Naphthalene ether oligomer with (meth)acrylic group at the end

Abstract

To provide a method of producing a polymer, and a monomer thereof, with heat resistance allowing use in a substrate or film in highly densified and highly integrated semiconductor elements, integrated circuits and communication equipment.SOLUTION: The invention provides a naphthalene ether oligomer with a terminal (meth)acrylic group represented by the general formula (1) in the figure. In the general formula (1), A1 represents one of a hydrogen atom, an acrylic group and a methacrylic group; A2 represents an acrylic group or methacrylic group; and n is an integer from 1 to 50.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a naphthalene ether oligomer having a (meth)acrylic group at its terminal and a process for producing the same, as well as a polymerizable composition containing a naphthalene ether oligomer having a (meth)acrylic group at its terminal, a polymerization process thereof, and a polymerized product thereof. [Background technology]

[0002] In recent years, as electronic devices become smaller, printed wiring has become more multi-layered in order to achieve higher integration of electronic elements, and the so-called build-up method, in which insulating layers and conductor layers are alternately formed and laminated, has been widely adopted. For this reason, the insulating resin materials used here are required to have heat resistance that can withstand the heat dissipation of highly integrated parts.

[0003] In addition, the 5G (5th generation mobile communication system) society that is expected to arrive soon will bring about 5G communication infrastructure services that will instantly transmit 4K / 8K ultra-high resolution videos and large amounts of data without delay and integrate them with autonomous driving and VR / AR technology. 5G is an unprecedented wireless technology with high-speed and large-capacity communication specifications exceeding 10Gbps, more than 10 times faster than existing LTE services, and various properties such as heat resistance are required for the substrate materials that support it. Currently, existing glass epoxy resins and polyimide resin bases are used as the main substrate materials for wireless devices for 5G, but materials with better low dielectric constant characteristics, higher heat resistance, and lower water absorption are required. In addition, flexible and heat-resistant polymer films and polymer materials such as copper-clad laminates using polymer films are required. In both cases, the heat resistance of polymer materials is an important factor.

[0004] On the other hand, (meth)acrylic resins such as polymethyl methacrylate are used in a wide variety of applications, including optical materials and electronic materials, due to their transparency. However, due to their low heat resistance, they cannot be used in areas that are subject to heat history or in applications that require heat resistance. For this reason, heat-resistant acrylate polymers and copolymers of acrylates and various monomers are being investigated.

[0005] A method of inserting polycyclic aromatic molecules into the polymer chains constituting the resin in order to impart heat resistance to the resin material is known. For example, various resins into which a fluorene skeleton is introduced as a polycyclic aromatic molecule have been studied. For example, fluorene epoxy (meth)acrylate derived from an epoxy resin derived from fluorene bisphenol and epichlorohydrin and (meth)acrylic acid is known (Patent Document 1, JP 2001-166469 A). This document discloses a urethane resin into which a fluorene skeleton is introduced to exhibit heat resistance.

[0006] Polymer compounds having naphthalene rings in the side chains are also known (Patent Document 2, JP-A-9-255726). They are polymers obtained from acryloyldimethylnaphthalene compounds, and are heat-resistant polymers containing naphthalene nuclei in the side chains. These acryloyldimethylnaphthalene compounds are synthesized by subjecting dimethylnaphthalene to a Friedel-Crafts reaction with a halopropionyl halide, followed by a dehydrohalogenation reaction.

[0007] Polycyclic aromatic-containing (meth)acrylic acid ester polymers obtained by reacting an alcohol having a polycyclic aromatic group in the molecule with a (meth)acrylic acid ester polymer have also been disclosed (Patent Document 3, JP 2006-312709 A). Anthracene rings, naphthalene rings, and fluorene rings are disclosed as polycyclic aromatic groups, and 9-fluorenemethanol, 9-fluoreneethanol, 1-naphthalenemethanol, 1-naphthaleneethanol, and 9-anthracenemethanol are disclosed as alcohols having a polycyclic aromatic group in the molecule. In all cases, the polycyclic aromatic group is in a side chain of the polymer chain, and can be said to be pendant.

[0008] Furthermore, the applicants have already disclosed 1,2,4-tri(meth)acryloyloxynaphthalene compounds as diacrylate compounds of naphthohydroquinone (Patent Document 4, JP 2010-138331 A). They have also disclosed 4,4'-dialkoxy-2,2'-binaphthalene-1,1'-di(meth)acrylate compounds (Patent Document 5, JP 2011-256119 A). They have disclosed that polymers containing a naphthalene skeleton in the main chain can be obtained by polymerizing these compounds. Furthermore, 2,3-(bis)arylthio-1,4-naphthalenediol di(meth)acrylate has also been disclosed as a diacrylate compound of naphthohydroquinone (Patent Document 6, JP 2007-131780 A).

[0009] On the other hand, various aromatic polyethers are also known. For example, there is polyphenylene ether resin (for example, Patent Document 7, JP-A-55-145752). It is a polymer in which benzene rings are connected by ether bonds. In addition, polyethylene naphthalate obtained by transesterification of naphthalenedicarboxylic acid ester and ethylene glycol has also been disclosed (Patent Document 8, JP-A-2014-133818). Naphthol resin obtained by polycondensation reaction of 1-naphthol and bischloromethylnaphthalene is also known (for example, Patent Document 9, JP-A-2015-189926). Polymers of these compounds have a high refractive index, but are insufficient in terms of heat resistance.

[0010] Also, aromatic polyethers having hydroxyl groups at their terminals have been disclosed (Patent Document 10, JP 2009-93919 A). The aromatic polyethers are listed as having the following aromatic moieties: 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2-phenyl-1,4-phenylene, 2-phenoxy-1,4-phenylene, 1,4-naphthylene, 2,3-naphthylene, 1,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene, biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl-3,4'-diyl, 3,3'-diphenylbiphenyl-4,4'-diyl, 3,3'-diphenoxybiphenyl-4,4'-diyl, 2,2'-diphenylpropane-4,4'-diyl, diphenylether-4,4'-diyl, diphenylsulfone-4,4'-diyl, and benzophenone-4,4'-diyl. The purpose of the invention is to synthesize an aromatic polyether having vinyl groups at the terminals and ion-exchange groups in the molecule, and to synthesize an electrolyte resin that is ion-exchangeable and crosslinked in the pores of a porous substrate, but there is no description of which aromatic compound is particularly suitable, no description of heat resistance, and only a condensate of 4,4'-biphenol is described in the examples. There is no disclosure of a compound having an acrylic group at the terminal. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2001-166469 A [Patent Document 2] Japanese Patent Application Publication No. 9-255726 [Patent Document 3] JP 2006-312709 A [Patent Document 4] JP 2010-138331 A [Patent Document 5] JP 2011-256119 A [Patent Document 6] JP 2007-131780 A [Patent Document 7] Japanese Patent Application Publication No. 55-145752 [Patent Document 8] JP 2014-133818 A [Patent Document 9] JP 2015-189926 A [Patent Document 10] JP 2009-93919 A Summary of the Invention [Problem to be solved by the invention]

[0012] Polymers containing naphthalene in the skeleton have heat resistance and various mechanical and optical physical properties of the naphthalene ring. However, polymers containing naphthalene in the skeleton are difficult to handle because they are poorly soluble and difficult to mold. On the other hand, acrylic resins have various excellent properties such as transparency, but have problems with heat resistance. Therefore, the object of the present invention is to provide an acrylic resin that has high heat resistance, excellent transparency, and is easy to handle. And, the object of the present invention is to provide a polymer that can be used for substrates and films of high-density and high-integration semiconductor elements, integrated circuits, and communication devices, and a method for producing the monomer thereof. [Means for solving the problem]

[0013] As a result of further intensive investigation into the structure and physical properties of naphthalene compounds, the inventors have found that the naphthalene ether oligomer having a (meth)acrylic group at its end as described in the present invention has high heat resistance due to the presence of multiple continuous naphthalene ether structures, and have also discovered a practical production method using easily available raw materials, thereby completing the present invention.

[0014] That is, a first gist of the present invention resides in a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (1).

[0015] [ka]

[0016] In the general formula (1), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0017] A second gist of the present invention resides in a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (2).

[0018] [ka]

[0019] In the general formula (2), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50.

[0020] A third gist of the present invention resides in a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (3).

[0021] [ka]

[0022] In the general formula (3), R is a hydrogen atom or a methyl group, and the hydrogen atom of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0023] The fourth gist of the present invention resides in a method for producing a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (1), which comprises subjecting a dihydroxynaphthalene compound represented by the following general formula (4) to a condensation reaction to produce a naphthalene ether oligomer represented by the following general formula (5), and reacting the resulting naphthalene ether oligomer with a compound represented by the following general formula (6):

[0024] [ka]

[0025] In general formula (4), the hydrogen atoms of the naphthalene ring may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0026] [ka]

[0027] In general formula (5), the hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0028] [ka]

[0029] In formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0030] [ka]

[0031] In the general formula (1), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0032] The fifth gist of the present invention resides in a method for producing a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (2), which comprises subjecting a 1,4-dihydroxynaphthalene compound represented by the following general formula (8) to a condensation reaction to obtain a naphthalene ether oligomer represented by the following general formula (9), and reacting the resulting naphthalene ether oligomer with a compound represented by the following general formula (6):

[0033] [ka]

[0034] In general formula (8), the hydrogen atoms of the naphthalene ring may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0035] [ka]

[0036] In general formula (9), the hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0037] [ka]

[0038] In formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0039] [ka]

[0040] In the general formula (2), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0041] The sixth gist of the present invention resides in a method for producing a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (1), which comprises reacting a dihydroxynaphthalene compound represented by the following general formula (4) with a compound represented by general formula (6) to obtain a monomethacrylate compound represented by general formula (10), and further co-condensing the monomethacrylate compound with the dihydroxynaphthalene compound represented by general formula (4).

