JPWO2015163182A1 - Polymer, composition, cured product, film adhesive, and laminate - Google Patents

Abstract

[Problem] An object of the present invention is to provide a polymer that forms a cured product having excellent heat resistance and excellent adhesive strength. [Solution] A polymer having a polynaphthylene structure containing at least one structural unit selected from the following formula (1) and the following formula (2). (In the formulas (1) and (2), R1 and R3 each represent a group bonded to the naphthalene ring via an oxygen atom, and are represented by an epoxy group or a group having an ethylenically unsaturated group, or -CH2OR5. R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group, and when there are a plurality of R1 and R3, R1 and R3 may be the same or different from each other. R2 and R4 each represents a group bonded to the naphthalene ring, and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. R2 and R4 may be the same or different from each other, a and c each represent an integer of 2 to 6, b and d each represents an integer of 0 to 4, and a + b = 6 And c + = A 6 .m and n each represents an integer of 2 or more.)

Description

  The present invention relates to a polymer, a composition, a cured product, a film adhesive, and a laminate.

  Fiber reinforced plastic (FRP) made from fiber and matrix resin has great advantages due to weight reduction, and is therefore used in components such as ships, automobiles, aircraft, and sporting goods. As such a matrix resin, an epoxy resin or a vinyl group-containing resin having excellent adhesive strength with fibers and metals and excellent heat resistance is used (Patent Documents 1 and 2).

JP 2003-238657 A JP 2010-13636 A

  Thus, the epoxy resin used for the fiber reinforced plastic matrix resin is required to be a polymer that forms a cured product having excellent heat resistance and excellent adhesive strength.

  An object of the present invention is to provide a polymer that forms a cured product excellent in heat resistance and adhesive strength, a composition containing the polymer, and a cured product obtained by curing these. .

The present invention provides the following [1] to [8].
[1] A polymer having a polynaphthylene structure containing at least one structural unit selected from the following formula (1) and the following formula (2).

(In the formulas (1) and (2), R ¹ and R ³ each represent a group bonded to the naphthalene ring via an oxygen atom, a group having an epoxy group or an ethylenically unsaturated group, or —CH ₂ represents a group represented by OR ⁵ , R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group, and when a plurality of R ¹ and R ³ are present, R ¹ and R ³ may be the same as or different from each other, and R ² and R ⁴ each represent a group bonded to a naphthalene ring and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. When a plurality of R ² and R ⁴ are present, R ² and R ⁴ may be the same or different from each other, a and c each represent an integer of 1 to 6; d represents an integer of 0 to 5, and a + b = 6 And c + d = 6, and m and n each represents an integer of 2 or more.)
[2] The polymer according to [1], wherein the polymer has a structural unit represented by the formula (1).
[3] The polymer according to [2], wherein the structural unit represented by the formula (1) is represented by the following formula (3).

(In the formula, R ¹ and m are the same as R ¹ and m in the formula (1), respectively.)
[4] A composition comprising the polymer according to any one of [1] to [3] and a solvent.
[5] The composition according to [4], further comprising a curing accelerator and a crosslinking agent.
[6] A cured product obtained by curing the polymer according to any one of [1] to [3].
[7] A cured product obtained by curing the composition according to any of [4] or [5].
[8] A film adhesive obtained by impregnating at least a fiber with the composition according to the above [4] or [5] and semi-curing the fiber.
[9] A laminate obtained by laminating a layered member via the film adhesive according to [8].

  The polymer of the present invention and the composition containing the polymer become a cured product having excellent heat resistance and excellent adhesive strength.

FIG. 1 is an infrared spectrum of the polymer (a1) synthesized in the example.

<1> Polymer The polymer of the present invention (hereinafter also referred to as “polymer (A)”) has a polynaphthylene structure containing at least one structural unit selected from the following formula (1) and the following formula (2). .

(In the formulas (1) and (2), R ¹ and R ³ each represent a group bonded to the naphthalene ring via an oxygen atom, a group having an epoxy group or an ethylenically unsaturated group, or —CH ₂ represents a group represented by OR ⁵ , R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group, and when a plurality of R ¹ and R ³ are present, R ¹ and R ³ may be the same as or different from each other, and R ² and R ⁴ each represent a group bonded to a naphthalene ring and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. When a plurality of R ² and R ⁴ are present, R ² and R ⁴ may be the same or different from each other, a and c each represent an integer of 1 to 6; d represents an integer of 0 to 5, and a + b = 6 And c + d = 6, and m and n each represents an integer of 2 or more.)
The polymer (A) has a polynaphthylene structure. The polymerization bond position in the structural unit represented by the formula (1) and the formula (2) is not limited.

