Polymer, curable resin composition, and uses thereof

Abstract

To provide a curable resin composition that has high transparency and high adhesion to a substrate, so that it can be used suitably as an adhesive in the production of optical components.SOLUTION: A polymer contains a crosslinked alicyclic structural unit derived from norbornene or the like, and a structural unit represented by formula (1). In formula (1), R11 is a group having a urethane bond and a terminal-reactive unsaturated double bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer, a curable resin composition containing the polymer, a cured product obtained by curing the curable resin composition, and an optical component including the cured product as an adhesive layer. [Background technology]

[0002] In recent years, with the demand for lighter weight, smaller size, and higher density, optically transparent resins are increasingly being used to replace inorganic glass in the fields of optical components and display element components such as liquid crystal displays. As optical components are increasingly being replaced with resins, further improvements are being required in the adhesives used to manufacture optical components, such as in terms of transparency, adhesion, and adhesion.

[0003] For example, Patent Document 1 describes that a resin composition containing an organosilane compound and a silyl group-containing cyclic olefin polymer can be used as a transparent material and an adhesive for optical materials. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2002-146145 Summary of the Invention [Problem to be solved by the invention]

[0005] However, as a result of investigations by the present inventors, it was found that there is room for improvement in terms of transparency and adhesiveness in the resin composition described in Patent Document 1. The present invention provides an adhesive composition that is excellent in transparency and adhesiveness and can be used in the production of optical components. [Means for solving the problem]

[0006] According to the present invention, An adhesive composition comprising a curable resin composition, The curable resin composition comprises A polymer containing a structural unit represented by formula (A) and a structural unit represented by formula (1), a radical polymerizable monomer, [ka] In formula (A), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2, [ka] In formula (1), R 11 is a group containing a urethane bond and a terminal reactive unsaturated double bond, An adhesive composition is provided. The present invention also provides a cured product of the above adhesive composition. The present invention also provides an article comprising the above-mentioned cured product. Further, according to the present invention, A structural unit represented by formula (A), A structural unit represented by formula (1), The structural unit represented by formula (MA) Rank and A polymer comprising: [ka] In formula (A), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a1 is 0, 1 or 2, [ka] In formula (1), R 11 is a group containing a urethane bond and a terminal reactive unsaturated double bond, [ka] Po Rimmer is provided. Further, according to the present invention, A structural unit represented by formula (A), A polymer comprising a structural unit represented by formula (1-2): [ka] In formula (A), R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, 1 is 0, 1 or 2, [ka] In formula (1-2), Q is a divalent organic group, and Z is a group having a (meth)acryloyl group represented by formula (2a): [ka] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group.

[0007] The present invention also provides a curable resin composition comprising the above polymer and a radically polymerizable monomer.

[0008] The present invention also provides a cured product obtained by curing the above curable resin composition.

[0009] Furthermore, the present invention provides an article comprising the above-mentioned cured product. [Effects of the Invention]

[0010] According to the present invention, there is provided a curable resin composition which has high transparency and excellent adhesion to substrates, and is therefore suitable for use as an adhesive in the production of optical components. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described. In this specification, the expression "a to b" in the description of a numerical range means not less than a but not more than b, unless otherwise specified. For example, "1 to 5% by mass" means "not less than 1% by mass but not more than 5% by mass."

[0012] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both groups having no substituents and groups having a substituent. For example, the term "alkyl group" encompasses not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups).

[0013] In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0014] In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" used herein represents a concept that encompasses both an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0015] [Polymer P] The polymer of this embodiment (hereinafter referred to as "polymer P") contains a structural unit represented by formula (A) and a structural unit represented by formula (1).

[0016] [ka]

[0017] In formula (A), R 1 , R 2 , R 3 and R 4are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0018] [ka]

[0019] In formula (1), R 11 is a group containing a urethane bond and a terminal reactive unsaturated double bond.

[0020] The polymer P of this embodiment has a structural unit represented by formula (A). Because the structural unit represented by formula (A) is chemically robust, the polymer P containing this structural unit is stable with little weight loss when subjected to heat treatment, and has excellent moldability and durability. The polymer P of this embodiment also has a structural unit represented by formula (1), which has a group containing a urethane bond and a terminal reactive unsaturated double bond. The polymer P has excellent adhesion and bonding properties to substrates due to the urethane bond, and high crosslinkability (curability) due to the terminal reactive unsaturated double bond. Furthermore, the polymer P of this embodiment is produced without using a basic catalyst, such as a tertiary amine, as will be described in detail in the production method described below. Therefore, the polymer P is free from coloration due to residual basic catalysts and therefore has high transparency. As a result, the polymer P of this embodiment has excellent adhesion and bonding properties to substrates and high transparency, making it suitable for use as an adhesive for manufacturing optical components.

[0021] In the structural unit represented by formula (A), R 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, straight-chain or branched-chain alkyl groups having 1 to 30 carbon atoms, and more specific examples include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0022] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0023] In formula (A), R 1 , R 2 , R 3 and R 4 is preferably hydrogen or an alkyl group, more preferably hydrogen. In addition, R 1 , R 2 , R 3 and R 4 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, R1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected. In formula (A), a1 is preferably 0 or 1, and more preferably 0.

[0024] The proportion of the structural units represented by formula (A) in all structural units of the polymer P is, for example, 5 to 50 mol %, preferably 10 to 50 mol %, and more preferably 35 to 50 mol %.