[0042] [ka]

[0043] In general formula (4), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0044] [ka]

[0045] In formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0046] [ka]

[0047] In the general formula (10), A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0048] [ka]

[0049] In the general formula (1), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0050] The seventh gist of the present invention resides in a method for producing a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (2), which comprises reacting a 1,4-dihydroxynaphthalene compound represented by the following general formula (8) with a compound represented by the general formula (6) to obtain a monomethacrylate compound represented by the general formula (11), and further co-condensing the monomethacrylate compound with the dihydroxynaphthalene compound represented by the general formula (8).

[0051] [ka]

[0052] In general formula (8), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0053] [ka]

[0054] In formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0055] [ka]

[0056] In the general formula (11), A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0057] [ka]

[0058] In the general formula (2), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0059] The eighth aspect of the present invention resides in a polymerizable composition comprising the naphthalene ether oligomer according to any one of the first to third aspects as a component.

[0060] A ninth aspect of the present invention resides in a polymerizable composition comprising, as components, the naphthalene ether oligomer described in any one of the first to third aspects and a compound having a polymerizable double bond group other than the naphthalene ether oligomer described in any one of the first to third aspects.

[0061] A tenth aspect of the present invention resides in a polymerization method, which comprises polymerizing the polymerizable composition according to the eighth or ninth aspect by heating or irradiating with light.

[0062] The eleventh aspect of the present invention resides in a polymer obtained by the method for polymerizing a polymerizable composition according to the tenth aspect.

[0063] In the description of the present invention, the term "(meth)acrylic group" refers to an "acrylic group" or a "methacrylic group". Effect of the Invention

[0064] The naphthalene ether oligomer having a (meth)acrylic group at its terminal of the present invention has high heat resistance due to the presence of multiple continuous naphthalene ether structures, and can be easily polymerized alone or copolymerized with other compounds having polymerizable double bonds due to the presence of (meth)acrylic groups at its terminal, making it useful as a heat-resistant polymer raw material, particularly as a resin raw material for 5G materials. In addition, the raw material is easily available and the manufacturing process is simple, so it can be produced at low cost.

[0065] The objects, features and advantages of the present invention will become more apparent from the following detailed description. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0066] (compound) The naphthalene ether oligomer having a (meth)acrylic group at its terminal according to the present invention is a compound represented by the following general formula (1).

[0067] [ka]

[0068] In the general formula (1), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0069] In the general formula (1), the hydrogen atom of the naphthalene ring may be substituted with another substituent, such as an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group, and the alkyl group may be branched.Examples of the aryl group having 5 to 15 carbon atoms include a phenyl group and a naphthyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, and the like. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the monoalkylamino group having 1 to 10 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, and the like. Examples of the monoarylamino group having 5 to 15 carbon atoms include a phenylamino group and a naphthylamino group. Examples of the dialkylamino group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a methylethylamino group, a methylpropylamino group, a piperidino group, a mono Examples of the diarylamino group having 5 to 15 carbon atoms include a diphenylamino group, etc., examples of the alkylthio group having 1 to 10 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, etc., and examples of the arylthio group having 5 to 15 carbon atoms include a phenylthio group, a naphthylthio group, etc. Examples of the alkoxycarbonyl group having 1 to 10 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, and the like. Examples of the aryloxycarbonyl group having 5 to 15 carbon atoms include a phenoxycarbonyl group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0070] Specific examples of the naphthalene ether oligomer having a (meth)acrylic group at the end represented by the general formula (1) of the present invention include, for example, monoacrylate of 1,6-dihydroxynaphthalene condensate, monoacrylate of 2,7-dihydroxynaphthalene condensate, monoacrylate of 1,4-dihydroxynaphthalene condensate, monoacrylate of 1,5-dihydroxynaphthalene condensate, monoacrylate of 2,3-dihydroxynaphthalene condensate, monoacrylate of 1,2-dihydroxynaphthalene condensate, monoacrylate of 1,3-dihydroxynaphthalene condensate, and the like. Monoacrylate, monoacrylate of 1,7-dihydroxynaphthalene condensation product, monoacrylate of 2,6-dihydroxynaphthalene condensation product, diacrylate of 1,6-dihydroxynaphthalene condensation product, diacrylate of 2,7-dihydroxynaphthalene condensation product, diacrylate of 1,4-dihydroxynaphthalene condensation product, diacrylate of 1,5-dihydroxynaphthalene condensation product, diacrylate of 2,3-dihydroxynaphthalene condensation product, diacrylate of 1,2-dihydroxynaphthalene condensation product, diacrylate of 1,3-dihydroxynaphthalene condensation product Acrylate, diacrylate of 1,7-dihydroxynaphthalene condensation product, diacrylate of 2,6-dihydroxynaphthalene condensation product, monomethacrylate of 1,6-dihydroxynaphthalene condensation product, monomethacrylate of 2,7-dihydroxynaphthalene condensation product, monomethacrylate of 1,4-dihydroxynaphthalene condensation product, monomethacrylate of 1,5-dihydroxynaphthalene condensation product, monomethacrylate of 2,3-dihydroxynaphthalene condensation product, monomethacrylate of 1,2-dihydroxynaphthalene condensation product, monomethacrylate of 1,3-dihydroxynaphthalene Monomethacrylate of 1,7-dihydroxynaphthalene condensation product, monomethacrylate of 2,6-dihydroxynaphthalene condensation product, dimethacrylate of 1,6-dihydroxynaphthalene condensation product, dimethacrylate of 2,7-dihydroxynaphthalene condensation product, dimethacrylate of 1,4-dihydroxynaphthalene condensation product, dimethacrylate of 1,5-dihydroxynaphthalene condensation product, dimethacrylate of 2,3-dihydroxynaphthalene condensation product, dimethacrylate of 1,2-dihydroxynaphthalene condensation product, 1,Examples of the dimethacrylate include 3-dihydroxynaphthalene condensate, 1,7-dihydroxynaphthalene condensate, and 2,6-dihydroxynaphthalene condensate.

[0071] Further, examples of compounds in which hydrogen atoms of the naphthalene skeleton are substituted include monoacrylates of 2-hydroxy-1,4-dihydroxynaphthalene condensates, diacrylates of 2-hydroxy-1,4-dihydroxynaphthalene condensates, monomethacrylates of 2-hydroxy-1,4-dihydroxynaphthalene condensates, dimethacrylates of 2-hydroxy-1,4-dihydroxynaphthalene condensates, monoacrylates of 2-methyl-1,4-dihydroxynaphthalene condensates, diacrylates of 2-methyl-1,4-dihydroxynaphthalene condensates, monomethacrylates of 2-methyl-1,4-dihydroxynaphthalene condensates, dimethacrylates of 2-methyl-1,4-dihydroxynaphthalene condensates, monoacrylates of 2,3-dichloro-1,4-dihydroxynaphthalene condensates, diacrylates of 2,3-dichloro-1,4-dihydroxynaphthalene condensates, monomethacrylate of 2-dichloro-1,4-dihydroxynaphthalene condensate, dimethacrylate of 2,3-dichloro-1,4-dihydroxynaphthalene condensate, monoacrylate of 2-carboxyl-1,4-dihydroxynaphthalene condensate, diacrylate of 2-carboxyl-1,4-dihydroxynaphthalene condensate, monomethacrylate of 2-carboxyl-1,4-dihydroxynaphthalene condensate, dimethacrylate of 2-carboxyl-1,4-dihydroxynaphthalene condensate, monoacrylate of 2-phenoxycarbonyl-1,4-dihydroxynaphthalene condensate, diacrylate of 2-phenoxycarbonyl-1,4-dihydroxynaphthalene condensate, monomethacrylate of 2-phenoxycarbonyl-1,4-dihydroxynaphthalene condensate, dimethacrylate of 2-phenoxycarbonyl-1,4-dihydroxynaphthalene condensate, and the like.

[0072] Further, for example, monoacrylate of 2-hydroxy-1,5-dihydroxynaphthalene condensate, diacrylate of 2-hydroxy-1,5-dihydroxynaphthalene condensate, monomethacrylate of 2-hydroxy-1,5-dihydroxynaphthalene condensate, dimethacrylate of 2-hydroxy-1,5-dihydroxynaphthalene condensate, monoacrylate of 2-methyl-1,5-dihydroxynaphthalene condensate, diacrylate of 2-methyl-1,5-dihydroxynaphthalene condensate, monomethacrylate of 2-methyl-1,5-dihydroxynaphthalene condensate, dimethacrylate of 2-methyl-1,5-dihydroxynaphthalene condensate, monoacrylate of 2,3-dichloro-1,5-dihydroxynaphthalene condensate, diacrylate of 2,3-dichloro-1,5-dihydroxynaphthalene condensate, monomethacrylate of a 2-carboxyl-1,5-dihydroxynaphthalene condensate, diacrylate of a 2-carboxyl-1,5-dihydroxynaphthalene condensate, monomethacrylate of a 2-carboxyl-1,5-dihydroxynaphthalene condensate, dimethacrylate of a 2-carboxyl-1,5-dihydroxynaphthalene condensate, monoacrylate of a 2-phenoxycarbonyl-1,5-dihydroxynaphthalene condensate, diacrylate of a 2-phenoxycarbonyl-1,5-dihydroxynaphthalene condensate, monomethacrylate of a 2-phenoxycarbonyl-1,5-dihydroxynaphthalene condensate, dimethacrylate of a 2-phenoxycarbonyl-1,5-dihydroxynaphthalene condensate, and the like.

