WO2004029126A1

WO2004029126A1 - Hardening accelerator for cationic polymerization type composition

Info

Publication number: WO2004029126A1
Application number: PCT/JP2003/012228
Authority: WO
Inventors: Hiroshi Sasaki; Naokazu Ito; Nobuaki Koike; Kazuki Ofusa
Original assignee: Toagosei Co., Ltd.
Priority date: 2002-09-26
Filing date: 2003-09-25
Publication date: 2004-04-08
Also published as: JPWO2004029126A1; AU2003275534A1; JP4251138B2

Abstract

A hardening accelerator for cationic polymerization type composition, and a composition containing the same. In particular, a hardening accelerator for use in cationic polymerization type composition, the cationic polymerization type composition excelling in surface hardening characteristics and hardening rate in air and capable of providing a hardened film of excellent adherence and surface hardness; and a composition containing the hardening accelerator. Compound (A) having in its molecule one or more substituents of the following general formula (1) alone realizes rapid initiation of cationic polymerization and induces rapid growing reaction. Further, the compound (A) can be used as a hardening accelerator for compounds having one or more ring-opening type cyclic ether groups in each molecule. (1) wherein R1 represents a C1-C6 branched or unbranched alkyl, and Z represents an oxygen atom.

Description

The present invention provides a cured coating film in a short time by irradiating active energy rays or heating which is useful for paints, inks, adhesives, coating agents, stereolithography, resist inks, and the like. The present invention relates to a curing accelerator used for a cation polymerization-type composition having excellent adhesion to a substrate and surface hardness, and a composition containing the curing accelerator.

In the field of polymerization using active energy rays such as ultraviolet (UV), photoinitiated radical polymerization using polyfunctional acrylates and unsaturated polyesters has been widely studied, and it has been widely applied to paints, inks, adhesives, coating agents, stereolithography. It is used industrially in many fields such as resist ink. However, since this radical polymerization is inhibited by oxygen in the air or the like, it is necessary to carry out the polymerization under an inert atmosphere in order to polymerize the monomer quickly and completely. For this reason, when the composition is polymerized in the air, the composition surface layer has a slow curing, and has a disadvantage that the surface is easily stained or damaged later. In addition, the active energy ray-curable resin of the radical polymerization type has a problem that it is hard to cure in air when the thin film is 2 to 3 m or less used in spray coating, Darabier printing and the like. In addition, a radical polymerization type active energy ray-curable resin has a problem that curing shrinkage is large and adhesion to a substrate is poor.

On the other hand, cationic polymerization by irradiation with active energy rays is not affected by polymerization inhibition by oxygen, unlike the above-described radical polymerization, and therefore can be completely polymerized even in the air. Representative monomers used for this cationic polymerization include epoxides and pinyl ethers. In particular, when epoxide is used as a monomer, it is possible to obtain a cured product having excellent heat resistance and chemical resistance. In addition, since it has low curing shrinkage, it has excellent adhesion to the substrate.

However, the photopolymerization rate of epoxy groups is relatively low Because of its slowness, it has been difficult to say that it is particularly suitable for applications that require rapid light curing, such as when coated on paper or plastic. That is, there are problems that the curing speed is slow and the surface of the coating film is easily damaged (for example, JP-A-05-125150 and JP-A-06-2282413). No.). As a means for solving such a problem of the curing speed, there is a method using an alicyclic epoxy compound which shows faster polymerization and curing performance than dalicidyl ethers.

On the other hand, it has been reported that the cation polymerization rate of an oxetanyl group is usually high (see, for example, JP-A-07-057311 and JP-A-07-068282). The compound having an oxetanyl group is used as a monomer for photoinitiated cationic polymerization, since the polymerization is accelerated by adding a compound having the compound to the epoxy compound, and the epoxy compound exhibits rapid hardness. See, for example, Japanese Patent Application Laid-Open No. 06-016804).

However, when the compound having an oxenyl group (oxen compound) and an epoxy compound are blended, the acceleration of polymerization occurs only with respect to the polymerization rate of the ox compound. No significant change is observed in the polymerization rate of Therefore, it is necessary to increase the amount of the oxetane compound in order to rapidly cure the compounded composition. However, since oxetane compounds are more expensive than glycidyl ethers that are used industrially in a wide range of fields, increasing the amount of added oxetane compounds was not desirable from an economic viewpoint.

In view of the above, a compound (promoter) capable of accelerating curing by cationic polymerization with an inexpensive daricidyl ether-based epoxy material has been eagerly desired. However, there are no reports on compounds having such an effect in the cases reported so far.

化合物 About compounds having alkyl glycidyl group

Poly (jS-methyldaricidyl) ester obtained from the reaction of a compound having at least two carbonyl groups in one molecule with 8-methyl-epchlorochlorohydrin is exemplified. Also, at least two free alcoholic hydroxy groups and / or phenolic hydroxy groups and appropriately substituted epichlorohydrin may be added under reaction conditions or after reaction in the presence of an acid catalyst. And poly () 3-methyldaricidyl) ether obtained from the treatment with acetic acid (see, for example, Japanese Patent Application Laid-Open No. H06-222841). No. 3). This merely exemplifies ester compounds and ether compounds containing alkyl glycidyl groups.

Japanese Patent Application Laid-Open No. 08-283339 is an example in which a polyvalent phenol is bonded to a / 3-alkyldaricidyl group, and bisphenol A or 1,6-dihydroxynaphthalene and Condensates with 3-methylepichlorohydrin (or) (a mixture of 3-methylepichlorohydrin and epichlorohydrin) have been reported. This condensate is melt-kneaded with an epoxy curing agent and an inorganic filler and then cured at 175 to form a semiconductor encapsulant. The melt-kneaded product has good fluidity and storage stability It has good nature. However, there is no description or reference to the cationic polymerization of the condensate, and there is no suggestion of polymerization characteristics.

(Methyl) epichlorohydrin, pisphenol A, bisphenol F and its ethylene oxide, propylene oxide modified epoxy resin, epoxy nopolak resin, phenol, biphenol, etc. A reaction product of (methyl) epiclor hydrin with (methyl) epiclor hydrin is exemplified. Further, a copolymer of methyldaricidyl (meth) acrylate is exemplified (see, for example, Japanese Patent Application Laid-Open No. 09-255,765). Thus, only an ester compound and an ether compound having a glycidyl group having an alkyl group on the oxysilane ring are merely exemplified.

Japanese Unexamined Patent Publication (Kokai) No. 10-60098 describes a substituent represented by the following formula (8) (however, R ₄ may be a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group). Only ether compounds having this substituent are illustrated.

(8) As mentioned above, most of these prior arts are exemplified, and moreover, there is no description or suggestion of polymerization characteristics in the information disclosed therein.