[0025] The structural unit represented by the above formula (1) preferably has a structure containing a urethane bond (—O—C(═O)NH—) and a terminal reactive unsaturated double bond (a methacryloyl group in Z), as represented by formula (1-1).

[0026] [ka]

[0027] In formula (1-1), Q is a divalent organic group, and the total number of carbon atoms in Q is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. Q is, for example, an alkylene or oxyalkylene, and the alkylene group may be linear or branched, but is preferably linear. The divalent organic group (e.g., an alkylene group) of Q may be substituted with any substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. The divalent organic group of Q may be any group other than an alkylene group, such as a divalent group formed by linking one or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxy groups, and the like.

[0028] In formula (1-1), Z is a group having a (meth)acryloyl group, represented by formula (2a).

[0029] [ka]

[0030] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10 The divalent organic group is preferably, for example, an alkylene group. Some of the -CH2- in this alkylene group may be ether groups (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0031] X 10 The divalent organic group (for example, an alkylene group) may be substituted with any substituent, such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Also, X 10 The divalent organic group may be any group other than an alkylene group, such as a divalent group formed by linking one or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxy groups, and the like.

[0032] The proportion of the structural units represented by formula (1) in all structural units of the polymer P is, for example, 5 to 50 mol %, preferably 10 to 40 mol %, and more preferably 15 to 30 mol %.

[0033] In one embodiment, the polymer P may comprise a structural unit represented by formula (2).

[0034] [ka]

[0035] In formula (2), R 21 is an organic group having a hydroxy group.

[0036] In one embodiment, the structural unit represented by formula (2) has a structure represented by formula (2-1).

[0037] [ka]

[0038] Q in formula (2-1) has the same meaning as Q in formula (1-1). When the polymer P contains a structural unit represented by formula (2), the proportion thereof relative to all structural units of the polymer P is, for example, 1 to 20 mol %, and more preferably 1 to 10 mol %.

[0039] In one embodiment, the polymer P may further include a structural unit represented by formula (MA) and / or a structural unit represented by formula (3) in addition to the above structural units.

[0040] [ka]

[0041] [ka]

[0042] In formula (3), R 31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and examples of the organic group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, and a carboxyl group.

[0043] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group. In equation (3), R 31 As the alkyl group, an alkyl group or a cycloalkyl group is preferred.

[0044] When the polymer contains a structural unit represented by formula (MA), the proportion thereof is, for example, 1 to 10 mol %, and more preferably 2 to 7 mol %, based on all structural units of the polymer P. When the polymer contains a structural unit represented by formula (3), the proportion thereof relative to all structural units of the polymer P is, for example, 10 to 50 mol %, and more preferably 25 to 50 mol %.

[0045] The upper limit of the Mw (weight average molecular weight) of the polymer P of this embodiment is, for example, 30,000 or less, preferably 20,000 or less, and more preferably 14,000 or less. This improves the mobility of the polymer P, allowing a more appropriate crosslinked structure to be formed. The lower limit of the Mw of the polymer P is, for example, 1,000 or more, preferably 2,000 or more, and more preferably 3,000 or more. This promotes the formation of a crosslinked structure when an adhesive composition containing the polymer P is cured.

[0046] The upper limit of the dispersity of polymer P, i.e., Mw (weight average molecular weight) / Mn (number average molecular weight), is, for example, 5.0 or less, preferably 4.0 or less, and more preferably 3.0 or less. This reduces the width of the molecular weight distribution of polymer P, allowing for the formation of a uniform crosslinked structure. The lower limit of Mw / Mn may be, for example, 1.0 or more, and can be 1.5 or more. The closer Mw / Mn is to monodispersion, the better. Mw / Mn is the dispersity indicating the width of the molecular weight distribution. By setting Mw / Mn of polymer P within the above range, the shape of a resin film made of an adhesive composition containing polymer P can be improved.

[0047] Here, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are polystyrene-equivalent values ​​obtained from a calibration curve of standard polystyrene (PS) obtained by, for example, GPC measurement. The measurement conditions are, for example, as follows: Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0048] [Method of manufacturing polymer P] In the first embodiment, the polymer P can be produced by a method including the following steps a1 to a3. (Step a1) a step of preparing a raw polymer p1 containing a structural unit represented by formula (A) and a structural unit represented by formula (MA) by a polymerization reaction of a copolymerizable raw material monomer; (Step a2) A step of reacting the raw polymer p1 obtained in Step a1 with a compound having two hydroxy groups to obtain a polymer precursor p2 containing a structural unit represented by Formula (A), a structural unit represented by Formula (2), and optionally a structural unit represented by Formula (MA); (Step a3) A step of treating the polymer precursor p2 obtained in step a2 with an isocyanate compound to convert some of the structural units of formula (2) into structural units represented by formula (1), thereby obtaining a target polymer P containing structural units of formula (A), structural units of formula (1), structural units of formula (2), and optionally structural units of formula (MA). Here, neither a basic catalyst nor an acidic catalyst is used in each of steps a1 to a3 for producing polymer P. As a result, no basic catalyst or acidic catalyst remains in the resulting polymer P, and coloration caused by these catalysts does not occur.

