WO2005037876A1 - Polymer having oxetanyl group and cation-curable resin composition containing the same - Google Patents

Abstract

[PROBLEMS] To provide a cationically polymerizable polymer with which the viscosity of a composition can be regulated in a wide region of from several tens of mPa·s to several tens of Pa·s; and to provide a composition containing the polymer. The composition has excellent curability and gives a cured article which has satisfactory adhesion and excellent flexibility, is soft, and has excellent recovery from deformation at room temperature although it has a low modulus. [MEANS FOR SOLVING PROBLEMS] The polymer is one obtained from: at least one member selected from the group consisting of a maleic-modified polybutadiene, maleic-modified polyisoprene, hydroxylated polybutadiene, hydroxylated polyisoprene, hydroxylated ethylene/butylene copolymer, hydroxylated hydrogenated polybutadiene, and hydroxylated hydrogenated polyisoprene; and a compound of the formula (1). [Chemical formula 1] (In the formula (1), R1 represents hydrogen or optionally branched C1-6 alkyl.)

Description

 Specification

 Polymer having oxetanyl group, and cationically curable resin composition containing the same

 Technical field

 [oooi] The present invention relates to a curable composition which is cationically polymerized by irradiation of active energy rays such as ultraviolet rays or electron beams and Z or heating, and a cationically polymerizable polymer to be used as a compounding material thereof, and The present invention relates to a resin composition comprising: Further, the present invention provides a cationically curable resin composition having good curability, which is capable of producing a cured product having excellent flexibility, low elastic modulus at room temperature and excellent resilience after shape change. About things.

 Background art

 [0002] Almost all curable resin compositions which undergo cationic polymerization upon irradiation with active energy rays such as ultraviolet rays or electron beams or upon heating are epoxy resins. Epoxy resins are generally excellent in heat resistance, adhesiveness, chemical resistance and the like, but most of them are two-part type thermosetting types by an addition reaction of an amine acid anhydride or the like. Curing systems based on cationic polymerization are not as widely used as epoxy resins. However, a cationically cured system does not have a polar group such as an amine ester, and is therefore advantageous in reducing the water absorption of a cured product. In the cationically curable system, a one-part type thermosetting resin can be obtained by using a latent thermal cationic polymerization initiator. Epoxy-based and oxetane-based light-powered thione-curable resin compositions containing a light-powered thione polymerization initiator have recently been receiving attention for the following reasons. In other words, epoxy compounds and oxetane compounds have a small shrinkage ratio during curing, have excellent adhesion to substrates, and have a low water absorption, as compared with (meth) acrylate resins, which account for the majority of photocurable resins. This has the advantage that polymerization is not inhibited by oxygen in the air. For these reasons, cation-curable resin compositions, especially photo-cation-curable resin compositions, have attracted attention. However, since it is more expensive than a hardening system using epoxy and amine, etc., it has attracted much attention in fields requiring special physical properties, such as electronic materials and optical materials, rather than general-purpose materials. .

[0003] One of the unique physical properties required for electronic materials and optical materials is, for example, room temperature (25 ° C (In the vicinity) is as soft as or more than the pressure-sensitive adhesive, but has excellent resilience after shape change. In other words, it is a physical property that the storage elastic modulus (G ') is low and the tan δ is low in the dynamic viscoelasticity measurement (hereinafter, low elastic modulus is abbreviated as low tan δ). However, no conventional epoxy-based cationically curable resin composition can be found excellent in such physical properties except for silicone-based. In addition, a cured product of a silicone resin is generally difficult to adhere to other materials, and thus its use is limited.

 [0004] However, to obtain a level of softness generally called a flexible resin, an epoxy-based composition using epoxy-modified polybutadiene is known. In addition, as an epoxy resin for improving flexibility over the currently available epoxidized polybutadiene, a polybutadiene having a carboxyl group at a terminal and a structure of two cyclohexene oxides in one molecule are provided. There is an addition reaction product with an epoxy conjugate having the formula (for example, see Patent Document 1). However, it is not clear to what extent this compound can exhibit its performance in view of its curability and low elastic modulus and low tan δ.

 [0005] An epoxy conjugate, an oxetane conjugate, and a photocurable resin composition for optical stereolithography having a photoinitiated thione polymerization initiator have been disclosed (see, for example, Patent Document 2). Although a wide variety of possible compounds and compositions are listed therein, they are different from the low-modulus resin targeted by the present invention.

[0006] A method for producing a macromonomer having an oxetane-containing group at a terminal is disclosed (for example, see Patent Document 3), and as a compound, polyisoprene containing an oxetane ring at one terminal is disclosed. However, the physical properties of the cationically curable resin have not been clarified, and the terminal structure does not show the structure in the present invention. In addition, since this compound contains many double bonds in the molecule, it is susceptible to deterioration due to oxidation. In addition, the production method of this patent can be obtained by adding a polymerization terminator having an oxetane ring to the active terminal of an aeon-polymerized polymer. Strict dehydration steps are required because they are inhibited by a small amount of water in the water, and production equipment suitable for such precise reactions is required. In addition, an initiator for ion polymerization such as butyllithium is not easy to handle because it is decomposed by moisture in the air. Patent Document 1: Japanese Patent Application Laid-Open No. 2001-329045 (Claims)

 Patent Document 2: JP-A-10-168165 (Claims)

 Patent Document 3: JP-A-7-309856 (Claims, Examples)

 Disclosure of the invention

 Problems to be solved by the invention

[0008] An object of the present invention is to provide a cationically polymerizable polymer that can widely adjust the viscosity of the composition to several lOmPa's to several lOPa's. The composition has excellent curability, and the cured product has good adhesion, excellent flexibility, flexibility, and low elastic modulus at room temperature (for example, around 25 ° C.). However, it also has excellent resilience after shape change. Another object of the present invention is to provide a composition containing the polymer.

 Means for solving the problem

 [0009] The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the following problems can be solved by the following, and completed the present invention.

 [0010] 1. Maleated polybutadiene, maleated polyisoprene, hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydroxyl-containing ethylene-butylene copolymer, hydroxyl-containing hydrogen-added polybutadiene, and hydroxyl-containing hydrogenated polyisoprene It is a polymer having an oxetanyl group obtained from at least one or more selected compounds and the formula (1).

 [0011] [Formula 1]

R ¹ of [0012] Formula (1) is to display the optionally branched alkyl group having a hydrogen atom or a C 1 one to six carbons.

[0013] 2. A compound obtained from maleated polybutadiene and Z or maleated polyisoprene and formula (1) Is a polymer having oxetal groups.

 3. Hydroxy group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydroxyl group-containing ethylene butylene copolymer, hydroxyl group-containing hydrogenated polybutadiene, and hydroxyl group-containing hydrogenated polyisoprene force At least one or more types selected from the formula (1) And a polymer having an oxetanyl group.

 4. A cationically curable resin composition comprising the polymer having an oxetanyl group described above, a cationic polymerization initiator activated by active energy rays, and a cationic polymerization initiator activated by Z or heat.

 5. A polymer having an oxetanyl group as described above, a compound having an epoxy group and a compound having an oxetanyl group other than a polymer having a Z or oxetal group, and a cationic polymerization initiator activated by an active energy ray. And a cationic polymerization initiator which is activated by z or heat or a cationic polymerization initiator.

 6. A cured product obtained by irradiating the cationically curable resin composition described above with active energy rays and Z or heating.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0014] The polymer having an oxetal group of the present invention is a compound having an oxetal group obtained from the maleated polybutadiene and Z or maleylene polyisoprene and the formula (1) (Referred to as maleated compound).

The polymer having an oxetal group of the present invention is at least one selected from the group consisting of hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydroxyl group-containing hydrogenated polybutadiene, and hydroxyl group-containing hydrogenated polyisoprene. And equation (1). The compound is a compound having two or more oxetanyl groups at the terminal represented by the following formula (2) (referred to as a compound represented by the formula (2)). It is included in polymers having oxetal groups. [0016] [Formula 2]

[0017] In the formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 16 carbon atoms which may have a branch, and R ² represents polybutadiene, polyisoprene, hydrogenated polybutadiene, or hydrogenated When R ² is a polymer having a branch, which represents polyisoprene, the formula (3) may be bonded to the branched terminal.

 [0018] [Formula 3]

[0019] to Table Yo, the alkyl group R ¹ has a branched hydrogen atom or a C 1 one six carbon of Formula (3).

The polymer having an oxetal group of the present invention includes a hydroxyl group-containing polybutadiene, a hydroxyl group-containing polyisoprene, a hydroxyl group-containing ethylene butylene copolymer, a hydroxyl group-containing hydrogenated polybutadiene, and a hydroxyl group-containing hydrogenated polyisoprene. It is obtained from at least one or more selected and formula (1). This is a compound having an oxetanyl group represented by the following formula (4) (referred to as a compound represented by the formula (4)). included. [0021] [Formula 4]

[0022] In the formula (4), R ¹ represents a hydrogen atom or an alkyl group having 1 16 carbon atoms which may have a branch, and R ² represents polybutadiene, polyisoprene, an ethylenebutylene copolymer, Represents hydrogenated polybutadiene or hydrogenated polyisoprene.

 That is, the polymer having an oxetanyl group of the present invention is a maleated compound having an oxetanyl group, a compound represented by the formula (2), and a compound represented by Z or the formula (4) . When the polymer having an oxetanyl group of the present invention is a mixture, they may be individually synthesized and mixed. In addition, the compound represented by the formula (2) and the compound represented by the formula (4) can be obtained as a mixture depending on the synthesis method.

