JP2009138116A - Cationic polymerizable resin composition and cured product thereof - Google Patents

Abstract

The present invention relates to a cationic polymerizable resin composition having a low viscosity, excellent workability, and can be cured very rapidly by irradiation with light to obtain a cured product excellent in transparency, flexibility and heat resistance. I will provide a.
The cationic polymerizable resin composition of the present invention comprises an oxetane ring-containing vinyl ether compound (A) and / or an alicyclic epoxy group-containing vinyl ether compound (B), and an oxetane group, an epoxy group, a hydroxyl group, a vinyl ether in the molecule. It has at least one group, or an aliphatic or alicyclic unsaturated hydrocarbon group, and includes an oligomer or polymer (C) having a molecular weight of 500 or more.
[Selection figure] None

Description

  The present invention relates to fields such as waveguides (optical waveguides, electro-optical mixed wiring boards, etc.), optical fibers, transparent sealing agents, ink jet inks, color filters, nanoimprints, flexible substrates, etc., especially flexible optical waveguides, transparent sealing agents, The present invention relates to a cationically polymerizable resin composition useful in the field of nanoimprint and a cured product thereof.

  In high-speed and high-density signal transmission between electronic devices and between wiring boards, signal transmission interference and attenuation become barriers in conventional transmission using electric wiring, and the limits of high speed and high density are beginning to appear. In order to overcome this problem, a technique for optically connecting electronic elements and wiring boards, so-called optical interconnection, has been studied. As the optical path, it is considered that a flexible optical waveguide having flexibility is preferable from the viewpoint of ease of coupling with an element or a substrate and ease of handling.

  Conventionally, epoxy-based compounds have been used for flexible optical waveguides. However, although epoxy compounds can provide cured products with excellent chemical resistance and adhesion, they have low polymerization reactivity (curability) and high skin irritation and toxicity, so there are difficulties in handling and safety. is there. Polyimide is also being considered for use in flexible optical waveguides, but it is necessary to adjust the polyimide at a high temperature, when using it as a polymer, the solvent is extremely limited, and it is very expensive. Usage is restricted due to the point.

  On the other hand, JP-A-10-25262 and JP-A-2003-73321 disclose several alicyclic vinyl ether compounds as polymerizable compounds. Although these compounds have low skin irritation and thus safety is improved, heat resistance and transparency are still insufficient and improvement is required.

  JP-A-10-316670 discloses a vinyl ether compound having an oxetane ring in the molecule. However, if this compound has a long glycol chain, the cured product has flexibility, but there is a problem in terms of heat resistance and transparency, and if the glycol chain is short, the cured product has insufficient flexibility, so it is not always satisfactory. It is not a thing. JP-A-7-233112 and JP-A-11-171967 disclose vinyl ether compounds containing an alicyclic epoxy group in which a cyclohexane ring and an oxirane ring are bonded in the molecule. However, although this compound is excellent in terms of heat resistance, transparency, and curing speed, it has poor flexibility and is difficult to apply in fields requiring flexibility such as flexible optical waveguides.

  Similarly, Japanese Patent Application No. 2007-078858 and Japanese Patent Application No. 2007-076219 disclose alicyclic epoxy group-containing vinyl ether compounds and oxetane ring-containing vinyl ether compounds, respectively, but these compounds are also heat resistant. Although it is excellent in terms of transparency and curing speed, it is poor in flexibility and difficult to apply in fields requiring flexibility such as flexible optical waveguides. Furthermore, JP-A-2006-2329298 shows an example of adding an epoxidized polybutadiene having a hydroxyl group at both ends to a cyclic ether compound having a vinyl ether structure, but contains only vinyl ether as a reactive group. Heat resistance and transparency are inferior to vinyl ethers containing reactive cyclic ethers in the same molecule.

Japanese Patent Laid-Open No. 10-25262 JP 2003-73321 A JP-A-10-316670 JP-A-7-233112 Japanese Patent Laid-Open No. 11-171967 Japanese Patent Application No. 2007-078858 Japanese Patent Application No. 2007-076219 JP 2006-232988 A

  Accordingly, an object of the present invention is to perform cationic polymerization that is easy to process with low viscosity, and can be cured very quickly by irradiation with light to obtain a cured product having excellent transparency, flexibility, and heat resistance. It is in providing a conductive resin composition. The cationically polymerizable resin composition according to the present invention is useful in the fields of optical fibers, transparent sealants, inkjet inks, color filters, nanoimprints, flexible substrates, etc., particularly flexible optical waveguides, transparent sealants, and nanoimprints. is there.

  As a result of intensive studies to solve the above-mentioned object, the present inventors have found that a cationic polymerizable resin composition containing a vinyl ether compound having a cationic polymerizable cyclic ether and a compound having a functional group capable of reacting with the vinyl ether compound. Has found that it is possible to obtain a cured product having low viscosity, excellent workability, extremely high curing speed, and excellent transparency, flexibility and heat resistance by curing. .

  That is, the present invention includes an oxetane ring-containing vinyl ether compound (A) and / or an alicyclic epoxy group-containing vinyl ether compound (B), and an oxetane group, an epoxy group, a hydroxyl group, a vinyl ether group, or an aliphatic or alicyclic group in the molecule. Provided is a cationically polymerizable resin composition comprising an oligomer or polymer (C) having at least one unsaturated hydrocarbon group and having a molecular weight of 500 or more.

（式中、Ｒ¹〜Ｒ¹²は水素原子又は置換基を有していてもよい炭素数１〜２０の炭化水素基を示し、ｎ¹〜ｎ⁴は整数を示す）
の構造又はこれらの組み合わせよりなり、末端に水酸基、若しくは水素原子を有する分子量５００以上のオリゴマー又はポリマー、又は、下記式（１ｅ）

（式中、Ｒ¹³は置換基を有していてもよい２価の炭化水素基を示し、ｎ⁵は整数を示す）
で表され、末端に水酸基、若しくは水素原子を有する分子量５００以上のオリゴマー又はポリマーであることが好ましく、少なくともエポキシ基及び脂肪族若しくは脂環式不飽和炭化水素基を有するオリゴマー又はポリマー、或いは、ポリカーボネートポリオール又は両末端に水酸基を有するエポキシ化ポリブタジエンがより好ましい。 As said oligomer or polymer (C), following formula (1a)-(1d)

(Wherein, R ¹ to R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, n ¹ ~n ⁴ is an integer)
Or an oligomer or polymer having a hydroxyl group or a hydrogen atom at the terminal and having a molecular weight of 500 or more, or the following formula (1e)

(In the formula, R ¹³ represents a divalent hydrocarbon group which may have a substituent, and n ⁵ represents an integer.)
It is preferably an oligomer or polymer having a molecular weight of 500 or more having a hydroxyl group or a hydrogen atom at the terminal, and an oligomer or polymer having at least an epoxy group and an aliphatic or alicyclic unsaturated hydrocarbon group, or polycarbonate More preferred are polyols or epoxidized polybutadiene having hydroxyl groups at both ends.

  The present invention also provides a cured product obtained by polymerizing the cationic polymerizable resin composition.

  It is preferable to form a clad and / or a core of the optical waveguide with the cured product.

  The cationic polymerizable resin composition is used for the production of flexible optical waveguides, transparent sealants, and nanoimprints.

  The present invention also provides a method for producing an optical waveguide, wherein a coating base film is prepared by applying the cationic polymerizable resin composition on a film, and an optical waveguide is manufactured by coating a core with the cladding base film. provide.

  Furthermore, the optical waveguide manufactured by the manufacturing method of the said optical waveguide is provided.

  The present invention further provides a method for producing a fine structure, in which the cationic polymerizable resin composition is subjected to nanoimprint processing to obtain a fine structure.

  The cationically polymerizable resin composition of the present invention comprises an oxetane ring-containing vinyl ether compound (A) having a cationic polymerizable cyclic ether (specifically, an oxetane ring or an alicyclic epoxy group) and a vinyl ether group in the same molecule. And / or an alicyclic epoxy group-containing vinyl ether compound (B) and a functional group reactive with the cationic polymerizable cyclic ether (specifically, an oxetane group, an epoxy group, a hydroxyl group, a vinyl ether group, an aliphatic group or an aliphatic group) Since it contains at least one cyclic unsaturated hydrocarbon group) and an oligomer or polymer (C) having a molecular weight of 500 or more, it has a low viscosity and can be easily processed, and can be cured very rapidly by light irradiation. . For this reason, the effect which improves productivity of hardened | cured material is show | played. Moreover, the cationically polymerizable resin composition according to the present invention, which can obtain a cured product excellent in transparency, flexibility, and heat resistance by curing, is excellent as an optical material. Further, since it is excellent in flexibility, it can be easily combined with an element or a substrate, and is excellent in handling and workability. Furthermore, it has excellent safety because it has little toxicity and skin irritation. For this reason, the cationically polymerizable resin composition according to the present invention is used in fields such as optical fibers, transparent sealants, inkjet inks, color filters, nanoimprints, flexible substrates, particularly flexible optical waveguides, optical fibers, transparent sealants, nanoimprints. It can be suitably used in the field.