R ¹ and R ³ are groups bonded to the naphthalene ring through an oxygen atom, and the bonding position is not limited. R ² and R ⁴ are groups bonded to the naphthalene ring, and the bonding positions are not limited.

Examples of the group having an epoxy group represented by R ¹ and R ³ include an epoxy group, a glycidyl group, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group; 3,4-epoxycyclohexylmethyl. Group, 3,4-epoxycyclohexylprop group, 3,4-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 2- (3,4-epoxycyclopentyl) ethyl group, 2- (4-methyl-3, And epoxycycloalkyl groups such as 4-epoxycyclohexyl) ethyl and 2- (3,4-epoxycyclohexyl) ethyl groups.

Examples of the group having an ethylenically unsaturated group represented by R ¹ and R ³ include a vinyl group, an allyl group, a styryl group, a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, and a (meth) acryloyl group. Examples include oxypropyl, vinylphenyl group, vinylbenzyl, styrylmethyl group, and styrylethyl group.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, Examples include hexyl group, octyl group, decyl group, dodecyl group, and hexadecanyl group.

Examples of the halogen atom represented by R ² and R ⁴ include a chloro group, a bromo group, and a fluoro group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ² and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t- Examples include a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and a hexadecanyl group.

  The polymer (A) may contain structural units other than the structural units represented by the formula (1) and the formula (2). Examples of the structural unit other than the structural units represented by the formula (1) and the formula (2) include structural units derived from other monomers described later.

  The total content (mol%) of the structural units represented by the formula (1) and the formula (2) contained in the polymer (A) is determined from the viewpoint of the heat resistance and adhesive strength of the cured product. It is usually 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% or more with respect to the total of all structural units contained in A).

Further, the total content (% by mass) of the structural units represented by the formula (1) and the formula (2) contained in the polymer (A) is heavy from the viewpoint of heat resistance and adhesive strength of the cured product. The amount is usually 60% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more with respect to the total of all the structural units contained in the coalescence (A). The said structural unit shows the structural unit derived from the monomer used for the synthesis | combination of a polymer. Moreover, the ratio of the structural unit of Formula (1) and Formula (2) in all the structural units of the said polymer (A) can be calculated from the integral value of < ¹ > H-NMR.

  It is preferable that a polymer (A) contains the structural unit represented by the said Formula (1) from a viewpoint of the heat resistance and adhesive strength of hardened | cured material. The content (mol%) of the structural unit represented by the formula (1) contained in the polymer (A) is contained in the polymer (A) from the viewpoints of heat resistance and adhesive strength of the cured product. Preferably it is 70 mol% or more with respect to the sum total of all the structural units, More preferably, it is 90 mol% or more, More preferably, it is 99 mol% or more. Moreover, the content rate (mass%) of the structural unit represented by the formula (1) contained in the polymer (A) is in the polymer (A) from the viewpoint of heat resistance and adhesive strength of the cured product. Preferably it is 80 mass% or more with respect to the sum total of all the structural units contained, More preferably, it is 90 mass% or more, More preferably, it is 99 mass% or more.

  Furthermore, the structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (3) from the viewpoints of heat resistance and adhesive strength of the cured product.

(In the formula, R ¹ and m are the same as R ¹ and m in the formula (1)).
The content (mol%) of the structural unit represented by the formula (3) contained in the polymer (A) is contained in the polymer (A) from the viewpoint of the heat resistance and adhesive strength of the cured product. Preferably it is 70 mol% or more with respect to the sum total of all the structural units, More preferably, it is 90 mol% or more, More preferably, it is 99 mol% or more.

  Further, the content (mass%) of the structural unit represented by the formula (3) contained in the polymer (A) is in the polymer (A) from the viewpoint of heat resistance and adhesive strength of the cured product. Preferably it is 80 mass% or more with respect to the sum total of all the structural units contained, More preferably, it is 90 mass% or more, More preferably, it is 99 mass% or more.