[0049] Alternatively, in the second embodiment, the polymer P can be produced by a method including the following steps b1 to a2. (Step b1) A step of preparing a polymer precursor p3 containing a structural unit represented by formula (A), a structural unit represented by formula (2), and a structural unit represented by formula (3) by a copolymerization reaction of copolymerizable raw material monomers. (Step b2) A step of treating the polymer precursor p3 obtained in Step b1 with an isocyanate compound to convert some of the structural units of Formula (2) into structural units represented by Formula (1), thereby obtaining a target polymer P containing structural units of Formula (A), structural units of Formula (1), structural units of Formula (2), structural units of Formula (3), and optionally structural units of Formula (MA). Neither a basic catalyst nor an acidic catalyst is used in each of steps b1 and b2 for producing polymer P. As a result, no basic catalyst or acidic catalyst remains in the resulting polymer P, and coloration caused by these catalysts does not occur.

[0050] (Method of producing polymer P in the first embodiment) The steps a1 to a3 in the method for producing the polymer P in the first embodiment will be described in detail. (Step a1) Step a1 is a step of preparing a raw polymer p1 containing a structural unit represented by formula (A) and a structural unit represented by formula (MA) by a polymerization reaction of copolymerizable raw monomers.

[0051] [ka]

[0052] [ka]

[0053] In step a1, a monomer represented by formula (Am) and maleic anhydride are polymerized (addition polymerized) to prepare a raw polymer p1 containing a structural unit of formula (A) and a structural unit of formula (MA). 1 , R 2 , R 3 and R 4 The definition of a1 is the same as that of formula (A), and the same applies to preferred embodiments.

[0054] [ka]

[0055] Examples of the monomer represented by general formula (Am) include bicyclo[2.2.1]-hept-2-ene (trivial name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride. In the polymerization, the monomer represented by general formula (Am) may be used alone or in combination of two or more kinds.

[0056] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferred. Examples of the polymerization initiator that can be used include azo compounds and organic peroxides.

[0057] Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN).

[0058] Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). The polymerization initiator may be used alone or in combination of two or more.

[0059] In addition, a chain transfer agent (molecular weight modifier) ​​may be used in the polymerization reaction, if necessary. Examples of the chain transfer agent include thiol group-containing compounds such as β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0060] As the polymerization solvent, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. The polymerization solvent may be a single solvent or a mixed solvent.

[0061] The synthesis of the raw material polymer p1 is carried out by dissolving the monomer represented by formula (Am), maleic anhydride, and a polymerization initiator in a solvent and charging the resulting solution into a reaction vessel, followed by heating to cause addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours.

[0062] When charging the monomer represented by general formula (Am) to maleic anhydride into a reaction vessel, the molar ratio is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1.

[0063] The raw polymer p1 may be a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, or the like. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability. After synthesis of the raw polymer p1, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out.

[0064] Specifically, the organic phase containing the synthesized raw polymer and low-molecular-weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried, thereby increasing the purity of the raw polymer.

[0065] (Step a2) In step a2, the raw polymer p1 obtained in step a1 is reacted with a compound having two hydroxy groups (referred to herein as a "hydroxy group-containing compound") to obtain a polymer precursor p2 containing a structural unit represented by formula (A), a structural unit represented by formula (2), and a structural unit represented by formula (MA). In step a2, the hydroxy group-containing compound acts on a portion of the structural unit of formula (MA) in the raw polymer p1 to produce a structural unit represented by formula (2-2). Therefore, the structural unit represented by formula (2) exists as a structural unit represented by formula (2-2). Note that Q in formula (2-2) has the same meaning as Q in the above formula (2-1).

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] The hydroxy group-containing compound used in step a2 includes a compound represented by formula (4). HO-Q-OH (4) Q in formula (4) has the same meaning as Q in formula (2-1).

[0070] In step a2, in addition to the compound represented by formula (4), a compound represented by formula (6) having one hydroxy group may be allowed to react with the raw polymer p1 obtained in step a1. HO-Q' (6) Here, Q' in formula (6) is, for example, an alkyl group or aryl group having 1 to 30 carbon atoms. When a compound represented by formula (6) is used, the compound of formula (6) acts on a part of the structural unit of formula (MA) in the raw polymer p1 to produce a structural unit represented by formula (2-4). Q' in formula (2-4) has the same meaning as Q' in formula (6).

[0071] [ka]

[0072] The synthesis of polymer precursor p2 in step a2 is carried out by charging raw polymer p1 and a hydroxy-containing compound into a reaction vessel, then heating the mixture to promote the ring-opening reaction of the structural unit (MA) with the hydroxy-containing compound. This reaction proceeds without using a catalyst. The heating temperature is, for example, 80 to 150°C, and the heating time is, for example, 5 to 20 hours.

[0073] (Step a3) In step a3, the polymer precursor p2 obtained in step a2 is treated with an isocyanate compound, whereby the -Q-OH of the structural unit of formula (2-2) in the polymer precursor p2 is reacted with the -N=C=O group of the isocyanate compound to convert it to a structural unit represented by formula (1). This produces the target polymer P, which contains the structural unit of formula (A), the structural unit of formula (1), the structural unit of formula (2-2), and the structural unit of formula (MA). In step a3, the structural unit of formula (1) exists as a structural unit represented by formula (1-2). Note that Q and Z in formula (1-2) have the same meanings as Q and Z in formula (1-1). The polymer P may also contain unreacted structural units of formula (2-2) and unreacted structural units of formula (MA).

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] The isocyanate compound used in step a3 includes a compound represented by formula (5). ZN=C=O (5) Z in the formula (5) has the same meaning as Z in the above formula (1-1), that is, it is a group having a (meth)acryloyl group represented by the formula (2a).

