ltd.).

  In the present invention, two or more kinds of thermal cationic polymerization initiators may be used in combination, but may be used alone. Moreover, in order to advance a polymerization reaction by heat treatment after shaping, you may use the thermal cationic polymerization initiator which decomposes | disassembles at high temperature.

(Addition amount of cationic polymerization initiator)
The addition amount of the cationic polymerization initiator is 0.05 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the component (A) (the total of the component (A) and the component (D) when the component (D) is contained) The amount is preferably not more than 0.1 part by mass and more preferably 5 parts by mass or less. If the addition amount of the cationic polymerization initiator is less than 0.05 parts by mass, the generation of polymerization active species is insufficient, and as a result, the polymerization conversion ratio of the resin composition decreases, so that the strength of the cured product may be insufficient. . When the addition amount of the cationic polymerization initiator exceeds 20 parts by mass, the polymerization initiation point is increased, and the polymerization is not sufficiently repeated, which may result in a cured product having insufficient strength.

[Radical polymerization initiator]
In the present invention, in particular, when the radical polymerizable compound (F) is contained, a radical polymerization initiator may be contained.

  Radical polymerization initiators are mainly classified into an intramolecular cleavage type and a hydrogen abstraction type. In the intramolecular cleavage type radical polymerization initiator, by absorbing light of a specific wavelength, a bond at a specific site is cut, and a radical is generated at the cut site, which becomes a polymerization initiator and is radically polymerizable Polymerization of the compound (F) starts. On the other hand, in the case of the hydrogen abstraction type, light of a specific wavelength is absorbed to be in an excited state, and the excited species cause a hydrogen abstraction reaction from the surrounding hydrogen donor, generating radicals, which become polymerization initiators and radicals Polymerization of the polymerizable compound (F) starts.

  As the intramolecular cleavage type photoradical polymerization initiator, alkylphenone type photoradical polymerization initiators, acyl phosphine oxide type photoradical polymerization initiators, and oxime ester type photoradical polymerization initiators are known. These are of the type in which the bond adjacent to the carbonyl group is alpha-cleaved to form a radical species. Examples of the alkylphenone photoradical polymerization initiator include benzyl methyl ketal photoradical polymerization initiator, α-hydroxyalkylphenone photoradical polymerization initiator, aminoalkylphenone photoradical polymerization initiator and the like. As a specific compound, for example, as a benzyl methyl ketal photoradical polymerization initiator, 2,2'-dimethoxy-1,2-diphenylethane-1-one (IRGACURE (R) 651, manufactured by BASF AG), etc. And, as an α-hydroxyalkylphenone photoradical polymerization initiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure (R) 1173, manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (IRGACURE (R) 184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE (R) 2959, BASF Corporation Product), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzen And the like. Examples of the aminoalkylphenone-based photoradical polymerization initiator include 2-methyl-1- (4-methylthiophenyl). ) -2-morpholinopropan-1-one (IRGACURE (R) 907, manufactured by BASF AG) or 2-benzylmethyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (IRGACURE (R) 369, manufactured by BASF, etc., but the invention is not limited thereto. As an acyl phosphine oxide type radical photopolymerization initiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide (Lucillin (R) TPO, BASF Corporation make), bis (2,4, 6 trimethyl benzoyl)-phenyl phosphine oxide There are (IRGACURE (R) 819, manufactured by BASF) and the like, but the invention is not limited thereto. (2E) -2- (Benzoyloxyimino) -1- [4- (phenylthio) phenyl] octan-1-one (IRGACURE (R) OXE-01, manufactured by BASF as an oxime ester photoradical polymerization initiator And the like, but is not limited thereto.

  As hydrogen abstraction type radical polymerization initiators, anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone Although it is mentioned, it is not limited to this.

  In the present invention, two or more types of photo radical polymerization initiators may be used in combination, or may be used alone. Moreover, in order to advance a polymerization reaction by the heat processing after modeling, you may contain the thermal radical polymerization initiator.