［式中、環Ｚはオキセタン環とともにスピロ構造を形成する非芳香族性炭素環を示し、分子内に存在していてもよく、存在していなくてもよい。Ｒは下記式（３）

（式中、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す）
で表される置換又は無置換ビニル基を示す。Ｗは置換又は無置換ビニルオキシ基（−ＯＲ基）とオキセタン環又は環Ｚとを連結する連結基であって、単結合又は（ｇ＋１）価の有機基を示す。Ｘはオキセタン環及び環Ｚの置換基であって、ハロゲン原子、置換基を有していてもよい炭化水素基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、オキソ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。ｇは１或いは２、ｆは０〜５の整数、ｈは１或いは２を示す。ｇ、ｆ、ｈが２以上の場合、括弧内の置換基は同一であってもよく、異なっていてもよい］
で表される化合物が挙げられる。 [Oxetane ring-containing vinyl ether compound (A)]
The oxetane ring-containing vinyl ether compound (A) in the present invention is not particularly limited as long as it is a compound having at least an oxetane ring and a vinyl ether structure in the molecule. As a typical example of the oxetane ring-containing vinyl ether compound (A), the following formula (2)

[Wherein, ring Z represents a non-aromatic carbocyclic ring that forms a spiro structure with an oxetane ring, and may or may not be present in the molecule. R is the following formula (3)

(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
The substituted or unsubstituted vinyl group represented by these is shown. W is a linking group that connects a substituted or unsubstituted vinyloxy group (—OR group) and an oxetane ring or ring Z, and represents a single bond or a (g + 1) -valent organic group. X is a substituent of the oxetane ring and ring Z, and may be protected by a halogen atom, a hydrocarbon group which may have a substituent, a hydroxyl group which may be protected by a protecting group, or a protecting group. A good amino group, a carboxyl group that may be protected with a protective group, a sulfo group that may be protected with a protective group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protective group. Show. g is 1 or 2, f is an integer of 0 to 5, and h is 1 or 2. When g, f, and h are 2 or more, the substituents in parentheses may be the same or different.
The compound represented by these is mentioned.

  In addition, when g = h = 1, the compound has at least a ring Z, X contains an aromatic or non-aromatic carbocycle, or W is aromatic or non-aromatic. It preferably contains a family carbon ring.

  The oxetane ring-containing vinyl ether compound (A) in the present invention preferably has an aromatic or non-aromatic carbon ring in the molecule, or has two or more vinyl ether structures in the molecule. Such a vinyl ether compound containing an oxetane ring and having a carbon ring in the molecule or having two or more vinyl ether structures in the molecule not only has an extremely fast curing speed, but also has transparency, heat resistance, etc. due to curing. It has a great advantage that a cured product having excellent physical properties can be obtained.

  In the oxetane ring-containing vinyl ether compound (A), examples of the aromatic carbocycle include a benzene ring and a naphthalene ring. Non-aromatic carbocycles include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclooctane rings, cyclododecane rings, and other cycloalkane rings (such as about 3 to 15-membered cycloalkane rings). A bridged alicyclic ring having about 6 to 20 carbon atoms such as a decalin ring, an adamantane ring and a norbornane ring; There may be two or more aromatic or non-aromatic carbocycles in the molecule. An aromatic or non-aromatic carbocycle is often present at a linking group site that connects the vinyl ether structure and the oxetane ring. In addition, the non-aromatic carbocycle may form a spiro structure together with the oxetane ring.

  The oxetane ring-containing vinyl ether compound (A) in the present invention may have only one vinyl ether structure when it has an aromatic or non-aromatic carbon ring, and it has aromaticity when it has two or more vinyl ether structures. Alternatively, it may not have a non-aromatic carbocyclic ring, but may have an aromatic or non-aromatic carbocyclic ring and have two or more vinyl ether structures in the molecule.

  In the formula (2), examples of the non-aromatic carbocycle in the ring Z include the non-aromatic carbocycles exemplified above. As the ring Z, a cyclopentane ring or a cyclohexane ring is preferable.

In the formula (2), R represents a substituted or unsubstituted vinyl group represented by the formula (3). In the formula (3), R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear C _1-4 (preferably C _1-3 ) alkyl groups such as methyl, ethyl, propyl and butyl; isopropyl, isobutyl, s-butyl, t- Examples thereof include branched C _1-4 (preferably C _1-3 ) alkyl groups such as butyl. R ¹ , R ² and R ³ are each preferably a hydrogen atom or a methyl group. Representative examples of the group represented by the formula (3) include vinyl group, isopropenyl group, 1-propenyl group, 2-methyl-1-propenyl group, 1,2-dimethyl-1-propenyl group and the like. It is done.

  In formula (2), W is a linking group that links a substituted or unsubstituted vinyloxy group (—OR group) and an oxetane ring or ring Z, and represents a single bond or a (g + 1) -valent organic group. As the organic group, a group having a carbon atom at a bonding site with an adjacent oxygen atom is usually used. Preferred organic groups include (i) a hydrocarbon group, (ii) one or more hydrocarbon groups, an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group (—CO—), and amino. And a group consisting of at least one group selected from the group (—NH—).

  The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a hydrocarbon group in which two or more of these are bonded.

  Examples of the hydrocarbon group include a divalent hydrocarbon group, methylene, methylmethylene (ethylidene), ethylmethylene (propylidene), dimethylmethylene (isopropylidene), ethylmethylmethylene, ethylene, propylene, trimethylene, tetra Linear or branched alkylene group having about 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 6) such as methylene and hexamethylene groups; 2 to 20 carbon atoms such as propenylene group (preferably Is a linear or branched alkenylene group of about 2 to 10, more preferably 2 to 6); 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1 , 4-cyclohexylene group and the like of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members). A cycloalkylidene group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropylene, cyclopentylidene and cyclohexylidene groups; 1,2-phenylene, 1, Examples include arylene groups such as 3-phenylene and 1,4-phenylene groups; benzylidene groups.

  The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group which may be protected with a protective group, a hydroxymethyl group which may be protected with a protective group, an amino group which may be protected with a protective group, and a protective group. And a carboxyl group, a sulfo group optionally protected by a protecting group, a halogen atom, an oxo group, a cyano group, a nitro group, a heterocyclic group, a hydrocarbon group, a haloalkyl group, and the like. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

  The heterocyclic group as the substituent is a heterocyclic group of about 3 to 15 members (in particular, 5 to 8 membered heterocycles) containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Cyclic group).

The hydrocarbon group as the substituent includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. As an aliphatic hydrocarbon group, it is a C1-C20 (preferably 1-10, more preferably 1-3) alkyl group; C2-C20 (preferably 2-10, more preferably 2-3). Alkenyl group having about 2 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 3). The alicyclic hydrocarbon group is a cycloalkyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members); 3 to 20 members (preferably 3 to 15 members, more preferably About 5 to 8 membered cycloalkenyl group; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms. The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Examples of the haloalkyl group as the substituent include haloalkyl groups having about 1 to 10 carbon atoms such as chloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups (particularly, C _{1- 3} haloalkyl group).

［式中、Ａ¹は２価の炭化水素基を示し、Ｙ¹は酸素原子（−Ｏ−）、硫黄原子（−Ｓ−）、カルボニル基（−ＣＯ−）、アミノ基（−ＮＨ−）又はこれらが２以上結合した基を示し、Ａ²は単結合又は（ｇ＋１）価の炭化水素基を示す。Ａ²が−ＯＲ側である。ｉ、ｊは、それぞれ０又は１であり、ｋは０〜５の整数を示す］
で表される基が含まれる。 Preferred examples of W include, for example, the following formula (4)

[Wherein A ¹ represents a divalent hydrocarbon group, Y ¹ represents an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group (—CO—), an amino group (—NH—) or they show two or more bonded groups, a ² represents a single bond or a (g + 1) -valent hydrocarbon radical. A ² is on the -OR side. i and j are each 0 or 1, and k represents an integer of 0 to 5]
The group represented by these is included.

Examples of the divalent hydrocarbon group for A ¹ include those exemplified above. Among these, as A ^1, methylene, ethylene, propylene, Isopiropiriden, trimethylene, linear or branched alkylene group having 1 to 6 carbon atoms such as a tetramethylene group is preferable.

As Y ¹ , an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group (—CO—), an amino group (—NH—), —COO—, —OCO—, —CONH—, — NHCO- and the like are preferable.

Examples of the (g + 1) -valent hydrocarbon group for A ² include those exemplified above. Among them, as A ² , a single bond; a linear or branched alkylene group having 1 to 6 carbon atoms such as methylene, ethylene, propylene, isopropylpyridene, trimethylene, tetramethylene group, 1,3-cyclopentylene, etc. 5 such as 5- to 8-membered cycloalkylene group such as 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene group, cyclopropylene, cyclopentylidene, cyclohexylidene group, etc. And an arylene group such as an ˜8-membered cycloalkylidene group, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene group, or a group in which two or more of these are bonded.

  W is particularly preferably a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, or a group in which the alkylene group is bonded to an oxygen atom or a sulfur atom.

  In formula (2), X is a substituent of the oxetane ring and ring Z, and is a halogen atom, a hydrocarbon group which may have a substituent, a hydroxyl group which may be protected with a protecting group, or a protecting group Protected with an amino group which may be protected with, a carboxyl group which may be protected with a protective group, a sulfo group which may be protected with a protective group, an oxo group, a nitro group, a cyano group, or a protective group An acyl group that may be present is shown. Examples of the protecting group include protecting groups commonly used in the field of organic synthesis.