[0079] [ka]

[0080] Specific examples of the isocyanate compound used in step a3 include, but are not limited to, 2-isocyanatoethyl (meth)acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, 2,(2-methacryloyloxyethyloxy)ethyl isocyanate, allyl isocyanate, 4-maleimidophenyl isocyanate, etc. One type of isocyanate compound may be used alone, or two or more types may be used in combination.

[0081] The polymer P in step a3 is prepared by charging the polymer precursor p2 and an isocyanate compound into a reaction vessel, then heating the vessel to promote the reaction between the isocyanate compound and the structural unit (2-2). This reaction proceeds without using a catalyst. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 2 to 10 hours.

[0082] The polymer P obtained using the method of the first embodiment described above does not contain a basic catalyst or an acidic catalyst, and therefore the cured product of such a polymer P has high transparency.

[0083] (Method of producing polymer P in the second embodiment) The steps b1 and b2 in the method for producing the polymer P in the second embodiment will be described in detail. (Step b1) Step b1 is a step of preparing a polymer precursor p3 containing a structural unit represented by formula (A), a structural unit represented by formula (2), and a structural unit represented by formula (3) by a polymerization reaction of copolymerizable raw material monomers. In this embodiment, the structural unit represented by formula (2) has a structure represented by formula (2-3). In formula (2-3), Q has the same meaning as Q in formula (2-1), and R is a hydrogen atom or a methyl group.

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] In step a1, a polymer precursor p3 is prepared by radical polymerization of a monomer represented by formula (Am), a monomer represented by formula (3m), and a compound represented by formula (2a-m).

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] The monomer represented by formula (Am) is the same as that described in step a1 in the method for producing polymer P in the first embodiment. R in equation (3m) 31 is R in Equation (3). 31 is synonymous with. Q in formula (2a-m) has the same meaning as Q in formula (2-1), and R in formula (2a-m) has the same meaning as R in formula (2a).

[0092] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferred. Examples of the polymerization initiator that can be used include azo compounds and organic peroxides.

[0093] Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN).

[0094] Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). The polymerization initiator may be used alone or in combination of two or more.

[0095] In addition, a chain transfer agent (molecular weight modifier) ​​may be used in the polymerization reaction, if necessary. Examples of the chain transfer agent include thiol group-containing compounds such as β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0096] As the polymerization solvent, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. The polymerization solvent may be a single solvent or a mixed solvent.

[0097] The synthesis of polymer precursor p3 is carried out by dissolving the monomer represented by formula (Am), the monomer represented by formula (3m), the (meth)acrylate compound represented by formula (2a-m), and a polymerization initiator in a solvent, charging the resulting solution into a reaction vessel, and then heating to cause a radical polymerization reaction. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. This radical polymerization reaction can proceed in the absence of a catalyst.

[0098] (Step b2) In step b3, the polymer precursor p3 obtained in step b1 is treated with an isocyanate compound, whereby the -Q-OH of the structural unit of formula (2-3) in the polymer precursor p3 is reacted with the -N=C=O group of the isocyanate compound to convert it to a structural unit represented by formula (1). This produces the target polymer P, which contains the structural unit of formula (A), the structural unit of formula (1), and the structural unit of formula (3). In step b2, the structural unit of formula (1) exists as a structural unit represented by formula (1-3). Note that Q and Z in formula (1-3) have the same meanings as Q and Z in formula (1-1) above.

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] The isocyanate compound used in step b2 may be the compound represented by the formula (5) as described above. ZN=C=O (5) Z in the formula (5) has the same meaning as Z in the above formula (1-1), that is, it is a group having a (meth)acryloyl group represented by the formula (2a).

[0104] [ka]

[0105] The preparation of the polymer P in step b2 is carried out by charging the polymer precursor p3 and an isocyanate compound into a reaction vessel, then heating the vessel to promote the reaction between the isocyanate compound and the structural unit (2-3). This reaction proceeds without using a catalyst. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 2 to 10 hours.

[0106] The polymer P obtained using the method of the second embodiment above does not contain a basic catalyst or an acidic catalyst, and therefore the cured product of such a polymer P has high transparency.

[0107] [Curable resin composition] The curable resin composition of this embodiment contains the above-mentioned polymer P and a radically polymerizable monomer capable of radically polymerizing with the polymer P. The radically polymerizable monomer is capable of crosslinking with the polymer P (capable of chemically bonding with the polymer P) due to the action of activated chemical species generated from a photopolymerization initiator. The radically polymerizable monomer may also form a polymer by polymerizing with itself rather than chemically bonding only with the polymer P.

[0108] The curable resin composition of the present embodiment contains such a radical polymerizable monomer, which allows the viscosity to be appropriately adjusted and provides excellent handleability. Furthermore, since the polymer P can be dissolved in the radical polymerizable monomer, a uniform resin film can be obtained by curing treatment, and a resin film with high transparency and no insoluble matter of the polymer P can be obtained.

[0109] As the radical polymerizable monomer used in the curable resin composition of this embodiment, a (meth)acrylate compound having one or more (meth)acryloyl groups is preferably used. Specific examples of such (meth)acrylate compounds include 2-ethylhexyl (meth)acrylate, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, (meth)acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, )methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)methacrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxyethoxyethyl (meth)acrylate, N-vinylpyrrolidone, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate-pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate, but are not limited to these. These (meth)acrylate compounds may be used alone or in combination of two or more.