An object of the present invention is to provide a curing accelerator for a force-ion polymerization type composition and a composition containing the same. That is, the present invention provides a dangling accelerator used in a cationic polymerization type composition which provides a cured film having excellent surface curability and curing rate in air, and excellent adhesion and surface hardness, and a composition containing the same. Is to do.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a compound having at least one substituent represented by the following general formula (1) in a molecule (the following formula (2)) alone In this case, the initiation of cationic polymerization is fast and a rapid growth reaction is exhibited. In addition, when this compound is blended with a compound having one or more ring-opening-polymerizable cyclic ether groups in the molecule, a good promoter (hardening The present inventors have found that high-speed polymerization is possible for a compound having one or more ring-opening-polymerizable cyclic ether groups in the molecule, thereby completing the present invention.

In the formula (1), is an optionally branched alkyl group having 1 to 6 carbon atoms, and Z is an oxygen atom.

That is, the present invention is a curing accelerator (compound (A)) for a cationically polymerizable composition comprising a compound having a substituent represented by the above formula (1). The compound is a curing accelerator for a cationically polymerizable composition represented by the following formula (2) (compound (A)).

In the formula (2), is an alkyl group having 1 to 6 carbon atoms which may have a branch, Z is an oxygen atom, m is an integer of 1 or more, and R ₂ is each m-valent Alkyls having 1 to 20 carbons which may have a branch, alkylene oxides having 1 to 20 carbons which may have a branch, modified alkylene oxides, and linear or branched poly ( Alkyleneoxy), polyester polyols, phenyls which may have a chain or branched alkyl group having 1 to 6 carbon atoms, xylylenes, bisphenols, biphenyls, or phenols Polak resin. The following formula (3), the following formula (4), the following formula (5), the following formula (6), and the following formula (3) may be used as the curing accelerator (compound (A)) for the cationic polymerization type composition. 7) can be exemplified. However, the curing accelerator for the cationically polymerizable composition (compound (A)) is not limited to these.

In the formula (3), is an alkyl group having 1 to 6 carbon atoms which may have a branch, and n is 0 or a positive number.

In the formula (4), is an optionally branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.

In the formula (5), is an alkyl group having 1 to 6 carbon atoms which may have a branch, and R ₃ is an alkyl group having 1 to 6 carbon atoms which may have a branch.

In the formula (6), is an optionally branched alkyl group having 1 to 6 carbon atoms.

In the formula (7), is an alkyl group having 1 to 6 carbon atoms which may have a branch, and n is 0 or a positive number. The composition of the present invention includes a curing accelerator for a cationically polymerizable composition (compound (A)), which is a compound having a substituent represented by the formula (1) or a compound represented by the formula (2); And a cationic polymerization initiator (B).

As the composition of the present invention, a cationic polymerization type composition comprising a compound (C) having at least one ring-opening-polymerizable cyclic ether group in a molecule and a cationic polymerization initiator (B) having a potential. And a compound having a substituent represented by the formula (1) or a compound represented by the formula (2), which is a curing accelerator for a thione polymerization type composition (compound (A)). It is a cationic polymerization type composition.

The composition of the present invention is a cationically polymerizable composition characterized in that at least a part of the compound (C) is an epoxy compound having one or more glycidyl ether residues in the molecule. .

The composition of the present invention is a cation polymerization type composition characterized in that at least a part of the compound (C) is an epoxy compound having one or more glycidyl ether residues and aromatic compounds in the molecule. Things.

As the composition of the present invention, at least a part of the compound (C) is a substituted or unsubstituted glycidyl ether of a substituted or unsubstituted phenolic resin, a substituted or unsubstituted glycidyl ether of a nopolak resin, a substituted or unsubstituted phenolic resin. A glycidyl ether or an epoxy compound having two or more dalicidyl ether residues in a molecule selected from a substituted or unsubstituted hydrogenated bisphenol resin glycidyl ether; A composition.

The composition of the present invention is a force-polymerizable composition characterized in that at least a part of the compound (C) is an oxetane compound having one or more oxenyl groups in the molecule. .

The composition of the present invention is a cationic polymerization type composition wherein the latent cationic polymerization initiator (B) is a photolatent onium salt.

The composition of the present invention, a cationic polymerization initiator having the potential (B) is in the Anion residues, S b F ₆ _{one, A s F 6 -, B} (C 6 F 5) 4 one, and A cationically polymerizable composition characterized by being an ionic salt having one kind selected from PF ₆ —.

The cured product of the present invention is obtained by irradiating the composition with an active energy ray to cure it, or It is more cured.

FIG. 1 shows the results of the P h 0 t o—DSC measurement of the curable resin composition described in Table 1 over time. FIG. 2 shows the results of the viscoelasticity measurement of the curable resin composition shown in Table 1 over time.

Description of the sign

Vertical axis of Fig. 1: Heat value (J / g)

Vertical axis of Fig. 2: Storage modulus (L o g (P a))

Horizontal axis in Fig. 1 and Fig. 2: UV irradiation time (sec)

Figures 1 and 2 are common

Garden: shows the result of Example 3 ▲: shows the result of Example 4 'Hata: shows the result of Example 5 ♦: shows the result of Comparative Example 1

Hereinafter, the present invention will be described in detail.

The present invention is a curing accelerator (compound (A)) for a cationic polymerization type composition comprising a compound having a substituent represented by the formula (1), wherein the compound is a cationic polymerization compound represented by the formula (2): It is a curing accelerator for mold compositions (compound (A)).

The cationically polymerizable composition in the present invention includes a curing accelerator for the cationically polymerizable composition (compound (A), hereinafter referred to as compound (A)) and a cationic polymerization initiator (B) having a potential (hereinafter referred to as ( B), and may also contain compound (C). Compound (A) and compound (C) are polymerizable components.

硬化 Curing accelerator for cationic polymerization type composition (Compound (A))

The curing accelerator for a cationically polymerizable composition of the present invention comprises a compound having a substituent represented by the above formula (1).

In the formula (1) is an alkyl group having 1 to 6 carbon atoms, which may have a branch; Considering the simplicity of the above, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Z is an oxygen atom.

The compound (A) having a substituent represented by the formula (1) is represented by the compound (A) represented by the above formula (2). That is, the compound (A) in the present invention is a compound having one or more dalicidyl groups having an alkyl group in the oxysilane ring represented by the formula (2) in the molecule.

The compound (A) represented by the formula (2) is obtained by adding an alkylepichlorohydrin represented by the following formula (9) to a hydroxyl group such as an alcohol or phenol represented by the following formula (10) in a molecule. The compound can be easily synthesized by reacting with a compound having at least one compound using a known method (for example, see JP-A-08-283379).