[0073] Further, for example, monoacrylate of 1-hydroxy-2,6-dihydroxynaphthalene condensate, diacrylate of 1-hydroxy-2,6-dihydroxynaphthalene condensate, monomethacrylate of 1-hydroxy-2,6-dihydroxynaphthalene condensate, dimethacrylate of 1-hydroxy-2,6-dihydroxynaphthalene condensate, monoacrylate of 1-methyl-2,6-dihydroxynaphthalene condensate, diacrylate of 1-methyl-2,6-dihydroxynaphthalene condensate, monomethacrylate of 1-methyl-2,6-dihydroxynaphthalene condensate, dimethacrylate of 1-methyl-2,6-dihydroxynaphthalene condensate, 1-carboxyl-2,6-dihydr monoacrylate of a 1-carboxyl-2,6-dihydroxynaphthalene condensate, diacrylate of a 1-carboxyl-2,6-dihydroxynaphthalene condensate, monomethacrylate of a 1-carboxyl-2,6-dihydroxynaphthalene condensate, dimethacrylate of a 1-carboxyl-2,6-dihydroxynaphthalene condensate, monoacrylate of a 1-phenoxycarbonyl-2,6-dihydroxynaphthalene condensate, diacrylate of a 1-phenoxycarbonyl-2,6-dihydroxynaphthalene condensate, monomethacrylate of a 1-phenoxycarbonyl-2,6-dihydroxynaphthalene condensate, dimethacrylate of a 1-phenoxycarbonyl-2,6-dihydroxynaphthalene condensate, and the like.

[0074] Further, for example, monoacrylate of 1-hydroxy-2,7-dihydroxynaphthalene condensate, diacrylate of 1-hydroxy-2,7-dihydroxynaphthalene condensate, monomethacrylate of 1-hydroxy-2,7-dihydroxynaphthalene condensate, dimethacrylate of 1-hydroxy-2,7-dihydroxynaphthalene condensate, monoacrylate of 1-methyl-2,7-dihydroxynaphthalene condensate, diacrylate of 1-methyl-2,7-dihydroxynaphthalene condensate, monomethacrylate of 1-methyl-2,7-dihydroxynaphthalene condensate, dimethacrylate of 1-methyl-2,7-dihydroxynaphthalene condensate, 1-carboxyl-2,7-dihydroxynaphthalene condensate, 1-hydroxy ... monoacrylate of a 1-carboxyl-2,7-dihydroxynaphthalene condensate, diacrylate of a 1-carboxyl-2,7-dihydroxynaphthalene condensate, monomethacrylate of a 1-carboxyl-2,7-dihydroxynaphthalene condensate, dimethacrylate of a 1-carboxyl-2,7-dihydroxynaphthalene condensate, monoacrylate of a 1-phenoxycarbonyl-2,7-dihydroxynaphthalene condensate, diacrylate of a 1-phenoxycarbonyl-2,7-dihydroxynaphthalene condensate, monomethacrylate of a 1-phenoxycarbonyl-2,7-dihydroxynaphthalene condensate, dimethacrylate of a 1-phenoxycarbonyl-2,7-dihydroxynaphthalene condensate, and the like.

[0075] Among the specific examples given above, in terms of ease of production, diacrylate of a 1,6-dihydroxynaphthalene condensate, diacrylate of a 2,7-dihydroxynaphthalene condensate, diacrylate of a 1,4-dihydroxynaphthalene condensate, dimethacrylate of a 1,6-dihydroxynaphthalene condensate, dimethacrylate of a 2,7-dihydroxynaphthalene condensate, and dimethacrylate of a 1,4-dihydroxynaphthalene condensate are preferred, and diacrylate of a 1,4-dihydroxynaphthalene condensate and dimethacrylate of a 4-dihydroxynaphthalene condensate (compounds of general formula (3) in which the hydrogen atoms of the naphthalene ring are not substituted) are particularly preferred in terms of physical properties and ease of availability of raw materials.

[0076] In the general formulas (1) and (2), n represents an integer of 1 to 50, but may be a compound in which n is a specific integer, or may be a mixture of compounds in which n is a different integer. In terms of ease of production and compatibility, n is preferably 1 to 20.

[0077] (Manufacturing method) Next, the method for producing the naphthalene ether oligomer having a (meth)acrylic group at its terminal according to the present invention will be described.

[0078] The naphthalene ether oligomer having a (meth)acrylic group at its end, represented by the general formula (1) of the present invention, is produced by a two-step reaction of a condensation reaction of a dihydroxynaphthalene compound and an esterification reaction of a phenolic hydroxyl group, but the order of the reactions is not important, so that two production methods are possible: a method of condensation reaction of a dihydroxynaphthalene compound and esterification of the obtained naphthalene ether oligomer (hereinafter referred to as "condensation-esterification"), and a method of monoesterification of a dihydroxynaphthalene compound and co-condensation reaction of the obtained monoester compound and the dihydroxynaphthalene compound (hereinafter referred to as "esterification-condensation").

[0079] (Condensation - Esterification) First, the method of condensation reaction of a dihydroxynaphthalene compound and esterification of the obtained naphthalene ether oligomer ("condensation-esterification") will be described. The naphthalene ether oligomer having a (meth)acrylic group at its end and represented by general formula (1) of the present invention can be obtained by condensing a dihydroxynaphthalene compound represented by the following general formula (4) in the presence of a catalyst to form a naphthalene ether oligomer represented by the following general formula (5), and then esterifying it with the following general formula (6).

[0080] [ka]

[0081] In general formula (4), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0082] [ka]

[0083] In general formula (5), the hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0084] [ka]

[0085] In formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0086] [ka]

[0087] In the general formula (1), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2 represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0088] (Reaction 1: Condensation reaction of dihydroxynaphthalene compounds) First, a method for synthesizing a naphthalene ether oligomer using a dihydroxynaphthalene compound as a starting material will be described. The naphthalene ether oligomer represented by the following general formula (5), which is a precursor of the naphthalene ether oligomer having a (meth)acrylic group at its end according to the present invention, can be obtained by a condensation reaction in the presence of a catalyst using a dihydroxynaphthalene compound represented by the following general formula (4) as a starting material according to reaction formula-1.

[0089] [ka]

[0090] In Reaction Formula-1, the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0091] Specific examples of the dihydroxynaphthalene compound used as the raw material in the reaction include 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2-hydroxy-1,4-dihydroxynaphthalene, 2-methyl-1,4-dihydroxynaphthalene, 2-carboxyl-1,4-dihydroxynaphthalene, 2-phenoxycarbonyl-1,4-dihydroxynaphthalene, and the like. From the viewpoint of easy availability, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 1,4-dihydroxynaphthalene are preferred, and 1,4-dihydroxynaphthalene is particularly preferred in terms of both physical properties and supply stability of the raw material.

[0092] Since many of the dihydroxynaphthalene compounds are unstable to oxygen, the hydroxyl groups may be protected by known protecting groups before use. For example, the condensation reaction may be carried out in a state where the hydroxyl groups are protected by acetyl groups or the like.

[0093] Examples of the catalyst used in Reaction Scheme-1 include mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, iron trichloride, zinc dichloride), solid acid catalysts (manufactured by Futamura Chemical Co., Ltd.), Amberlyst (manufactured by Organo Corporation), Nafion (manufactured by DuPont; Nafion is a registered trademark of DuPont), tetraalkoxytitanium compounds (tetraisopropoxytitanium, tetra-n-butoxytitanium, tetramethoxytitanium), and organic tin compounds (dibutyltin dilaurate, dibutyltin oxide).

[0094] The amount of catalyst added is preferably 0.01% by weight or more and less than 50% by weight, more preferably 0.1% by weight or more and less than 20% by weight, based on the dihydroxynaphthalene compound represented by the general formula (4). If it is less than 0.01% by weight, the reaction is not completed, and if it is more than 50% by weight, side reactions occur, lowering the yield and purity, which is not preferable.

[0095] The reaction is carried out in a solvent or without a solvent. The solvent used may be of any type as long as it does not react with the catalyst used, and examples of the solvent that can be used include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, halogenated carbon solvents such as methylene chloride, ethylene dichloride, and chlorobenzene, and alcohol solvents such as methanol, ethanol, and 1-propanol.

[0096] The reaction temperature of the reaction is usually 20° C. or higher and 200° C. or lower, preferably 50° C. or higher and 150° C. or lower. If the reaction temperature is lower than 20° C., the reaction takes too long, and if the reaction temperature is higher than 200° C., impurities increase and the purity of the target compound decreases, both of which are undesirable.