  The weight average molecular weight computed by the gel permeation chromatography method of a polymer (A) is 1,000-100,000 normally. The weight average molecular weight is a value calculated by the method described in the examples.

A polymer (A) can also be used independently, and can also be used as a composition mentioned later or hardened | cured material.
<1-1> Synthesis of Polymer The polymer of the present invention can be synthesized by combining known methods. For example, it can be synthesized by the method shown in the synthesis route shown in the following formula (4). Polynaphthylene having a phenolic hydroxyl group (hereinafter also referred to as “hydroxypolynaphthylene”) by a coupling reaction using a naphthalene derivative having a phenolic hydroxyl group as a monomer and other copolymerizable monomers as necessary. ) Is synthesized (hereinafter also referred to as “step 1”).

  Next, the hydroxypolynaphthylene is reacted with a halide having an ethylenically unsaturated group to synthesize polynaphthylene having an ethylenically unsaturated group (hereinafter also referred to as “Step 2”).

  Next, the ethylenically unsaturated group of the polynaphthylene having an ethylenically unsaturated group is oxidized to synthesize a polynaphthylene having an epoxy group (hereinafter also referred to as “step 3”).

(In the formula (4), R ⁵ represents a group having an ethylenically unsaturated bond group. R ⁶ represents a group having an epoxy group. R ² , a, b and m are each in the formula (1). (Same as these symbols.)
Here, the polymer (A) in which R ¹ and R ³ in the formula (1) are groups having an ethylenically unsaturated bond group can be synthesized by performing up to the step 2, and the formula (1) In the above, the polymer (A) in which R ¹ and R ³ are groups having an epoxy group can be synthesized by performing up to the step 3.

In the formula (1), the polymer (A) in which R ¹ and R ³ are groups having an ethylenically unsaturated bond group is a synthetic intermediate of the polymer (A) which is a group having an epoxy group. .
<1-1-1> Step 1
Step 1 is a step of synthesizing polynaphthylene having a phenolic hydroxyl group by a coupling reaction using a naphthalene derivative having a phenolic hydroxyl group as a monomer, together with another copolymerizable monomer as necessary.

  Examples of the naphthalene derivative having a phenolic hydroxyl group include 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-methyl-1-hydroxynaphthalene, 6-phenyl-2-hydroxynaphthalene, 1,3-dihydroxynaphthalene, 2 , 3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, and 3-methyl-2,6- Dihydroxynaphthalene is mentioned. The said naphthalene derivative which has a phenolic hydroxyl group may be used individually by 1 type, and may use 2 or more types together.

  Examples of the other copolymerizable monomers include phenol, p-isopropenylphenol, ethynylstyrene, propargylic acid, 6-hexynoic acid, 2-propyn-1-ol, and 1-butyn-3-ol. , 3-butyn-3-ol, 1-pentyn-3-ol, 4-pentyn-1-ol, 3-ethynylaniline, 4-ethynylaniline, and phenylacetylene. The other copolymerizable monomers may be used alone or in combination of two or more.

  Examples of the coupling reaction include a coupling reaction using a one-electron oxidizing agent. In this case, the coupling reaction involves dissolving the naphthalene derivative having the phenolic hydroxyl group in a reaction solvent, and oxygen in the presence of a catalyst. This can be done by supplying

  The reaction conditions in the coupling reaction using the one-electron oxidant are usually 10 ° C. to 100 ° C. and 0.1 to 10 hours, and the type of catalyst, the naphthalene derivative, and the other copolymerization are possible. It is appropriately adjusted depending on the kind of the monomer.

  Examples of the one-electron oxidizing agent include silver carbonate (Fetizon reagent), di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) copper (II)] chloride, di-μ. -Hydroxo-bis [(N, N, N ', N'-tetramethylpropylenediamine) copper (II)] chloride, di- [mu] -hydroxo-bis [(N, N, N', N'-tetraethylethylenediamine) Copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetraethylethylenediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ', N'-tetramethyl-1,6-hexanediamine) copper (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethyl-1,8-naphthalenediamine) ) Copper (II)] chloride Di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) titanium (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetra Organometallic compounds such as methylethylenediamine) cerium (II)] chloride, di-μ-hydroxo-bis [(N, N, N ′, N′-tetramethylethylenediamine) iron] chloride; peracetic acid, m-chloroperbenzoic acid Peracids such as acids; peroxides such as hydrogen peroxide and t-butyl hydroperoxide; diazo compounds such as 2′-azobisisobutyronitrile; halogens or halogen acids such as chlorine, bromine and sodium bromate; And enzymes such as laccase, peroxidase, tyrosinase and urushiol. The said one-electron oxidizing agent may be used individually by 1 type, and may use 2 or more types together.