  The addition amount of the photo radical polymerization initiator 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 with respect to 100 parts by mass of the radical polymerizable compound (F) It is below. When the amount of photo radical polymerization initiator is small, polymerization tends to be insufficient. If the amount of initiator is large, the light transmission may be reduced and the polymerization may be nonuniform.

  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, persulfates, etc. Can be exemplified as preferred. As an azo compound, 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethyl valeronitrile, 1,1'- Azobis (1-acetoxy-1-phenylethane) and the like can be mentioned. Examples of the peroxide include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate. Persulfates include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

  The addition amount of the thermal radical polymerization initiator is preferably 0.1 parts by mass to 15 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (F). It is below. If the polymerization initiator is added in excess, the molecular weight may not be extended and the physical properties may be reduced.

[Other curing agent]
The following heat latent curing agents can be used as the curing agent (C). The heat latent curing agent refers to a curing agent that causes heat curing to proceed by heating.

  As the acid anhydrides (acid anhydride based curing agents), known or commonly used acid anhydride based curing agents can be used and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride etc., methyl hexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride etc), dodecenyl succinic anhydride, methyl endo methylene tetrahydrophthalic anhydride, Phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nadic anhydride, methyl nadic anhydride , Hydrogenated methyl nadic anhydride, 4 (4-Methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic acid anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene -Maleic anhydride copolymer etc. are mentioned. Among them, acid anhydride [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl endo methylene tetrahydrophthalic anhydride, etc.] which is liquid at 25 ° C. is preferable from the viewpoint of handleability. On the other hand, the acid anhydride solid at 25 ° C. is, for example, dissolved in acid anhydride liquid at 25 ° C. to form a liquid mixture, the curing agent (C) of the curable epoxy resin composition of the present invention Tend to be improved as the From the viewpoints of heat resistance and transparency of the cured product, as the acid anhydride curing agent, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable.

  As amines (amine-based curing agents), known or commonly used amine-based curing agents can be used and are not particularly limited. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine Aliphatic polyamines such as polypropylene triamine; mensene diamine, isophorone diamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexyl methane, bis (aminomethyl) cyclohexane, N-aminoethyl piperazine, 3,9- Alicyclic polyamines such as bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamide Mononuclear polyamines such as tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyl tolylene-2,4-diamine, 3,5-diethyl tolylene-2,6-diamine, Examples include aromatic polyamines such as biphenylene diamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine, and the like.

  As phenols (phenolic curing agents), known or commonly used phenolic curing agents can be used and are not particularly limited. For example, novolak type phenolic resin, novolak type cresol resin, paraxylylene modified phenolic resin, paraxylylene / metaxylylene modified phenol Aralkyl resins such as resins, terpene-modified phenolic resins, dicyclopentadiene-modified phenolic resins, triphenolpropane and the like can be mentioned.

  As a polyamide resin, the polyamide resin etc. which have any one or both of a primary amino group and a secondary amino group in a molecule | numerator are mentioned, for example.

  As the imidazoles (imidazole-based curing agents), known or commonly used imidazole-based curing agents can be used and are not particularly limited. For example, 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-dia −66- [2-Methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc. Can be mentioned.

  Examples of the 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 addition amount of the other curing agent is preferably 0.1 parts by mass or more based on 100 parts by mass of the component (A) (the total of the component (A) and the component (D) when the component (D) is contained) It is 75 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less. When the amount of heat latent polymerization initiator is small, the polymerization tends to be insufficient, and when it is too large, the crosslinking reaction proceeds to tend to deteriorate the toughness.

<Oxetane Compound (D) (Component (D))>
The curable resin composition of the present invention preferably contains an oxetane compound other than the component (A).

  The oxetane compound (D) may be composed of only one kind of oxetane compound, or may be composed of a plurality of oxetane compounds. The compound is not particularly limited as long as it is a compound having an oxetanyl group. The number of oxetanyl groups in the oxetane compound (D) is not particularly limited. For example, a monofunctional oxetane compound having one oxetanyl group in the molecule, a bifunctional oxetane compound having two oxetanyl groups in the molecule, a trifunctional oxetane compound having three oxetanyl groups in the molecule, an oxetanyl group in the molecule Although the tetrabasic or higher functional oxetane compound etc. which have 4 or more are mentioned, it is not limited to these. In addition, as the oxetane compound (D), an oxetane compound having an aromatic ring or an ether bond in the molecule may be used.