[0097] The reaction time in this reaction varies depending on the reaction temperature, but is usually about 0.5 to 20 hours, more preferably 1 to 10 hours.

[0098] After the reaction is complete, unreacted raw materials, solvents, and catalysts are removed as necessary by washing, distillation under reduced pressure, filtration, or other procedures, either alone or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization is performed from a poor solvent such as alcohol or hexane as necessary. Alternatively, the product can be dried up as is to obtain crystals. If the product is liquid, it can be dried up as is and purified by distillation as necessary to obtain naphthalene ether oligomers.

[0099] (Second reaction: Esterification reaction of naphthalene ether oligomer) Next, a method for synthesizing a naphthalene ether oligomer having a (meth)acrylic group at its terminal using the naphthalene ether oligomer obtained in the first reaction as a raw material will be described. The naphthalene ether oligomer having a (meth)acrylic group at its terminal of the present invention, represented by the following general formula (1), can be obtained by esterification reaction of the naphthalene ether oligomer represented by the following general formula (5) as a starting material with the following general formula (6) according to reaction formula-2.

[0100] [ka]

[0101] In reaction scheme 2, A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group; A 2represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50. Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0102] In reaction formula-2, specific examples of the naphthalene ether oligomer used as the raw material include 1,6-dihydroxynaphthalene condensate, 2,7-dihydroxynaphthalene condensate, 1,4-dihydroxynaphthalene condensate, 1,5-dihydroxynaphthalene condensate, 2,3-dihydroxynaphthalene condensate, 1,2-dihydroxynaphthalene condensate, 1,3-dihydroxynaphthalene condensate, 1,7-dihydroxynaphthalene condensate, 2,6-dihydroxynaphthalene condensate, 2- Examples of the hydroxy-1,4-dihydroxynaphthalene condensate include hydroxy-1,4-dihydroxynaphthalene condensate, 2-methyl-1,4-dihydroxynaphthalene condensate, 2-carboxyl-1,4-dihydroxynaphthalene condensate, and 2-phenoxycarbonyl-1,4-dihydroxynaphthalene condensate. From the viewpoint of availability, 1,6-dihydroxynaphthalene condensate, 2,7-dihydroxynaphthalene condensate, and 1,4-dihydroxynaphthalene condensate are preferred, and 1,4-dihydroxynaphthalene condensate is particularly preferred.

[0103] In Reaction Scheme-2, specific examples of the compound represented by general formula (6) serving as a raw material for the esterification reaction include acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, and methacrylic acid iodide.

[0104] Among the specific examples given above, the chloro compounds are preferred in terms of availability and reactivity.

[0105] In reaction formula 2, the amount of the compound represented by formula (6) used is preferably 2.0 times by mol or more and less than 10.0 times by mol, more preferably 2.2 times by mol or more and less than 5.0 times by mol, based on the hydroxyl groups of the naphthalene ether oligomer. If it is less than 2.0 times by mol, the reaction does not go to completion, and if it is more than 10.0 times by mol, side reactions occur, lowering the yield and purity, which is not preferable.

[0106] Examples of the basic compound used in Reaction Scheme-2 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, and lutidine.

[0107] The amount of the basic compound added is preferably 2.0 times by mol or more and less than 10.0 times by mol, more preferably 2.2 times by mol or more and less than 8.0 times by mol, based on the amount of the naphthalene ether oligomer. If it is less than 2.0 times by mol, the reaction does not go to completion, and if it is more than 10.0 times by mol, side reactions occur, lowering the yield and purity, which is not preferable.

[0108] The reaction is carried out in a solvent or without a solvent. The solvent used may be of any type as long as it does not react with the raw material used, and examples of the solvent include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, halogenated carbon solvents such as methylene chloride, ethylene dichloride, and chlorobenzene, alcohol solvents such as methanol, ethanol, and 1-propanol, and water, and these solvents may be used in combination of two or more types.

[0109] When dissolving the naphthalene ether oligomer in an aqueous solution of an inorganic base and reacting it with the compound represented by general formula (6), it is effective to use a phase transfer catalyst. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide, benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride, trioctylbutylammonium chloride, and benzyldimethyloctadecylammonium chloride.

[0110] The amount of the phase transfer catalyst added is preferably 0.01 to less than 1.0 mole times, more preferably 0.03 to less than 0.5 mole times, based on the naphthalene ether oligomer. If it is less than 0.01 mole times, the reaction rate is slow, and if it is more than 1.0 mole times, the purity of the product is reduced, which is not preferable.

[0111] The reaction temperature of the reaction is usually 0° C. or higher and 100° C. or lower, preferably 10° C. or higher and 50° C. or lower. If the reaction temperature is lower than 0° C., the reaction takes too long, and if the reaction temperature is higher than 100° C., impurities increase and the purity of the target compound decreases, both of which are undesirable.

[0112] The reaction time in this reaction varies depending on the reaction temperature, but is usually about 0.5 to 20 hours, more preferably 1 to 10 hours.

[0113] After the reaction is complete, unreacted raw materials, solvents, and catalysts are removed as necessary by washing, distillation under reduced pressure, filtration, or other procedures, either alone or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization is performed from a poor solvent such as alcohol or hexane as necessary. Alternatively, the product can be dried up as is to obtain crystals. If the product is liquid, it can be dried up as is and purified by distillation as necessary to obtain naphthalene ether oligomers having terminal (meth)acrylic groups.

[0114] The naphthalene ether oligomer having a (meth)acrylic group at the end obtained by this reaction is a compound having a plurality of continuous naphthalene ether structures, but depending on the reaction conditions, etc., the number of naphthalene ether structures becomes a mixture having a certain distribution between 1 and 50. When used for the purpose of the present invention, there is no particular need to separate a compound having a specific number of naphthalene ether structures, and the mixture may be used as it is. It may contain some unreacted material. In addition, depending on the application, A 1 is a hydrogen atom and A is 2 It may also be a mixture of compounds in which the (meth)acrylic group is present.

[0115] (Esterification - Condensation) Next, the method of monoesterification of a dihydroxynaphthalene compound and co-condensation reaction of the obtained monoester compound and a dihydroxynaphthalene compound ("esterification-condensation") will be described. The naphthalene ether oligomer having a (meth)acrylic group at the end and represented by general formula (1) of the present invention can be obtained by reacting a dihydroxynaphthalene compound represented by the following general formula (4) with a compound represented by general formula (6) to obtain a monomethacrylate compound represented by general formula (10), which is then co-condensed with the dihydroxynaphthalene compound represented by general formula (4).

[0116] [ka]

[0117] In general formula (4), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0118] [ka]

[0119] In formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.

[0120] [ka]

[0121] In the general formula (10), A 2 represents either an acrylic group or a methacrylic group. The naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.

[0122] [ka]

[0123] In the general formula (1), A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group, and A 2 represents either an acrylic group or a methacrylic group. The naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0124] (First reaction: Monoesterification reaction of dihydroxynaphthalene compound) First, a method for synthesizing a monoester compound of a dihydroxynaphthalene compound using a dihydroxynaphthalene compound as a starting material will be described. The monoester compound of a dihydroxynaphthalene compound represented by the following general formula (10), which is a precursor of the naphthalene ether oligomer having a (meth)acrylic group at its end according to the present invention, can be obtained by esterification reaction of a dihydroxynaphthalene compound represented by the following general formula (4) as a starting material with a compound represented by the following general formula (6) according to reaction formula-3.

[0125] [ka]

[0126] In reaction formula-3, the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group. A 2 represents either an acrylic group or a methacrylic group.

[0127] In reaction formula-3, specific examples of the dihydroxynaphthalene compound used as the raw material include 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2-hydroxy-1,4-dihydroxynaphthalene, 2-methyl-1,4-dihydroxynaphthalene, 2-carboxyl-1,4-dihydroxynaphthalene, and 2-phenoxycarbonyl-1,4-dihydroxynaphthalene. From the viewpoint of availability, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 1,4-dihydroxynaphthalene are preferred, and 1,4-dihydroxynaphthalene is particularly preferred.

[0128] Since the dihydroxynaphthalene compound is unstable to oxygen, it may be used in a state in which the hydroxyl group is protected by a known protecting group.

[0129] In Reaction Scheme 3, specific examples of the compound represented by general formula (6) that serves as a raw material for the esterification reaction include acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, and methacrylic acid iodide.

[0130] Among the specific examples given above, the chloro compounds are preferred in terms of availability and reactivity.

[0131] In reaction formula 3, the amount of the compound represented by formula (6) used is preferably 1.0 molar or more and less than 5.0 molar times, more preferably 1.2 molar or more and less than 3.0 molar times, relative to the dihydroxynaphthalene compound. If it is less than 1.0 molar times, the reaction does not go to completion, and if it is 5.0 molar times or more, the amount of diester compound increases, lowering the yield and purity, which is not preferable.

[0132] Examples of the basic compound used in Reaction Scheme-3 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, and lutidine.

[0133] The amount of the basic compound added is preferably 1.0 molar or more and less than 5.0 molar times, more preferably 1.2 molar or more and less than 3.0 molar times, relative to the dihydroxynaphthalene compound. If it is less than 1.0 molar times, the reaction does not go to completion, and if it is 5.0 molar times or more, the amount of the diester compound increases, lowering the yield and purity, which is not preferable.