[0110] The curable resin composition of this embodiment preferably does not contain a non-reactive solvent. By not containing a non-reactive solvent, the solvent does not volatilize during the curing treatment, making it suitable for use as an adhesive. Here, the term "non-reactive solvent" refers to a solvent that does not have a polymerizable or crosslinkable reactive group and that can volatilize upon heat treatment. "Not containing a non-reactive solvent" means that the composition is substantially free of a non-reactive solvent, and refers to the case where the content of the non-reactive solvent relative to the entire curable resin composition is 0.1% by mass or less.

[0111] The amount of the radical polymerizable monomer in the curable resin composition of this embodiment can be, for example, 10 to 90 mass%, preferably 30 to 90 mass%, and more preferably 45 to 90 mass%, based on the total mass of the curable resin composition. The amount of the radical polymerizable monomer is, for example, 10 to 2000 mass%, preferably 12 to 1900 mass%, more preferably 15 to 1500 mass%, even more preferably 15 to 1000 mass%, even more preferably 20 to 400 mass%, and particularly preferably 20 to 150 mass%, based on the mass of the polymer P. By using the radical polymerizable monomer within the above range, a curable resin composition with excellent coatability and curability can be obtained.

[0112] (Photoradical polymerization initiator) The curable resin composition of the present embodiment may contain a photoradical polymerization initiator. By blending the photoradical polymerization initiator, the curable resin composition of the present embodiment can be cured by light irradiation.

[0113] As the photoradical polymerization initiator, compounds known in the art can be used, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, Alkylphenone compounds such as pan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin methyl ether, benzoin Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxynaphthyl) halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, Examples of suitable photoradical polymerization initiators include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. These initiators may be used singly or in combination of two or more.

[0114] The amount of the photoradical polymerization initiator to be blended is, for example, 1 to 60 parts by mass, preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, still more preferably 2 to 15 parts by mass, and particularly preferably 2 to 8 parts by mass, relative to 100 parts by mass of polymer P.

[0115] (Other ingredients) The curable resin composition of the present embodiment may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, a surfactant, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic assistant, a silane coupling agent, and a polyhydric phenol compound, depending on various purposes and required properties.

[0116] [Application] The curable resin composition of the present embodiment can be used in the production of optical components, and can be used as an adhesive for optical components. Specifically, the curable resin composition of the present embodiment can be used as an adhesive for optical lenses such as in-vehicle lenses, an adhesive for optical pickups, an adhesive for optical path coupling, or a photocurable adhesive for optical bonding.

[0117] The adhesive composition of this embodiment can be placed between an optical component and an adherend, and cured by irradiating the optical component and / or the adherend with light, thereby adhering the optical component to the adherend. The cured adhesive composition exists as an adhesive layer between the optical component and the adherend.

[0118] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0119] EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0120] Example 1 Polymer A having a structure represented by formula (PA) was synthesized by the following method. Maleic anhydride (460 g, 4.69 mol) and 2-norbornene (441.6 g, 4.69 mol) were weighed into a suitable reaction vessel equipped with a stirrer and condenser and dissolved in methyl ethyl ketone and toluene. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until it reached 80°C. A methyl ethyl ketone solution of dimethyl 2,2'-azobis(2-methylpropionate) (43.2 g, 0.19 mol) and n-dodecyl mercaptan (47.5 g, 0.23 mol) was added sequentially over 1 hour, followed by an additional 7 hours of heat treatment. This yielded a copolymer of 2-norbornene and maleic anhydride. The solution was then cooled to room temperature. The resulting solution was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer, yielding 758 g of a white solid. The weight average molecular weight (Mw) of the polymer thus obtained was 3,600, and the dispersity (Mw / Mn) was 1.58. The above-mentioned 2-norbornene / maleic anhydride copolymer (100 g) and 1,6-hexanediol (200 g, 1.69 mol) were weighed into an appropriately sized reaction vessel equipped with a stirrer and a condenser, and then heated at 120°C for 16 hours. A large amount of pure water was added dropwise to this reaction solution to precipitate the polymer. The filtered solid was dried in a vacuum dryer at 40°C for 16 hours and then dissolved in propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 20%. To 100 g of this PGMEA solution, 2-isocyanatoethyl acrylate (Karenz AOI, 3.3 g, 0.023 mol) was added and heated at 60°C for 5 hours. After that, a large amount of pure water was added dropwise to precipitate the polymer. The solid was collected by filtration and dried in a vacuum dryer at 40°C for 16 hours to obtain Polymer A. The yield was 17.5 g, with a Mw of 9,800 g / mol, a Mw / Mn of 2.24, and a double bond equivalent of 1,650 g / eq.