In the formula (9), is an alkyl group having 1 to 6 carbon atoms which may have a branch.

LJ m ^{L j} m (io)

In the formula (10), Z is an oxygen atom, m is an integer of 1 or more, and R ₂ is an alkyl having 1 to 20 carbon atoms which may have a branch and corresponds to m valence. , Optionally branched alkylene oxide modified alkyls having 1 to 20 carbon atoms, linear or branched poly (alkylenoxy) s, polyester polyols, linear or branched carbons having 1 to 6 carbon atoms Phenyls, xylylenes, bisphenols, biphenyls, and phenol nopolak trees J3 which may have an alkyl group. Specific examples of the compound represented by the formula (10) will be given below.

〇 Aliphatic alcohols or their alkylene oxide modified products

Aliphatic alcohols or alkylene oxide modified products thereof (Alkyl having 1 to 20 carbon atoms, which may have a branch, having 1 to 20 carbon atoms, which may have a branch, corresponding to m value) Modified alkylene oxides of alkyls] include carbons such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, and 2-ethylhexanol. Aliphatic monohydric alcohols which may have a branch of 1 to 20 or alkylene oxide-modified products thereof such as ethylene oxide-modified products or propylene oxide-modified products (hereinafter referred to as alkylene oxide-modified products) ), Dalicols such as ethylene glycol, propylene glycol, neopentyl glycol, and the like, and alkylene oxide modifications thereof are 1,3-propanediol, 1,4-butanediol, Aliphatic dihydric alcohols such as 1,6-hexanediol or alkylene oxide modified products thereof are used in trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorby !, Aliphatic polyvalent alcohols containing alicyclic groups such as And alkanols and alkylene oxide modified products thereof.

〇Poly (alkyleneoxy) s or alkylene oxide modified products thereof

Poly (alkyleneoxy) s or their modified alkylene oxides [chain or branched poly (alkyleneoxy) s corresponding to the m value] include polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene. Examples thereof include linear or branched poly (alkyleneoxy) s such as glycol, and alkylene oxide modified products thereof.

として As polyester polyols

Polyester polyols of polyhydric alcohols and polyhydric ruponic acids are exemplified.

〇Phenols

Phenols [phenyls and xylylenes which may have a linear or branched alkyl group having 1 to 6 carbon atoms corresponding to the m-valency] include unsubstituted phenols and cumylphenols or cumylphenols; Examples thereof include phenol derivatives which may have a monovalent chain or branched alkyl group having 1 to 6 carbon atoms, xylylenes and the like, and modified alkylene oxides thereof. Further, phenols which may have a linear or branched alkyl group having 1 to 6 carbon atoms, which are divalent or more, such as catechols and pyrogallols, and modified alkylene oxides thereof are also exemplified. Can be 〇 As bisphenols

Examples thereof include bisphenol derivatives such as bisphenol A and bisphenol F, and modified alkylenoxides thereof.

として As biphenyls

Examples thereof include biphenyl derivatives which may have 1 to 6 chain or branched alkyl groups, and modified alkylene oxides thereof.として As phenolic resins

Phenol nopolak resin, polyvinyl phenol and the like. In the formula (10), m is an integer of 1 or more, preferably 1 to 5, and more preferably 1 to 3. That is, m in the formula (2) is an integer of 1 or more, preferably 1 to 5, and more preferably 1 to 3. Preferred as the compound (A) are those obtained from an alkyl alcohol having 1 to 8 carbon atoms which may have a branch and the formula (9), and those having 1 to 8 carbon atoms which may have a branch. Polyethylene glycol obtained from an ethylene alcohol modified form of an alkyl alcohol and formula (9); ethylene glycol obtained from ethylene glycol and formula (9); propylene glycol obtained from propylene glycol and formula (9) And the formula (9), polypropylene glycol and the formula (9), phenol and the formula (9), phenol in the ethylene glycol modified form and the formula (9) Obtained from catechol and formula (9), obtained from an ethylene glycol modified form of catechol and formula (9), obtained from pyrogallol and formula (9) Of ethylene glycol modified with pyrogallol and formula (9), obtained from diphenylphenol and formula (9), ethylene glycol modified of biphenylphenol and formula (9) Obtained from bisphenol A and formula (9), obtained from ethylene glycol modification of bisphenol A and formula (9), obtained from bisphenol F and formula (9) thing, Examples thereof include those obtained from the modified ethylene glycol of bisphenol F and the formula (9), and those obtained from the phenol nopolak resin and the formula (9). The compound represented by the formula (9) used in the present invention can be synthesized by using a known method (for example, see JP-A-2002-193959).

Equation (9) can be obtained, for example, from the following equation (11).

CH ₂ = CR ₁ CH ₂ C 1 (11)

In the formula (11), is an optionally branched alkyl group having 1 to 6 carbon atoms.

For example, formula (11) is converted to chlorohydrin with chlorine water, and purified by distillation or the like. Then, the obtained chlorohydrin compound is subjected to ring reaction using an alkali compound to obtain crude alkylepichlorohydrin. As the alkali metal compound used in this cyclization reaction, hydroxides, carbonates, bicarbonates, and the like of alkali metal or alkali earth metal can be used. , Calcium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate and the like, and a mixture thereof can also be used.

The crude alkylepichlorohydrin can be purified and distilled, for example, to yield formula (9). In this case, the alkyl group having 1 to 6 carbon atoms which may have a branch is preferably a methyl group or an ethyl group, and more preferably a methyl group. As a method for obtaining the compound (A) represented by the formula (2) from the formulas (9) and (10), a known method for obtaining an epoxy compound can be used.

For example, to obtain the compound (A) represented by the formula (2) from the polyvalent phenol as an example of the formula (9) and the formula (10), the compound (A) can be obtained by reacting with an alkali compound. . As the alkali compound, hydroxides, carbonates, bicarbonates, and the like of alkali metals or alkaline earth metals can be used. Specifically, sodium hydroxide, calcium hydroxide, potassium oxide, carbonate Examples thereof include sodium and sodium hydrogen carbonate, and a mixture thereof can also be used. The reaction temperature at this time is 30 to 120.

The method for obtaining the compound (A) from the monohydric alcohol or polyhydric alcohol represented by the formula (10) and the formula (9) can be obtained in the same manner as the above method. Depending on the synthesis method for obtaining the compound (A) represented by the formula (2) from the formula (9) and the formula (10) in which m is 2 or more, polymerization is carried out. To which the cationic polymerization promoting group to be bonded is obtained. Such a polymer can also be used as a hardening accelerator (compound (A)) for the cationically polymerizable composition of the present invention. Examples of a polymer from which such a polymer is obtained include those in which m in Formula (10) is 2 or more. Examples of actual compounds include resorcinol, bisphenol A, bisphenol F, and norpolnandimethanol. it can. Next, specific examples of the compound (A) will be described.