[0134] The reaction is carried out in a solvent or without a solvent. The solvent used may be of any type as long as it does not react with the raw material used, and examples of the solvent include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, halogenated carbon solvents such as methylene chloride, ethylene dichloride, and chlorobenzene, alcohol solvents such as methanol, ethanol, and 1-propanol, and water, and these solvents may be used in combination of two or more types.

[0135] The reaction temperature of the reaction is usually 0° C. or higher and 100° C. or lower, preferably 10° C. or higher and 50° C. or lower. If the reaction temperature is lower than 0° C., the reaction takes too long, and if the reaction temperature is higher than 100° C., impurities increase and the purity of the target compound decreases, both of which are undesirable.

[0136] After the reaction is complete, unreacted raw materials, solvents, and catalysts are removed as necessary by washing, distillation under reduced pressure, filtration, or other procedures, either alone or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization is performed from a poor solvent such as toluene or hexane as necessary. Alternatively, the product can be dried up as is to obtain crystals. If the product is liquid, it can be dried up as is and purified by distillation or other procedures as necessary to obtain a monoester compound of the dihydroxynaphthalene compound.

[0137] (Second reaction: co-condensation reaction of dihydroxynaphthalene monoester compound and dihydroxynaphthalene compound) Next, a method for synthesizing a naphthalene ether oligomer having a (meth)acrylic group at its terminal using the dihydroxynaphthalene monoester compound obtained in the first reaction as a starting material will be described. The naphthalene ether oligomer having a (meth)acrylic group at its terminal of the present invention, represented by the following general formula (1), can be obtained by co-condensation reaction of a dihydroxynaphthalene monoester compound represented by the following general formula (10) with a dihydroxynaphthalene compound represented by the following general formula (4) in the presence of a catalyst, according to reaction formula-4.

[0138] [ka]

[0139] In reaction scheme 4, A 1 represents a hydrogen atom, an acrylic group, or a methacrylic group, and A 2 represents either an acrylic group or a methacrylic group. The naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer from 1 to 50.

[0140] In reaction formula 4, specific examples of the dihydroxynaphthalene monoester compound used as the raw material include 1,6-dihydroxynaphthalene monoacrylate, 2,7-dihydroxynaphthalene monoacrylate, 1,4-dihydroxynaphthalene monoacrylate, 1,5-dihydroxynaphthalene monoacrylate, 2,3-dihydroxynaphthalene monoacrylate, 1,2-dihydroxynaphthalene monoacrylate, 1,3-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 2,6-dihydroxynaphthalene monoacrylate, ...1,7-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,7-dihydroxynaphthalene monoacrylate, 1,7-di hydroxynaphthalene monoacrylate, 2-hydroxy-1,4-dihydroxynaphthalene monoacrylate, 2-methyl-1,4-dihydroxynaphthalene monoacrylate, 2-carboxyl-1,4-dihydroxynaphthalene monoacrylate, 2-phenoxycarbonyl-1,4-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monomethacrylate, 2,7-dihydroxynaphthalene monomethacrylate, 1,4-dihydroxynaphthalene monomethacrylate, 1,5-dihydroxynaphthalene monomethacrylate acrylate, 2,3-dihydroxynaphthalene monomethacrylate, 1,2-dihydroxynaphthalene monomethacrylate, 1,3-dihydroxynaphthalene monomethacrylate, 1,7-dihydroxynaphthalene monomethacrylate, 2,6-dihydroxynaphthalene monomethacrylate, 2-hydroxy-1,4-dihydroxynaphthalene monomethacrylate, 2-methyl-1,4-dihydroxynaphthalene monomethacrylate, 2-carboxyl-1,4-dihydroxynaphthalene monomethacrylate, 2-phenoxycarbonyl-1,4 From the viewpoint of easy availability, 1,6-dihydroxynaphthalene monoacrylate, 1,6-dihydroxynaphthalene monomethacrylate, 2,7-dihydroxynaphthalene monoacrylate, 2,7-dihydroxynaphthalene monomethacrylate, 1,4-dihydroxynaphthalene monoacrylate, and 1,4-dihydroxynaphthalene monomethacrylate are preferred, and 1,4-dihydroxynaphthalene monoacrylate and 1,4-dihydroxynaphthalene monomethacrylate are particularly preferred.

[0141] In reaction formula-4, specific examples of the dihydroxynaphthalene compound serving as the other raw material include 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2-hydroxy-1,4-dihydroxynaphthalene, 2-methyl-1,4-dihydroxynaphthalene, 2-carboxyl-1,4-dihydroxynaphthalene, and 2-phenoxycarbonyl-1,4-dihydroxynaphthalene. From the viewpoint of availability, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 1,4-dihydroxynaphthalene are preferred, and 1,4-dihydroxynaphthalene is particularly preferred.

[0142] Since the dihydroxynaphthalene compound is unstable to oxygen, it may be used in a state in which the hydroxyl group is protected by a known protecting group.

[0143] Examples of the catalyst used in Reaction Scheme-4 include mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, iron trichloride, zinc dichloride), solid acid catalysts (manufactured by Futamura Chemical Co., Ltd.), Amberlyst (manufactured by Organo Corporation), Nafion (manufactured by DuPont; Nafion is a registered trademark of DuPont), tetraalkoxytitanium compounds (tetraisopropoxytitanium, tetra-n-butoxytitanium, tetramethoxytitanium), and organic tin compounds (dibutyltin dilaurate, dibutyltin oxide).

[0144] The amount of catalyst added is preferably 0.01% by weight or more and less than 50% by weight, more preferably 0.1% by weight or more and less than 20% by weight, based on the dihydroxynaphthalene monoester compound represented by the general formula (10). If it is less than 0.01% by weight, the reaction is not completed, and if it is more than 50% by weight, side reactions occur, resulting in a decrease in yield and purity, which is not preferable.

[0145] The reaction is carried out in a solvent or without a solvent. The solvent used may be of any type as long as it does not react with the catalyst used, and examples of the solvent that can be used include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, halogenated carbon solvents such as methylene chloride, ethylene dichloride, and chlorobenzene, and alcohol solvents such as methanol, ethanol, and 1-propanol.

[0146] The reaction temperature of the reaction is usually 20° C. or higher and 200° C. or lower, preferably 50° C. or higher and 150° C. or lower. If the reaction temperature is lower than 20° C., the reaction takes too long, and if the reaction temperature is higher than 200° C., impurities increase and the purity of the target compound decreases, both of which are undesirable.

[0147] The reaction time in this reaction varies depending on the reaction temperature, but is usually about 0.5 to 20 hours, more preferably 1 to 10 hours.

[0148] After the reaction is complete, unreacted raw materials, solvents, and catalysts are removed as necessary by washing, distillation under reduced pressure, filtration, or other procedures, either alone or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization is performed from a poor solvent such as alcohol or hexane as necessary. Alternatively, the product can be dried up as is to obtain crystals. If the product is liquid, it can be dried up as is and purified by distillation as necessary to obtain naphthalene ether oligomers.

[0149] The naphthalene ether oligomer having a (meth)acrylic group at the end obtained by this reaction is a compound having a plurality of continuous naphthalene ether structures, but depending on the reaction conditions, etc., the number of naphthalene ether structures becomes a mixture having a certain distribution between 1 and 50. When used for the purpose of the present invention, there is no particular need to separate a compound having a specific number of naphthalene ether structures, and the mixture may be used as it is. It may contain some unreacted material. In addition, depending on the application, A 1 is a hydrogen atom and A is 2 It may also be a mixture of compounds in which the is a (meth)acrylic group.

[0150] (Polymerizable composition) The polymerizable composition of the present invention is characterized by containing the above-mentioned naphthalene ether oligomer having a (meth)acrylic group at its terminal as a component.

[0151] The polymerizable composition of the present invention may contain a compound having a polymerizable double bond group other than the naphthalene ether oligomer as necessary. The compound having a polymerizable double bond group other than the naphthalene ether oligomer that may be contained is not particularly limited, and may be a conventionally known radical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, or (meth)acrylic acid ester. These radical polymerizable compounds may be one type or a mixture of two or more types.

[0152] Examples of the (meth)acrylic acid ester include monofunctional acrylic monomers having one (meth)acryloyl group in the molecule, and polyfunctional acrylic monomers having two or more (meth)acryloyl groups in the molecule.

[0153] Examples of monofunctional acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, (meth)acrylates of alkylene oxide modified phenol derivatives, 2- Examples of the acrylates include ethylhexyl carbitol (meth)acrylate, ethoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, N-(meth)acryloyloxyethyl hexahydrophthalimide, ω-carboxypolycaprolactone (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, and (meth)acrylic acid dimer.

[0154] Examples of polyfunctional acrylic monomers include neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol hydroxypivalic acid di(meth)acrylate, caprolactone-modified neopentyl glycol hydroxypivalic acid di(meth)acrylate, alkylene oxide-modified neopentyl glycol di(meth)acrylate, alkylene oxide-modified 1,6-hexanediol di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, Examples of the di(meth)acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, aliphatic modified dipentaerythritol penta(meth)acrylate having 2 to 5 carbon atoms, aliphatic modified dipentaerythritol tetra(meth)acrylate having 2 to 5 carbon atoms, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris[(meth)acryloxyethyl]isocyanurate, caprolactone modified tris[(meth)acryloxyethyl]isocyanurate, and ditrimethylolpropane tetra(meth)acrylate.