  Specific examples of the oxetane compound (D) include, for example, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- (4) -Hydroxybutyl) oxymethyl oxetane, 3-ethyl-3-hexyloxymethyl oxetane, 3-ethyl-3-allyloxymethyl oxetane, 3-ethyl-3-benzyloxymethyl oxetane, 3-ethyl-3-methacryloxymethyl oxetane Monooxetane compounds such as oxetane, 3-ethyl-3-carboxyoxetane, 3-ethyl-3-phenoxymethyl oxetane; bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis [3-ethyl -(3-Oxetanyl) methoxymethyl] biphenyl, 1,4-bis 3-ethyl-3-oxetanylmethoxy) methylbenzene, xylylene bisoxetane, bis [(ethyl (3-oxetanyl)] methyl carbonate, bis [ethyl (3-oxetanyl)] ethyl adipate, bis [ethyl terephthalate (3) -Oxetanyl)] methyl, 1,4-cyclohexanecarboxylic acid bis [ethyl (3-oxetanyl)] methyl, bis {4- [ethyl (3-oxetanyl) methoxycarbonylamino] phenyl} methane, α, ω-bis- { Dioxetane compounds such as 3- [1-ethyl (3-oxetanyl) methoxy] propyl (polydimethylsiloxane); and polyoxetane compounds such as oligo (glycidyl oxetane-co-phenyl glycidyl ether), but are limited to these It is not a thing.

  Among the above, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3- (3-ethyl-3-hydroxymethyl), since they have low viscosity and are easy to handle and show high reactivity. Ethyl-3- (4-hydroxybutyl) oxymethyl oxetane, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4'-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl, 1 , 4-bis (3-ethyl-3-oxetanylmethoxy) methylbenzene and xylylene bisoxetane are preferable, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3-hydroxymethyl oxetane , 3-ethyl-3- (4-hydroxybutyl) oxymethyl oxetane, bis [1- Chill (3-oxetanyl)] methyl ether, 4,4'-bis [3-ethyl - (3-oxetanyl) methoxymethyl] biphenyl are more preferred.

  As the oxetane compound (D), commercially available products having a cationically polymerizable monomer as a main component can be used, and, for example, alone oxetane (R) OXT-121, OXT-221, EXOH, POX, OXA, OXT- 101, OXT-211, OXT-212 (made by Toagosei Co., Ltd.), ETERNACOLL (R) OXBP, OXTP (made by Ube Industries, Ltd.), etc. are mentioned.

  The oxetane compound (D) is preferably a compound represented by the following general formula (4).

In the general formula (4), X ₈ is a residue selected from the group consisting of a residue of a divalent alcohol or -O-, -C-O-, ether bond, carbonate bond, urethane bond, urea bond It represents a divalent linking group containing one or more and may contain an aromatic ring. The divalent compound represented by the general formula (4) is suitable for increasing the elastic modulus of the curable resin (A).

As a compound shown by General formula (4), the compound etc. which were illustrated as said dioxetane compound are mentioned. Examples of commercially available products include Aron Oxetane (R) OXT-121, OXT-221 (manufactured by Toagosei Co., Ltd.), and ETERACOLL (R) OXBP (manufactured by Ube Industries, Ltd.). Among these, bis [1-ethyl (3-oxetanyl)] methyl ether, in particular, has an ether bond to ensure toughness by having flexibility, and the molecular weight of X ₈ is small and the crosslink density is improved. In the point which can be done, in order to acquire the effect of the present invention. In addition, 4,4′-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl has an aromatic ring and is an aromatic ring of the component (A) of the present invention, a cyclic group of the component (B) The interaction with the structure is strong, which is preferable in terms of improving the heat resistance.

  The oxetane compound (D) is preferably a compound represented by the following general formula (5).