As a halogen atom in X, a fluorine, chlorine, a bromine atom etc. are mentioned, for example. Examples of the hydrocarbon group of the “hydrocarbon group which may have a substituent” in X include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl An aliphatic hydrocarbon group such as a group (preferably a C _1-10 alkyl group, more preferably a C _1-5 alkyl group); an alicyclic hydrocarbon group such as a cyclopentyl, cyclohexyl group (preferably a 3-15 membered cyclohexane). Alkyl groups); aromatic hydrocarbon groups such as phenyl and naphthyl groups; groups in which two or more of these are bonded. Examples of the substituent that these hydrocarbon groups may have include, for example, halogen atoms such as fluorine, chlorine and bromine atoms, C _1-4 alkyl groups such as methyl groups, and C _1-5 such as trifluoromethyl groups. C _1-4 alkoxy groups such as haloalkyl groups, hydroxyl groups, methoxy groups, amino groups, dialkylamino groups, carboxyl groups, alkoxycarbonyl groups such as methoxycarbonyl groups, acyl groups such as nitro groups, cyano groups, acetyl groups, etc. Can be mentioned.

Examples of the acyl group in X include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; acetoacetyl groups; aromatic acyl groups such as benzoyl groups, and the like.

  When X is 2 or more, they may be bonded to each other to form a ring together with the carbon atom constituting the ring Z or oxetane ring in formula (2). Examples of such rings include alicyclic carbocycles such as cyclopentane ring, cyclohexane ring and perhydronaphthalene ring (decalin ring); lactone rings such as γ-butyrolactone ring and δ-valerolactone ring. .

  In the formula (2), g is 1 or 2, preferably 1. f is an integer of 0 to 5, preferably an integer of 0 to 3. h is 1 or 2. When f, g, and h are 2 or more, the substituents in parentheses may be the same or different. In addition, when g = h = 1, at least ring Z is present, X contains an aromatic or non-aromatic carbocycle, or W is an aromatic or non-aromatic carbon. It preferably contains a ring.

  Among the compounds represented by the formula (2), compounds represented by the following formula (2a), (2b), (2c) or (2d) are preferable.

[Wherein m represents 0 or 1; R, W, and X are the same as described above. However, in the formula (2b), at least one of W and X contains an aromatic or non-aromatic carbocycle]

  Typical examples of the oxetane ring-containing vinyl ether compound (A) of the present invention include the following compounds. In formula, n shows the integer of 0-6.

  The oxetane ring-containing vinyl ether compound (A) in the present invention can be produced by utilizing a known reaction as a method for producing a vinyl ether compound. A preferred embodiment includes a method in which an alcohol (hydroxy compound) corresponding to the oxetane ring-containing vinyl ether compound (A) and a vinyl ester compound are reacted in the presence of a transition element compound. For example, in the oxetane ring-containing vinyl ether compound (A) represented by the formula (2), an alcohol (hydroxy compound) in which R is a hydrogen atom in the formula (2) and a vinyl ester compound are used in the presence of a transition element compound. It can manufacture by making it react.

［式中、環Ｚ²は非芳香族性炭素環を示し、分子内に存在していてもよく、存在していなくてもよい。Ｒは前記式（３）で表される置換又は無置換ビニル基を示す。Ｗ²は置換又は無置換ビニルオキシ基（−ＯＲ基）とシクロヘキサン環又は環Ｚとを連結する連結基であって、単結合又は（ｇ＋１）価の有機基を示す。Ｒ^a、Ｒ^bは、同一又は異なって、水素原子又はアルキル基を示す。ｇ、ｈは前記と同様であり、ｇは１或いは２、ｈは１或いは２を示す。ｇ、ｈが２の場合、括弧内の置換基は同一であってもよく、異なっていてもよい］
で表される化合物が挙げられる。 [Alicyclic epoxy group-containing vinyl ether compound (B)]
The alicyclic epoxy group-containing vinyl ether compound (B) in the present invention has at least an alicyclic epoxy group (a group in which the epoxy ring and the alicyclic share two carbon atoms) and a vinyl ether structure in the molecule. If it is a compound, it will not specifically limit. As a typical example of the alicyclic epoxy group-containing vinyl ether compound (B), the following formula (5)

[Wherein, ring Z ² represents a non-aromatic carbocycle, and may or may not be present in the molecule. R represents a substituted or unsubstituted vinyl group represented by the formula (3). W ² is a linking group that links a substituted or unsubstituted vinyloxy group (—OR group) and a cyclohexane ring or ring Z, and represents a single bond or a (g + 1) -valent organic group. R ^a and R ^b are the same or different and each represents a hydrogen atom or an alkyl group. g and h are the same as above, g is 1 or 2, and h is 1 or 2. when g and h are 2, the substituents in parentheses may be the same or different.]
The compound represented by these is mentioned.

（式中、Ｗ³は単結合又は２価の有機基を示す。シクロヘキサン環を構成する炭素原子が−ＯＲ基と結合している）
で表される基であることが好ましい。 In the compound, when both R ^a and R ^b are hydrogen atoms, at least ring Z ² is present or W ² is represented by the following formula (6):

(Wherein W ³ represents a single bond or a divalent organic group. The carbon atom constituting the cyclohexane ring is bonded to the —OR group)
It is preferable that it is group represented by these.

  This compound is a vinyl ether compound containing an alicyclic epoxy group (1,2-epoxycyclohexane ring = a group consisting of 7-oxabicyclo [4.1.0] heptane ring), and further at a specific position in the molecule. It has a non-aromatic carbon ring or has an alkyl group at the junction of the cyclohexane ring and oxirane ring constituting the alicyclic epoxy group. Such a vinyl ether compound has not only an extremely high curing rate, but also has a great advantage that a cured product having excellent physical properties such as transparency and heat resistance can be obtained by curing.

In formula (5), ring Z ² represents a non-aromatic carbocycle. Ring Z ² may or may not be present in the molecule. Examples of the non-aromatic carbocycle include the same examples as those of the non-aromatic carbocycle exemplified in the section of the oxetane ring-containing vinyl ether compound (A).

In the formula (5), R represents a substituted or unsubstituted vinyl group represented by the formula (3). In the formula (3), R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As a C1-C4 alkyl group, the example similar to the example of a C1-C4 alkyl group quoted in the term of the said oxetane ring containing vinyl ether compound (A) can be given.

In Formula (5), W ² is a linking group that links a substituted or unsubstituted vinyloxy group (—OR group) and a cyclohexane ring or ring Z, and represents a single bond or an (m + 1) -valent organic group. As the organic group, a group having a carbon atom at a bonding site with an adjacent oxygen atom is usually used. Preferred organic groups include (i) a hydrocarbon group, (ii) one or more hydrocarbon groups, an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group (—CO—), and amino. And a group consisting of at least one group selected from the group (—NH—).

  The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a hydrocarbon group in which two or more of these are bonded.

  Examples of the hydrocarbon group include the same examples as those mentioned in the section of the oxetane ring-containing vinyl ether compound (A). Moreover, the hydrocarbon group may have a substituent. Examples of the substituent include the same examples as those mentioned in the section of the oxetane ring-containing vinyl ether compound (A).

Preferable examples of W ² include the same examples as those mentioned in the section of the oxetane ring-containing vinyl ether compound (A). As W, in particular, a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, or the alkylene group, an oxygen atom (—O—), a sulfur atom (—S—) and a carbonyl group A group in which at least one group selected from the group (—CO—) is bonded is preferable.

The bonding position of W ^{2 on} the cyclohexane ring or ring Z ² is not particularly limited. However, when ring Z is not present, the 4-position and the cyclohexane ring are bonded to the oxirane ring at the 4-position and 2-position. The fifth position is preferred.

In formula (5), R ^a and R ^b are the same or different and each represents a hydrogen atom or an alkyl group. Examples of the alkyl group include linear or branched alkyl having about 1 to 15 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, and decyl groups. Groups. Among these, an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 3 carbon atoms (for example, a methyl group) is preferable.

In the formula (5), f is 1 or 2, preferably 1. h is 1 or 2. When g and h are 2, the substituents in parentheses may be the same or different. When both R ^a and R ^b are hydrogen atoms, it is preferable that at least a ring Z ² exists in the molecule or W ² is a group represented by the above formula (6).

In Formula (6), W ³ represents a single bond or a divalent organic group. Examples of the divalent organic group include a divalent hydrocarbon group or a divalent hydrocarbon group, an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group (—CO—), and an amino group. And a group in which at least one group selected from (—NH—) is bonded. Examples of the divalent hydrocarbon group include those exemplified above. W ³ is particularly preferably a single bond or an alkyleneoxy group having 1 to 6 carbon atoms (the oxygen atom is at the right end).

  Among the compounds represented by the formula (5), compounds represented by the following formula (5a), (5b) or (5c) are preferable.

[Wherein, R ^{b ′} represents an alkyl group having 1 to 6 carbon atoms. Rings Z ² , R, R ^a , R ^b , W ² , W ³ , g and h are the same as described above. However, in the formula (5a), W ² connects the —OR group and the ring Z ² ]

In the formula (5a), R ^a and R ^b are each preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, a methyl group). . It is also preferred that at least one of R ^a and R ^b is a hydrogen atom. As the ring Z, in particular, a cycloalkane ring having about 5 to 12 members such as a cyclopentane ring, a cyclohexane ring and a cyclooctane ring; a bridged alicyclic ring having about 8 to 15 carbon atoms such as a decalin ring and a norbornane ring. preferable. As W, a single bond, a hydrocarbon group having 1 to 15 carbon atoms, or one or more hydrocarbon groups having 1 to 15 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), A group in which at least one group selected from a carbonyl group (—CO—) and an amino group (—NH—) is bonded is particularly preferable.

In the formula (5b), R ^a and R ^b are each preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, a methyl group). . It is also preferred that at least one of R ^a and R ^b is a hydrogen atom. W ¹ is particularly preferably a single bond or an alkyleneoxy group having 1 to 6 carbon atoms (the oxygen atom is at the right end).