  The amount of the one-electron oxidant to be used is usually 0.0001 to 10 mol with respect to 1 mol of the naphthalene derivative having a phenolic hydroxyl group.

  As the reaction solvent in the coupling reaction using a one-electron oxidizing agent, the naphthalene derivative having the phenolic hydroxyl group, the other copolymerizable monomer, the one-electron oxidizing agent, and the phenolic obtained by the coupling reaction Any polyhydrylene having a hydroxyl group may be used, for example, methanol, 2-methoxyethanol, 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, ethyl lactate, lactic acid propane, butyl lactate, N, N-dimethylformamide is mentioned.

  After the coupling reaction is completed, the reaction solution contains impurities other than polynaphthylene having a phenolic hydroxyl group such as a catalyst residue. For this reason, after completion | finish of reaction, it is preferable to refine | purify by a well-known purification method, for example, a reprecipitation method and a liquid washing method.

Moreover, the weight average molecular weight computed by the gel permeation chromatography method of the polynaphthylene which has a phenolic hydroxyl group can be adjusted by changing the kind and quantity of the said one-electron oxidizing agent and reaction solvent.
<1-1-2> Step 2
The step 2 is a step of synthesizing a polynaphthylene having an ethylenically unsaturated group by reacting the hydroxypolynaphthylene synthesized in the step 1 with a halide having an ethylenically unsaturated group.

  Examples of the halide having an ethylenically unsaturated group include allyl chloride, allyl bromide, 4-chloro-1-butene, 3-chloro-1-butene, 1-chloro-3-methyl-2-butene, Examples include chloromethyl acrylate, chloromethyl methacrylate, chloroethyl acrylate, and chloroethyl methacrylate. The halide having an ethylenically unsaturated group may be used alone or in combination of two or more.

  The usage-amount of the halide which has the said ethylenically unsaturated group is 1-5 mol normally with respect to 1 mol of phenolic hydroxyl groups of the naphthalene derivative converted into an ethylenically unsaturated group.

  The reaction in Step 2 is usually carried out after converting the phenolic hydroxyl group of the naphthalene derivative having a phenolic hydroxyl group to an alkali metal salt using an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide. At this time, the usage-amount of an alkali metal hydroxide is 1-5 mol normally with respect to 1 mol of phenolic hydroxyl groups of the naphthalene derivative converted into an ethylenically unsaturated group.

  The reaction in Step 2 is usually performed using a polar solvent such as n-propanol, 2-propanol, n-butanol, acetone, methyl ethyl ketone, dimethyl sulfoxide, N, N-dimethylformamide as a reaction solvent.

  The reaction conditions in the reaction of the step 2 are usually 10 ° C. to 100 ° C. and 0.1 to 10 hours.

After completion of the reaction in Step 2, the reaction solution contains impurities other than polynaphthylene having an ethylenically unsaturated group such as a catalyst residue. For this reason, after completion | finish of reaction, it is preferable to refine | purify by a well-known purification method, for example, a reprecipitation method and a liquid washing method.
<1-1-3> Step 3
The step 3 is a step of oxidizing the ethylenically unsaturated group of the polynaphthylene having an ethylenically unsaturated group synthesized in the step 2 to synthesize a polynaphthylene having an epoxy group.

  In the step 3, the oxidation is usually performed using an oxidizing agent in a reaction solvent. Examples of the oxidizing agent include nitric acid, m-chloroperbenzoic acid, peracetic acid, and performic acid.

  Examples of the reaction solvent include alcohols such as methanol, ethanol and propanol; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and cyclohexane; halogens such as chloroform; and aromatic carbonization such as benzene and toluene. Hydrogen is mentioned.

  The oxidation may be performed in a two-layer system of water and an organic solvent layer using a phase transfer catalyst such as a quaternary ammonium salt.

  The conditions for the oxidation are usually 10 ° C. to 100 ° C. and 2 to 40 hours.