 The resin containing a polymer having an oxetanyl group of the present invention, which is obtained by using a hydrogenated product as a synthesis raw material, has a high stability and has good stability. The polymer having an oxetanyl group of the present invention using a polymer having a double bond, such as polybutadiene, as a raw material for synthesis has good compatibility when producing a composition.

 [0024] The cationically curable resin composition of the present invention comprises a cationic polymerization initiator activated by an active energy ray and / or a cation activated by heat with the polymer having an oxetanyl group of the present invention. And a polymerization initiator. Alternatively, the cationically curable resin composition of the present invention comprises a polymer having an oxetanyl group of the present invention, a compound having an epoxy group and an oxetane group other than Z or a polymer having an oxetanal group of the present invention. And a cationic polymerization initiator activated by an active energy ray and a cationic polymerization initiator activated by Z or heat.

 [0025] The cationically curable resin composition of the present invention comprises a compound represented by the formula (2):

A compound represented by formula (4), a maleidary compound having a Z or oxetanyl group, a cationic polymerization initiator activated by an active energy ray, and an active compound by Z or heat. It is compounded with a cationic polymerization initiator for imparting properties. The cationically curable resin composition of the present invention comprises a compound represented by the formula (2), a compound represented by the formula (4), and a cationic polymerization initiator activated by an active energy ray and / or heat. It is a blend of a cation polymerization initiator that activates. The composition of the present invention may contain a compound having an oxetanyl group other than these, or may contain an epoxidized compound. The present invention is a cured product obtained by irradiating the above-mentioned cationically curable resin composition with an active energy ray, and applying Z or heating.

 [0026] The cationically curable resin composition of the present invention comprises a compound represented by the formula (2) and a cationic polymerization initiator activated by an active energy line and / or a force activated by heat. Curable resin composition containing a compound having an epoxy group and a compound having an oxetanyl group other than the compound represented by Z or the compound represented by the above formula (2). .

 The cationically curable resin composition of the present invention comprises a compound represented by the formula (4), a cationic polymerization initiator activated by an active energy line, and / or a force activated by heat. It is a mixture of a polymerization initiator. The cationically curable resin composition of the present invention is a cationically curable resin composition which may further contain a compound containing an epoxy group and a compound having Z or two or more oxetal groups in one molecule. is there. Alternatively, a compound having one oxetanyl group in one molecule other than the above formula (4) may be included.

 [0028] The cationically curable resin composition of the present invention is activated by a maleic compound having an oxetal group, a cationic polymerization initiator activated by an active energy ray, and Z or heat. It contains a cationic polymerization initiator. Furthermore, a maleated compound having an oxetanyl group, a cationic polymerization initiator activated by an active energy ray and a cationic polymerization initiator activated by Z or heat, a compound having an epoxy group and a Z or oxetanyl group The compound contains a compound having an oxetal group other than the maleated compound. When emphasis is placed on curability, it is preferable to incorporate an epoxy compound.

[0029] On the other hand, when an elastic adhesive or the like should be used to appropriately adjust the low elastic modulus and toughness, When polybutadiene or polyisoprene having a low maleation ratio is used as a raw material, two or more compounds per molecule other than a compound having two or more epoxy groups and a maleated compound having a Z or oxetal group in one molecule are used. A compound having two or more oxetanyl groups can be also blended. Here, a compound containing both an epoxy group and an oxetanyl group in one molecule may be blended.

 [0030] The production of the compound represented by the formula (2) does not require a strict dehydration step, difficult handling, and no compound. For example, polybutadiene, polyisoprene, hydrogenated polybutadiene and Z or hydrogenated polyisoprene having two or more terminal hydroxyl groups are tosylated or mesylated, and then reacted with a compound of the formula (1) to give a compound of the formula (2) The compounds represented can be obtained.

 [0031] The method for producing the compound represented by the formula (4) does not require a strict dehydration step, difficult handling, and does not require a compound. For example, ethylene butylene copolymer having one hydroxyl group at one end, polybutadiene, polyisoprene, hydrogenated polybutadiene and Z or hydrogenated polyisoprene are reacted with a compound of formula (1) after reacting with a compound of formula (1). The compound represented by (4) can be obtained. Another example is the reaction of a polybutadiene, polyisoprene, hydrogenated polybutadiene and Z or a part of the hydroxyl groups of hydrogenated polyisoprene having hydroxyl groups at both ends with a compound of formula (1) after tosylation or mesylation. In this method, a compound having two or more oxetadyl groups may be contained in the product.

 [0032] Maleated compound having dioxetanyl group

As the maleated polybutadiene or maleated polyisoprene used in the synthesis of the maleated compound having an oxetal group of the present invention, various ones can be used. This may be derived from a radical polymerization or an ion polymerization. These molecular weights are not particularly limited, but are preferably 500-100,000 in terms of viscosity average molecular weight, more preferably 1,000-80,000, and most preferably 1,000-80,000. 5,000 to 40,000. If the molecular weight is less than 500, it may be difficult for the cured product to obtain a cationically curable resin having a low elastic modulus. On the other hand, if the molecular weight is more than 100,000, the compatibility with other monomers or polymerization initiators is deteriorated, which is not preferable. The ratio of maleic anhydride, that is, the number of acid anhydrides introduced per molecule of polymer, is preferably 1 or more per molecule on average, more preferably 2 to 10 on average. , Particularly preferably an average of 2 There are five. When the maleidation ratio is 1 or less on average, the amount of non-reactive polymer increases, which tends to cause bleed-out and increase in tan δ, which are hardened properties, and is also not preferable because of poor solvent resistance. On the other hand, if the average of the maled ridges exceeds 10 units, it is necessary to reduce the addition ratio of the one represented by the formula (1) in order to realize the low elasticity characteristic of the present invention. Since the acid anhydride remains, water resistance and low water absorbency are not preferred.

 [0033] Examples of the maleilei polybutadiene used in the present invention include Nisso Nisso- 達 1015, Nihon Shonen Petroleum Danigaku 1000-80, and Idemitsu Petroleum Danigaku Poly bd R-45M. A and the like. Examples of the maleiledipolyisoprene used in the present invention include LIR403 manufactured by Kuraray.

 The maleated compound having an oxetal group of the present invention can be easily synthesized by adding the compound represented by the formula (1) to the above-mentioned maleated polybutadiene or maleinido polyisoprene.

 [0035] The preferred addition rate of the compound represented by the formula (1) in the maleixiary compound having an oxetal group according to the present invention is different depending on the maleidary index, and is an average of 1 per unit weight of the applied polymer per molecule. The number is preferably 20 and more preferably 2 to 5 on average. If the average is less than one, the amount of non-reactive polymer increases, which tends to cause premature out of the cured product and increase in tan δ, and is inferior in solvent resistance. Conversely, when the average is more than 20, it is not preferable to realize the low elastic modulus which is a feature of the present invention. When an epoxy conjugate having a hydroxyl group such as glycidol is added to maleated polybutadiene or maleated polyisoprene, the carboxylic acid generated by this addition is added to the epoxy group of another polymer to form a gel. Dagger. However, since the compound represented by the formula (1) used in the present invention hardly undergoes an addition reaction with a carboxyl group, a maleated compound having an oxetal group can be easily synthesized.

In addition, the maleated compound having an oxetanyl group of the present invention may be obtained by adding other alcohols other than the compound represented by the formula (1) to maleated polybutadiene or maleated polyisoprene. As the alcohol used herein, those having one hydroxyl group in one molecule are preferable, and have a functional group that inhibits cationic polymerization of an amine compound or the like. If not, various things can be suitably used. Further, a carboxylic acid generated after adding an alcohol to an acid anhydride may be esterified with these alcohols.

 [0036] 化合物 Compound represented by formula (2)

 The polybutadiene, polyisoprene, hydrogenated polybutadiene or hydrogenated polyisoprene having two or more terminal hydroxyl groups used for synthesizing the compound represented by the formula (2) used in the composition of the present invention is: If two or more terminals are hydroxyl groups, the polymerization method is not particularly limited, and the polymerization method may be radical polymerization or radical polymerization. Examples of the product obtained by Ayuon polymerization include G-1000, GI-2000, GI-3000 manufactured by Nippon Soda, and Polytail HA manufactured by Mitsubishi Idani Gaku. The one produced by a-one polymerization has two hydroxyl groups because it has no branch. Examples of products obtained by radical polymerization include R45HT manufactured by Idemitsu Petrochemical Co., Ltd., and Polytail H obtained by hydrogenating the mixture with Mitsubishi Idani. Radical polymerization has branches, so most of them have two hydroxyl groups, but also those with more hydroxyl groups. When importance is placed on oxidation resistance, those obtained by hydrogenating them are preferable. Here, in the present invention, the polymerization method used for synthesizing the compound represented by the formula (2) is not particularly limited, but the hydrogenated product derived from the radical polymerization is a solid, Hydrogenated polybutadiene derived from aeon polymerization is particularly preferred in view of ease of production because of poor solubility in a solvent.

 Although the molecular weight of the compound used for synthesizing the compound represented by the formula (2) is not particularly limited, it is preferably 500 to 50,000 in terms of polystyrene equivalent average molecular weight (Mw) by GPC. Even more preferably, it is 1,000 to 10,000. If the molecular weight is less than 500, the cured product may not be able to obtain a cationically curable resin having a low elastic modulus, which is not preferable.If the molecular weight is more than 50,000, the other It is not preferable because the compatibility with the monomer and the polymerization initiator is deteriorated.