In the formula (3), the formula (1) may be bonded to any of the o-position, the m-position and the p-position, and is preferably the o-position or the m-position. In the formula (3), is an alkyl group having 1 to 6 carbon atoms which may have a branch, and is preferably a methyl group or an ethyl group, and more preferably a methyl group. N in the formula (3) is 0 or a positive number, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0 to 1. As formula (4), formula (1) may be bonded to any of the o-position, m-position, p-position, o'-position, m'-position, or p'-position. Position, o 'position, or p' position. (The o position, m position, and p position are those in which the group of formula (1) is bonded to the benzene ring at one end of formula (4). The o ', m', and p 'positions indicate that they are bonded to the opposite terminal benzene ring). Ri in the formula (4) is an alkyl group having 1 to 6 carbon atoms and may have a branch, and is preferably a methyl group or an ethyl group, and more preferably a methyl group.

N in the expression (4) can be adjusted by, for example, the amount of the expression (9) used for bisphenol F. From this, n in the formula (4) is 0 or a positive number, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0 to 1. In formula (4), when n is a positive number, the bond position between bisphenols F may be any position, such as p, p, position, o, p, position, o ', p position or o, o' position. Is preferred. In the formula (5), R ₃ may be bonded to any one of the o-position, m-position, and!)-Position, and is preferably the o-position or the p-position. In the formula (5), there is a branch having 1 to 6 carbon atoms. A methyl group or an ethyl group is preferable, and a methyl group is more preferable. R _{3 in the} formula (5) is an alkyl group having 1 to 6 carbon atoms which may have a branch, preferably a butyl group, a t-butyl group or a hexyl group, and more preferably a t-butyl group.

In the formula (6), 1 ^ is an alkyl group having 1 to 6 carbon atoms which may have a branch, preferably a methyl group or a methyl group, and more preferably a methyl group. As the formula (7), the formula (1) may be bonded to any of the 0-position, the m-position, the p-position, the o'-position, the m'-position, or the p'-position. Position, o 'position, or p' position. (The 0 position, m position, and p position are those in which the group of formula (1) is bonded to the benzene ring at one end of formula (7). The o ', m', and p 'positions indicate that they are bonded to the opposite terminal benzene ring). In the formula (7), is an alkyl group having 1 to 6 carbon atoms which may have a branch, preferably a methyl group or an ethyl group, more preferably a methyl group.

N in the equation (7) can be adjusted by, for example, the amount of the equation (9) used for bisphenol A. From this, n in the formula (7) is 0 or a positive number, preferably from 0 to 10, more preferably from 0 to 5, and particularly preferably from 0 to 1. Then, when n in equation (7) is a positive number, the bonding position between bisphenols A may be any, and p, p, position, o, p, position, o ', p position or o, o' Position is preferred. Examples of the compound (A) include Formula (3), Formula (4), Formula (5), Formula (6), and Formula (7). Preferably, Formula (3), Formula (4), And equation (5).

〇 (B) ingredient

The component (B) in the present invention is a latent cationic polymerization initiator, which is activated by active energy or heat to generate an acid component, and serves as a cation of the ring-opening polymerizable group in the composition. It acts to induce ring-opening polymerization. These may be used in combination. As the cationic polymerization initiator having photolatent, any photoinitiated thione polymerization initiator that can be activated by irradiation with active energy rays such as light to induce ring opening of the ring-opening polymerizable group should be used. Examples of the photodynamic thione polymerization initiator include ionic salts and organometallic complexes. Examples of the ionic salt in the photoinitiated thione polymerization initiator include diazonium salt, sulfonium salt and odonium salt. Examples of the organic metal complexes in the photoinitiated thione polymerization initiator include an iron-allene complex, a titanocene complex, and an arylsilano-aluminum complex. For example, Optoma SP-150 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) Optoma SP-170 {trade name, manufactured by Asahi Denka Kogyo Co., Ltd.}, UVE-101 (trade name, General Electronics And CD-1012 (trade name, manufactured by SATOMA) can also be used.

The Anion residues of the cationic polymerization initiator (B) having the potential, SbF ₆ _{one, As F 6 -, B (} C 6 F 5) 4 -, PF 6 - is Oniumu salt with one selected from It is preferred.

As the cationic polymerization initiator having a thermal potential, any thermal cationic polymerization initiator can be used as long as it is activated by heating to induce ring opening of the ring-opening polymerizable group. Quaternary ammonium salts, phosphonium salts and Examples include various onium salts such as sulfonium salts and organometallic complexes. Examples of such anonymous salts include Adeka Opton CP-66 and Adeka Opton CP-77 {both are trade names, manufactured by Asahi Deni Dani Kogyo Co., Ltd.}, Sun Aid SI-60L, Sun Aid SI-80L, and Sun Aid SI Commercial compounds such as 100 L {all trade names, manufactured by Sanshin Chemical Co., Ltd.} and CI series {manufactured by Nippon Soda Co., Ltd.} can be used. Examples of the organometallic complexes include, for example, an alkoxysilane-aluminum complex.

The mixing ratio of the component (B) to the cationically polymerizable composition is from 0.01 to 100 parts by mass of the compound (A) when the polymerizable component in the composition is only the compound (A). 5 parts by mass is preferable, and 0.1 to 4 parts by mass is more preferable. When both the compound (A) and the compound (C) are contained in the cationically polymerizable composition, the mixing ratio of the component (B) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable component. The range is preferably 0.1 to 4 parts by mass. When the compounding ratio of the latent cationic polymerization initiator is less than 0.01 parts by mass, the ring-opening reaction of the ring-opening polymerizable group can sufficiently proceed even when activated by the action of light or heat. In some cases, heat resistance and water absorption after polymerization may be insufficient. Also, even if the amount is more than 5 parts by mass, the effect of promoting the polymerization does not increase any more, and on the contrary, Any other properties may be degraded.