In the formula (5c), R ^a is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. R ^{b ′} is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. As W, a single bond, a hydrocarbon group having 1 to 15 carbon atoms, or one or more hydrocarbon groups having 1 to 15 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), A group in which at least one group selected from a carbonyl group (—CO—) and an amino group (—NH—) is bonded is particularly preferable.

Typical examples of the alicyclic epoxy group-containing vinyl ether compound (B) of the present invention include the following compounds. In the formula, p and q are 0 or 1. A ³ represents a linear or branched alkylene group having 2 to 10 carbon atoms (preferably 2 to 6 carbon atoms).

  The alicyclic epoxy group-containing vinyl ether compound (B) of the present invention can be produced by utilizing a known reaction as a method for producing a vinyl ether compound. A preferred embodiment includes a method in which an alcohol (hydroxy compound) corresponding to the alicyclic epoxy group-containing vinyl ether compound (B) and a vinyl ester compound are reacted in the presence of a transition element compound. That is, the alicyclic epoxy group-containing vinyl ether compound (B) represented by the formula (5) is obtained by combining an alcohol (hydroxy compound) in which R is a hydrogen atom in the formula (5) and a vinyl ester compound as a transition element compound. It can manufacture by making it react in presence. The alcohol (hydroxy compound) corresponding to the alicyclic epoxy group-containing vinyl ether compound (B) can be synthesized from a known compound by using a known reaction.

[Oligomer or polymer (C)]
The oligomer or polymer (C) in the present invention has at least one oxetane group, epoxy group, hydroxyl group, vinyl ether group, or aliphatic or alicyclic unsaturated hydrocarbon group in the molecule, and has a molecular weight of 500 or more (specifically The molecular weight is 500 to 100,000, preferably 3000 to 30,000.

As the oligomer or polymer (C) in the present invention, the above formulas (1a) to (1d)
An oligomer or polymer having a molecular weight of 500 or more having a hydroxyl group or a hydrogen atom at the terminal, or an oligomer or polymer having a molecular weight of 500 or more represented by the formula (1e) and having a hydroxyl group or a hydrogen atom at the terminal. Preferably there is.

  When the molecular weight of the oligomer or polymer (C) is less than 500, the flexibility of a cured product obtained by curing the cationic polymerizable resin composition tends to be difficult to obtain. On the other hand, if the molecular weight exceeds 100,000, the viscosity tends to be too high and handling tends to be difficult.

In the formulas (1a) to (1d), the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent as R ^{1 to} R ¹² includes an aliphatic hydrocarbon group and an alicyclic hydrocarbon. Groups, aromatic hydrocarbon groups and their combined groups. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10, more preferably an alkyl group of about 1 to 3); an alkenyl group of about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as vinyl, allyl, 1-butenyl group; Examples thereof include alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as propynyl groups.

As the alicyclic hydrocarbon group, a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as pentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4 4.0.1, ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Preferred hydrocarbon groups include C _1-10 alkyl groups, C _2-10 alkenyl groups, C _2-10 alkynyl groups, C _3-15 cycloalkyl groups, C _6-10 aromatic hydrocarbon groups, C _3-15 A cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are included.

  The hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls. Group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. May be. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

Examples of the divalent hydrocarbon group which may have a substituent as R ¹³ in the formula (1e) and the substituent which may be present in the hydrocarbon group include those represented by the formula (2) The example similar to the example of the bivalent hydrocarbon group in W in the inside, and the substituent which you may have can be given.

  As the oligomer or polymer (C) in the present invention, a polycarbonate polyol represented by the following formula (7) [in particular, a polycarbonate polyol represented by the following formula (8)], or at least an epoxy group and an aliphatic or alicyclic group Cationic polymerizable resin compositions having an unsaturated hydrocarbon group [in particular, epoxidized polybutadiene having hydroxyl groups at both ends represented by the following formula (9)] are preferred.

（式中、ｒは１０以上の整数を示し、Ｒ¹⁷、Ｒ¹⁸は同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す）

(Wherein, r represents an integer of 10 or more, and R ¹⁷ and R ¹⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

（式中、ｓは１０以上の整数を示す）

(In the formula, s represents an integer of 10 or more)

［式中、ｔは２，３−エポキシ−１，４−テトラメチレン基からなる繰り返し単位の繰り返しの数を示し、ｕは２−ブテニレン基からなる繰り返し単位の繰り返しの数を示す。２，３−エポキシ−１，４−テトラメチレン基と２−ブテニレン基は、ランダム重合していてもよく、ブロック重合していてもよい。式（９）で表される両末端に水酸基を有するエポキシ化ポリブタジエンの繰り返し単位の繰り返しの数は（ｔ＋ｕ）で表される。ｔ、ｕはそれぞれ１以上の整数を示し、（ｔ＋ｕ）は１０以上の整数を示す］

[Wherein, t represents the number of repeating units composed of 2,3-epoxy-1,4-tetramethylene groups, and u represents the number of repeating units composed of 2-butenylene groups. The 2,3-epoxy-1,4-tetramethylene group and the 2-butenylene group may be randomly polymerized or block polymerized. The number of repeating units of the epoxidized polybutadiene having hydroxyl groups at both ends represented by the formula (9) is represented by (t + u). t and u each represent an integer of 1 or more, and (t + u) represents an integer of 10 or more.]

  In the present invention, as the oligomer or polymer (C), the trade name “PB3600” (manufactured by Daicel Chemical Industries, Ltd.), the trade name “CD220PL” (manufactured by Daicel Chemical Industries, Ltd.) and the like can be suitably used. The trade name “PB3600” (manufactured by Daicel Chemical Industries, Ltd.) can be preferably used.

[Cationically polymerizable resin composition]
The cationically polymerizable resin composition according to the present invention includes the oxetane ring-containing vinyl ether compound (A) and / or an alicyclic epoxy group-containing vinyl ether compound (B), and an oxetane group, an epoxy group, a hydroxyl group, a vinyl ether group in the molecule, Or an oligomer or polymer (C) having at least one aliphatic or alicyclic unsaturated hydrocarbon group and having a molecular weight of 500 or more.

  The content of the oxetane ring-containing vinyl ether compound (A) and / or the alicyclic epoxy group-containing vinyl ether compound (B) in the cationic polymerizable resin composition according to the present invention is 6 to 85 of the entire cationic polymerizable resin composition. % By weight is preferable, and 20 to 80% by weight is more preferable. When the content of the oxetane ring-containing vinyl ether compound (A) and / or the alicyclic epoxy group-containing vinyl ether compound (B) is less than 6% by weight, the curing rate is very slow and unusable for practical use. On the other hand, when it exceeds 85% by weight, sufficient flexibility cannot be obtained in the cured product. The cationically polymerizable resin composition of the present invention uses the oxetane ring-containing vinyl ether compound (A) and / or the alicyclic epoxy group-containing vinyl ether compound (B) in an amount within the above range, and therefore has excellent curability and sufficient flexibility. Can be obtained. For this reason, it is extremely advantageous as a material in a field where high heat resistance, transparency, flexibility and curability are required, particularly in an optical field such as an optical waveguide. In the present invention, the heat resistance is evaluated by the weight reduction rate due to heating and the light loss after heating.

  The content of the oligomer or polymer (C) in the cationic polymerizable resin composition according to the present invention is preferably 5 to 94% by weight, more preferably 10 to 80% by weight, based on the whole cationic polymerizable resin composition. . When the content of the oligomer or polymer (C) is less than 5% by weight, the flexibility of the cured product obtained by curing the cationic polymerizable resin composition tends to be difficult to obtain, and it is used as a flexible optical waveguide or the like. Tend to be difficult to do. On the other hand, when the content of the oligomer or polymer (C) exceeds 94% by weight, the viscosity of the cationically polymerizable resin composition tends to be too high, making it difficult to use.

  If necessary, other additives may be added to the cationic polymerizable resin composition according to the present invention, for example, a polymerization initiator may be contained. The polymerization initiator is not particularly limited as long as it can cause ionic polymerization such as a photocationic polymerization initiator, and a known polymerization initiator, a photoacid generator, or the like can be used. .

As the cationic photopolymerization initiator, is composed of a cation portion and an anion portion, the anion site, PF ₆ ^- is preferably formed of the same or higher charge density than that. This is because the solubility is extremely good, and excellent cationic curability can be exerted to significantly improve the curing speed, and a cured product having excellent transparency can be provided. PF ₆ ^- and composed than the charge density is low anionic sites, reactivity, although the solubility of the cationic photopolymerization initiator is improved, since the coloring resistance is reduced, the areas where transparency is required Is not preferred. Here, “charge density” in the present invention is used in the meaning described in JVCrivello and JHW Lam, Macromolecules, 1307, Vol. 10, 1997. As the anion moiety having the “charge density equal to or higher than PF ₆ ⁻ ”, an anion having a fluorine atom and high nucleophilicity can be used. Specifically, PF ₆ ⁻ , BF ₄ ⁻ and CF ₃ SO _4- ^{and the} like.

  Examples of the photopolymerization initiator in the present invention include sulfonium salts such as triallylsulfonium hexafluorophosphate and triarylsulfonium hexafururoantimonate; diaryliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium Tetrakis (pentafluorophenyl) borate, iodonium salts such as iodonium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafurophosphate; Can be used. Since the oxetane ring-containing vinyl ether compound (A) and / or the alicyclic epoxy group-containing vinyl ether compound (B) in the present invention easily dissolves such a polymerization initiator, the preparation of the polymerizable composition is easy.