[0038] The compound represented by the formula (2) of the present invention can be obtained, for example, from a product obtained by tosylating or mesylating the hydroxyl group of the above-mentioned raw material polymer (referred to as a tosyli sword or a mesyl sill). . The tosylated compound or mesylidani is obtained, for example, by a method in which the raw material polymer and a tertiary amine or pyridine (hereinafter simply referred to as tertiary amines) are dissolved in a solvent, and the mixture is heated with calo-heat by adding tosyl or mesyl chloride. Can be The tertiary amines used herein include triethylamine, triethylamine and triethylamine. Triethylamine can be particularly preferably used because of its low toxicity and easy availability, such as butyramine, N, N-dimethylbenzylamine, 4- (N, N-dimethyl) -aminopyridine. Examples of the solvent include ether solvents such as tetrahydrofuran (THF), 1,2-diethoxetane, and dibutyl ether; aliphatic hydrocarbon solvents such as heptane; aromatic hydrocarbon solvents such as toluene; And the like. Particularly preferred are ether solvents. Regarding the selection of the tossil mouth ride and the messyl mouth ride, the tossil mouth ride is preferable in consideration of ease of handling. The charged amount of tosyl chloride or mesyl chloride and tertiary amines is preferably at least 1.2 to 6 moles, more preferably at least equimolar to the hydroxyl group of the polymer. Further, it is preferable that the tertiary amine is used in an excess amount as compared with the tosyl sulfide. The reaction temperature is not particularly limited as long as it does not involve a side reaction or decomposition and a sufficient reaction rate can be obtained, but is preferably in the range of room temperature to 150 ° C, more preferably 50 ° C to 150 ° C. It is preferable to be in the range of C. The atmosphere of the reaction system does not require strict dehydration as in the anion polymerization, and may be in the air. However, it is preferable to pass through an inert gas such as nitrogen gas.

 [0039] In the present invention, the compound represented by the formula (1) can be directly injected after the above-mentioned Tosylido or Messilido. However, when an excess amount of the tosyl-mouth ride / mes-silk-ride is used relative to the hydroxyl group, it is preferable to purify once and then use the formula (1). The reason is that the ether compound (for example, di (1-ethyl (3-oxetal)) methyl ether is obtained by reacting the tosylate or mesylate of the compound represented by the formula (1) with the compound represented by the formula (1). May be generated. In other words, these compounds have a high boiling point and are difficult to separate from the desired compound represented by the formula (2). It is preferable to purify the sword or mesirui sword and use the power.

[0040] Examples of the purification of the toshiroi swords or the mesyli stalks are as follows. First, a solution of the reaction product is poured into a solvent in which the tosylated product or mesylated product is insoluble and the tosyl sulfide or mesyl sulfide is soluble, for example, a ketone solvent such as alcohol having 13 to 13 carbon atoms or acetone, and the target substance is added. It is a method of collecting by precipitation. As a method of further increasing the purity, this precipitate is dissolved in a hydrocarbon solvent such as hexane and heptane, or an ether solvent such as THF, 1,2-jetoxetane and dibutyl ether, and purified by reprecipitation. repeat Method. In the purification, a more preferable method is to mix a solution of the compound represented by the formula (2) in a hydrocarbon solvent with an alcohol having 13 to 13 carbon atoms, separate the mixture into two layers, and wash the mixture. is there. In this method, the solvent used can be reduced. Here, a method of washing with water according to a conventional method is also included. Since this method may emulsify, washing with an alcohol having 13 to 13 carbon atoms, particularly methanol, is particularly preferable. Here, it is also possible to use a mixed solvent of water and methanol.

[0041] The tosylated product or the mesylated product is capable of binding an oxetal group by reacting with the compound represented by the formula (1). It is preferable to add an alkali catalyst during this reaction. This reaction can be carried out without a solvent, but it is preferable that the solvent be dissolved in a solvent. Examples of the alkali catalyst used in this reaction include alkali metal hydroxides and tertiary amines. Preferred are sodium hydroxide sodium and potassium hydroxide, and particularly preferred is water hydroxide. It is potassium salt. Here, a method in which the compound represented by the formula (1) is converted to alkoxide by sodium hydride or the like may be mentioned, but it is not easy to handle industrially, so it is more preferable to use an alkali metal hydroxide. preferable. Examples of the solvent in this reaction include hydrocarbon solvents such as hexane and heptane, and ether solvents such as THF, 1,2-diethoxyethane and dibutyl ether. Preferred solvents are ether solvents. Among them, those having a high boiling point, for example, 1,2-diethoxytan and dibutyl ether can be particularly preferably used.

[0042] The amount of the compound represented by the formula (1) with respect to the tosyl stilt or the mesyl stilt is not particularly limited as long as it is at least equimolar with the tosyl or mesyl group of the polymer in terms of mole. , 1.2 times or more. The upper limit is not particularly limited, but is preferably 100 times or less from the viewpoint of the yield relative to the volume of the reactor. When the compound represented by the formula (1) is used in excess, the target polymer and the solution containing the compound represented by the formula (1) may be separated into two layers. The layer containing the indicated compound can be recovered, distilled and reused.

 The reaction temperature is preferably from 60 ° C to 150 ° C, particularly preferably from 90 ° C to 130 ° C.

The atmosphere of this reaction system is used for the decomposition of tosylate and mesylate by water and the generation of peroxide. In terms of suppression, it is preferable to use a nitrogen atmosphere.

 [0043] In the purification after the reaction, it is possible to carry out a method of reprecipitating by pouring into a large amount of methanol or the like (reprecipitation purification) according to a conventional method, but using less solvent. The following method is particularly preferable in view of the possibility. That is, a method of removing excess compound represented by the formula (1), which precipitates tosylate and separates into two layers, is followed by washing with a two-layer system of a hydrocarbon solvent such as hexane and methanol. It is. Here, washing with water is not preferred because it may cause emulsification. Since the purified compound represented by the formula (2) is contained in the hydrocarbon solvent layer, it can be obtained by desolvating this layer.

 [0044] 化合物 Compound represented by formula (4)

 Ethylenebutylene copolymer having one end having a hydroxyl group, polybutadiene, polyisoprene, hydrogenated caropolybutadiene, and hydrogenated compound for synthesizing the compound represented by formula (4) used in the composition of the present invention The polymerization method of polyisoprene is not particularly limited as long as it has a hydroxyl group at one end. Examples thereof include an ethylene butylene copolymer by coordination polymerization, polybutadiene / polyisoprene having a hydroxyl group at one end obtained by a-on living polymerization, and a hydrogenated product thereof. Further, the polymerization method is also particularly limited when using polybutadiene, polyisoprene, hydrogenated polybutadiene, or Z and hydrogenated polyisoprene having hydroxyl groups at both ends for the synthesis of the compound represented by the formula (4). However, it may be an a-on living polymerization or a radical polymerization. The molecular weight of the substance used for synthesizing the formula (1) is not particularly limited, but is preferably 500 to 50,000, more preferably 1 to 500,000 in terms of polystyrene-equivalent average molecular weight (Mw) by GPC. , 000— 10,000. If the molecular weight is less than 500, it may not be possible to obtain a low-elasticity cationically curable resin.If the molecular weight is more than 50,000, it is not preferable. This is not preferred because of poor compatibility with the agent.

[0045] The compound represented by the formula (4) of the present invention can be synthesized in the same manner as the compound represented by the formula (2). When using as in the case of formula (2), it is preferable that More preferably, it is 1.2 to 6 moles. However, when using a polymer in which a plurality of hydroxyl groups having a hydroxyl group at both ends are bonded, a mole of tosyl or mesyl chloride having a smaller number of hydroxyl groups than that of the hydroxyl group is charged, and then directly tosilied or mesiled. The method of introducing the compound represented by the formula (1) is preferred because of its simplicity.

 When a polymer having a plurality of hydroxyl groups having hydroxyl groups at both ends is used, the polymer may contain less than two oxetal groups on average. Individual.

 [0046] The above-mentioned tosyl rid or mesyl rid can be combined with a compound represented by the formula (1) to bind an oxetal group. An alkali catalyst is inserted during this reaction. Is preferred. This reaction can be carried out without solvent, but it is preferable to dissolve it in a solvent. Examples of the alkali catalyst used in the present reaction include alkali metal hydroxides and tertiary amines. Preferred are sodium hydroxide sodium and potassium hydroxide, and particularly preferred are hydroxides. It is dani potassium. Here, there is a method in which the compound represented by the formula (1) is converted to alkoxide with sodium hydride or the like. However, since it is not easy to handle industrially, it is preferable to use an alkali metal hydroxide. Is preferred. Examples of the solvent used in this reaction include hydrocarbon solvents such as hexane and heptane, and ether solvents such as THF, 1,2-diethoxytan, and dibutyl ether. Among them, those having a high boiling point, for example, 1,2-diethoxyxetane and dibutyl ether can be particularly preferably used.

 [0047] The amount of the compound represented by the formula (1) to be added to the above-mentioned tosyl- or mesyl-irridated product is particularly limited as long as it is at least equimolar to the tosyl group or the mesyl group of the polymer in terms of mole. However, it is preferably 1.2 times or more. The upper limit is not particularly limited, but is preferably 100 times or less from the viewpoint of the yield relative to the volume of the reactor. When the compound represented by the formula (1) is used in excess, the target polymer and the solution containing the compound represented by the formula (1) may be separated into two layers. The layer containing the represented compound can be recovered, distilled, and reused.