〇 Compound (C): Compound having at least one ring-opening polymerizable cyclic ether group in the molecule (C) Compound (C) in the present invention has at least one ring-opening polymerizable cyclic ether group in the molecule Examples of the compound include an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, and a spiroorthoester compound which is a reaction product of an epoxy compound and Pectone. One of these compounds can be used alone, or two or more of them can be used in combination. Examples of the epoxy compound in the compound (C) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated pisphenol F diglycidyl ether. Ter, brominated bisphenol S diglycidyl ether, epoxy nopolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclo Hexylmethyl 3,4,1-epoxycyclohexanecarboxyl ester, 2- (3,4-epoxycyclohexyl 5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, Bis (to 3,4—epoxycyclo (Silmethyl) adipate, vinylcyclohexenoxide, 4-pinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl 3 ', 4 , 1 epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentene genoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether , Ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxyhexylhydrohexylphthalate, di-2-ethylhexylepoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediglycidyl ether, Li serine triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene Dali co one distearate Dali glycidyl ethers; Echirengu Rico Ichiru, propylene glycol, one to aliphatic polyhydric alcohol such as glycerin or Polydaricidyl ethers of polyether polyols obtained by adding two or more alkylene oxides; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; Cresole, butylphenol or monoglycidyl ethers of polyether alcohol obtained by adding alkylene oxide thereto; glycidyl esters of higher fatty acids; epoxidized soybean oil; epoxy butyl stearate; octyl epoxy stearate Epoxidized amadi oil; epoxidized polybutadiene; In the above-mentioned epoxy compounds, substituted or unsubstituted bisphenol resin dalycidyl ether, substituted or unsubstituted nopolak resin glycidyl ether, substituted or unsubstituted phenol resin glycidyl ether, substituted or unsubstituted hydrogenated bisphenol resin dali Epoxy compounds having two or more dalycidyl ether residues in the molecule selected from sidyl ethers are preferred. As the oxetane compound in the compound (C), any compound having one or more oxetane rings in the molecule can be used without particular limitation. Specific examples include various oxetane compounds described in JP-A-8-85775 and JP-A-8-134405, among which the oxetanyl group is one. Compounds having one or more compounds are preferred. Examples of monofunctional oxetanes include 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl 3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl 3- (chloromethyl) oxetane and the like. Examples of the bifunctional oxetane include 1,4-bis [(3-ethyl-3 oxetanylmethoxy) methyl] benzene, bis {[1-1ethyl (3-hydroxyxetanyl)] methyl} ether and the like. Can be These compounds are manufactured by Toagosei Co., Ltd., manufactured by Aronoxetane OXT-101, OXT-121, O XT- 211, 〇XT-221, and O XT-212 (trade names). ) Is commercially available. When the compound (C) is contained in the cationically polymerizable composition, the amount of the compound (II) to be added is 0.01 to 500 parts by mass based on 100 parts by mass of the compound (C). Preferably used in In addition, 0.1 to 250 parts by mass is preferable, and 1 to 100 parts by mass is particularly preferable. 〇 Optional ingredients

The following components can be added to the cationically polymerizable composition of the present invention, if necessary.

Powdered reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powdered silica , Fused silica, crystalline silica and other silicon compounds, aluminum hydroxide and other metal hydroxides, and others, such as kaolin, myriki, quartz powder, graphite, and molybdenum disulfide, as well as fibrous reinforcing agents and filling Agents such as glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber and polyamide fiber. These can be blended in an amount of 10 to 900 parts by mass with respect to 100 parts by mass of the composition of the present invention.

Colorants, pigments, flame retardants such as titanium dioxide, iron black, molybdenum red, navy blue, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromo compounds and triphenyl phosphate. These can be added in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the composition of the present invention.

Furthermore, various hardening monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the resin in the final adhesive layer, molded article and the like. Examples include one or more combinations of diluents for epoxy resins such as monoepoxy, phenolic resins, alkyd resins, melamine resins, fluorine resins, vinyl chloride resins, acrylic resins, silicone resins, polyester resins, etc. be able to. The mixing ratio of these resins can be used without any limitation as long as it does not impair the original properties of the resin composition of the present invention. For example, the amount is preferably 50 parts by mass or less based on 100 parts by mass of the composition of the present invention. Examples of means for blending the composition of the present invention and optional components include heat-melt mixing, melt-kneading using a roll or a kneader, wet mixing using an appropriate organic solvent, and dry mixing. The composition of the present invention is cured by heat when a thermal cationic polymerization initiator is used, or by an active energy ray when an active energy linear cationic polymerization initiator is used. Thermal cation weight In such a case, the reaction is usually carried out at a temperature at which the thermal cationic polymerization initiator starts generating a cationic species or a Lewis acid, and usually at 50 to 200.

The light source that can be used when performing polymerization with active energy rays is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less.For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp , A chemical lamp, a black light lamp, a microphone mouth wave excitation mercury lamp, and a metal octride lamp. The light irradiation intensity of the composition is controlled for each target product and is not particularly limited, but a light wavelength range effective for activating a cationic polymerization initiator having photolatent property. (Light of 300 to 420 nm is usually used, although it depends on the polymerization initiator.) The light irradiation intensity is preferably 0.1 to 100 mW / cm ² . When the light irradiation intensity in the composition is less than 0. 1 mWZ cm ^2, the reaction too time increases, when it exceeds 10 OmWZcm ^2, by polymerization heat generated during the heat and compositions Isa spokes from the lamp, There is a possibility that the cohesive strength of the obtained pressure-sensitive adhesive layer is reduced, yellowed or the support is deteriorated. The light irradiation time for the composition is controlled for each target product and is not particularly limited, but is expressed as a product of the light irradiation intensity and the light irradiation time in the light wavelength region. It is preferable that the integrated light amount is set to be 10 to 5,000 Om J / cm ² . When integrated quantity of light to said adhesive composition is less than 1 OmJZcm ^2, insufficient generation of reactive species from the initiator, there may occur a low under the adhesive properties of the resulting pressure-sensitive adhesive layer, 5 If it exceeds 100 OmJZcm ² , the irradiation time becomes extremely long, which is disadvantageous for improving productivity. Also, after 0.1 to several minutes after irradiation with active energy rays, most compositions dry to the touch due to cationic polymerization, but it is also preferable in some cases to use heating in combination to promote the reaction of cationic polymerization. .

In the case of performing polymerization by heat, heat can be applied by a generally known method, and the conditions and the like are not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, parts in each example mean parts by mass. <Synthesis example 1>

Synthesis of methylepichlorohydrin (MECH)

5 mm diameter glass beads were filled to a height of 500 mm, and 15 liters of circulating water per hour was flown from the top of the glass absorption tower whose internal temperature was kept at 25 ° C. From the lower part of the absorption tower, 25 liters of chlorine gas was blown per hour, and the obtained chlorine water was sent to a 5-liter glass reactor equipped with a stirrer. 125 g of metalyl chloride and 500 g of distilled water were dropped per hour into the reactor kept at 28 ° C. The chlorohydrination reaction solution overflowing from the reactor was taken into a separatory funnel, and the total organic layer and the aqueous layer corresponding to the amount of distilled water dropped out were taken out. The remaining aqueous layer was returned to the absorption tower as circulating water.

The obtained chlorohydrination reaction organic layer was cut at a reflux ratio of 10 and the first fraction was cut by 40% by mass in a rectification column filled with Lahiscilling to a height of 100 Omm.