  As a commercial item of a photocationic polymerization initiator, for example, “Irgacure 250” (manufactured by Ciba Japan Co., Ltd.), “Uvacure 1591” (manufactured by Daicel Cytec Co., Ltd.) and the like are available.

  The amount of the polymerization initiator used is usually about 0.01 to 50% by weight, preferably about 0.1 to 20% by weight, based on the cationic polymerizable resin composition. When the polymerization initiator is added within the above range, a cationic polymerizable resin composition having an excellent balance between polymerization rate and storage stability can be obtained.

  In addition, the cationically polymerizable resin composition according to the present invention includes a curable compound (for example, epoxy) other than the oxetane ring-containing vinyl ether compound (A) and / or the alicyclic epoxy group-containing vinyl ether compound (B) as necessary. Compounds, oxetane compounds, vinyl ether compounds, etc.), for example, may have the trade name “Celoxide 2021P” (manufactured by Daicel Chemical Industries). Since the trade name “Celoxide 2021P” (manufactured by Daicel Chemical Industries, Ltd.) is easy to form a bond with the adherend, for example, by adding 1 to 30% by weight in the cationic polymerizable resin composition, the cationic polymerizable resin is added. The adhesion of the cured product of the composition to the adherend can be improved.

  Further, if necessary, curing-expandable monomers (spiroorthocarbonates, dithiocarbonates, etc.), photosensitizers (anthracene sensitizers, etc.), resins, adhesion improvers, reinforcing agents, softeners, plasticizers Viscosity modifiers, solvents, inorganic or organic particles (such as nanoscale particles), and various conventionally known additives such as fluorosilane may be contained.

（式中、Ｒ¹⁹〜Ｒ³⁶はそれぞれ、水素原子、ハロゲン原子、酸素原子、ハロゲン原子を含んでいてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す）
で表されるビシクロエポキシ化合物、又は、下記式（１１）

（式中、Ｒ³⁷〜Ｒ⁴¹はそれぞれ、水素原子、ハロゲン原子、酸素原子、ハロゲン原子を含んでいてもよい炭化水素、又は置換基を有していてもよいアルコキシ基を示す。ｖは１〜６の整数を示し、ｗ１、ｗ２はそれぞれ０〜３の整数を示す。Ｘ、Ｙ、Ｚはそれぞれ、酸素原子、又は硫黄原子を示す）
で表されるカーボネート系化合物等が挙げられる。 Addition of the curable expansive monomer can reduce the curing shrinkage rate, so that effects such as reduction in residual stress and improvement in adhesion can be expected. The cure-expandable monomer is represented by the following formula (10)

(Wherein R ^{19 to} R ³⁶ each represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent)
Or a bicycloepoxy compound represented by the following formula (11)

(In the formula, each of R ^{37 to} R ⁴¹ represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon which may contain a halogen atom, or an alkoxy group which may have a substituent. -6 represents an integer, and w1 and w2 each represent an integer of 0 to 3. X, Y, and Z each represents an oxygen atom or a sulfur atom)
The carbonate type compound etc. which are represented by these are mentioned.

  The said photosensitizer improves the effect | action of the said photocationic polymerization initiator more, and accelerates | stimulates the photocationic polymerization of a cationically polymerizable resin composition more. Although it does not specifically limit as such a photosensitizer, For example, a carbonyl compound, an organic sulfur compound, a persulfide, a redox type compound, an azo compound, a diazo compound, a halogen compound, a photoreducible dye, etc. can be utilized. Specific examples of the photosensitizer include, for example, benzoin derivatives such as benzoin methyl ether and benzoin isopropyl ether; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino). Benzophenone derivatives such as benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; anthracene derivatives such as dipropoxyanthracene and dibutoxyanthracene . These photosensitizers may be used independently and 2 or more types may be used together.

  The cationically polymerizable resin composition of the present invention is a conventional oxetane ring-containing vinyl ether compound (A) and / or alicyclic epoxy group-containing vinyl ether compound (B), oligomer or polymer (C), and, if necessary, conventional additives. It can manufacture by stirring and mixing using a well-known apparatus. In addition, the production of the cationic polymerizable resin composition of the present invention is preferably performed in a state where ultraviolet rays are blocked, and the obtained cationic polymerizable resin composition can be stored in a cool and dark place in a light-shielded container. preferable.

  Since the cation polymerizable resin composition according to the present invention contains an oxetane ring-containing vinyl ether compound (A) and / or an alicyclic epoxy group-containing vinyl ether compound (B), and an oligomer or polymer (C), it is processed with low viscosity. It has the characteristic that it is easy, and has the characteristic that the curing rate is extremely fast. In addition, by curing, there is a great advantage that a cured product having excellent transparency, heat resistance and flexibility can be obtained. As a result, the cationic polymerizable resin composition according to the present invention can be used for paints, coating materials, inks such as inkjet inks, adhesives, resists, plate making materials, molding materials, color filters, flexible substrates, sealing materials, etc. It can be used in a wide range of fields such as optical fields such as waveguides (optical waveguides, mixed substrates, etc.) and optical fibers. In particular, it is extremely useful for optical applications such as flexible optical waveguides. Moreover, it can use preferably as a resin composition used for a transparent sealing agent and nanoimprint technology.

[Cured product]
The cured product of the present invention can be obtained by irradiating and polymerizing the cationic polymerizable resin composition according to the present invention. For example, an ink jet method using the cationic polymerizable resin composition of the present invention is used. It can be manufactured by forming a desired image or shape by a conventional method such as a lithography method, and then exposing.

  For the exposure, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam, a laser beam, or the like can be used as an irradiation source. Curing control can be performed by appropriately setting the intensity of light used for exposure, temperature, irradiation time, etc., and by selecting the constituent components of the cationic polymerizable resin composition (addition of a curing control agent, etc.). it can. Of these, means for controlling the curing by controlling the temperature during and after exposure (post-baking) is preferably used.

  The cationic polymerizable resin composition of the present invention can be cured by performing a heat treatment at a temperature of, for example, about 50 to 180 ° C. after exposure. Such heat treatment after the exposure is effective for curing a thick film, curing an unirradiated portion, or curing a cationic polymerizable resin composition containing a filler or a pigment.

  The cured product of the present invention is excellent in transparency, heat resistance, flexibility and the like. Therefore, in the fields of waveguides (optical waveguides, electric / light mixed wiring boards, etc.), optical fibers, transparent sealants, inkjet inks, color filters, nanoimprints, flexible substrates, etc., especially flexible optical waveguides, transparent sealants, nanoimprints Very useful in the field.

  The transparency in the present invention can be evaluated by the transmittance of light having a wavelength of 400 to 850 nm. According to the present invention, it is possible to obtain a cured product having excellent transparency with the transmittance of, for example, 70% or more, preferably 80% or more, particularly 85% or more.

  The flexibility in the present invention can be evaluated based on flexibility, and can be determined, for example, by determining whether or not a crack (crack) is generated by winding a 200 μm thick film-like cured product around a rod having a radius of 2 mm. ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material which has the softness | flexibility which can be bent without generating a crack (crack) can be obtained.

  The heat resistance in the present invention means that the weight of the cured product is maintained even when the cured product obtained by irradiating the cationic polymerizable resin composition with light is subjected to a heat treatment. Since the cured product of the cationic polymerizable resin composition in the present invention is excellent in heat resistance, it is extremely useful in the field exposed to heat after curing.

[Optical waveguide]
The optical waveguide is an optical circuit composed of a high refractive index portion called a core and a low refractive index portion called a clad. The cationic polymerizable resin composition according to the present invention is easy to process because of its low viscosity, and in addition to being able to obtain a cured product with high productivity because of its extremely high curing rate, the obtained cured product is flexible. It has heat resistance to the extent that it can work with solder or the like. In addition, the cured product of the cationically polymerizable resin composition according to the present invention can maintain excellent transparency not only immediately after curing but also after heating, and thus exhibits excellent optical properties such that light loss is extremely suppressed. In that respect, it is extremely useful as a material for forming the cladding and core of an optical waveguide. For example, when the cationic polymerizable resin composition according to the present invention is used as a cladding forming material, the cationic polymerizable resin composition according to the present invention has a high refractive index material (for example, 1-acryloxy-4-methoxynaphthalene). Can be used as a material for forming the core. Conversely, when the cation polymerizable resin composition according to the present invention is used as a core forming material, a material obtained by adding a low refractive index material to the cation polymerizable resin composition according to the present invention is used as a cladding forming material. Can be used as

  The optical waveguide according to the present invention can be prepared, for example, by coating the cationic polymerizable resin composition according to the present invention on a film to produce a clad base film, and covering the core with the clad base film. it can.

  More specifically, for example, a cation polymerizable resin composition according to the present invention is applied on a substrate to form a clad layer, a core layer is laminated on the clad layer, and after applying a resist, through a mask. An optical waveguide is formed by RIE (Reactive Ion Etching) method, etc., in which an optical waveguide is formed by exposing, developing and etching, then removing the resist to form a core, and forming an upper cladding layer so as to cover the core Can be produced.

  For the purpose of adjusting the refractive index, a nano-sized metal oxide or the like can be added to the cationic polymerizable resin composition for use in an optical waveguide. Examples of the metal oxide include zirconium oxide and titanium oxide, and the size is, for example, about 1 to 100 nm. Further, for the purpose of suppressing curing shrinkage, it is preferable to add a curing expandable compound such as bicyclohexene oxide and / or 2,2-dimethylpropyl carbonate.