[0155] Examples of oligomers having one or more (meth)acryloyl groups in the molecule include epoxy (meth)acrylates, polyester (meth)acrylates, and urethane (meth)acrylates.

[0156] Epoxy (meth)acrylate is obtained by the reaction of epoxy resin with (meth)acrylic acid. Examples of epoxy resin include bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resin. Examples of bisphenol A type epoxy resin include Epicoat 827 (trade name, the same applies below), Epicoat 828, Epicoat 1001, Epicoat 1004, etc., manufactured by Japan Epoxy Resins Co., Ltd., and examples of bisphenol F type epoxy resin include Epicoat 806, Epicoat 4004P, etc. Furthermore, examples of novolac type epoxy resin include Epicoat 152, Epicoat 154, etc.

[0157] Polyester (meth)acrylates are obtained by the reaction of polyester polyols with (meth)acrylic acid. Polyester polyols are obtained by the reaction of polyhydric alcohols with polybasic acids. Examples of polyhydric alcohols include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol, and bis-[hydroxymethyl]-cyclohexane. Examples of polybasic acids include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.

[0158] The urethane (meth)acrylate may be obtained by a three-way reaction of a polyol, an organic polyisocyanate, and a hydroxy (meth)acrylate compound, or may be obtained by a two-way reaction of an organic polyisocyanate and a hydroxy (meth)acrylate compound without using a polyol. Examples of polyols include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by the reaction of the polyhydric alcohol and the polybasic acid, caprolactone polyols obtained by the reaction of the polyhydric alcohol, the polybasic acid, and ε-caprolactone, and polycarbonate polyols (e.g., polycarbonate polyols obtained by the reaction of 1,6-hexanediol and diphenyl carbonate). Examples of organic polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate. The product obtained by the reaction of three components or the product obtained by the reaction of two components may be used alone or in combination.

[0159] The radically polymerizable composition of the present invention may further contain a cationic polymerizable compound or an anionic polymerizable compound in combination depending on the conditions.

[0160] Examples of the cationic polymerizable compound that may be used in combination include epoxy compounds, oxetane compounds, vinyl ethers, and the like. Examples of epoxy compounds that are common include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, product name: Celloxide 2021P, Celloxide is a registered trademark of Daicel Corporation), (3,3',4,4'-diepoxy)bicyclohexyl (manufactured by Daicel Corporation, product name: Celloxide 8010), and bis(3,4-epoxycyclohexyl)adipate. Examples of epoxy-modified silicones include UV-9300 manufactured by Toshiba GE Silicones. Examples of aromatic glycidyl compounds include 2,2'-bis(4-glycidyloxyphenyl)propane, and the like. Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (manufactured by Toa Gosei Co., Ltd., trade name: OXT-101), 2-ethylhexyloxetane (manufactured by Toa Gosei Co., Ltd., trade name: OXT-212), xylylene bisoxetane (manufactured by Toa Gosei Co., Ltd., trade name: OXT-121), and 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (manufactured by Toa Gosei Co., Ltd., trade name: OXT-221). Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether. These cationically polymerizable compounds may be used alone or in mixtures of two or more kinds.

[0161] [Polymerization initiator] A polymerization initiator can be added to the polymerizable composition of the present invention as necessary. The polymerizable compound may start polymerization without a polymerization initiator at high temperatures, and a polymerization initiator is not necessarily required in the present invention. However, it is preferable to use a polymerization initiator because the polymerization reaction can be started smoothly. As the polymerization initiator, a radical polymerization initiator is used. As the radical polymerization initiator, there is no particular limitation as long as it generates radicals active against the polymerizable compound by being given energy. In general, a commercially available radical polymerization initiator can be used. Usually, for convenience, one that is used by giving thermal energy is called a thermal radical polymerization initiator, and one that is used by giving light energy is called a photoradical polymerization initiator. In the present invention, both a thermal radical polymerization initiator and a photoradical polymerization initiator can be used. Depending on the conditions, a cationic polymerization initiator and an anionic polymerization initiator may be used in combination.

[0162] Examples of the thermal radical polymerization initiator include organic peroxides and azo compounds. Specific examples of the organic peroxides include peroxyesters such as t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxyisopropyl carbonates, peroxyketals such as 1,1-bis(t-hexylperoxy)-3,5,5-trimethylcyclohexane, and diacyl peroxides such as lauroyl peroxide. Specific examples of the azo compounds include azonitriles such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyro)nitrile, and 1,1'-azobis(cyclohexane-1-carbonitrile).

[0163] In addition, in order to use a thermal radical polymerization initiator at a relatively low temperature, a so-called redox initiator system can be used in which a reducing agent (radical polymerization accelerator) such as a transition metal, amine, or ascorbic acid is combined with an oxidizing agent initiator such as a peroxide or hydroperoxide. In this case, for example, a mixture of an oxidizing agent initiator and a reducing agent may be used as a thermal polymerization initiator, or an oxidizing agent initiator may be added as a thermal polymerization initiator and then a reducing agent may be added together with or separately from a polymerization control agent, or a reducing agent may be added as a thermal polymerization initiator and then an oxidizing agent initiator may be added together with or separately from a polymerization control agent. However, even within the temperature range used for polymerization, if an oxidizing agent initiator and a reducing agent are added, the polymerization reaction may runaway in some cases, so it is preferable to add an oxidizing agent initiator as a thermal polymerization initiator and then a reducing agent together with or separately from a polymerization control agent.

[0164] Examples of the photoradical polymerization initiator that can be used include onium salts, benzyl methyl ketals, α-hydroxyalkylphenones, oxime esters, α-aminoacetophenones, acylphosphine oxides, biimidazoles, triazines, and thioxanthones.

[0165] As the onium salt, an iodonium salt or a sulfonium salt is usually used. As the iodonium salt, 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentamethoxyphenylborate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate, etc. can be mentioned, for example, Irgacure 250 manufactured by BASF (Irgacure is a registered trademark of BASF), Roadsil 2074 manufactured by Rhodia (Roadsil is a registered trademark of Rhodia), IK-1 manufactured by San-Apro, etc. can be used. On the other hand, examples of sulfonium salts include S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexamethoxyphosphate, triphenylsulfonium hexamethoxyphosphate, etc., and examples of such products that can be used include CPI-100P, CPI101P, and CPI-200K manufactured by Daicel Corporation, Irgacure 270 manufactured by BASF, and UVI6992 manufactured by Dow Chemical Co. These photopolymerization initiators may be used alone or in combination of two or more kinds.

[0166] Examples of benzyl methyl ketal polymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name "Irgacure 651" manufactured by BASF Co., Ltd.), and examples of α-hydroxyalkylphenone polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocur 1173" manufactured by BASF Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 1173" manufactured by BASF Co., Ltd.), and ... and α-hydroxyalkylphenone polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocur 1173" manufactured by BASF Co., Ltd.), and 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 1173" manufactured by BASF Co., Ltd.). Examples of such hydroxyl groups include 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name "Irgacure 2959" manufactured by BASF), and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-1-one (trade name "Irgacure 127" manufactured by BASF).

[0167] In particular, the benzyl methyl ketal polymerization initiator 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name "Irgacure 651", manufactured by BASF), the α-hydroxyalkylphenone polymerization initiator 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocur 1173", manufactured by BASF), and 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 184", manufactured by BASF) are preferred.

[0168] Also usable are acetophenone-based polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, and 2-isobutoxy-2-phenylacetophenone, benzyl-based polymerization initiators such as benzyl and 4,4'-dimethoxybenzyl, and anthraquinone-based polymerization initiators such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone, 2-(phenylthio)anthraquinone, and 2-(hydroxyethylthio)anthraquinone.

[0169] Examples of the biimidazole polymerization initiator include 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0170] Examples of the α-aminoketone polymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (trade name "Irgacure 907" manufactured by BASF), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (trade name "Irgacure 369" manufactured by BASF), and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-4-yl-phenyl)butan-1-one (trade name "Irgacure 379" manufactured by BASF).

[0171] Examples of acylphosphine oxide polymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name "Irgacure TPO" manufactured by BASF), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name "Irgacure 819" manufactured by BASF), and the like.

[0172] Examples of the oxime ester polymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime) (trade name "Irgacure OXE01" manufactured by B.A.S.F. Co., Ltd.), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (trade name "Irgacure OXE02" manufactured by B.A.S.F. Co., Ltd.), [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name "Irgacure OXE03" manufactured by B.A.S.F. Co., Ltd.), and the like.

[0173] Examples of the triazine-based polymerization initiator include 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0174] Examples of the thioxanthone-based polymerization initiator include 2,4-diethylthioxanthone and 2-isopropylthioxanthone.

[0175] The onium salt-based polymerization initiator, benzyl methyl ketal-based polymerization initiator, α-hydroxyalkylphenone-based polymerization initiator, oxime ester-based photopolymerization initiator, α-aminoacetophenone-based photopolymerization initiator, acylphosphine oxide-based photopolymerization initiator, biimidazole-based polymerization initiator, triazine-based polymerization initiator, and thioxanthone-based polymerization initiator that can be used in the present invention can each be used alone, or two or more types can be used in combination depending on the application, etc.