The organic layer from which the low-boiling components have been cut and the aqueous layer taken out are taken in a reactor equipped with a stirrer, the vessel is kept at 30 or less with ice water, and a 48% aqueous sodium hydroxide solution is added to the mixed aqueous layer at a pH of 11 or below. The solution was dripped slowly until it became. Crude methyl chlorochlorohydrin was obtained from this cyclization reaction solution by distillation and liquid-liquid layer separation.

The crude methylepichlorohydrin obtained was cut in a rectification column filled with lahiscilling to a height of 100 Omm at a reflux ratio of 10 and the initial distillation and the pot liquid were each cut by 5% by mass to give a purity of 99.5%. %, A purified methylepichlorohydrin was obtained in a yield of 55% by mass based on the raw material methallyl chloride used in the reaction. The purity was calculated by measuring with gas chromatography (analysis conditions: capillary column: TC-WAX (GL Science), carrier gas: helium, detection: FID). Example 1>

Synthesis of phenylmethyldaricidyl ether (PMGE)

639.5 g of MECH (6.0 mol) synthesized in Synthesis Example 1, 282.3 g of phenol (3.0 mol) and 19.4 g of tetra-n-butylammonium bromide (0 mol) .06 mol) was charged into a 200 Oml glass reactor, and 156.4 of a 48% by mass aqueous sodium hydroxide solution (3.75 mol) was added dropwise so that the temperature inside the reactor did not exceed 40. After the addition was completed, the reaction solution was stirred at 50 for 6 hours. Add 580 g of water to the reaction solution and add the organic layer and water. Separated into layers. Further, the organic layer was washed twice with 200 g of water to obtain 773.2 g of an organic layer. The obtained organic layer was purified by distillation (130 ° CZ130 OPa) to obtain 303.6 g of 99% pure PMGE (the following formula (12)). Purity analysis was performed in the same manner as in Synthesis Example 1.

Example 2>

Synthesis of bisphenol A-methyldaricidyl ether derivative (BAMGE)

In a 1000 ml three-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 532 g of 114.15 g (0.5 Omo 1) of bisphenol A and MECH synthesized in Synthesis Example 1 were added. 75 g (5. Omo 1) and 10.1 g of tetra-n-butylammonium bromide as a catalyst were added, and the temperature was raised to 50 with stirring. To this, 80.00 g (1. Omo 1) of a 50% by mass aqueous sodium hydroxide solution was added dropwise from a dropping funnel over 1 hour. After completion of the dropwise addition, the reaction was continued at 50 ^ for 6 hours. Thereafter, the reaction mixture was cooled to room temperature, 350 g of pure water and 600 g of toluene were added, and the mixture was stirred well, and then separated into an organic layer and an aqueous layer using a separating funnel. The organic layer was washed four times with 50 Om 1 of water. Then, low-boiling components were removed at 70 ° C under reduced pressure to obtain 146.84 g of a white solid. The yield based on bisphenol A was 79.7%. The epoxy value of this compound was 3.64 me qZg. From the results of high-resolution nuclear magnetic resonance ^ H-NMR, 270 MHz), the compound (B AMGE) represented by the following formula (13) was determined.

The assignments of high-resolution nuclear magnetic resonance are shown in Table 1 below (this measurement used tetramethylsilane as a reference substance, and the solvent used was double-mouthed form). Two

PMGE, phenyldaricidyl ether (PGE), and diphenyl-2-thiophenoxyphenylsulfonium hexafluoro mouth-monitone, a photopolymerizable cationic polymerization initiator (PI, SR Akhtar, JV CriveUo, JL Lee, J. Org. Chem., 55, 13, 4222 (1990)) and the mass blending ratio shown in Table 2 (polysynthetic components such as PMGE and PGE and the corresponding cationic polymerization initiator). And the molar ratio to is 200: 1. For example, in Example 4, PMGE is 2 mmol, PGE is 18 mmo? 1 is 0.1 mmo1, and the mixture is sufficiently stirred and mixed at room temperature. A cationically polymerizable composition was obtained. Each photopolymerizability was evaluated by differential thermal analysis (Photo-DSC measurement) and viscoelasticity measurement during light irradiation.

Table 2

The measurement was performed by the following method. That is, the heat generated from each composition was measured by differential thermal analysis using Photo-DSC while irradiating ultraviolet rays. The storage elastic modulus was measured while irradiating ultraviolet rays with time to cure each composition.

〇 Ultraviolet irradiation Irradiation was performed with 365 nm monochromatic light (2. OmW / cm ² ) using a bandpass filter. 〇Pho to—DSC measurement: The composition was irradiated with ultraviolet rays at 20 ° C. using DSC220 C (manufactured by Seiko Instruments Inc.) to perform differential thermal analysis.

〇Measurement of viscoelasticity: Lower side of the composition on the quartz plate using a VAR—50 Visco analyser (manufactured by Realogica Inst. AB) equipped with a parallel plate (diameter = 20 mm) UV light was applied to the sample, and the storage elastic modulus was measured over time.

The results of the Photo-DSC measurement are shown in FIG. 1, and the results of the viscosity measurement are shown in FIG.

As is clear from Fig. 1, the heat generation of polymerization of PMGE alone (Example 3) by light irradiation is rapid, and it is clear that the ring-opening polymerization proceeds faster than the homogenization of PGE shown in Comparative Example 1. . It is also evident that the addition of PMGE to PGE (Examples 4 and 5) accelerates the polymerization of these blended compositions.

From the measurement results of the storage modulus during polymerization shown in Fig. 2, the polymer was formed by high-speed polymerization in the case of PMGE alone (Example 3) or in combination with PGE (Examples 4 and 5). It turns out that there is. In particular, in Example 3 in which PMGE was added at 40 mol%, a high storage modulus was obtained.

In the parts by mass shown in Table 3, PMGE, PGE, bisphenol A diglycidyl ether (BADGE), 3-ethyl-13 phenoxymethyloxetane (Toagosei, trade name: O XT- 211) , OXT-221 (trade name, manufactured by Toagosei Co., Ltd .: bis (3-ethyl-3, -xentanylmethyl) ether), and SP-170 (trade name, manufactured by Asahi Denka) as a photolatent cationic polymerization initiator. The compositions of Examples 6, 7 and Comparative Examples 2 to 4 were used. Table 3 also shows the measurement results of these photocuring properties. The measurement was conducted by applying a composition of about 10 m thickness on a steel plate with a bar coater, and then using a conveyor-type light irradiation device equipped with a 120 W / cm ultra-high pressure mercury lamp at a lamp height of 10 cm. The composition was irradiated with ultraviolet light at a conveyor speed of 1 OmZmin and the number of passes until the composition surface became tack-free (no stickiness) was measured (displayed as "number of passes required for hardening"). Table 3

As is clear from the measurement results in Table 3, by changing PGE to PMGE, the oxetane compound OXT-221 (OXT-221) was also obtained in the BADGE compound system (Example 6, Comparative Example 2), which is a glycidyl ether derivative. In Example 7 and Comparative Examples 3 and 4), a large increase in the curing rate was confirmed.