[0121] [ka]

[0122] Example 2 Polymer B having a structure represented by formula (PB) was synthesized by the following method. Maleic anhydride (460 g, 4.69 mol) and 2-norbornene (441.6 g, 4.69 mol) were weighed into a suitable reaction vessel equipped with a stirrer and condenser and dissolved in methyl ethyl ketone and toluene. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until it reached 80°C. A methyl ethyl ketone solution of dimethyl 2,2'-azobis(2-methylpropionate) (43.2 g, 0.19 mol) and n-dodecyl mercaptan (47.5 g, 0.23 mol) was added sequentially over 1 hour, followed by an additional 7 hours of heat treatment. This yielded a copolymer of 2-norbornene and maleic anhydride. The solution was then cooled to room temperature. The resulting solution was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer, yielding 758 g of a white solid. The weight average molecular weight (Mw) of the polymer thus obtained was 3,600, and the dispersity (Mw / Mn) was 1.58. The above-mentioned 2-norbornene and maleic anhydride copolymer (100 g) and triethylene glycol (200 g, 1.33 mol) were weighed into an appropriately sized reaction vessel equipped with a stirrer and a condenser, and then heated at 120°C for 16 hours. A large amount of pure water was added dropwise to this reaction solution to precipitate a polymer. The filtered solid was dried in a vacuum dryer at 40°C for 16 hours and then dissolved in propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 20%. To 100 g of this PGMEA solution, 2-isocyanatoethyl acrylate (Karenz AOI, 3.3 g, 0.023 mol) was added, and the mixture was heated at 60°C for 5 hours. After that, a large amount of pure water was added dropwise to precipitate the polymer. The solid was collected by filtration and dried in a vacuum dryer at 40°C for 16 hours to obtain Polymer B. The yield was 17.0 g, with a Mw of 10,900 g / mol, a Mw / Mn of 2.55, and a double bond equivalent of 1,710 g / eq.

[0123] [ka]

[0124] Example 3 Polymer C having a structure represented by formula (PC) was synthesized by the following method. Maleic anhydride (460 g, 4.69 mol) and 2-norbornene (441.6 g, 4.69 mol) were weighed into a suitable reaction vessel equipped with a stirrer and condenser and dissolved in methyl ethyl ketone and toluene. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until it reached 80°C. A methyl ethyl ketone solution of dimethyl 2,2'-azobis(2-methylpropionate) (43.2 g, 0.19 mol) and n-dodecyl mercaptan (47.5 g, 0.23 mol) was added sequentially over 1 hour, followed by an additional 7 hours of heat treatment. This yielded a copolymer of 2-norbornene and maleic anhydride. The solution was then cooled to room temperature. The resulting solution was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer, yielding 758 g of a white solid. The weight average molecular weight (Mw) of the polymer thus obtained was 3,600, and the dispersity (Mw / Mn) was 1.58. The above-mentioned 2-norbornene / maleic anhydride copolymer (100 g) and tetraethylene glycol (200 g, 1.03 mol) were weighed into an appropriately sized reaction vessel equipped with a stirrer and a condenser, and then heated at 120°C for 16 hours. A large amount of pure water was added dropwise to this reaction solution to precipitate a polymer. The filtered solid was dried in a vacuum dryer at 40°C for 16 hours and then dissolved in propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 20%. To 100 g of this PGMEA solution, 2-isocyanatoethyl acrylate (Karenz AOI, 3.3 g, 0.023 mol) was added, and the mixture was heated at 60°C for 5 hours. After that, a large amount of pure water was added dropwise to precipitate the polymer. The solid was collected by filtration and dried in a vacuum oven at 40°C for 16 hours to obtain Polymer C. The yield was 16.8 g, with a Mw of 12,600 g / mol, a Mw / Mn of 2.93, and a double bond equivalent of 3,290 g / eq.

[0125] [ka]

[0126] Example 4 Polymer D having a structure represented by formula (PD) was synthesized by the following method. Cyclohexylmaleimide (840 g, 4.69 mol) and 2-norbornene (441.6 g, 4.69 mol) were weighed and dissolved in methyl ethyl ketone and toluene in a suitable reaction vessel equipped with a stirrer and condenser. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until the temperature reached 80°C. A methyl ethyl ketone solution of dimethyl 2,2'-azobis(2-methylpropionate) (43.2 g, 0.19 mol), n-dodecyl mercaptan (47.5 g, 0.23 mol), and 4-hydroxybutyl acrylate (270.5 g, 1.88 mol) was added sequentially over 1 hour, followed by an additional 7 hours of heat treatment. This yielded a copolymer of 2-norbornene, cyclohexylmaleimide, and 4-hydroxybutyl acrylate. The solution was then cooled to room temperature. The solution was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer to obtain 1545 g of a white solid. The weight average molecular weight (Mw) of the polymer thus obtained was 4,600, and the dispersity (Mw / Mn) was 1.74. This polymer was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 50%. 2-Isocyanatoethyl acrylate (Karenz AOI, 5.2 g, 0.037 mol) was added to 100 g of this polymer solution and heated at 60 °C for 5 hours. A large amount of pure water was added dropwise to precipitate the polymer. The solid was collected by filtration and dried in a vacuum oven at 40 °C for 16 hours to obtain Polymer D. The yield was 40.8 g, with a Mw of 5,000 g / mol, a Mw / Mn of 1.72, and a double bond equivalent of 1,720 g / eq.