[0176] When the polymerizable composition of the present invention contains a photoradical polymerization initiator, the composition may contain a photopolymerization sensitizer. Examples of the photopolymerization sensitizer include acridone derivatives such as N-methylacridone and N-butylacridone, anthracene derivatives such as anthracene, 9,10-dialkoxyanthracene and 9-alkoxyanthracene, and thioxanthone derivatives such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

[0177] Furthermore, the polymerizable composition of the present invention may contain a binder polymer such as an acrylic resin, a styrene resin, an epoxy resin, etc. Also, it may contain an alkali-soluble resin.

[0178] Furthermore, the composition may contain a pigment and / or a dye. When a pigment is contained, a dispersant for the pigment may be contained.

[0179] As the pigment, both inorganic and organic pigments can be used. As the inorganic pigment, carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, and titanium oxide can be used. As the organic pigment, azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and polycyclic pigments such as quinophthalone pigments, dye chelates (e.g., basic dye chelates, acid dye chelates, etc.), dye lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments can be used. These pigments may be used alone or in combination of two or more.

[0180] The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. The dyes may be used alone or in combination of two or more. A pigment and a dye may also be used in combination.

[0181] The dispersant for dispersing the pigment is not particularly limited, and examples thereof include pigment dispersions such as polymeric dispersants, etc. Specific examples thereof include those containing one or more of polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, sulfur-containing polymers, fluorine-containing polymers, and epoxy resins as the main component.

[0182] In addition to the above, the polymerizable composition of the present invention may contain various resin additives such as a diluent, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, a flame retardant, a surface modifier, a penetration promoter, a moisturizing agent, a fixing agent, an antifungal agent, a preservative, an antioxidant, an ultraviolet absorber, a chelating agent, a pH adjuster, a stabilizer, a lubricant, and a plasticizer, as long as the effects of the present invention are not impaired.

[0183] (Polymerization method) For example, when the polymerizable composition of the present invention is thermally polymerized, it can be polymerized by a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a melt kneading method, etc. In the bulk polymerization method, the solution polymerization method, the suspension polymerization method, and the emulsion polymerization method, a normal batch polymerization reactor or a continuous polymerization reactor can be used. On the other hand, in the melt kneading method, a single screw extruder, a twin screw extruder, a pressure kneader, a Banbury kneader, etc. can be used.

[0184] In the solution polymerization method, the suspension polymerization method, and the emulsion polymerization method, a solvent is used. As the solvent used in the solution polymerization method, one having good solubility with the radical polymerizable compound and the radical polymerization initiator used is preferable. For example, toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, N,N-dimethylacetamide, acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, etc. can be mentioned.

[0185] The polymerizable composition of the present invention may contain a surfactant. The surfactant may be any known one and is not particularly limited. Examples of the surfactant include anionic surfactants such as alkyl sulfate ester salts, alkylaryl sulfonates, sulfosuccinate ester salts, fatty acid salts, polyoxyethylene alkylaryl sulfate ester salts, and polyoxyethylene alkyl sulfate ester salts (here, "salts" include potassium salts, sodium salts, and ammonium salts), and hydrophilic nonionic surfactants such as sorbitan esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene alkyl esters. Any of these may be used alone, or two or more may be used in combination.

[0186] In emulsion polymerization, an emulsifier may be used, such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium sulfosuccinate ester, Abex anionic surfactant (Alcolac), alkylphenoxypolyethoxyethanol (HLB=13-19), ethoxy fatty acid alcohol (HLB=13-19), block copolymer of ethylene oxide and propylene oxide, etc.

[0187] In addition, a water-soluble protective colloid may be used in the emulsion polymerization. Representative examples of such protective colloids include hydroxyethyl cellulose, poly(ethylene oxide-propylene oxide) polyvinyl alcohol, polyethylene oxazoline, polyvinylpyrrolidone (PVP), and copolymers of the above compounds. The protective colloid is usually used at a ratio of 0.1 to 1.5% by weight based on the monomer.

[0188] In addition, in suspension polymerization, a dispersion stabilizer can also be used. Examples of the dispersion stabilizer include water-soluble or oil-soluble partially saponified polyvinyl alcohol; water-soluble cellulose such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; water-soluble polymers such as acrylic acid polymers, methyl vinyl ether-maleic anhydride copolymers, styrene-maleic anhydride copolymers, and gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan monostearate, glycerin monostearate, and ethylene oxide propylene oxide block copolymers; water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, and sodium laurate; sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; phosphates such as calcium phosphate; metal oxides such as aluminum oxide and titanium oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; and other inorganic compounds, which can be used alone or in combination of two or more.

[0189] In addition, during polymerization, 0 to 50% by weight (relative to monomer) of hydrophilic polymers such as starch, cellulose, starch or cellulose derivatives, polyvinyl alcohol, polyacrylic acid (salts), crosslinked polyacrylic acid (salts), etc., and 0 to 10% by weight of various foaming agents such as (hydrogen) carbonates, carbon dioxide, azo compounds, inert organic solvents, etc.; chelating agents; inorganic fine particles such as kaolin, talc, silicon dioxide, etc.; polyaluminum chloride, aluminum sulfate, magnesium sulfate, etc. may be added to the reaction system.

[0190] By using the melt kneading method, a polymer can be synthesized by heating, melting, and kneading the polymer, thereby cutting the polymer main chain, extracting hydrogen, etc. For melt kneading, a thermoplastic polymer is usually used, for example, polyolefin such as polyethylene and polypropylene, acrylic resin such as polymethyl methacrylate, styrene resin such as polyvinyl alcohol, polystyrene, ABS resin, AS resin, vinyl chloride resin, vinylidene chloride resin, etc. In addition, condensation resin such as polyester and polyamide, engineering plastic such as polycarbonate, polyphenylene ether, polyacetal, etc., thermoplastic elastomer, etc. can also be used.

[0191] The melt-kneading temperature varies depending on the resin used, but is usually from 100 to 400° C. It is also possible to incorporate a monomer having a polymerizable double bond and a radical polymerization initiator into the resin and then melt-knead the resin.

[0192] When the polymerizable composition is irradiated with light to polymerize and photocure, the photopolymerizable composition can be molded into a film and photocure, or can be molded into a block and photocure. The composition can also be polymerized in a state where droplets are applied to a substrate as a UV ink. When the composition is molded into a film and photocure, the liquid photopolymerizable composition is applied to a substrate such as a polyester film using a bar coater or the like to a thickness of 5 to 300 microns. On the other hand, the composition can also be applied to a thinner or thicker thickness by spin coating or screen printing.

[0193] The coating film made of the polymerizable composition thus prepared is irradiated with ultraviolet light having a wavelength range of 300 nm to 500 nm at 1 to 1000 mW / cm. 2A photocured product can be obtained by irradiating light with an intensity of about 100 nm. Examples of light sources that can be used include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, gallium-doped lamps, black lights, 405 nm UV LEDs, 395 nm UV LEDs, 385 nm UV LEDs, 365 nm UV LEDs, blue LEDs, white LEDs, Fusion's D bulbs, V bulbs, etc. Natural light such as sunlight can also be used.

[0194] (Pyrolysis temperature measurement method) The thermal decomposition temperature of the resin composition was determined by the temperature at which the weight of the resin composition decreased by 5% at a heating rate of 10°C / min. Specifically, the 5% weight loss temperature was determined for a 10 mg powdered resin composition sample in a Shimadzu differential thermal and thermogravimetric simultaneous analyzer (DTA-50) in a nitrogen atmosphere (nitrogen flow rate: 100 ml / min) at a heating rate of 10°C / min. EXAMPLES

[0195] The present invention will be described in detail below with reference to examples, which are presented for illustrative purposes. That is, the following examples are not intended to be exhaustive or to limit the present invention to the exact form described. Thus, the present invention is not limited to the following described examples, unless it exceeds the spirit of the present invention. Also, all parts and percentages are by weight, unless otherwise specified.

[0196] The compounds of the present invention were identified using the following instruments. Infrared (IR) spectrophotometer: PerkinElmer, FT-IR (Spectrum Two) Nuclear magnetic resonance apparatus (NMR): Manufactured by JEOL Ltd., model ECS-400 Average molecular weight (GPC): JASCO Corporation, 2000 series

[0197] (Synthesis Example 1) Synthesis of 1,4-dihydroxynaphthalene condensation product In a 150 ml four-neck flask equipped with a stirrer and a thermometer, 20.0 g (125 mmol) of 1,4-dihydroxy, 30 g of toluene as a solvent, and 3.0 g (31 mmol) of methanesulfonic acid as a catalyst were added under a nitrogen atmosphere and stirred at 100 to 110°C for 1 hour. After cooling to room temperature, hexane was added and dispersed, and the solid-liquid separation was performed by suction filtration. The wet cake was washed with ion-exchanged water and then dried to obtain a gray solid with a yield of 15.6 g.