  The number of oxetanyl groups contained in the compound represented by the general formula (5) is not particularly limited. For example, a bifunctional oxetane compound having two oxetanyl groups in the molecule, a trifunctional oxetane compound having three oxetanyl groups in the molecule, a tetrafunctional or more oxetane compound having four or more oxetanyl groups in the molecule, and the like can be mentioned. However, it is not limited to these. Among them, preferred is a bifunctional oxetane compound having two oxetanyl groups in the molecule.

In the above general formula (5), X ₄ is a divalent linking group linked by a carbon atom constituting an aromatic ring. As X ₄ , for example, a hydrocarbon group having a structure having only one aromatic ring, a hydrocarbon group having a structure having an aromatic ring bonded via a single bond, and an aromatic ring bonded via an aliphatic carbon atom A hydrocarbon group having a structure, a hydrocarbon group having a structure in which an aromatic ring is bonded via an aliphatic cyclic hydrocarbon group, a hydrocarbon group having a structure in which a plurality of benzene rings are fused and polycyclic, and an aralkyl group having an aromatic ring And a hydrocarbon group having a structure in which an aromatic ring is bonded via an oxygen atom or a sulfur atom, and the like. Specific examples include phenylene group, biphenylene group, naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, fluorenediyl group, diphenylmethanediyl group, diphenylethanediyl group, diphenylpropanediyl group, diphenyl ether diyl group, diphenyl sulfone A diyl group, a triphenyl ethane diyl group, a tetraphenyl methane diyl group etc. are mentioned, These may be unsubstituted or may have a substituent. As a substituent which may be possessed, a C1-C6 linear or branched alkyl group etc. are mentioned, for example. Among them, preferred is a phenylene group, a biphenylene group or a diphenylmethanediyl group which may have a substituent. X ₄ may have a group containing an oxetanyl group.

X ₅ and X _{6 each} independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms represented by X ₅ and X ₆ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, Acyclic alkyl groups such as s-butyl group, t-butyl group, pentyl group and hexyl group; and cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Of these, preferred are methyl and ethyl.

L ₅ and L _{6 each} independently represent a divalent linking group containing a bond selected from the group consisting of —O—, —C—O—, an ester bond and an ether bond. Hereinafter, “a bond selected from the group consisting of —O—, —C—O—, an ester bond and an ether bond” may be referred to as “second specific bond”. L ₅ and L ₆ may be a linking group directly linked to the adjacent group (methylene group, X ₄ ) at the second specific bond, or one or more between the second specific bond and the adjacent group The linking group may be linked via a carbon atom of When the second specific bond is -O- or -C-O-, the oxygen atom of the second specific bond is a carbon atom or an intervening group between the second specific bond and the adjacent group It is preferable to combine with the carbon atom of the adjacent group to form an ether bond. Specific examples of L _5, L _6, for example, the general formula (1-a) (1- d) , and the like. L ₅ and L ₆ may have a group containing an oxetanyl group.

  The average value of the repeating structural units represented by s is a real number of 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less from the viewpoint of the toughness of the cured product, and from the viewpoint of the viscosity of the oxetane compound. 5 or more and 3 or less are more preferable.

  Examples of the compound represented by the general formula (5) include ETERNACOLL (R) OXBP (manufactured by Ube Industries, Ltd.), ETERNACOLL (R) OXIPA (manufactured by Ube Industries, Inc.), and commercially available products such as Aron Oxetane OXT-121 (manufactured by Toagosei Co., Ltd.) An article can be suitably used.

  As a specific example of a compound shown by General formula (5), the compound represented by the following structure is preferable from a viewpoint of coexistence of toughness and an elasticity modulus.

  The content of the oxetane compound (D) is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 10 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the components (A) and (D). 15 parts by mass or more and 70 parts by mass or less are more preferable. When the content of the oxetane compound (D) is at least 5 parts by mass, a cured product having a sufficient elastic modulus can be obtained. If the content of the oxetane compound (D) exceeds 90 parts by mass, the crosslink density may be increased, and sufficient toughness may not be obtained.

<Cationically Polymerizable Compound (E) (Component (E))>
The curable resin composition of the present invention may contain, for example, an epoxy resin as a cationically polymerizable compound other than the component (A) and the component (D).