[0127] [ka]

[0128] (Comparative Example 1) Polymer E having a structure represented by formula (PE) was synthesized by the following method. Maleic anhydride (735 g, 7.5 mol), 2-norbornene (706 g, 7.5 mol), dimethyl 2,2'-azobis(2-methylpropionate) (69 g, 0.3 mol), and n-dodecyl mercaptan (76 g, 0.38 mol) were weighed and dissolved in methyl ethyl ketone and toluene in a suitable reaction vessel equipped with a stirrer and condenser. Dissolved oxygen was removed from the solution by nitrogen bubbling, and the solution was then heat-treated at 80°C for 15 hours while stirring. This yielded a copolymer of 2-norbornene and maleic anhydride. The solution was then cooled to room temperature. The solution was reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer, yielding 1230 g of a white solid. The weight average molecular weight (Mw) of the polymer thus obtained was 3,800, and the dispersity (Mw / Mn) was 1.44. The above-mentioned 2-norbornene / maleic anhydride copolymer (150 g) was weighed and dissolved in MEK (280 g) in an appropriately sized reaction vessel equipped with a stirrer and condenser. 2-Hydroxyethyl acrylate (HEA, 113.3 g, 0.976 mol) and triethylamine (15 g) were then added and heated at 70°C for 6 hours. After acid treatment with formic acid, the reaction mixture was added dropwise to a large amount of pure water to precipitate the polymer. The solid collected by filtration was dried in a vacuum dryer at 40°C for 16 hours to obtain Polymer E. The yield was 182.3 g, with a Mw of 4,000, a Mw / Mn ratio of 1.75, and a double bond equivalent of 1,460.

[0129] [ka]

[0130] (Preparation of Curable Resin Composition) In Examples 1 to 4 and Comparative Example 1, a mixed solution was obtained by dissolving each polymer in a radical polymerizable monomer according to the following Table 1. Then, this mixed solution was filtered through a 0.2 μm nylon filter to obtain a curable resin composition. Details of each component in Table 1 are as follows:

[0131] (polymer) Polymer A: Polymer A prepared in Example 1 Polymer B: Polymer B prepared in Example 2 Polymer C: Polymer C prepared in Example 3 Polymer D: Polymer D prepared in Example 4 Polymer E: Polymer E prepared in Comparative Example 1 (Radical polymerizable monomer) THFA: Tetrahydrofurfuryl acrylate

[0132] In Reference Examples 1 to 5, triethylamine was added to the formulations of the above Examples and Comparative Examples to prepare curable resin compositions for reference.

[0133] (Evaluation of cured products of photocurable resin compositions) The obtained curable resin composition was applied and photocured under the following conditions to obtain a cured film. The obtained cured film was evaluated for the following items. The evaluation results are shown in Table 1. (transparency) The transparency of the cured product of the curable resin composition was evaluated using light transmittance as an index. First, the above-mentioned curable resin composition was filled between two glass substrates with a gap of 80 μm, and then the composition was irradiated with a conveyor-type UV irradiator (I-Grandage ECS-4011GX / N manufactured by I-Graphics Co., Ltd.) equipped with a high-pressure mercury lamp at an illuminance of 760 mW / cm. 2 , cumulative light intensity 820mJ / cm 2 Under the above conditions, the glass substrate was cured by passing each conveyor once over the front and back surfaces. The glass substrate used was a Corning 1737 glass substrate measuring 50 mm in length and 50 mm in width. The gap was adjusted by using a fluororesin tape called "Nitoflon" with a thickness of 80 μm as a spacer. The light transmittance TA (%) of the obtained cured resin film for light with a wavelength of 400 nm was measured. The light transmittance TA was measured using an ultraviolet-visible spectrophotometer. The results are shown in Table 1. A higher light transmittance value indicates higher transparency of the cured resin film.

[0134] (Adhesiveness) The adhesive properties of the curable resin compositions of Examples 1 to 4 and Comparative Example 1 were evaluated using the shear adhesive strength in a tensile shear adhesive strength test as an index. First, the curable resin composition was applied to an adherend [25 mm × 80 mm × 2 mm thick acrylic plate (Acrysunde Co., Ltd.: Acrysunde Plate 001, transparent, 2 mm thick)], and the adherend [acrylic plate] was attached to an area of ​​25 mm × 10 mm. The plate was then clamped with eye clips and then irradiated with UV light (irradiation conditions: high-pressure mercury lamp, illuminance: 100 mW / cm). 2 , Accumulated light intensity: 500mJ / cm 2 The eye clips were removed from the test specimens carried out by the conveyor, and the specimens were turned over and passed through the conveyor again, whereupon UV irradiation was performed from the back side (integrated light intensity: 1000 mJ / cm 2 ) to obtain test pieces for adhesion tests. The adhesive strength of the obtained test specimen for adhesion test was measured at a test speed of 0.5 mm / min in accordance with the tensile shear adhesive strength test method for rigid adherends of JIS K6850. A higher shear adhesive strength value indicates a higher adhesive strength.

[0135] [Table 1]

[0136] No change in light transmittance was observed when comparing Comparative Example 1, which contains polymer E synthesized using triethylamine as a catalyst, with Reference Example 5, in which triethylamine was further added to polymer E. This is thought to be because polymer E in Comparative Example 1 is colored by the remaining triethylamine, and therefore the coloring is small even when additional triethylamine is added. The resin compositions of Examples 1 to 4, which used Polymers A to D, had higher light transmittance and better transparency than Comparative Example 1. Furthermore, the resin compositions of Examples 1 to 4 had better adhesion than Comparative Example 1. Comparing Example 4, which contains Polymer D, with Reference Example 4, coloration occurred due to a color reaction between the maleimide structure of Polymer D and triethylamine, and a decrease in light transmittance was observed in Reference Example 4. From these results, it is predicted that if Polymer D is synthesized by a conventional method using an amine catalyst, an adhesive composition with poor transparency will be obtained. Comparing Examples 1 to 3, which used Polymers A to C, respectively, with Reference Examples 1 to 3, which added triethylamine to Polymers A to C, there was almost no change in light transmittance. This is thought to be because most of the maleic anhydride-derived structures in Polymers A to C reacted with the hydroxy group-containing compound, leaving few unreacted anhydride rings. The resin compositions of Examples 2 and 3 containing polymers B and C had particularly excellent adhesive properties. This is thought to be due to the high polarity and flexibility of the polyoxyalkylene chains of polymers B and C.