BAMGE, PGE, bisphenol A diglycidyl ether (BADGE), and SP_170 (trade name, manufactured by Asahi Denka) as a photolatent cationic polymerization initiator were blended in the blending parts shown in Table 4 The compositions of Example 8 and Comparative Example 5 were used. Table 4 also shows the measurement results of the photocurability.

Table 4

As is evident from the measurement results in Table 4, it was confirmed that the addition of BAMGE greatly increased the curing rate.

合成 Synthesis of resorcinol-methyldaricidyl ether derivative (RMGE)

In a 2000 ml three-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 165.18 g (1.5 mol) of resorcinol, 1598.28 g of MECH synthesized in Synthesis Example 1 (15mo 1) and tetra-n-butylammonium bromide as catalyst 17.63 g of amide was added, and the temperature was raised to 90 ° C with stirring. To this, 250 g (3 m 01) of a 48% by mass aqueous sodium hydroxide solution was added dropwise from a dropping funnel over 3 hours. After completion of the dropwise addition, the reaction was continued at 90 ° C for 1 hour. Thereafter, the reaction mixture was cooled to room temperature, 70 Og of pure water was added, and the mixture was stirred well, and then separated into an organic layer and an aqueous layer using a separating funnel. The organic layer was washed twice with 60 Oml of water. Then, low boiling components were removed under reduced pressure at 70 to obtain 365 g of a pale yellow liquid. The yield based on resorcinol was 97.2%. The obtained compound was purified by distillation (166 ° C, 133 Pa) to obtain a compound having a purity of 98%. Purity analysis was performed in the same manner as in Synthesis Example 1.

From the results of high-resolution nuclear magnetic resonance 11-NMR, 270 MHz), it was determined to be a compound (RMGE) represented by the following formula (14). The results of high-resolution nuclear magnetic resonance measurement are shown below. (This measurement used tetramethylsilane as a reference substance, and the solvent used was double-mouthed form).

Number

Synthesis of bisphenol F-methyldaricidyl ether derivative (BFMGE)

In a 2000 ml three-necked round bottom flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, 200.23 g (lmol) of bisphenol F ("BPF-D", p. A mixture of p'-form (34%), o, p-form (48%), and o, o'-form (18%), 1065.5 g (10 mol) of MECH synthesized in Synthesis Example 1, And tetra-n as a catalyst —12.66 g of butylammonium bromide was added, and the temperature was raised to 90 ° C. with stirring. To this, 166.66 g (2mol) of a 48% by mass aqueous sodium hydroxide solution was added dropwise from a dropping funnel over 3 hours. After completion of the dropwise addition, the reaction was continued at 90 ° C for 1 hour. Thereafter, the reaction mixture was cooled to room temperature, 400 g of pure water was added, and the mixture was stirred well, and then separated into an organic layer and an aqueous layer using a separating funnel. The organic layer was washed twice with 400 ml of water. Then, the low-boiling components were removed at 70 ° C. under reduced pressure to obtain 333.9 g of a pale yellow liquid. The yield based on bisphenol F was 98.1%. The resulting compound was purified by distillation (53 Pa at 208) to give a compound of 98% purity. Purity analysis was performed in the same manner as in Synthesis Example 1. The results of measurement by this high-resolution nuclear magnetic resonance (NMR, 270 MHz) are shown below. (This measurement used tetramethylsilane as a reference substance, and the solvent used was bichloroform.)

p pm cleavage state proton number assignment

7. 248-6. 790 Multiline 8 e, e ', e

4. 032-6. 510 2 d, d ,, d

4.032- 6.510 4c, j ', c

2.856- 2.681 4 b, b ,, b

1. 466- 1.396 6a, aa From these results, the compound synthesized in Example 10 was a mixture of those represented by the following formulas (15), (16) and (17) (BFMGE ).

(16)

Synthesis of OP-t-butylphenylmethyldaricidyl ether (BPMGE)

In a 1000 ml three-necked round-bottomed flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 150.22 g (lmol) of p-t-butylphenol, ME # 11 synthesized in Synthesis Example 1, was added. 53. 75 g (5 mol) and 6.27 g of tetra-n-butylammonium bromide as a catalyst were added, and the mixture was heated to 90 with stirring. To this, 83.33 g (lmol) of a 48% by mass aqueous sodium hydroxide solution was added dropwise from a dropping funnel over 3 hours. After the completion of the dropwise addition, the reaction was continued at 90 for 1 hour. Thereafter, the reaction mixture was cooled to room temperature, 140 g of pure water was added, and the mixture was stirred well, and then separated into an organic layer and an aqueous layer using a separating funnel. The organic layer was washed twice with 300 ml of water. Next, the low boiling components were removed at 70 ° C. under reduced pressure to obtain 215.4 g of a pale yellow liquid. The yield based on p-t-butylphenol was 97.8%. The obtained compound was purified by distillation (135-532 Pa) to obtain a compound having a purity of 99%. Purity analysis was performed in the same manner as in Synthesis Example 1. The results of measurement by this high-resolution nuclear magnetic resonance-NMR, 270 MHz, using tetramethylsilane as a reference substance, and using chloroform as a solvent) are shown below.

ppm cleavage state proton number assignment

7. 322- 6.820 4 e

4. 007-3. 911 2d

2.856- 2.701 2 c

1.472 Single line 3 b

1.292 9a

From these results, the one synthesized in Example 11 was determined to be BPMGE represented by the following formula (18).

RMGE, resorcinol diglycidyl ether (abbreviated as RGE, distilled from Nagase ChemteX Denacol EX-201 and purified to 99% purity), BFMGE, bisphenol F Glycidyl ether (abbreviated name BFGE, Epoxy 806 manufactured by Japan Epoxy Resin), bisphenol A diglycidyl ether (BADGE), BPMGE, p-t-butylphenyl dalicydyl ether (abbreviated name: BPGE, Nagase Chemtex Denacol EX-146) Then, SP-170 (trade name, manufactured by Asahi Denka) was blended as a photolatent cationic polymerization initiator to obtain compositions of Examples 12 to 16 and Comparative Examples 6 to 8. The measurement results of these photocuring properties are also shown in Table 5. (The photocuring was measured in the same manner as in Example 6. In addition, the “number of passes” in Table 5 is the number of passes required for curing. ).