The reaction temperature is preferably from 60 ° C to 150 ° C, particularly preferably from 90 ° C to 130 ° C. The atmosphere of the present reaction system is preferably a nitrogen atmosphere, from the viewpoint of suppressing the formation of peroxidized products.

 Purification after this reaction can be performed in the same manner as for the compound represented by the formula (2).

[0048] The cationically curable resin composition of the present invention

The maleimide compound having an oxetal group according to the present invention, the compound represented by the formula (2) and the compound represented by the formula (4) are excellent in cationic polymerizability, so that the cation activated by an active energy ray is excellent. By blending a polymerization initiator and a cationic polymerization initiator activated by Z or heat, it can be used as a cationically curable resin composition. The active energy ray-curable resin of the cationically curable resin composition can achieve physical properties that are difficult to achieve with conventional ones. In terms of the storage stability of the compound represented by the formula (2) and the compound represented by the formula (4) and the oxidation resistance of the cured product, R ² in the formula is an ethylene-butylene copolymer, hydrogen It is preferably added polybutadiene or hydrogenated polyisoprene.

 [0049] Cationic polymerization initiators for initiating cationic polymerization of the cationically curable resin composition of the present invention upon irradiation with active energy rays include diazopam salts, odonium salts, sulfonium salts, selenium salts, selenium salts, and pyridiniums. Salts, ferrosenium salts, phosphonium salts, and chopyrylium salts, and the like, preferably edoniadium salts and sulfodium salts, and more preferably diaryldonium salts and dialkylphenacyl sulfonium salts. It is a salt, and in particular, a diaryodonium salt can be suitably used.

 [0050] In the case where a photoinitiated thione polymerization initiator such as a rhododium salt or a sulfonium salt is used in the cation-curable resin composition of the present invention, BF-, AsF-, SbF-, PF- ,

 4 6 6 6 and B (C F) — and the like, preferably SbF—, PF—, or B (C F) —, particularly

 6 5 4 6 6 6 5 4

 Preferably, it is SbF— or B (C F) —.

 6 6 5 4

[0051] Specific examples of the photoinitiated thione polymerization initiator include bis (dodecylphenyl) odonium hexafluoroantimonate (manufactured by GE Toshiba Silicone Co., Ltd., a main component of UV-9380C), Pemtetrakis (pentafluorophore) borate (PHOTOINITIATOR2074, manufactured by Rhodia), bis (alkyl (C = 10-14) phenol-dodium) Hexafluoroantimonate (optical power thione manufactured by Wako Pure Chemical Industries, Ltd.) Polymerization initiator WPI-016) No.

 [0052] As the active energy ray for curing the cationically curable resin composition of the present invention, X-rays, electron beams, ultraviolet rays, visible light, and the like can be used, and preferably, ultraviolet rays or visible light are used. And particularly preferably ultraviolet light. When ultraviolet light is used, its wavelength range is not particularly limited, but is preferably 150 to 400 nm, more preferably 200 to 380 nm. When ultraviolet rays are used, cationic polymerization can be started efficiently.

 [0053] The cationically curable resin composition of the present invention may further contain a sensitizer, if necessary, in order to further enhance the activity of the photoinitiated thione polymerization initiator. As the sensitizer that can be used in the present invention, it is possible to use, for example, the compounds disclosed by Krivero in Advanced in Polymer Science (Ad v. In Plymer Sci., 62, 1 (1984)). Specifically, there are pyrene, perylene, ataridine orange, thioxanthone, 2-cloth thioxanthone and benzoflavin. In addition, compounds widely used as photoradical polymerization initiators can also be used, and specific examples thereof include benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4-dichlorothioxanthone. Benzoin ethers such as thioxanthones, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenyl-one 1one; 2-hydroxy-2 —Methyl-1 —Phenylpropane 1one, 1- (4 isopropylphenyl) -2-hydroxy-2-methylpropane 1one, 1-hydroxycyclohexylphenyl ketone, etc., α-hydroxyalkylenones, camphorquinone, etc. — Dicarborini dari products and the like. In the present invention, thioxanthones and a-hydroxyalkylphenones can be particularly preferably used.

 [0054] The blending amount of the photovoltaic thione polymerization initiator in the cationically curable resin composition of the present invention can be appropriately adjusted according to the type of active energy ray and the amount of irradiation. For example, in the case of ultraviolet rays

The amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, and still more preferably 13 to 13 parts by mass, based on a total of 100 parts by mass of the cationically curable resin composition. is there. If the amount of the cationic polymerization initiator is less than 0.1 part, the curability may be poor.On the other hand, if the amount is more than 10 parts by mass, the components which are truly necessary for the cured product may be reduced and the cured product Low physical properties In some cases, the color of the cured product may be intensified, or the coloring of the cured product may become intense.

[0055] The amount of the sensitizer added to the cationically curable resin composition of the present invention can be appropriately adjusted according to the type of active energy ray and the amount of irradiation. For example, in the case of ultraviolet light, the amount is preferably 5 parts by mass or less, more preferably 0.2-2 parts by mass, based on 100 parts by mass of the total thione curable resin composition. If the compounding amount of the sensitizer is more than 5 parts by mass, the physical properties of the cured product may be reduced by reducing the components necessary for the cured product, or the cured product may be colored intensely.

When the active energy ray is ultraviolet light or visible light, the cation-curable resin composition is exposed to air. At this time, the humidity of the atmosphere is preferably low, preferably 80% RH or less, More preferably, it is 70% RH or less. Here, when ultraviolet or visible light is installed in the production line, a method of sending dry air before the light irradiation device or a method of installing a heating device to reduce humidity can be adopted.

[0057] A compound that initiates cationic polymerization by being activated by heat, ie, a thermal cationic polymerization initiator, can also be used in the cationically curable resin composition of the present invention. As this one

And various quaternary salts such as quaternary ammonium salts, phosphonium salts and sulfodium salts, and combinations of alkoxysilanes and aluminum complexes. Available products include Adeka Opton CP-66 and Adeka Opton CP-77 (with a trade name of Asahi Den-I-Dai Kogyo Co., Ltd.), San-Aid SI-60L, San-Aid SI-80L, and San-Aid SI-10OL ( V, deviations are trade names, manufactured by Sanshin Chemical Industry Co., Ltd., and CI series (manufactured by Nippon Soda Co., Ltd.).

 [0058] The mixing ratio of the thermal cationic polymerization initiator to the cationically curable resin composition of the present invention is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the cationically curable resin composition. Is more preferably 0.1 to 5 parts, and even more preferably 0.5 to 3 parts. If the compounding ratio is less than 0.01 parts by mass, the ring-opening reaction of the ring-opening polymerizable group may not be able to proceed sufficiently even if the compound is activated by the action of heat. Further, even if it is added in an amount of more than 10 parts by mass, the effect of promoting the polymerization is not further increased, and the physical properties of the cured product may be undesirably reduced.

[0059] Focusing on a light-powered thione-curable resin composition, a maleated disulfide having an oxetanyl group can be used. Compound, a compound represented by the formula (2) and Z or a compound represented by the formula (4), a compound containing an epoxy group, and a resin composition containing a photoinitiated thione polymerization initiator. Preferred. In the photodynamic thione polymerization, the oxetane compound has better polymerizability than the epoxy compound, but the reaction at the initiation stage of the polymerization is slow, so that a small amount of the oxetane conjugate is added to the composition containing the oxetane conjugate. By doing so, the overall curability is improved.

 Various epoxy compounds can be used as the epoxy compound used for improving the overall curability, and may be monofunctional or polyfunctional. The epoxy group of the epoxy compound may be a compound obtained by oxidizing a double bond in a molecule or a glycidyl ether. As a compound obtained by oxidizing a double bond in a molecule, a compound obtained by oxidizing a chain molecule such as olefin or polybutadiene which is not limited to an alicyclic epoxy may be used.

 Preferred examples of blending for obtaining a cured product at room temperature (for example, around 25 ° C.) which has a low elasticity comparable to that of the pressure-sensitive adhesive but also has excellent resilience after shape change are described below. One is a composition containing a maleated compound, a compound represented by Z or the formula (2), a compound having one oxetanyl group in one molecule, and a cationic polymerization initiator. In the case of a photocurable resin containing a light-powered thione polymerization initiator, it is preferable that the composition further contains a compound containing an epoxy group from the viewpoint of curability.

 Another example is a composition comprising a compound represented by the formula (4), a compound having two or more cationically polymerizable groups in one molecule, and a cationic polymerization initiator. In order to reduce the viscosity while maintaining good curability, it is preferable to further add a compound having one oxetal group in one molecule to the composition. Further, in the case of a photocurable resin containing a photo-induced thione polymerization initiator, it is preferable that the composition further contains a compound containing an epoxy group from the viewpoint of curability.

A compound having one oxetanyl group in one molecule is more preferable than a compound having one epoxy group in one molecule from the viewpoint of not only curability but also safety. That is, most of epoxy conjugates having a low molecular weight are suspected to be mutagenic, but in the case of oxetane compounds, for example, 3-oxyl-3- (2-ethylhexyloxymethyl) having a small molecular weight is used. ) Oxetane is negative for mutagenicity.

 [0061] In general, a polymer is a viscoelastic material, so it is difficult to clearly distinguish between a solid and a liquid. However, here, a material having a tan δ force ^ or less in dynamic viscoelasticity measurement is referred to as a solid. I do.