Claims

1. An adhesive composition comprising a curable resin composition, The curable resin composition comprises a polymer containing a structural unit represented by formula (A) and a structural unit represented by formula (1); a radical polymerizable monomer, 【Chemistry 1】 In formula (A), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, １ is 0, 1 or 2, 【Chemistry 2】 In formula (1), R １１ is a group containing a urethane bond and a terminal reactive unsaturated double bond, Adhesive composition.

2. 2. The adhesive composition of claim 1, The polymer further comprises a structural unit represented by formula (2): 【Transformation 3】 In formula (2), R ２１ is an organic group having a hydroxy group.

3. The adhesive composition according to claim 1 or 2, The polymer further comprises at least one selected from a structural unit represented by formula (MA) and a structural unit represented by formula (3), 【Chemistry 4】 【Transformation 5】 In formula (3), R ３１ is a hydrogen atom or an organic group having 1 to 30 carbon atoms.

4. The adhesive composition according to any one of claims 1 to 3, R in the formula (1) １１ further comprising an oxyalkylene group.

5. The adhesive composition according to any one of claims 1 to 4, an adhesive composition, wherein the group containing a urethane bond and a terminal reactive unsaturated double bond is a group containing a urethane bond and a (meth)acryloyl group.

6. The adhesive composition according to any one of claims 1 to 5, The adhesive composition, wherein the radical polymerizable monomer comprises a (meth)acrylate compound having one or more (meth)acryloyl groups.

7. The adhesive composition according to any one of claims 1 to 6, The adhesive composition, wherein the curable resin composition further contains a photoradical polymerization initiator.

8. A cured product of the adhesive composition according to any one of claims 1 to 7.

9. The cured product according to claim 8 , which is in the form of a film.

10. An article comprising the cured body of claim 8.

11. The article of claim 10 which is an optical component.

12. A structural unit represented by formula (A), A structural unit represented by formula (1), A polymer comprising a structural unit represented by formula (MA): 【Transformation 6】 In formula (A), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, １ is 0, 1 or 2, 【Transformation 7】 In formula (1), R １１ is a group containing a urethane bond and a terminal reactive unsaturated double bond, 【Transformation 8】 polymer.

13. The polymer of claim 12, Further comprising a structural unit represented by formula (3), 【Chemistry 9】 A polymer in which, in formula (3), R 31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms.

14. 14. The polymer of claim 12 or 13, Further comprising a structural unit represented by formula (2): 【Chemistry 10】 In formula (2), R ２１ is an organic group having a hydroxy group,

15. 15. The polymer of any one of claims 12 to 14, R in the formula (1) １１ but further comprising an oxyalkylene group.

16. 16. A polymer according to any one of claims 12 to 15, The polymer, wherein the group containing a urethane bond and a terminal reactive unsaturated double bond is a group containing a urethane bond and a (meth)acryloyl group.

17. A polymer according to any one of claims 12 to 16; and a radical polymerizable monomer.

18. The curable resin composition according to claim 17, wherein the radical polymerizable monomer comprises a (meth)acrylate compound having one or more (meth)acryloyl groups.

19. The curable resin composition according to claim 17 or 18, further comprising a photoradical polymerization initiator.

20. An adhesive composition comprising the curable resin composition according to any one of claims 17 to 19.

21. A cured product of the curable resin composition according to any one of claims 17 to 19.

22. 22. The cured product of claim 21 in the form of a film.

23. 22. An article comprising the cured body of claim 21.

24. 24. The article of claim 23, which is an optical component.

25. A structural unit represented by formula (A): A polymer comprising a structural unit represented by formula (1-2): 【Chemistry 11】 In formula (A), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; a 1 represents 0, 1 or 2; 【Chemistry 12】 In formula (1-2), Q represents a divalent organic group, and Z represents a group having a (meth)acryloyl group represented by formula (2a): 【Chemistry 13】 A polymer represented by formula (2a), wherein X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group.

26. The polymer of claim 25, Further comprising at least one structural unit selected from the structural unit represented by formula (MA) and the structural unit represented by formula (3), 【Chemistry 14】 【Chemistry 15】 A polymer in which, in formula (3), R 31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms.

27. The polymer of claim 25 or 26, Further containing a structural unit represented by formula (2-2), 【Chemistry 16】 In formula (2-2), Q is a divalent organic group.

28. The polymer of any one of claims 25 to 27, A polymer in which Q in the formula (1-2) is an oxyalkylene group.

29. A polymer according to any one of claims 25 to 28, and a radical polymerizable monomer.

30. The curable resin composition of claim 29, wherein the radical polymerizable monomer comprises a (meth)acrylate compound having one or more (meth)acryloyl groups.

31. A curable resin composition described in claim 29 or 30, further containing a photoradical polymerization initiator.

32. An adhesive composition comprising a curable resin composition according to any one of claims 29 to 31.

33. A cured product of the curable resin composition described in any one of claims 29 to 31.

34. A cured body according to claim 33 in the form of a film.

35. An article comprising the hardened body described in claim 33.

36. The article described in claim 35, which is an optical component.

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