  As epoxy resins other than the component (A) used in the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, Cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, phenol aralkyl epoxy resin, naphthol novolac epoxy resin, naphthol aralkyl epoxy resin, naphthol -Phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolak epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin Type epoxy resins, biphenyl-modified novolak type epoxy resin, a naphthylene ether type epoxy resin and the like.

  These epoxy resins may be oligomerized as a polymer, but in the case of a photocurable resin which can be suitably used in the present invention, the crystallinity is low and it is hard to solidify, but the cured product tends to be hard. Bisphenol-type epoxy resin is preferred. Among the bisphenol-type epoxy resins, monomers such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are preferable from the viewpoint that the photocurable resin composition has a low viscosity.

  The epoxy resin of the present invention preferably has an aromatic ring in order to improve the hardness of the cured product.

  In order to realize the effects of the present invention, the content of the cationically polymerizable compound (E) is 100 parts by mass of the component (A) (the total of the component (A) and the component (D) when containing the component (D)) 0 parts by mass or more and 75 parts by mass or less are preferable. If the amount of the cationically polymerizable compound (E) is excessive, the effects of the present invention may be impaired.

<Radical Polymerizable Compound (F) (Component (F))>
The curable resin composition of the present invention may contain, for example, a (meth) acrylate compound as the radically polymerizable compound (F).

  Examples of (meth) acrylate compounds include monofunctional (meth) acrylate compounds having one (meth) acryloyl group in the molecule, and polyfunctional (meth) acrylate compounds having two or more (meth) acryloyl groups. Be In the present invention, any polymerizable (meth) acrylic compound that can be polymerized by a general method can be used. A monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound can be used in mixture of 1 or more types arbitrarily.

  As a monofunctional (meth) acrylate compound, 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, phenyl glycidyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, phenyl cellosolve (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, biphenyl (Meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, benzyl (meth) acrylate and the like.

  As a polyfunctional (meth) acrylate compound, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nona ethylene glycol di (meth) Acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di ( Meta) acrylate, 1,6-hexamethylene di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate And pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and tris (meth) acryloxy Ethyl isocyanurate etc. can be mentioned.

  In order to realize the effects of the present invention, the content of the radically polymerizable compound (F) is 100 parts by mass of the component (A) (when the component (D) is contained, the total of the component (A) component (D)) On the other hand, 0 parts by mass or more and 75 parts by mass or less are preferable. If the amount of the radically polymerizable compound (F) is excessive, the effects of the present invention may be impaired.

<Curable resin composition>
In the curable resin composition of the present invention, various additives may be contained as other optional components, as long as the objects and effects of the present invention are not impaired. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers, polysulfide oligomers, etc .; polymerization inhibitors such as phenothiazine, 2,6-di-t-butyl-4-methylphenol etc .; polymerization start assistants; leveling agents; wettability improvers; surface activity Agents; plasticizers; UV absorbers; silane coupling agents; inorganic fillers; pigments; dyes, and the like.

  In the composition of the present invention, the necessary components (A), (B) and (C) and, if necessary, an appropriate amount of the component (D) and other optional components are charged in a stirring vessel. They can be produced by stirring at a temperature of at most 50 ° C, preferably at a temperature of 50 ° C to 100 ° C. 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 content of the total of the component (A) and the component (B) (the total of the component (A), the component (B) and the component (D) when the component (D) is contained) does not include the component (C) Preferably 100 parts by mass to 100 parts by mass, more preferably 25 parts by mass to 100 parts by mass, and still more preferably 75 parts by mass to 100 parts by mass with respect to 100 parts by mass of the curable resin composition. The effects of the present invention can be sufficiently obtained.

  The viscosity at 25 ° C. of the composition of the present invention is preferably 50 mPa · s or more and 10,000 mPa · s or less, more preferably 70 mPa · s or more and 5,000 mPa · s or less.

  The composition of the present invention obtained as described above is suitably used as a photocurable resin composition in optical three-dimensional shaping method. That is, the photocurable resin composition of the present invention is selectively irradiated with active energy rays such as ultraviolet rays, electron beams, X-rays, radiation and the like to provide energy necessary for curing by an optical three-dimensional shaping method. It is possible to produce a three-dimensional object of a desired shape.