  Suitability as an optical waveguide can be determined by known waveguide characteristic evaluation. Such waveguide property evaluation is not particularly limited, and for example, a method of measuring light loss by a known method for a simple waveguide formed from a cured product of a cationic polymerizable resin composition can be used. The cured product of the cationic polymerizable resin composition according to the present invention has, for example, an optical waveguide having an optical loss of 0.3 dB / cm or less (preferably 0.2 dB / cm or less) at a wavelength of 850 nm by a cutback method. It has characteristics. Moreover, since the optical waveguide formed with the hardened | cured material of the cationic polymerizable resin composition which concerns on this invention has heat resistance, even if it heats, the raise of a light loss can be suppressed remarkably.

  Since the optical waveguide according to the present invention is formed by the cationic polymerizable resin composition according to the present invention, the optical waveguide has flexibility and can be bent freely, and a crack (crack) is generated by bending. The optical loss value does not increase. Therefore, it can be used by being appropriately deformed according to the shape of the optical waveguide installation site. In addition, since the heat resistance is high, it is possible to perform operations such as soldering, and even if heated, an increase in the light loss value can be suppressed, so that it can be used in a high heat environment. Moreover, transparency is high and transparency is not impaired even if it heats.

[Transparent sealant]
For sealing an optical semiconductor element, a transparent sealant excellent in transparency, heat resistance, moisture resistance, adhesion and crack resistance is required. Since the cationically polymerizable resin composition according to the present invention has the above properties, it can be suitably used as a transparent sealing agent for sealing an optical semiconductor element.

[Nanoimprint processing]
The processing method using the nanoimprint technique is a technique capable of producing a fine structure having a pattern on the order of nm at high speed and at low cost, and is preferably used because of its short process and excellent productivity.

More specifically, nanoimprint processing is performed by pressing an imprint stamp (also referred to as a mold or a plate) having a fine pattern on a photocurable composition applied on a substrate, and then exposing and curing the pattern. This is a transfer technique, and specifically comprises the following steps.
Step 1: Applying a photocurable resin composition on a substrate to produce an uncured film Step 2: Uncured film (film material) from the glass transition temperature (Tg) to the softening point of the resin composition When the resin is softened by heating, the imprint stamp having a fine pattern is pressed to transfer the pattern. Step 3: The coating material to which the fine pattern is transferred is cooled or photocured. Step 4: The imprint stamp is removed. To obtain an imprinted microstructure

  The cationically polymerizable resin composition according to the present invention can obtain a fine structure by performing nanoimprint processing. The cationically polymerizable resin composition for nanoimprint processing uses various known additives such as photosensitizers, resins, adhesion improvers, reinforcing agents, softeners, plasticizers, viscosity modifiers, and solvents as necessary. An agent may be added.

  Since the cationic polymerizable resin composition according to the present invention is rapidly cured by light irradiation, the productivity is high. In addition, since the cured product has flexibility, the cured product is easily removed when the imprint stamp is removed. Further, when the imprint stamp is removed, the original shape is restored again, so that a fine structure that faithfully reproduces the nm order pattern can be obtained. Furthermore, the obtained fine structure has properties excellent in transparency and heat resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Synthesis example 1
280 mL of a mixed solution of 24.9 g (0.23 mol) of sodium carbonate and toluene was heated to 95 ° C., 1.4 g of propionic acid was added, and 16 g of vinyl acetate was added dropwise while maintaining 95 ° C., and 15 minutes later Di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ was added in an amount of 1.27 g (1.9 mmol). Next, 40 g (0.19 mol) of oxetane-3,3-dimethanol was added dropwise over 3 hours, and 79.8 g of vinyl acetate was added dropwise while maintaining a reaction temperature of 95 ° C. under a nitrogen atmosphere. Went. After completion of the dropwise addition, the mixture was stirred for 1 hour, and the reaction solution was analyzed by gaxromatography. As a result, 3,3-bis (vinyloxymethyl) oxetane represented by the following formula (12) was obtained at a yield of 90% ( 3-vinyloxymethyloxetane-3-yl) methanol was produced in 2% yield. The reaction solution was purified by distillation to obtain 31 g of 3,3-bis (vinyloxymethyl) oxetane having a purity of 99%.
¹ H-NMR (CDCl ₃ ) δ: 6.5 (2H, dd), 4.53 (4H, s), 4.2 (2H, d), 4.05 (2H, d), 3.93 (4H, s)

Synthesis example 2
3-Chloromethyl-3-ethyloxetane (0.1 mol), 1,4-cyclohexanediol (0.5 mol) and tetrabutylammonium bromide (0.01 mol) were added to toluene (500 g), and the temperature was raised to 90 ° C. Later, 5N-NaOH aqueous solution (100 g) was added dropwise and stirred for 5 hours. The toluene solution (toluene layer) was washed with water, concentrated, and purified by silica gel chromatography to obtain 99% pure 4- (3-ethyloxetane-3-yl-methoxy) cyclohexanol.
100 mL of a mixed solution of sodium carbonate (0.06 mol) and toluene was heated to 95 ° C. While maintaining 95 ° C., 4.2 g of vinyl acetate was added dropwise, and 15 minutes later, di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (0. 5 mmol) was added. Then, 4- (3-ethyloxetane-3-yl-methoxy) cyclohexanol (0.05 mol) was added dropwise over 2 hours, and vinyl acetate 12.2 was maintained under a nitrogen atmosphere while maintaining the reaction temperature 95 ° C. The reaction was carried out while adding 6 g dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour and analyzed by gas chromatography. As a result, 3-ethyl-3- (4-vinyloxycyclohexyloxymethyl) oxetane represented by the following formula (13) was found to be 92%. Was generated at a rate. ^{When 1} H-NMR (CDCl ₃ ) was measured, as in Synthesis Example 1, signals specific to the vinyl group were observed at 6.5 ppm, 4.2 ppm, and 4.04 ppm.

Synthesis example 3
12.6 g (0.1 mol) of (4-methylcyclohex-3-enyl) methanol was epoxidized at 65 ° C. using a 5 wt% peracetic acid-ethyl acetate solution. By purification by distillation, 12 g of 98% pure (6-methyl-7-oxabicyclo [4.1.0] hept-3-yl) methanol was obtained.
100 mL of a mixed solution of sodium carbonate (0.06 mol) and toluene was heated to 95 ° C. While maintaining 95 ° C., 4.2 g of vinyl acetate was added dropwise, and 15 minutes later, di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ (0. 5 mmol) was added. Subsequently, (6-methyl-7-oxabicyclo [4.1.0] hept-3-yl) methanol (0.05 mol) was added dropwise over 2 hours, and the reaction temperature was maintained at 95 ° C. under a nitrogen atmosphere. The reaction was performed while adding dropwise 12.6 g of vinyl acetate. After the completion of the dropwise addition, the mixture was stirred for 1 hour, and the reaction solution was analyzed by gas chromatography. As a result, 1-methyl-4-vinyloxy-7-oxabicyclo [4.1.0] heptane represented by the following formula (14) was obtained. It was produced in a yield of 95%. ^{When 1} H-NMR (CDCl ₃ ) was measured, as in Synthesis Example 1, signals specific to the vinyl group were observed at 6.5 ppm, 4.2 ppm, and 4.05 ppm.

Synthesis example 4
4-Chloromethylcyclohexene (0.1 mol), 1,4-cyclohexanediol (0.5 mol) and tetrabutylammonium bromide (0.01 mol) were added to toluene (500 g), and the temperature was raised to 90 ° C. Aqueous NaOH (100 g) was added dropwise and stirred for 5 hours. The toluene solution (toluene layer) was washed with water, concentrated and purified by silica gel chromatography to obtain 13 g of 99% pure 4- (cyclohex-3-enylmethoxy) cyclohexanol.
4- (Cyclohex-3-enylmethoxy) cyclohexanol was epoxidized in the same manner as in Synthesis Example 3 to obtain 8 g of 4- (7-oxabicyclo [4.1.0] hept-3-ylmethoxy) cyclohexanol. It was.
Further, in place of (6-methyl-7-oxabicyclo [4.1.0] hept-3-yl) methanol, the above 4- (7-oxabicyclo [4.1.0] hept-3-ylmethoxy) cyclo Using hexanol, vinyl etherification was performed in the same manner as in Synthesis Example 3 to synthesize 3- (4-vinyloxycyclohexyloxymethyl) -7-oxabicyclo [4.1.0] heptane represented by the following formula (15). . ^{When 1} H-NMR (CDCl ₃ ) was measured, as in Synthesis Example 1, signals specific to the vinyl group were observed at 6.5 ppm, 4.2 ppm, and 4.04 ppm.

[Curing product of cationically polymerizable resin composition]
Examples 1-9 and Comparative Examples 1-5

A cationically polymerizable resin composition was prepared by mixing and dissolving the vinyl ether compound, oligomer or polymer and photocationic polymerization initiator in the types and amounts shown in Table 1.
A Teflon (registered trademark) plate having a thickness of 1 mm or 200 μm is cut into a sample shape (15 mm × 60 mm), a PET film coated with Teflon (registered trademark) on one side, and then sandwiched vertically by a glass plate (glass plate / PET / Teflon (registered trademark) / PET / glass plate).
The prepared Teflon (registered) was prepared by injecting the prepared cationic polymerizable resin composition into the cut-out portion of the sample shape with a syringe, and then irradiating ultraviolet rays (UV) under the following conditions using a conveyor type ultraviolet irradiation device. A cured product having a thickness of 1 mm or 200 μm corresponding to the (trademark) plate was formed.
The curing rate of the obtained cationic polymerizable resin composition, and the gel fraction, curing rate, initial light loss, light loss after heating, flexibility, heat resistance, and thermal decomposition temperature of the obtained cured product are as follows. Measurement and evaluation.