 A cured product having a small tan δ is excellent in restorability after a shape change even if the elastic modulus is low. Here, room temperature refers to around 25 ° C, and is actually in the range of 0 ° C to 40 ° C because it is often used inside electronic equipment used indoors. In this temperature range, the glass transition temperature is preferably -10 ° C or less, more preferably -10 ° C or less, in order to make the cured product excellent in resilience after shape change while having low elastic modulus. Is below 25 ° C, particularly preferably below 40 ° C.

Further, the cured product obtained from the composition of the present invention has a dynamic viscoelastic modulus (G ′) at 25 ° C. of 1 × 10 ⁸ by adjusting the content of the compound of the present invention and the compound to be blended. What is less than Pa can be obtained, or less than 10 ⁷ Pa can be obtained, or less than 10 ⁶ Pa can be obtained.

When focusing on the compound represented by the formula (2) and the compound represented by the formula (4), the formulas (2) and (4) in terms of storage stability and oxidation resistance of the cured product are considered. Preferably, R ² is an ethylene butylene copolymer, hydrogenated polybutadiene, or hydrogenated polyisoprene.

 When the degree of low elastic modulus such as an elastic adhesive is to be adjusted to an appropriate level in balance with toughness or the like, a compound having two or more epoxy groups in one molecule and Z or It is preferable to compound a compound having two or more oxetanyl groups in one molecule other than the polymer of the present invention. Here, a compound containing both an epoxy group and an oxetal group in one molecule may be blended.

 [0064] Various compounds can be used as the compound having one epoxy group used in the cationically curable resin composition of the present invention. Examples of this commercialized compound include α-olefin epoxides such as 1,2-epoxyhexadecane, phenol glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, Glycidyl metathallate and the like are mentioned.

[0065] A compound containing two or more epoxy groups used in the cationically curable resin composition of the present invention. Various compounds can be used as the product.

 Examples of commercially available compounds include dicyclopentagendioxide, limonenedioxide, 4 bulcyclohexenedioxide, and (3,4 epoxycyclohexynolemethinole 3,4-epoxycyclohexanol oleboxylate. , Di (3,4-epoxycyclyl hexyl) adipate, bisphenol A epoxy resin, halogenated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S diglycidyl ether, Bisphenol F type epoxy resin, omp-cresol novolak type epoxy resin, phenol novolak type epoxy resin, 1, 6 xandiol diglycidyl ether, polytetramethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pen Erythritol tetraglycidyl ether, internal epoxidized polybutadiene, compound in which both ends of polybutadiene are glycidyl etherified, compound in which butadiene double bond in styrene butadiene copolymer is partially epoxidized, and ethylene butylene A compound in which a part of polyisoprene of a block copolymer of a polymer and polyisoprene is epoxidized (K-RATON L-207) A compound obtained by epoxidizing the butyl group of a ring-opening polymer of 4-vinylcyclohexene oxide, Examples include epoxidized vegetable oils, etc. Here, the number of epoxy groups per molecule is not particularly limited, but is preferably 50 or less, particularly preferably 20 or less. If the number of the groups is more than 50, it is not preferable because a small amount of the compound improves the elastic modulus.

Examples of the compound having one oxetal group in one molecule used in the cationically curable resin composition of the present invention (in Katsuki, a product name or a developed product name, manufactured by Toagosei Co., Ltd.) include 3-ethyl-3 — (2-Ethylhexyloxymethyl) oxetane (Aronoxetane OXT—212 (EHOX)) 3-Ethyl-3— (Cyclohexyloxymethyl) oxetane (CHOX) 3-Ethyl-3- (dodecyximethyl) oxetane (OXR— 12) 3-Ethyl-3- (octadecasiloxymethyl) oxetane (OXR-18) 3-Ethyl-3- (phenoxymethyl) oxetane (Aron oxetane OXT- 211 (POX)) 3-Ethyl-3-hydroxymethyloxetane OXA) and the like.

[0067] As the compound containing two or more oxetal groups used in the cationically curable resin composition of the present invention, various compounds can be used. To give an example of this compound, Product name or developed product name, manufactured by Toagosei Co., Ltd., 1,4 bis {[(3-Ethyl 3-3-xetal-methyl) methoxy] methyl} benzene (aronoxetane OXT-121 (XDO)), di [1-ethyl (3- Oxeta-l)] Methyl ether (Aronoxetane OXT-221 (DOX)), Oxetael lucesquioxane (OX-SQ), phenol novolak oxetane (PNOX-1009), norbornane dimethanol and 3-ethyl-3-chloromethyl Oxetane (hereinafter abbreviated as OXC) ether (NDMOX), trimethylolpropane and OXC ether (TMPOX), hydroquinone and OXC ether (HQOX), resorcinol and OXC ether (RSOX) , 2,2 Biphenyl and etherified product of OXC (2,2, -BPOX), 4,4, -Biphenol and etherified product of OXC (4,4, -BPOX), Bisphenol F and etherified product of OXC (BisFOX ), Tricyclodecanedimethanol and OXC ether compound, alkoxide by O XA and silicon (OX SC) and the like.

 Here, the number of oxetal groups per molecule is not particularly limited, but is preferably 20 or less, more preferably 5 or less, and particularly preferably 3 or less.

 [0068] It is preferable that the composition containing these is finally dissolved uniformly and transparently. Preferred in terms of compatibility when blended into the composition are KRATON's L207, 1,2 epoxyhexadecane, norbornane dimethanol dioxetane, 3-ethyl-3- (2-ethylhexyloxy) Examples thereof include methyl) oxetane (EHOX), 3-ethyl-3- (cyclohexyloxymethyl) oxetane (CHOX), and 3-ethyl-3- (dodecyximethyl) oxetane (OXR-12).

 [0069] The composition of the present invention may optionally contain a filler such as silica, alumina, or other metal oxides. Thereby, thixotropy can be imparted. When used as an electrical insulating material, it is preferable to mix a material having an ion exchange ability, more preferably an inorganic material, and particularly preferably an anion exchange ability. Examples of suitable inorganic anion exchangers include IXE-500, IXE-530, IXE-550, IXE-700, IXE-800 and the like (the deviations are also manufactured by Toagosei).

[0070] Further, a coupling agent such as a silane coupling agent can be added to the composition of the present invention for the purpose of improving adhesion to an inorganic material. In this example, the silane coupling agent is j8 (3,4-epoxycyclohexyl) ethyltrimethoxysilane K-Danigaku KBM-303), y-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical KB M-403), γ-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical ΚΒΕ-403), γ-glycidide Xypropylmethyljetoxysilane (Shin-Etsu Chemical Co., Ltd. 402), 3-ethyl-3-([3 (triethoxysilyl) propoxy] methyl} oxetane (Toagosei Co., Ltd., 610) and the like.

[0071] When oxidation resistance is required, an antioxidant can be added to the composition of the present invention. In such a case, as the compound represented by the formula (2) and the compound represented by the formula (4), R ² is an ethylenebutylene copolymer, a hydrogenated polybutadiene, or a hydrogenated polyisoprene. Especially preferred! / ,.

 [0072] Examples of the antioxidant to be contained in the composition of the present invention include a phenol-based antioxidant, an antioxidant, a phosphorus-based antioxidant, and an amine-based antioxidant. Particularly preferred are phenolic antioxidants.

 Examples of phenolic antioxidants include hydroquinone monomethyl ether, 2,6-di-tert-butylhydroxytoluene, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4, butylidenebis (3-methyl-6 — T-butylphenol), triethyleneglycol-rubis— [3- (3,1-tert-butyl-4-hydroxy-5-methylphenyl)] propionate, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4) —Hydroxyphenyl) propionate] (Tinoku's Specialty Chemicals, Irganox 1010), n-octadecyl — 3— (3,, 5, z-t-butyl-4, -hydroxyphenyl) propionate, 4,4, — And thiobis (3-methyl-6-t-butyl) phenol.

[0073] The cationically curable resin composition of the present invention can give a cured product that is at least as soft as an adhesive from a soft cured product generally called a flexible resin. Further, the cationically curable resin composition of the present invention can be a material having excellent elasticity after shape change while having a low elasticity comparable to that of an adhesive. Accordingly, the cationically curable resin composition of the present invention is suitably used as an adhesive, a coating agent, a sealing agent, a sealing agent, an insulating material, etc., mainly for electronic materials and optical materials. it can. In particular, the cation-curable resin composition of the present invention, which is obtained by curing with an active energy ray, is preferable since physical properties that cannot be achieved by conventional ones can be realized. Among them The use of ultraviolet or visible light as the active energy ray is particularly preferable because it can be produced by a relatively inexpensive and small production line.

 [0074] Whether the cationically curable resin composition of the present invention is selected from an active energy ray-curable system and a thermosetting system can be properly used depending on the application. For example, when used as a resist or in applications where a fine shape is imparted by a stamper (mold) or the like, a curing system using an active energy ray such as an ultraviolet curing system is suitable. Also, for coating, screen printing, bonding of transparent materials, etc., a curing system using an active energy ray is suitable in terms of high production speed and energy saving. However, the adhesion between opaque materials

In applications where active energy rays cannot reach the resin, such as sealing of parts containing metal, etc., a thermosetting system is suitable. However, even in applications such as bonding between opaque materials, for example, after irradiating light to a photocurable resin applied to an opaque material, another dark It is also possible to bond various materials together and complete the curing by a dark reaction. Further, after the curing by the active energy ray, the heating and curing can be performed together.