<Cured product>
The curable resin (A), the polyhydric alcohol (B) and the curing agent (C) are essential components of the composition of the present invention, and a cured product can be obtained by curing these. The curing method can be adjusted according to the curing agent contained and can be cured using any known method such as active energy ray curing or heat curing. A plurality of curing methods may be combined.

In the obtained cured product of the present invention, since the curable resin (A) has an aromatic ring, the interaction between the molecules is strong, and when the oxetane compound (D) is contained, the oxetane compound (D) is a curable resin ( It has the effect of promoting the curing of A). In addition, since X _{3 of} the curable resin (A) is a flexible skeleton, the skeleton can be cured in a bent state, and rigid X ₁ and X ₂ are relatively free in the cured product. Can be arranged. Therefore, after curing, the rigid structures of the curable resin (A) interact with each other very effectively. Further, taking the case where the component (A) is an epoxy resin as an example, in a cationic polymerization system, a protonated epoxy group is unstable, and there is a problem that the polymerization chain is difficult to extend. In the present invention, it is considered that extension of the polymer chain occurs by reacting an unreacted epoxy group by adding an appropriate amount of polyhydric alcohol (B) to the resin composition. Further, the toughness is improved by effectively generating an interaction with the oxygen atom of the curable resin (A) or the oxetane compound (D) due to the hydrogen bond. In addition, it is considered that due to the effect of the physical chain cross-linking by the extension of the polymer chain and the hydrogen bond, the polymer chains can not move freely and the elastic modulus is improved. From these facts, it is considered that although the elastic modulus and the toughness are usually contradictory physical properties, it is possible to exhibit the characteristic curing that makes the two contradictory physical properties be compatible.

<Method of manufacturing three-dimensional object>
The curable resin composition which concerns on this embodiment can be used suitably for the manufacturing method of the three-dimensional molded item by the optical three-dimensional modeling method (optical modeling method). Hereinafter, the manufacturing method of the three-dimensional object using the curable resin composition which concerns on this embodiment is demonstrated.

  A conventionally known method can be used as the optical shaping method. That is, in the method for producing a three-dimensional object according to the present embodiment, the curable resin composition according to the present embodiment is selectively irradiated with an active energy ray such as light to photocure the curable resin composition layer by layer. And the like, and a process of manufacturing a three-dimensional object by repeating this.

In the step of curing the curable resin composition layer by layer, the curable resin composition is selectively irradiated with active energy rays based on slice data of a three-dimensional object to be produced. There is no restriction | limiting in particular as an active energy ray irradiated to a curable resin composition, if it is an active energy ray which can harden the curable resin composition concerning this embodiment. Specific examples of the active energy ray include ultraviolet rays, visible rays, infrared rays, electromagnetic waves such as X rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Among these, ultraviolet light is most preferable in terms of the absorption wavelength of the curing agent (C) to be used and the cost of equipment introduction. The exposure amount is not particularly limited, preferably not 0.001J / cm ² or more 10J / cm ² or less. If the amount is less than 0.001 J / cm ² , the curable resin composition may not be sufficiently cured. If the amount is more than 10 J / cm ² , the irradiation time becomes long and the productivity is lowered.

  The method for irradiating the curable resin composition with active energy rays is not particularly limited. For example, in the case of irradiating light as active energy rays, the following method can be adopted. As a first method, a method of scanning this light two-dimensionally with respect to the curable resin composition using point-like condensed light such as laser light can be mentioned. At this time, the two-dimensional scanning may be a point drawing method or a line drawing method. As a second method, there is a surface exposure method in which light is irradiated to the shape of cross-sectional data using a projector or the like. In this case, the active energy ray may be irradiated planarly through a planar drawing mask formed by arraying a plurality of micro light shutters such as a liquid crystal shutter or a digital micro mirror shutter.

  In this step, after obtaining a shaped article by the optical shaping method, the surface of the obtained shaped article may be washed with a cleaning agent such as an organic solvent. In addition, post curing may be performed to cure unreacted residual components that may remain on the surface or the inside of the shaped object by performing light irradiation or heat treatment on the obtained shaped object.