UV curing conditions:
UV irradiation device: trade name “UVC-02516S1AA02” (manufactured by USHIO)
Metal halide lamp Irradiation conditions: 160W
Conveyor speed: 2m / min
Number of irradiation: 1 time

In addition, each code | symbol in the vinyl ether compound of Table 1, an oligomer or a polymer, and a photocationic polymerization initiator is as follows.
[Vinyl ether compounds]
(A1): 3,3-bis (vinyloxymethyl) oxetane obtained in Synthesis Example 1
(A2): 3-ethyl-3- (4-vinyloxycyclohexyloxymethyl) oxetane obtained in Synthesis Example 2
(B1): 1-methyl-4-vinyloxy-7-oxabicyclo [4.1.0] heptane obtained in Synthesis Example 3
(B2): 3- (4-vinyloxycyclohexyloxymethyl) -7-oxabicyclo [4.1.0] heptane obtained in Synthesis Example 4
(X): 1,4-cyclohexanedimethanol divinyl ether (manufactured by Aldrich)
[Oligomer or polymer]
(PB3600): Epoxidized polybutadiene having hydroxyl groups at both ends (trade name “PB3600”, manufactured by Daicel Chemical Industries, Ltd.)
(CD220PL): Polycarbonate diol (trade name “CD220PL”, manufactured by Daicel Chemical Industries, Ltd.)
(Celoxide 2021P): Cyclic ether compound (trade name “Celoxide 2021P”, manufactured by Daicel Chemical Industries, Ltd.)
[Photocationic polymerization initiator]
(Irgacure 250): Trade name “Irgacure 250” (manufactured by Ciba Japan Co., Ltd.)
(PI 2074): Product name “PI 2074” (manufactured by Rhodia)

Evaluation test (gel fraction)
The 200 μm thick cured products obtained in the examples and comparative examples were put in a methyl ethyl ketone solvent, the initial weight before extraction and the weight after extraction drying were measured, and the gel fraction was calculated by the following formula.
Gel fraction (%) = (weight after extraction drying) / (initial weight before extraction) × 100

(Curing speed)
The cationic polymerizable resin compositions obtained in the examples and comparative examples were irradiated with ultraviolet rays using the belt conveyor and evaluated according to the following criteria.
Evaluation criteria A cured product was obtained: ○
Thickened and not solidified: ×

(Initial light loss and light loss after heating)
The cured product having a thickness of 1 mm obtained in Examples and Comparative Examples was cut into a width of 1 mm by dicing to obtain a sample for measuring optical loss. A detector having a detection section of 5 mmφ that is incident on a light source having a wavelength of 850 nm using a polymer clad fiber (PCF) by a cut-back method for samples immediately after curing (initial stage) and after heat treatment at 200 ° C. for 1 hour (after heating). The light loss (dB / cm) was measured.

(Flexibility)
The cured product having a thickness of 200 μm obtained in Examples and Comparative Examples was wound around a rod having a radius of 2 mm, and the presence or absence of cracks (cracks) was visually observed and evaluated according to the following criteria.
Evaluation criteria No cracks were observed: ○
Cracks were observed: ×

(Heat-resistant)
The cured products having a thickness of 200 μm obtained in Examples and Comparative Examples were subjected to heat treatment in an oven at 200 ° C. for 2 hours, and the change in weight (weight reduction degree) before and after the heat treatment was measured and evaluated according to the following criteria.
Evaluation criteria The weight change was 5% or less:
The weight change was greater than 5% and less than 10%:
Weight change was greater than 10%: ×

(Pyrolysis temperature)
Using the cured product having a thickness of 200 μm obtained in Examples and Comparative Examples as samples, the thermal decomposition temperature top peak of the samples was measured by DSC (Differential Scanning Calorimetry) and evaluated according to the following criteria.
Evaluation Criteria Decomposition temperature top peak was 300 ° C. or higher: ○
Decomposition temperature top peak was below 300 ° C: x

  From the said Table 1, it turned out that the cationically polymerizable resin composition which concerns on this invention has high reactivity from a gel fraction showing the value of 94% or more. It was also found that heat resistance and flexibility were excellent, and an increase in light loss due to heating could be suppressed. On the other hand, when not using the oligomer or polymer (C) in this invention as an oligomer or a polymer, it turned out that it is lacking in a softness | flexibility. Moreover, when other than the oxetane ring-containing vinyl ether compound (A) or the alicyclic epoxy group-containing vinyl ether compound (B) is used as the vinyl ether compound, the initial light loss is large due to low transparency, and furthermore, it does not have heat resistance. Further increase in light loss was observed by heating.

[Waveguide characteristics]
Examples 10 to 19 and Comparative Examples 6 to 10

A cationically polymerizable resin composition was prepared by mixing and dissolving the vinyl ether compound, oligomer or polymer and photocationic polymerization initiator in the types and amounts shown in Tables 2 and 3.
On the film base, the cationic polymerizable resin compositions obtained in Examples and Comparative Examples were applied so that the cured product had a thickness of 60 μm, and then ultraviolet rays were applied under the following conditions using a conveyor type ultraviolet irradiation device. By irradiating, a waveguide clad base film was produced.

  Next, 70 parts by weight of vinyl ether compound (A1), 30 parts by weight of epoxidized polybutadiene (PB3600) having hydroxyl groups at both ends, 5 parts by weight of a cationic photopolymerization initiator (Irgacure 250), a high refractive index material (1-acryloxy- 4-methoxynaphthalene (manufactured by Kawasaki Kasei Co., Ltd.) 40 parts by weight was mixed and dissolved, and the obtained compound was applied onto the above-mentioned waveguide clad base film so that the thickness of the cured product was 60 μm, A core having a width of 60 μm was prepared by using a graphic method.

Thereafter, the cationic polymerizable resin composition used for the production of the waveguide clad base film is applied so that the thickness of the cured product is 60 μm, and ultraviolet light is irradiated under the following conditions using a conveyor type ultraviolet irradiation device. This produced a waveguide. In addition, the conveyor type ultraviolet irradiation device used the same thing as the above on the same conditions.
The obtained waveguide was measured and evaluated for the initial light loss, flexibility, and bending durability by the following methods. The results are shown in Tables 2 and 3.

  In addition, each code | symbol in the vinyl ether compound of Table 2, 3, an oligomer or a polymer, and a photocationic polymerization initiator is the same as that of the above.

Evaluation test (initial light loss)
For the waveguides obtained in the examples and comparative examples, light from a laser diode (LD) light source having a wavelength of 850 nm is incident using a graded index type (GI) multi-fiber having a core diameter of 50 μm, and propagating light is incident. Light loss (dB / cm) was measured by receiving light with a 200 μm polymer clad fiber (PCF).

(Flexibility)
The optical loss (dB / cm) of the waveguides obtained in the examples and comparative examples (waveguide length: 5 cm) was measured by a cut-back method using a light source having a wavelength of 850 nm. Subsequently, light is wound around a rod with a radius of 2 mm (bending at 360 °), light loss (dB / cm) is measured by a cutback method using a light source with a wavelength of 850 nm, and light in the case of winding compared to the case without winding. Flexibility was evaluated from the increase in loss.

(Bending durability)
The waveguides obtained in the examples and comparative examples (waveguide length: 5 cm) were bent 1 million times with a bending endurance tester under conditions of a radius of curvature of 5 mm and a bending speed of about 1 second, and then a wavelength of 850 nm. Light loss (dB / cm) was measured by a cut-back method using a light source, and bending durability was evaluated from the increase in light loss compared to before bending.

  From Tables 2 and 3, it was found that the optical waveguide according to the present invention has flexibility and can suppress an increase in optical loss due to bending at 360 °. It was also found that an increase in optical loss due to repeated bending can be suppressed. On the other hand, when the oligomer or polymer (C) in the present invention is not used as the oligomer or polymer, the flexibility is poor, and the waveguide is cracked by bending to 360 ° or by bending repeatedly, There was an increase in optical loss even without any occurrence.

[Transparent sealant]
Examples 20-25, Comparative Examples 11-13

A cationically polymerizable resin composition was prepared by mixing and dissolving the kinds and amounts of vinyl ether compounds, oligomers or polymers and photocationic polymerization initiators shown in Table 4.
The transparency, the influence of heat and humidity on transparency, the adhesion, the influence of heat and humidity on adhesion, and the crack resistance of the obtained cationic polymerizable resin composition were measured and evaluated by the following methods.

Evaluation test (transparency)
The cationic polymerizable resin compositions obtained in Examples and Comparative Examples were applied to a substrate (glass plate coated with a release coating) that can be removed using an applicator with a thickness of 100 μm, and a conveyor type ultraviolet irradiation device. Was cured by irradiating with ultraviolet rays, and peeled off from the substrate to prepare a sample. In addition, the conveyor type ultraviolet irradiation device used the same thing as the above on the same conditions.
About the obtained sample, the light transmittance (T%) in wavelength 400nm was measured using the spectrophotometer (brand name "UV-2450", Shimadzu Corporation make), and it evaluated according to the following reference | standard.
Evaluation criteria Excellent transparency (light transmittance is 85 T% or more): ○
Usable range (light transmittance is 75 T% or more and less than 85 T%): Δ
Poor transparency (light transmittance is less than 75T%): ×

(Transparency after heating and humidification)
About the sample produced by the said transparency test, after heating at 260 degreeC for 1 minute in a hot air oven, it was left to stand in 85 degreeC and 85% RH environment for 1 week. Thereafter, the light transmittance (T%) at a wavelength of 400 nm was measured in the same manner as in the transparency test, and evaluated according to the same criteria.