<Example>

 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by these Examples and Comparative Examples. The numerical values in the composition table are parts by mass.

<Example 1>

 合成 Synthesis of hydrogenated polybutadiene (HAOX) having oxetanyl at both ends

 <Toshiroi of hydrogenated polybutadiene having hydroxyl groups at both ends>

In a 500 ML separable flask, 86.8 g (80 mmol as hydroxyl group), 142 g of tetrahydrofuran (THF), 142 g of triethylamine, .2 g (240 mmol) were charged, and a stir bar, a thermometer, and a cooling tube were attached to a lid having four ports, and the mixture was stirred and dissolved in an oil bath while passing nitrogen gas through. After dissolution, 30.5 g (160 mmol) of tosyl sulfide was added thereto, and the mixture was stirred and reacted at 62 ° C for 21 hours. After the completion of the reaction, this crude reaction product was slowly added to 950 g of methanol stirred at room temperature, further stirred for 30 minutes, and then left for 1 hour. It was. After standing, the methanol layer was removed by decantation, and 190 g of n-xane was added to the precipitate to dissolve it. This was transferred to a separatory funnel, and the methanol layer separated into two layers was removed. Then, 25 g of methanol was added, shaken vigorously, and allowed to stand. Then, the methanol layer was removed. This operation was repeated twice. At the last washing, 48 g of n-xane was added. The n-xane layer containing the product was transferred to a separable flask, and the solvent was distilled off under reduced pressure in an oil bath at 65 ° C or lower to obtain 80 g of a pale yellow transparent product. From the 'H-NMR ^ vector, it was confirmed that the hydroxyl group of the polymer was tosylated.

 <Oxetanation of Hydrogenated Kafun Polybutadiene with Both Ends Tosylated>

In a 500 ML separable flask, 62.0 g of tosylated hydrogenated kamotsu polybutadiene, 62.0 g of di-n-butyl ether 6-ethyl-3-hydroxymethyloxetane (OXA, manufactured by Toagosei) 116 g 95% hydroxylamine 5.9 g of potassium was charged, and a stir bar, a thermometer, and a cooling tube were attached to a lid having four ports, and the mixture was stirred and reacted at 120 ° C. for 4.5 hours in an oil bath while passing nitrogen gas. After the completion of the reaction, only the liquid was transferred to a separatory funnel by decantation because a precipitate had formed. The precipitate was washed with 100 g of n-xane, and the washed solution was also added to the separatory funnel by decantation. Since the liquid had separated into two layers, the lower layer containing OXA was removed. Next, 123 g of methanol was added, and the mixture was shaken vigorously. After adding 24 g of n-xane, the mixture was gently mixed and allowed to stand, separated into two layers, and the lower layer was removed. Thereafter, washing with 62 g of methanol was repeated three times. At this time, n-xane was appropriately added in the range of 30 to 90 g to speed up the separation of the two layers. Transfer the n-xan layer containing the product to a 500 ML separable flask, remove most of the solvent in a 100-120 ° C oil bath while passing nitrogen through, and then remove the remaining small amount of solvent. 5 hours under reduced pressure at 1 50 ° C oil bath, light to give the product 50g as a yellow transparent (HAOX) the ¹ H- NMR ^ vector of Polytail HA and products as a raw material in Figure 1 and Figure 2 respectively Indicated. From the NMR ^ vector, it was confirmed that the tosyl group at the terminal of the polymer was replaced by OXA. The GPC of the product was measured and the molecular weight distribution was confirmed. The polystyrene equivalent Mw was 3876 MwZMn and 1.31. On the other hand, the raw material polymer had an Mw force of 3656 MwZMn of 1.37.

<Example 2> 合成 Synthesis of L1203OX

 <Tosylido of ethylene butylene copolymer having a hydroxyl group at one end>

A 2 L separable flask was charged with 240 g (about 60 mmol as a hydroxyl group) of ethylene butylene copolymer having a hydroxyl group at one end (manufactured by KRATON Polymers, about 60 mmol), 328 g of tetrahydrofuran (THF), and 36.4 g of triethylamine. A stirring rod, a thermometer, and a cooling tube were attached to the mouth lid, and the mixture was stirred and dissolved in an oil bath while passing nitrogen gas through. After dissolution, 51.5 g (270 mmol) of tosyl sulfide was added thereto, and the mixture was stirred and reacted at 62 ° C for 27 hours. After the completion of the reaction, the crude reaction product was slowly added to 2.5 kg of isopropyl alcohol (IPA) stirred at room temperature, and then stirred for 30 minutes and left for 1 hour. After removing the IPA layer by decantation, 700 g of n-hexane was added to dissolve the precipitate. This was transferred to a 2 L separatory funnel, stirred with 120 g of methanol, stirred, and further mixed with 300 g of n-hexane and lightly mixed to separate two layers. After the lower methanol layer was removed, 120 g of methanol was further kneaded, shaken, and allowed to stand for 15 minutes to remove the lower methanol layer. After repeating the above washing with methanol twice more, the n-hexane layer containing the product was transferred to a separable flask, and the solvent was distilled off at 65 ° C or lower in an oil bath under reduced pressure. 222 g of a pale yellow transparent product were obtained. From the ¹ H-NMR spectrum of the product, it was confirmed that the hydroxyl groups of the polymer were tosylated.

<Oxetane conversion of tosylated ethylene butylene copolymer>

In a 2 L separable flask, 204 g of tosylated ethylenebutylene copolymer, 204 g of di-n-butyl ether, 255 g of 3-ethyl-3-hydroxymethyloxetane (OXA, manufactured by Toagosei Co., Ltd.), 255 g, 95% potassium hydroxide 6. 5 g was charged, and a stirring rod, a thermometer, and a cooling tube were attached to a lid having four ports, and the mixture was stirred and reacted at 120 ° C. for 6 hours in an oil bath while passing nitrogen gas. After the completion of the reaction, a precipitate was formed, so that only the liquid was transferred to a 2 L separatory funnel by decantation, and the precipitate was washed with 200 g of n-hexane. Added. Since the solution in the separatory funnel had separated into two layers, the lower layer containing OXA was removed. Next, 200 g of methanol and 500 g of n-hexane were added and stirred, and then 100 g of n-hexane was further added and mixed gently to separate two layers. The lower layer was removed, and washing with 200 g of methanol was further repeated three times. At this time, NOxane lOOg was added where appropriate for rapid and clear layer separation. The n-xane layer containing the product was transferred to a 2 L separable flask, and most of the solvent was distilled off in an oil bath at 100 to 110 ° C while passing nitrogen gas through. Then, a small amount of the remaining solvent was removed. The pressure was reduced in an oil bath at 150 ° C for 5 hours to obtain 183 g of a pale yellow transparent product. L-12 03 and product ¹ H- NMR ^ vectors are shown in FIGS. 3 and 4, respectively. From this, it was confirmed that the tosyl group at the terminal of the polymer was replaced by OXA. Further, the molecular weight distribution was confirmed by measuring the GPC of the product, and the polystyrene equivalent Mw was 5630 Mw / Mn was 1.04. On the other hand, the raw material polymer has Mw of 5510 and MwZMn of 1.03.

 <Example 3>

 ^^ (LTOX— ί) of maleic compound

In a 500 ML separable flask, 100 g of maleated polyisoprene LIR-403 manufactured by Kuraray (viscosity average molecular weight 25,000, 3 functional groups per molecule, about 8 mmol as acid anhydride), 3-ethyl-3-hydroxy 4.65 g (40 mmol) of methyloxetane (OXA, manufactured by Toagosei Co., Ltd.) and 100 g of xylene are charged, and the lid is put. A stirrer, a cooling pipe, and a nitrogen introduction pipe are attached, and immersed in an oil bath to stir. did. After purging with nitrogen at a flow rate of 200 mlZ for 30 minutes, the reaction was carried out for 16 hours while the flow rate of nitrogen was set to 50 mlZ, the bath temperature was set to 150 ° C, and xylene was refluxed. The reaction rate was determined from the peak of the acid anhydride in the IR spectrum (the absorbance at 1790 cm and the peak at 2930 cm ¹ as CH stretching vibration. The reaction rate after 16 hours was 81%.

 After 0.1 g of IrganoxlOlO (manufactured by Chinoku Specialty Chemicals) as an antioxidant was added to this solution, xylene was distilled off under reduced pressure at 100 ° C. The yield was 100%, and the residual OXA was 0.3% (by gas chromatography). The product polymer was pale yellow and transparent, and had a viscosity at 50 ° C. of 153 Pa · s.

<Example 4>

 Synthesis of Maleated Compound Having Dioxetanyl (LIOX-2)

In a 500 ML separable flask, 90 g (about 7.2 mmol as an acid anhydride) of Kuraray LIR-403, a maleated polyisoprene, and 3-ethyl-3-hydroxymethyloxetane (O 4.19 g (36 mmol) of XA, manufactured by Toagosei Co., Ltd., and 60 g of 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (EHOX, manufactured by Toagosei Co., Ltd.), and then the lid is stirred. A machine, a cooling pipe, and a nitrogen inlet pipe were attached, and they were immersed in an oil bath and stirred. After purging with nitrogen at a flow rate of 200 mlZ for 30 minutes, the flow rate of nitrogen was set to 50 mlZ, the reaction was carried out at a liquid temperature of 165 ° C for 4 hours, and then at 140 ° C for 4 hours. The reaction rate was determined in the same manner as in Example 1 to be 84%. The product here is a composition containing a maleated compound having an oxetanyl group (58%), EH OX (40%), and OXA (2%), with a pale yellow transparent appearance and a viscosity at 25 ° C. Was 10.9 Pa's.