  EXAMPLES The present invention will be described in detail by way of the following examples, but the present invention is not limited to these examples.

Example 1
Each component was placed in a lightproof bottle according to the following formulation, and stirred until uniform using a stirring defoamer to prepare a curable composition.
Component (A): Curable resin Ai (n = 1) (manufactured by DIC "EXA 4816" (purity 99%)) 70 parts by mass Component (B): 1,4-benzenedimethanol 6 parts by mass Component (C ): Photoacid generator "CPI-210S" (manufactured by San-Apro Co., Ltd.) 2 parts by mass Component (D): oxetane compound represented by the following formula (manufactured by Toagosei Co., Ltd. "OXT-221") 30 parts by mass

[Creation of cured product and mechanical property evaluation]
· Preparation of film-like test pieces (for evaluation of elastic modulus)
A cured product was produced by the following method using the prepared curable composition. First, a 300 μm spacer was sandwiched between two quartz glasses, and the curable composition was poured into the 300 μm wide gap. The curable composition that has been poured in is irradiated with ultraviolet light of 5 mW / cm ² for 300 seconds (total energy 1500 mJ / cm ² ) with an ultraviolet irradiator (HOYA CANDEO OPTRONICS, trade name "LIGHT SOURCE EXECURE 3000"), and a photocured product I got The resulting cured product was placed in a heating oven at 50 ° C., and placed in a heating oven at 100 ° C. for 1 hour to perform heat treatment for 2 hours to obtain a cured product.

· Preparation of columnar test pieces (for toughness evaluation)
Using the prepared curable composition, a cured product was prepared 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 quartz glasses, and a curable resin was poured into the mold. With respect to the curable composition poured in, ultraviolet rays of 5 mW / cm ² were irradiated from the both sides of the mold for 120 seconds by the ultraviolet irradiator used in the preparation of the film-shaped test piece to perform temporary curing. Thereafter, main curing was performed by irradiating ultraviolet light from the both sides again for 600 seconds to obtain a cured product (7200 mJ / cm ² as a total energy). The resulting cured product was placed in a heating oven at 50 ° C., and placed in a heating oven at 100 ° C. for 1 hour to perform heat treatment for 2 hours to obtain a cured product.

・ Measurement and evaluation of elastic modulus (test method of tensile property)
The resulting light-heat-cured product having a thickness of about 300 μm was punched into a No. 8 dumbbell shape to prepare a test piece. This test piece is measured at a test temperature of 23 ° C. and a tensile speed of 10 mm / min using a tensile tester (trade name “Strograph EII”, manufactured by Toyo Seiki Seisakusho Co., Ltd.) according to JIS K 7127, and the tensile modulus of elasticity is measured. Was measured as an index of stiffness. The results are shown in Table 1.

· Measurement and evaluation of toughness (how to determine Charpy impact characteristics)
About the obtained test piece of 80 mm in length, 10 mm in width and 4 mm in thickness, in accordance with JIS K 7111, the central portion of the test piece by a notch forming machine (manufactured by Toyo Seiki Seisakusho, trade name "notching tool A-4") 2 mm deep and 45 ° notch. After that, using an impact tester (manufactured by Toyo Seiki Seisaku-sho, trade name "IMPACT TESTER IT"), it is destroyed with 2 J of energy from the back of the notch of the test piece. The energy required for breakage was calculated from the angle at which the hammer that was raised to 150 ° was raised after breakage of the specimen, and this was used as an index of toughness. The results are shown in Table 1.