[0198] (1)IR (cm -1 ):3342, 1674, 1633, 1594, 1514, 1457, 1378, 1258, 1220, 1150, 1067, 976, 917, 826, 760, 691, 666, 549, 463. (2) 1 H-NMR (400MHz, DMSO-d6): δ=4.291(bs), 6.558-8.191(m), 10.125(bs). (3) Number average molecular weight: Mn=320

[0199] (Synthesis Example 1) Synthesis of 1,4-dihydroxynaphthalene condensate dimethacrylate In a 150 ml four-neck flask equipped with a stirrer and a thermometer, 5.0 g (15.6 mmol) of 1,4-dihydroxynaphthalene condensate, 10 g of toluene, 27.8 g (70 mmol) of 10% NaOH aqueous solution, 0.8 g (1.2 mmol) of 50% tetrabutylammonium bromide aqueous solution, and 5 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO) were added under a nitrogen atmosphere and stirred. At a reaction temperature of 15 to 20 ° C, a solution of 4.9 g (49.6 mmol) of methacryloyl chloride in 7.5 g of toluene was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred for another 1 hour, and the insoluble matter precipitated during the reaction was filtered off. The filtrate was washed with ion-exchanged water, and the toluene layer was concentrated to obtain a brown resin with a yield of 6.3 g.

[0200] (1)IR (cm -1):3069, 2926, 1734, 1675, 1635, 1598, 1508, 1457, 1424, 1378, 1313, 1291, 1258, 1218, 1112, 1075, 1040, 1011, 943, 875, 830, 806, 759, 730, 695, 674, 644, 586, 551, 493, 465. (2) 1 H-NMR (400MHz, DMSO-d6): δ=2.095(s), 5.996(s), 6.441(s), 7.144-8.242(m). (3) Number average molecular weight: Mn=440

[0201] (Polymerization Example 1) Homopolymerization 1 g of the 1,4-dihydroxynaphthalene condensate dimethacrylate obtained in Synthesis Example 1, 80 mg of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator, and 9 g of toluene as a solvent were mixed at room temperature and stirred at 60° C. for 6 hours and at 80° C. for 2 hours, resulting in gelation. After cooling, the toluene was concentrated and distilled off, and the obtained ochre solid was dispersed and washed with methanol, filtered, and dried to obtain 0.7 g of an ochre solid.

[0202] Toluene, acetone, and dimethylformamide, which are good solvents for 1,4-dihydroxynaphthalene condensate dimethacrylate, were added to the obtained polymer, but it did not dissolve at all. Therefore, it was confirmed that the polymer was 1,4-dihydroxynaphthalene condensate dimethacrylate.

[0203] (Polymerization Example 2) Copolymerization 1 g of the 1,4-dihydroxynaphthalene condensate dimethacrylate obtained in Synthesis Example 1, 0.5 g of methyl methacrylate, 80 mg of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator, and 9 g of toluene as a solvent were mixed at room temperature and stirred at 80° C. for 1 hour, resulting in gelation. After cooling, the toluene was concentrated and distilled off, and the obtained ochre solid was dispersed and washed with methanol, filtered, and dried to obtain 1.3 g of an ochre solid.

[0204] Toluene, acetone, and dimethylformamide, which are good solvents for 1,4-dihydroxynaphthalene condensate dimethacrylate, were added to the obtained polymer, but it did not dissolve at all. Therefore, it was confirmed that the polymer was a copolymer of 1,4-dihydroxynaphthalene condensate dimethacrylate and methyl methacrylate.

[0205] (Evaluation Example 1) 10 mg of the 1,4-dihydroxynaphthalene condensate dimethacrylate obtained in Synthesis Example 1, 1.0 g (10 mmol) of methyl methacrylate as a polymerizable compound, and 0.32 g (2.0 mmol) of azobisisobutyronitrile as a thermal polymerization initiator were mixed with 2 g of N-methylpyrrolidone, and the mixture was purged with nitrogen for 10 minutes, and then stirred at 80°C for 8 hours. The solution in the test tube was cooled to room temperature and poured into water to cause reprecipitation. The precipitate was filtered and dried under reduced pressure at 80°C for 4 hours to obtain a resin composition with the yield shown in Table 1. The 5% weight loss temperature was determined using the above-mentioned "thermal decomposition temperature measurement method," and is shown in Table 1.

[0206] (Evaluation Example 2) The same procedure as in Example 1 was carried out except that the amount of 1,4-dihydroxynaphthalene condensate dimethacrylate was changed to 100 mg. The results are shown in Table 1.

[0207] Comparative Example 1 1.0 g (10 mmol) of methyl methacrylate as a polymerizable compound and 0.32 g (2.0 mmol) of azobisisobutyronitrile as a thermal polymerization initiator were mixed with 2 g of N-methylpyrrolidone, and the mixture was purged with nitrogen for 10 minutes, and then stirred at 80°C for 8 hours. The solution in the test tube was cooled to room temperature and poured into water to cause reprecipitation. The precipitate was filtered and dried under reduced pressure at 80°C for 4 hours to obtain a resin composition with the yield shown in Table 1. The 5% weight loss temperature was determined using the above-mentioned "thermal decomposition temperature measurement method," and is shown in Table 1.

[0208] [Table 1]

[0209] From the polymerization examples, it is understood that the naphthalene ether oligomer having a (meth)acrylic group at the end of the present invention can be polymerized by radical polymerization alone and can also be copolymerized with a compound having a polymerizable double bond such as methyl methacrylate. In addition, in the evaluation examples of the copolymer, the 5% weight loss temperature increases with an increase in the content of the naphthalene ether oligomer having a (meth)acrylic group, which shows that the naphthalene ether oligomer having a (meth)acrylic group improves the heat resistance of the copolymer. [Industrial Applicability]

[0210] The naphthalene ether oligomer having a (meth)acrylic group at its end as shown in the present invention has high heat resistance due to the presence of multiple continuous naphthalene ether structures, and can be easily polymerized alone or copolymerized with other compounds having polymerizable double bonds due to the presence of (meth)acrylic groups at its end, making it useful as a heat-resistant polymer raw material, particularly as a resin raw material for 5G materials. In addition, the raw material is easily available, and the manufacturing process is simple, making it inexpensive to manufacture, making it an extremely useful compound industrially.

Claims

1. A naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (2): 【Chemistry 1】 (In the general formula (2), A １ represents a hydrogen atom, an acryl group or a methacryl group; A ２ represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50.

2. A naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (3): 【Chemistry 2】 (In the general formula (3), R is a hydrogen atom or a methyl group, the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom; and n is an integer from 1 to 50.)

3. A method for producing a naphthalene ether oligomer having a (meth)acrylic group at its terminal, represented by the following general formula (2), which is characterized by producing a naphthalene ether oligomer represented by the following general formula (9) by a condensation reaction of a 1,4-dihydroxynaphthalene compound represented by the following general formula (8), and reacting the resulting naphthalene ether oligomer with a compound represented by the following general formula (6). 【Chemistry 3】 (In general formula (8), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.) 【Chemistry 4】 (In general formula (9), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom; and n is an integer from 1 to 50.) 【Chemistry 5】 (In general formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.) 【Chemistry 6】 (In the general formula (2), A １ represents a hydrogen atom, an acryl group or a methacryl group; A ２ represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50.

4. A method for producing a naphthalene ether oligomer having a (meth)acrylic group at its end, represented by the following general formula (1), characterized in that a dihydroxynaphthalene compound represented by the following general formula (4) is reacted with a compound represented by general formula (6) to obtain a monomethacrylate compound represented by general formula (10), and the monomethacrylate compound is further co-condensed with the dihydroxynaphthalene compound represented by general formula (4). 【Chemistry 7】 (In the general formula (4), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.) 【Chemistry 8】 (In general formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.) 【Chemistry 9】 (In the general formula (10), A ２ represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50. 【Chemistry 10】 (In the general formula (1), A １ represents a hydrogen atom, an acryl group or a methacryl group; A ２ represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50.

5. A method for producing a naphthalene ether oligomer having a (meth)acrylic group at its end, represented by the following general formula (2), characterized in that a 1,4-dihydroxynaphthalene compound represented by the following general formula (8) is reacted with a compound represented by the general formula (6) to obtain a monomethacrylate compound represented by the general formula (11), which is then co-condensed with the dihydroxynaphthalene compound represented by the general formula (8): 【Chemistry 11】 (In general formula (8), the naphthalene ring may be substituted with hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom.) 【Chemistry 12】 (In general formula (6), Z represents a chlorine atom, a bromine atom, or an iodine atom, and R represents a hydrogen atom or a methyl group.) 【Chemistry 13】 (In the general formula (11), A ２ represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50. 【Chemistry 14】 (In the general formula (2), A １ represents a hydrogen atom, an acryl group or a methacryl group; A ２ represents an acrylic group or a methacrylic group. The hydrogen atoms of the naphthalene ring may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 5 to 15 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 5 to 15 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a monoarylamino group having 5 to 15 carbon atoms, a dialkylamino group having 1 to 10 carbon atoms, a diarylamino group having 5 to 15 carbon atoms, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 5 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 5 to 15 carbon atoms, or a halogen atom. n is an integer of 1 to 50.

6. A polymerizable composition comprising the naphthalene ether oligomer according to claim 1 or 2 as a component.

7. A polymerizable composition comprising the naphthalene ether oligomer according to claim 1 or 2 and a compound having a polymerizable double bond group other than the naphthalene ether oligomer according to claim 1 or 2.

8. A polymerization method, comprising polymerizing the polymerizable composition according to claim 6 or 7 by heating or irradiating with light.

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