(Adhesion)
After applying the cationic polymerizable resin composition obtained in Examples and Comparative Examples to a steel plate (length: 150 mm × width: 25 mm × thickness: 1.5 mm) at a thickness of 50 μm, ultraviolet rays were applied using a conveyor type ultraviolet irradiation device. A sample was cured by irradiation. In addition, the conveyor type ultraviolet irradiation device used the same thing as the above on the same conditions. The presence or absence of peeling was visually observed by a cross cut test and evaluated according to the following criteria.
Evaluation criteria Adhesiveness good [no peeling (zero peeling of 100 squares)]: ○
Usable range [with partial peeling (1-5 squares peeled out of 100 squares)]: Δ
Adhesiveness failure [peeling off is remarkable (more than 6 squares out of 100 squares)]: ×

(Adhesion after heating and humidification)
About the sample produced by the said adhesive test, after heating at 260 degreeC for 1 minute in a hot air oven, it was left to stand under 85 degreeC and 85% RH environment for 1 week. Thereafter, the adhesion was measured in the same manner as in the above-described adhesion test, and evaluated according to the same criteria.

(Crack resistance)
The cationically polymerizable resin compositions obtained in Examples and Comparative Examples were applied to a steel plate with a thickness of 20 μm using an applicator. The sample was cured by irradiating with ultraviolet rays using a conveyor type ultraviolet irradiation device. By this method, five samples were prepared for each of the examples and comparative examples. In addition, the conveyor type ultraviolet irradiation device used the same thing as the above on the same conditions.

The obtained sample was allowed to stand at −40 ° C. (Condition 1) for 30 minutes in a constant temperature and humidity chamber (trade name “TSE-11-A”, manufactured by ESPEC Corporation), and then at 85 ° C. (Condition 2). The cycle of leaving for 30 minutes was repeated 500 cycles continuously. In addition, the condition change from Condition 1 to Condition 2 and from Condition 2 to Condition 1 was performed at a temperature increase or temperature decrease rate of 5 ° C./min.
After repeating 500 cycles, a dye penetrant flaw detection solution (trade name “KD-CHECK RDP-1”, manufactured by Nippon Matec Co., Ltd.) was applied to the adhesion interface of the sample, and the presence or absence of cracks or peeling was visually observed. Evaluation was made according to criteria.
Evaluation criteria No cracking or peeling was observed in any of the five samples:
Of the five samples, even one crack or peeling was observed: ×

  From Table 4, the cationically polymerizable resin composition according to the present invention is excellent in transparency and adhesion, and does not impair transparency and adhesion by heating and humidification. Moreover, since it has heat resistance, it is excellent in crack resistance. On the other hand, when not using an oligomer or a polymer (C), it turned out that it is inferior in the point of adhesiveness and crack resistance. In addition, when not using the oxetane ring-containing vinyl ether compound (A) and the alicyclic epoxy group-containing vinyl ether compound (B), transparency and adhesion are remarkably lowered by heating and humidification, and crack resistance is poor. I understood.

[Nanoimprint test]
Examples 26-32, Comparative Examples 14-17

A cationically polymerizable resin composition was prepared by mixing and dissolving the types and amounts of vinyl ether compounds, oligomers or polymers and photocationic polymerization initiator shown in Table 5.
The obtained cationic polymerizable resin composition was spin-coated on a 4-inch silicon wafer pretreated with hexamethyldisilazane at 3000 to 6000 rpm for 60 seconds to form a 0.1 μm thick film. The coatability was evaluated for the state of the surface of the film to which the polymerizable resin composition was applied. When a cationic polymerizable resin composition containing a solvent was used, a drying treatment was performed at room temperature for 5 minutes in order to remove the solvent after film formation. The film thickness after drying was about 100 nm.

  As the imprinting apparatus, a computer-controlled tester (trade name “NM-0401”, manufactured by Myeongchang Kiko Co., Ltd.) was used. It is possible to maintain the specified pressure for a specific time by programming the loading, relaxation rate, heating temperature, etc. As an example and a comparative example, nanoimprinting was performed using a nano stamper having a 200 nm line and space pattern. In addition, the nano stamper used what gave the surface the fluorine processing with the fluorine processing agent (brand name "OPTOOL", Daikin Chemical Co., Ltd. make).

Next, in a state where the nano stamper and the film are in contact with each other, ultraviolet rays are irradiated (1200 J / cm ² ) using the attached high-pressure mercury lamp to obtain a cured product having a fine pattern, and a cationic polymerizable resin for the nano stamper. The peelability of the cured product, the pattern accuracy, and the remaining film thickness were evaluated.

In addition, each code | symbol in the vinyl ether compound of Table 5, an oligomer, or a polymer is the same as that of the above.
In addition, propylene glycol monomethyl ether acetate (PGMEA) was used as a solvent. Further, as a photocationic polymerization initiator, a trade name “PI 2074” (manufactured by Rhodia) was used.

(Applicability)
After the cationic polymerizable resin compositions obtained in Examples and Comparative Examples were spin-coated on a silicon wafer, the surface state was visually observed and evaluated according to the following criteria.
Evaluation criteria A uniform coating film was obtained:
The film repelling was observed after spin coating: x

(Peelability)
After curing by ultraviolet irradiation, the releasability when the nanostamper was peeled from the cured product of the cationic polymerizable resin composition was evaluated according to the following criteria.
Evaluation criteria It was easily peeled off by applying force to the imprint stamp: ○
Could not peel easily: ×

(Pattern accuracy)
After imprinting, the 1 mm square pattern formed on the silicon wafer was evaluated according to the following criteria.
Evaluation criteria Pattern deformation and pattern omission on the silicon wafer were 1 or less: ○
There were 2 to 10 pattern deformations and pattern omissions on the silicon wafer: Δ
There were 10 or more pattern deformations and pattern omissions on the silicon wafer: x

(Remaining film thickness)
After imprinting, the nano stamper was peeled off, and the residual film thickness was evaluated using a scanning electron microscope (SEM) for the pattern shape formed on the silicon wafer.
Evaluation criteria The remaining film thickness was 10 nm or less:
The remaining film thickness was greater than 10 nm and less than 50 nm: Δ
The remaining film thickness was 50 nm or more: x

  From Table 5 above, the cationic polymerizable resin composition according to the present invention is excellent in applicability because of its low viscosity, and the cured product of the cationic polymerizable resin composition according to the present invention has flexibility, It was found that after nanoimprinting, peeling from the nano stamper is easy, and the remaining film thickness attached to the nano stamper after peeling can be suppressed. It was also found that the pattern can be reproduced with high accuracy. On the other hand, when the oligomer or polymer (C) in the present invention is not used as the oligomer or polymer, when the spin coating is performed on the silicon wafer as the base material, a part of the repelling is observed and there is a problem in the coating property. all right. Further, peeling from the nano stamper became difficult and the remaining film became thick.

Claims (12)

  An oxetane ring-containing vinyl ether compound (A) and / or an alicyclic epoxy group-containing vinyl ether compound (B), and an oxetane group, an epoxy group, a hydroxyl group, a vinyl ether group, or an aliphatic or alicyclic unsaturated hydrocarbon group in the molecule. A cationically polymerizable resin composition comprising at least one oligomer or polymer (C) having a molecular weight of 500 or more. The oligomer or polymer (C) is represented by the following formulas (1a) to (1d)

(Wherein, R ¹ to R ¹² is .n ¹ ~n ⁴ indicating a hydrogen atom or a hydrocarbon group substituted carbon atoms which may based on have 1-20 is an integer)
Or an oligomer or polymer having a hydroxyl group or a hydrogen atom at the terminal and having a molecular weight of 500 or more, or the following formula (1e)

(In the formula, R ¹³ represents a divalent hydrocarbon group which may have a substituent, and n ⁵ represents an integer.)
The cationically polymerizable resin composition according to claim 1, which is an oligomer or polymer having a molecular weight of 500 or more having a hydroxyl group or a hydrogen atom at a terminal.   The cationically polymerizable resin composition according to claim 1 or 2, wherein the oligomer or polymer (C) has at least an epoxy group and an aliphatic or alicyclic unsaturated hydrocarbon group.   The cationically polymerizable resin composition according to claim 1 or 2, wherein the oligomer or polymer (C) is a polycarbonate polyol or an epoxidized polybutadiene having hydroxyl groups at both ends.   Hardened | cured material obtained by polymerizing the cationically polymerizable resin composition in any one of Claims 1-4.   The cationically polymerizable resin composition according to any one of claims 1 to 4, which is used for producing an optical waveguide.   The hardened | cured material of Claim 5 which forms the clad and / or core of an optical waveguide.   An optical waveguide produced by coating the cationic polymerizable resin composition according to any one of claims 1 to 4 on a film to produce a clad base film, and covering the core with the clad base film. Production method.   An optical waveguide manufactured by the method according to claim 8.   The cationically polymerizable resin composition according to any one of claims 1 to 4, which is used for a transparent sealant.   The cationically polymerizable resin composition according to any one of claims 1 to 4, which is used for nanoimprinting.   The manufacturing method of the fine structure which gives a nanoimprint process to the cationically polymerizable resin composition in any one of Claims 1-4, and obtains a fine structure.