Examples 2 to 5, Comparative Examples 1 to 2
A curable composition was prepared and evaluated in the same manner as in Example 1 except that the contents of the respective components and the number of hydroxyl groups of the component (B) were changed as shown in Table 1. The results are shown in Table 1. In addition, the component (B) used by each Example and the comparative example is as follows.
Example 2: 1, 6-hexanediol Example 3: Trimethylolpropane Example 4: Erythritol Example 5: Erythritol Comparative Example 2: Mannitol

  It was confirmed that the toughness value and the elastic modulus are improved in Examples 1 to 5 as compared with Comparative Example 1 in which the polyhydric alcohol is not added. In addition, when a polyhydric alcohol having two hydroxyl groups was used (Examples 1 and 2), the highest toughness value and elastic modulus were obtained in the system to which the oxetane compound (D) was added. Moreover, in Example 5, although the oxetane compound (D) was not added, the hardened | cured material which has toughness and an elastic modulus was fully able to be created. When the number of hydroxyl groups of the polyhydric alcohol is 6 (Comparative Example 2), the toughness value is reduced to about half that in the case where no polyhydric alcohol is added (Comparative Example 1).

Claims (13)

(A) A curable resin represented by the following general formula (1),

[X ₁ and X ₂ are independently a divalent linking group containing an aromatic ring.
X ₃ is an alkylene group having 4 to 18 carbon atoms, and a carbon atom constituting the alkylene group may be replaced by an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom.
L ₁ , L ₂ , L ₃ and L ₄ are independently -O-, -C-O-, -S-, -C-S-, ester bond, urethane bond, ether bond, thiourethane bond and thioether It is a divalent linking group containing one or more bonds selected from the group consisting of bonds.
Y ₁ and Y ₂ are each independently an epoxy group, a cycloalkene oxide group or an oxetanyl group.
n is an average value of repeating structural units and is a real number of 0.1 or more and 10 or less. ]
(B) a polyhydric alcohol having 2 or more and 5 or less hydroxyl groups,
(C) a curing agent,
A curable resin composition containing at least 0.1 part by mass and at most 20 parts by mass of the polyhydric alcohol (B) with respect to 100 parts by mass of the curable resin (A) Curable resin composition. Said X ₁ and said X ₂ may have a substituent, phenylene group, biphenylene group, naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, fluorenediyl group, diphenylmethanediyl group, diphenylethanediyl group, It is a diphenyl propane diyl group, diphenyl ether diyl group, or diphenyl sulfone diyl group, The curable resin composition of Claim 1 characterized by the above-mentioned. _3. The curable resin composition according to claim 1, wherein X ₃ is a non-cyclic alkylene group having a linear or branched structure which may have a substituent. The L ₁ , the L ₂ , the L ₃ and the L _{4 each} represent a bond selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ether bond and a thioether bond A curable resin composition according to any one of the preceding claims, characterized in that it comprises. The curable resin composition according to any one of claims 1 to 4, wherein Y ₁ and Y ₂ are epoxy groups.   The molecular weight of the said polyhydric alcohol (B) is 1,000 or less, The curable resin composition as described in any one of the Claims 1 thru | or 5 characterized by the above-mentioned.   Furthermore, an oxetane compound (D) is contained, and the polyhydric alcohol (B) is contained in an amount of 0.1 parts by mass or more and 20 parts by mass with respect to a total of 100 parts by mass of the curable resin (A) and the oxetane compound (D). The curable resin composition according to any one of claims 1 to 6, which is contained in an amount of at most parts by mass. The said oxetane compound (D) is shown by following General formula (4), The curable resin composition of Claim 7 characterized by the above-mentioned.

[X ₈ is a divalent alcohol residue or a divalent having one or more bonds selected from the group consisting of —O—, —C—O—, an ether bond, a carbonate bond, a urethane bond, and a urea bond And a linking group, which may contain an aromatic ring. ]   The oxetane compound (D) is contained in an amount of 5 parts by mass or more and 90 parts by mass or less based on 100 parts by mass in total of the curable resin (A) and the oxetane compound (D). 7. The curable resin composition according to 8.   The curable resin composition according to any one of claims 1 to 9, wherein the curing agent (C) is a photoacid generator.   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 10. A method for producing a three-dimensional object, comprising the steps of photocuring a curable resin composition layer by layer based on slice data to form a shaped object,
The method for producing a three-dimensional object, wherein the curable resin composition is the curable resin composition according to any one of claims 1 to 10.   The method for producing a three-dimensional object according to claim 12, further comprising the step of subjecting the three-dimensional object to a heat treatment to obtain a three-dimensional object.