<Synthesis Example 1>

 合成 Synthesis of urethane acrylate (PTGUA)

 In a 500 ML separable flask, 88.8 g (0.40 mol) of isophorone diisocyanate (IPDI), 0.34 g of dibutyltin dilaurate, and 0.102 g of 2,6-di-t-butyl-4 methylphenol (BHT) are charged. Then, while air was blown, 203.8 g (0.20 mol) of polytetramethylene glycol having a molecular weight of about 1000 (PTG1000SN manufactured by Hodogaya Chemical Industry Co., Ltd.) was added dropwise, and the mixture was further reacted at 60 ° C. for 1 hour. Next, 46.4 g (0.40 mol) of 2-hydroxyethyl acrylate was added dropwise and reacted at 80 ° C. for 1 hour to obtain urethane acrylate.

 [0083] The abbreviations in the composition recipe are described below.

 HAOX: product obtained in Example 1

 L 1203OX: product obtained in Example 2

 LIOX-1: product obtained in Example 3

 LIOX-2: product obtained in Example 4

 UVR6216: 1,2 Epoxyhexadecane (Dow Chemical Japan 11 \ ^ 6216) EHOX: 3-Ethyl-3- (2-ethylhexyloxymethyl) oxetane (Toagosei Aronoxetane OXT-212)

L207: L207 manufactured by KRATON Polymers (block copolymer of ethylene butylene copolymer and epoxy diisoprene, molecular weight based on hydroxyl group in NMR is about 6000, epoxy equivalent is about 670 gZmol, Tg-53.C) POX: 3-Ethyl-3- (phenoxymethyl) oxetane (Toagosei Aronoxetane OXT-211)

 CHOX: 3-Ethyl-3- (cyclohexyloxymethyl) oxetane (C HOX manufactured by Toagosei)

 L 1203: L 1203 manufactured by KRATON Polymers (Ethylene butylene copolymer having a hydroxyl group at one end, 分子 The molecular weight based on the hydroxyl group of NMR is about 4000, Tg-63 ° C)

 NDMOX: norbornane dimethanol dioxetane (Toagosei Co., Ltd., aronoxetane NDMOX (development product))

 PGE: Ferruglycidyl ether (Denacol EX-141 manufactured by Nagase ChemteX) PTGUA: Urethane acrylate synthesized in Synthesis Example 1

 BADMA: Bimethanol A dimethatalylate of alcohol prepared by adding four ethylene oxides to bisphenol A (Light ester BP—4EM, manufactured by Kyoeisha-Danigaku)

 M120: 2-ethylhexyl carbitol atalylate (Toagosei Aronix M-120)

 EHMA: 2-ethylhexyl methacrylate

 POA: fenokishechiruatarilate (light atarilate POA manufactured by Kyoeisha I-Dagaku)

WPI016: Bis (alkyl (C = 10-14) phenol-dodium) hexafluoroanthimonate (WPI Pure Photoinitiated Thion polymerization initiator WPI-016)

 # 2074: Trillcumylodonum tetrakis (pentafluorophore) borate (PHOTOINITIATOR2074 manufactured by Kuchiichi Dia)

 Del 173: Dinocur's photochemical radical polymerization initiator Darocur 1173 (Specialized Chemicals Co., Ltd.)

 Irgl84: Photo-radical polymerization initiator Irgacurel 84 (1-hydroxycyclohexyl roof ketone, manufactured by Specialty Chemicals Co., Ltd., used as a sensitizer for photo-thione polymerization in the present invention)

WPI003: Bis (alkyl (C = 10-14) phenol-hexafluorohexene) Sulfate (Wako Pure Chemical's thione polymerization initiator WPI-003)

<Example 5>

 配合 Formulation of composition containing compound represented by formula (2) and evaluation of properties

 The components shown in Tables 1 and 2 were mixed according to a conventional method to prepare a cationically curable composition, and the physical properties were evaluated.

[Table 1] Example 6 Example 7 Example 8 Example 9 Comparative Example 1

 HAOX 1 00 90 50

 L1 203OX around 40

 UVR621 6 1 0 8

 EHOX 42 40

 Next 207 20

 POX 50

 PGE 50

 WPI01 6 2 2

 # 2074 2 2 2

De l 1 73 1 1 1 1 1

[0086] [Table 2]

PTGUA; BAD A Ml 20; EHMA; POA Irg 1 84 Comparative Examples 2 and 3 30; 20 30; 5; 15 1

[0087] For the compositions shown in Tables 1 and 2, the viscosity and curability of the composition and the dynamic viscosity of the cured product were measured. Table 3 shows the results of these evaluations.

[0088] Viscosity

 The viscosity (Pa's) of each composition at 25 ° C. was measured with an E-type viscometer manufactured by Toki Sangyo Co., Ltd., and the results are shown in Table 3.

 動 的 Measurement of dynamic viscoelasticity of cured product: Preparation of 1mm thick cured product and measurement of dynamic viscoelasticity

A lmm-thick frame was made on a polytetrafluoroethylene plate, and the compositions of Examples and Comparative Examples shown in Table 1 were poured into each frame, and then ultraviolet rays were irradiated with a 60 WZcm high-pressure mercury lamp. Was irradiated. Irradiation was performed at an intensity of 150 mWZcm ² at 365 nm for 2 minutes, and after confirming that the back surface was cured, the film was turned upside down and irradiated under the same conditions. The dynamic viscoelasticity of the obtained cured product was measured at a frequency of 1 Hz using RDS-II made by TA Instruments Then, the storage modulus (G ') and tan δ were evaluated. Table 3 shows the physical property values at 25 ° C. For the cured products of Examples 8 and 9, the dynamic viscoelastic spectrum (temperature dependence) is shown in FIG.

 〇Curing process and measurement of dynamic viscoelasticity of cured product (measuring temperature: 25 ° C)

The curing process by light irradiation and the viscoelasticity after curing were measured using a photocuring viscoelasticity measuring device manufactured by Reologia (Sweden). That is, the composition of Comparative Example 1 shown in Table 1 and the compositions of Comparative Examples 2 and 3 shown in Table 2 were placed on a quartz plate and sandwiched from above with a rotor having a diameter of 10 mm (gap 0.2 mm). The viscoelasticity was measured by irradiating a mercury xenon lamp (L8222 manufactured by Hamamatsu Photonitas, adjusted to 50 mW Zcm ² (intensity at 365 nm)) from the lower part of the quartz plate at 25 ° C. while applying shear strain at a frequency of 1 Hz, and measuring the viscoelasticity. Table 3 shows the elastic modulus G '(Pa) and tan δ of the cured product. For Comparative Examples 1 and 2, the values finally reached after the resin was photocured are shown. For Comparative Example 3, so that G 'is around 10 ⁵ Pa, shows a value when stopped in the middle of the curing morphism light irradiation. In Comparative Example 1, it was confirmed by NMR ^ vector that the monomer was consumed.

評 価 Evaluation of brittleness of cured product

 The brittleness of each of Examples 6-9 was evaluated as follows, and the comparative examples 13 and 13 were each a cured product obtained by using a photocurable viscosity measuring apparatus. Table 3 shows the results.

 〇: It does not break even if it is greatly deformed.

 Δ: Breaks when deformed significantly.

 X: Breaks apart with slight deformation.

 1: The term brittleness is inappropriate because of the intermediate properties between solid and liquid.

硬化 Curability of coating film

The compositions of Examples 6-9 and Comparative Example 1 were coated on a PET film with a bar coater to a film thickness of 20 microns, and this was coated with a 80 WZcm high-pressure mercury lamp (1 lamp) and a lamp height of 1 Ocm. In, at a conveyor speed of 10 mZ or 30 mZ, the curability was evaluated by the number of passes until the coating film changed to a solid. The results are shown in Table 3 (through solidification). Enter the number of times. Hereinafter, the description of the curability is the same. o At this time, the atmosphere was at a temperature of 26 ° C and a relative humidity of 66%.

[0089] [Table 3]

[0090] The results of Examples 6-9 show the following about the cationically curable resin composition of the present invention. That is, the viscosity before curing can be adjusted to a wide range, and a solid having good curability and a very low elastic modulus and excellent resilience after shape change can be provided. In addition, the cationically curable resin composition of the present invention is superior in heat resistance as compared with a composition using the existing epoxy resin L207 as a crosslinking component.

 [0091] <Example 10>

 Done in O (4) · including the west that · '^ ffi

 After mixing the components shown in Table 4 according to a conventional method to prepare a cationically curable composition, various physical properties were evaluated.

 [Table 4] Example Example Example Example Example Comparative example Comparative example Comparative example

1 1 1 2 1 3 1 4 4 5 6

LI 203OX 80 40 40 80

 207 20 20 20 20 20 20

EHOX 40 40

CHOX 40 40 shi 1 203 80

 POX 50

PGE 50

WPI01 6 2 1.1.5 2

 # 2074 1 1 2 1

Irg 1 84 1 1 1 1 1 1

De l 1 73 1 [0093] For the compositions described in Tables 4 and 2, the viscosities and the curing process and the dynamic viscoelasticity of the cured products were measured. Table 5 shows the results of these evaluations.