Table 5

In a 1L 3-neck round bottom flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel and a nitrogen gas inlet, 78.11 g (0.5mo1) of norpolnandimethanol and methylhydric hydrhydrin 159.83 While stirring g (1.5 mol) and DMS-4 Oml, 134.66 g (2.4 mol) of solid potassium hydroxide was added thereto. 50 ° C in a water bath The reaction was continued for 6 hours with stirring not to exceed.

After the completion of the reaction, the reaction solution cooled to room temperature was transferred to a separating funnel, and 330 g of pure water and 700 g of ethyl acetate were added, followed by thorough stirring. After separating the organic layer and the aqueous layer, the organic layer was washed five times with 50 Oml of pure water. Thereafter, the solvent was distilled off under reduced pressure to obtain a methyldaricidyl derivative of norpolnane represented by the following formula (25). Hereinafter, it is called NDMDG.

The measurement results of ¹ H-NMR (double-mouthed form solvent) of NDMDG are shown below.

6 (p m); 1.0-2.4 (m, 16H), 2.5—2.8 (m, 4H), 3.0—3.6 (m, 8H)

製造 Manufacture of UV curable composition

The components shown in Table 6 (the mixing ratios are shown in parts by mass) were dissolved and mixed according to a conventional method to produce a composition.

The curability was evaluated using the obtained composition. That is, the obtained composition was applied to a polycarbonate resin at a film thickness of 30 m using a bar coater, and this was applied to a conveyor spinner at a lamp height of 10 cm using an 80 WZcm collecting light type high pressure mercury lamp. At a speed of 5 m / min, the resin was repeatedly passed under a mercury lamp to be cured. It was applied under these conditions, and it was cured by repeatedly passing it under a mercury lamp at a lamp height of 10 cm and a conveyor speed of 5 mZ using a high-pressure mercury lamp of 80 WZcm and a condensing type. Under these conditions, the curability was evaluated by the number of passes (the number of passes) until the tackiness disappeared from the surface of the applied composition. Table 6 shows the results. Table 6

The abbreviations in Table 6 have the following meanings.

DOX: bis [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.) EPL: polyethylene glycol diglycidyl ether (repeated 4),

Kyoeisha Chemical Co., Ltd. Epolite 200 E

DNC: Polyethylene glycol lauryl glycidyl ether (repeated 15), Nagase Chemtech Co., Ltd. Denacol EX—171

WP I: odonium salt-based photo-induced thione polymerization initiator, WP 1-016 manufactured by Wako Pure Chemical Industries, Ltd.

The compound of the present invention having one or more substituents represented by the formula (1) in the molecule and the latent power containing a thione polymerization initiator and having one or more ring-opening polymerizable cyclic ether groups in the molecule The composition, which may contain a compound, can be rapidly cured, and in particular, has a great industrial value in that it can rapidly polymerize glycidyl ethers that are widely available at low cost. Use in dogs can be expected from dogs.

Claims

The scope of the claims

1. A curing accelerator for a cationically polymerizable composition comprising a compound having a substituent represented by the following formula (1) (compound (A)).

(In the formula (1), is an alkyl group having 1 to 6 carbon atoms which may have a branch, and Z is an oxygen atom.)

2. The curing accelerator for a cationically polymerizable composition according to claim 1, wherein the compound having a substituent represented by the formula (1) is represented by the following formula (2) (compound (A)).

(In the formula (2), is an alkyl group having 1 to 6 carbon atoms which may have a branch, Z is an oxygen atom, m is an integer of 1 or more, and R ₂ is m Alkyls having 1 to 20 carbons which may have a branch, alkylene oxides having 1 to 20 carbons which may have a branch, modified alkylene oxides, linear or branched poly (alkylene ), Polyester polyols, phenols having 1 to 6 carbon atoms, which may have a linear or branched alkyl group, xylylenes, bisphenols, phenols, phenol nopolak resins 3. The compound represented by the formula (2) according to claim 2 is a compound represented by the following formula (3), the following formula (4), the following formula (5), the following formula (6) and Z or the following formula: (7) A curing accelerator for a cationically polymerizable composition (compound (A)).

(3)

(In the formula (3), is an optionally branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.)

(Ri in the formula (4) is an optionally branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.)

(In the formula (5), is an alkyl group having 1 to 6 carbon atoms which may have a branch, and R ₃ is an alkyl group having 1 to 6 carbon atoms which may have a branch.)

(In the formula (6), is an alkyl group having 1 to 6 carbon atoms which may have a branch.)

(In the formula (7), is an optionally branched alkyl group having 1 to 6 carbon atoms, and n is 0 or a positive number.)

4. A curing accelerator for a cationically polymerizable composition which is a compound having a substituent represented by the formula (1) according to claim 1 or a compound represented by the formula (2) according to claim 2 (compound (A )) And a cationic polymerization initiator (B) having latent potential.

5. A cationically polymerizable composition containing a compound (C) having at least 1% of a ring-opening polymerizable cyclic ether group in the molecule and a latent cationic polymerization initiator (B), 3. A compound having a substituent represented by the formula (1) described above or a compound represented by the formula (2) described in claim 2. A cationically polymerizable composition comprising a curing accelerator for a cationically polymerizable composition (compound (A)).

6. The cationically polymerizable composition according to claim 5, wherein at least a part of the compound (C) is an epoxy compound having one or more glycidyl ether residues in the molecule.

7. The cationically polymerizable composition according to claim 5, wherein at least a part of the compound (C) is an epoxy compound having at least one glycidyl ether residue and an aromatic group in a molecule.

8. At least a part of the compound (C) is a substituted or unsubstituted glycidyl ether of a bisphenol resin, a substituted or unsubstituted glycidyl ether of a nopolak resin, a substituted or unsubstituted glycidyl ether of a phenol resin, substituted or unsubstituted. 6. The cationically polymerizable composition according to claim 5, wherein the epoxy compound has two or more daricidyl ether residues in a molecule selected from substituted hydrogenated pyridine resin daricidyl ether.

9. The cationically polymerizable composition according to claim 5, wherein at least a part of the compound (C) is an oxenone compound having one or more oxenyl groups in the molecule.

10. The cationic polymerization type composition according to claims 4 to 9, wherein the latent cationic polymerization initiator (B) is an ionic salt having photolatent.

As 1 1 cationic polymerization initiator (B) is Anion residue having the potential, S b F ₆ _{one, A s F 6 -.,} B (C 6 F 5) 4 one, the one selected from PF ₆ one The cationic polymerizable composition according to any one of claims 4 to 9, wherein the composition is an onium salt.

12. A cured product obtained by curing the cationically polymerizable composition according to any one of claims 4 to 11.