[0094] [Table 5]

 [0095] Curability of coating film

 The compositions of Examples 12 and 13 and Comparative Example 6 described in Table 4 were coated on a PET film to a film thickness of 20 μm using a bar coater, and this was applied to a 80 WZcm high-pressure mercury lamp (one lamp) and a lamp height. At 10 cm, at a conveyor speed of 50 mZ or 80 mZ, the curability was evaluated by the number of passes until the coating changed to a solid. The atmosphere at this time was a temperature of 26 ° C and a relative humidity of 66%. Table 6 shows the results.

 [0096] [Table 6]

 [0097] Preparation of 1mm thick cured product and measurement of dynamic viscoelasticity

A lmm-thick frame was formed on a polytetrafluoroethylene plate, and after pouring the compositions of Examples 12 and 13 shown in Table 4, ultraviolet rays were irradiated from a high-pressure mercury lamp. Irradiation was performed for 2 minutes at an intensity of 365 mWZcm ² at 365 nm, and after confirming that the back surface was cured, the film was turned upside down and irradiated under the same conditions. The dynamic viscoelasticity of the obtained cured product was measured at a frequency of 1 Hz using a RDS-II trowel manufactured by TA Instruments, and the storage modulus (G,) and tan were measured. δ was evaluated. Figure 6 shows the temperature dependence of this dynamic viscoelastic spectrum.

[0098] <Example 15>

 Formulation of a composition containing a maleated compound having oxetanyl and its physical properties Μ

 For the compositions described in Table 7, the viscosity and the dynamic viscoelasticity of the cured product were measured. Table 7 shows the results of these evaluations. The curability of the compositions shown in Table 8 was evaluated, and the results are shown in Table 8.

 The evaluation method of the physical properties is shown below.

[Table 7] Example 16 Example 17 Example 18

 LIOX-1 50

 LIOX-2 70 66

 ΕΗΟΧ '' 50 25 23

 NDMOX 6

 Factory

 UVR6216 5 5

 L1203OX

 Next 207

 WPI016 1.5 1.1.5 1.5

 Del 173 1 1 1

 Viscosity (Pa's) 4.10 1.78 1.70

G '(Pa) 1. 2 10 s 1. 5 10 4 8. 7 10 4 tan o 0.064 0. 25 0.072

[0100] 硬化 Curability of coating film

 A composition described in Table 8 (Examples 19 to 21) was coated on a PET film to a film thickness of 20 microns using a bar coater, and a high-pressure mercury lamp of 160 WZcm (1 lamp), a lamp height of 10 cm, and a conveyor were used. At a speed of 10 mZ, the curability was evaluated by the number of passes when the coating film changed to a solid. The results are shown in Table 8. The atmosphere at this time was a temperature of 26 ° C. and a relative humidity of 66%.

[0101] [Table 8] Example 19 Example 20 Example 21

LIOX- 1 50 50 50

EHOX 50 50 45

PGE 5

WPI01 6 1.5

 WPI003 3 3

 Del 1 73 1 1 1 Curability (pass) 1 5 2

[0102] Measurement of dynamic viscoelastic spectrum (temperature dependence) of cured product

A lmm-thick frame was made on a plate made of polytetrafluoroethylene, and the compositions of Examples 14 and 16 were poured into the respective frames, and then irradiated with ultraviolet rays from a 60 WZcm high-pressure mercury lamp. . Irradiation was performed for 2 minutes at an intensity of 365 mWZcm ² at 365 nm, and after it was confirmed that curing was performed up to the back surface, the film was turned upside down and irradiated under the same conditions. The dynamic viscoelastic spectrum (temperature dependence) of the obtained cured product was measured at a frequency of 1 Hz using VAR-100 manufactured by Reologia. FIG. 7 shows the viscoelastic spectrum.

 The texture of the cured products of Examples 14 and 16 was very soft, but excellent in the resilience after shape change, and was not broken even when deformed significantly and had no brittleness. .

 Industrial applicability

Since the polymer having an oxetal group of the present invention is excellent in cationic curability, it can be suitably used as a compounding material for a curable composition, and in particular, a cured product excellent in flexibility Also, it can be suitably used when a cured product having a low elastic modulus and excellent resilience after shape change is required at room temperature. Further, the composition of the present invention can be suitably used as an active energy ray-curable resin such as a photo-curable resin. It is also possible to make the viscosity before curing relatively high. The cured product has a very low elastic modulus, excellent heat resistance, and is not brittle. Therefore, it can be suitably used as an electronic material or an optical material requiring the above physical properties.

In addition, the process for preparing the polymers of the present invention uses readily available materials and does not require rigorous dewatering equipment or operations, so relatively small amounts of specific electronic and optical materials, etc. It is a production method suitable for the production of Brief Description of Drawings

FIG. 1 shows a ¹ H-NMR spectrum of a hydrogenated polybutadiene having hydroxyl groups at both ends (Polytail HA manufactured by Mitsubishi Chemical Corporation), which is a raw material polymer of Example 1.

FIG. 2 shows a ¹ H-NMR ^ vector of a hydrogenated polybutadiene having an oxetal group at both terminals, which is a product of Example 1 (HAOX).

FIG. 3 shows a ¹ H-NMR ^ vector of an ethylene butylene copolymer having a hydroxyl group at one end (L 1203 manufactured by KRATON), which is a raw material polymer of Example 2.

FIG. 4 shows a ¹ H-NMR ^ vector of an ethylenebutylene copolymer having an oxetanyl group at one end, which is a product of Example 2.

 FIG. 5 shows a dynamic viscoelastic spectrum (temperature dependence) of a cured product obtained by curing the compositions of Examples 8 and 9 with ultraviolet light.

 FIG. 6 shows a dynamic viscosity spectrum (temperature dependence) of a cured product obtained by curing the compositions of Example 12 and Example 13 with ultraviolet light.

 FIG. 7 shows a dynamic viscosity spectrum (temperature dependence) of a cured product obtained by curing the compositions of Examples 14 and 16 with ultraviolet light.

 Explanation of symbols

 [0106] The horizontal axis in Fig. 1-4: PPM value of iH-NMR ^ vector.

Vertical axis in Fig. 14: ¹ H—arbitrary value in NMR ^ vector.

 Horizontal axis in Fig. 5-7: Temperature ° C

 Right vertical axis in Fig. 5-7: The value of tan δ (log scale).

 Left vertical axis in Fig. 5-7: Storage modulus (G,) value (Pa, logarithmic scale).

 Bold solid line in FIG. 5: Curve indicating the storage modulus (G ′) of a cured product obtained by curing the composition of Example 8 with ultraviolet light.

 5, solid line: curve showing the storage modulus (G ′) of a cured product obtained by curing the composition of Example 9 with ultraviolet light.

 Thick broken line in FIG. 5: Curve showing tan δ of a cured product obtained by curing the composition of Example 8 with ultraviolet light.

Thin dashed line in FIG. 5: tan δ of a cured product obtained by curing the composition of Example 9 with ultraviolet light curve.

 Bold solid line in FIG. 6: Curve showing the storage modulus (G ′) of a cured product obtained by curing the composition of Example 12 with ultraviolet light.

 FIG. 6, thin solid line: curve showing the storage modulus (G ′) of a cured product obtained by curing the composition of Example 13 with ultraviolet light.

 Thick broken line in FIG. 6: shows tan δ of the cured product obtained by curing the composition of Example 12 with ultraviolet light.Narrow broken line of FIG. 6 shows tan δ of the cured product obtained by curing the composition of Example 13 with ultraviolet light. 7 is a curve showing the storage modulus (G ') of a cured product obtained by curing the composition of Example 14 with ultraviolet light.

 Thick solid line in FIG. 7: Curve indicating the storage modulus (G ′) of a cured product obtained by curing the composition of Example 16 with ultraviolet light.

 Thin dashed line in FIG. 7: shows the tan δ of the cured product obtained by curing the composition of Example 14 with ultraviolet light.Bold broken line in FIG. 7 shows tan δ of the cured product obtained by curing the composition of Example 16 with ultraviolet light.

Claims

Claims [1] A group comprising maleated polybutadiene, maleated polyisoprene, hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydroxyl-containing ethylene-butylene copolymer, hydroxyl-containing hydrogen-added polybutadiene, and hydroxyl-containing hydrogenated polyisoprene. A polymer having an oxetanyl group obtained from at least one or more compounds selected from the group consisting of a compound and the following formula (1). [Formula 5]

(R ^{1 in the} formula (1) represents a hydrogen atom or an alkyl group which may have a branch having 1 to 6 carbon atoms.)

 [2] A polymer having maleixin polybutadiene and Z or maleidani polyisoprene, and an oxetanyl group capable of obtaining the above formula (1) and strength.

 [3] Hydroxy group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydroxyl group-containing ethylene butylene copolymer, hydroxyl group-containing hydrogenated polybutadiene, and hydroxyl group-containing hydrogenated polyisoprene. 1) The polymer having an oxetal group obtained from 1).

 [4] A cation comprising the oxetal group-containing polymer according to claim 13 and a cationic polymerization initiator activated by an active energy ray and / or a cation polymerization initiator activated by heat. Curable resin composition.

 5. The cationically curable resin composition according to claim 4, further comprising a compound having an oxetaryl group other than a compound having an epoxy group and a polymer having a Z or oxetal group.

[6] An active energy ray is added to the cationically curable resin composition according to claim 4 or 5. Cured product obtained by irradiation and z or heating.