After completion of the reaction in step 3, the reaction solution contains impurities other than polynaphthylene having an epoxy group such as a catalyst residue. For this reason, after completion | finish of reaction, it is preferable to refine | purify by a well-known purification method, for example, a reprecipitation method and a liquid washing method.
<2> Composition The composition of the present invention contains the polymer (A) and a solvent (hereinafter, also referred to as “solvent (B)”) as essential components. "Curing accelerator (C)") and a crosslinking agent (hereinafter also referred to as "Crosslinking agent (D)").
<2-1> Solvent (B)
The solvent (B) is used for uniformly mixing the polymer (A) and other components to improve the handleability, adjust the viscosity of the composition, and improve the storage stability of the composition. It is.

  Examples of the solvent (B) include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. Monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as butyl cellosolve; Carbitols such as Tol; lactate esters such as ethyl lactate; aliphatic carboxylic acid esters such as ethyl acetate, isopropyl acetate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl propionate, methyl pyruvate, ethyl pyruvate; ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide; γ-butyrolacun Lactones such as; aromatic hydrocarbons such as toluene and xylene; and alcohols such as methanol, ethanol, and propanol.

  Among these, ketones, ethers, and alcohols are preferable because the polymer (A) can be uniformly dissolved.

  A solvent (B) may be used individually by 1 type, and may be used in combination of 2 or more types.

The usage-amount of a solvent (B) is a quantity from which the solid content density | concentration of a composition will be 1-90 mass% normally, and is suitably adjusted with the objective and use of a composition.
<2-2> Curing accelerator (C)
The curing accelerator (C) is for the purpose of accelerating the crosslinking reaction of the group having an epoxy group or the group having an ethylenically unsaturated double bond, which is a crosslinkable group of the polymer (A), and accelerates the curing rate. A curing accelerator used in a normal crosslinking reaction can be used.

When the crosslinkable group of the polymer (A) is a group having an epoxy group, examples of the curing accelerator (C) include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, anhydrous Acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride; diethylammonium triflate, triethylammonium triflate, Trifluorate salts such as diisopropylammonium triflate and ethyl isopropylammonium triflate; Boron compounds such as metal fluoroboron complex and boron trifluoride complex; Bis (perfluoroalkylsulfonyl) methane metal salt; PCl ₅ , TiCl _4, Al p- toluenesulfonic acid, organic acids such as p- toluenesulfonic acid ester;; l _3, inorganic acids such as TeOMe dicyandiamide, diethyl toluene diamine, bases such as meta-xylene diamine; and the like.

  When the crosslinkable group of the polymer (A) is a group having an ethylenically unsaturated double bond, examples of the curing accelerator (C) include IRGACURE127, 184, 369, 651, 754, 907, 2959, OXE01, and OXE02 (manufactured by BASF, trade name), pentafluorophenyl borate toluylcumyl iodonium salt, Sun-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110L, SI-145, SI-145, SI-150, SI-160, SI-110L, and SI-180L Radical polymerization initiators such as (Sanshin Chemical Industry Co., Ltd., product name).

  A hardening accelerator (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of a hardening accelerator (C) is 0.5-50 mass parts normally with respect to a total of 100 mass parts of the said polymer (A) and a crosslinking agent (B), Preferably it is 1-30 mass parts. is there. When content of a hardening accelerator (C) is the said range, the hardened | cured material which has the outstanding adhesive strength can be obtained.
<2-3> Crosslinking agent (D)
The crosslinking agent (D) is used for the purpose of adjusting the curing rate of the composition or for the purpose of improving the adhesive strength.

  The crosslinking agent (D) may be any compound that undergoes a crosslinking reaction by heat. For example, a compound having an epoxy group (hereinafter also referred to as “epoxy crosslinking agent”), a benzoxazine ring-containing compound (hereinafter referred to as “benzoxazine”). A compound having active methylene (hereinafter also referred to as “active methylene crosslinking agent”), a compound having an oxetane group (hereinafter also referred to as “oxetane crosslinking agent”), a compound having an isocyanate group (hereinafter referred to as “crosslinking agent”). And an “oxazoline ring-containing compound” (hereinafter, also referred to as “oxazoline cross-linking agent”). These crosslinking agents may be low molecular weight or high molecular weight.

  The said epoxy crosslinking agent shows the compound which has an epoxy group except the said polymer (A).

  Examples of the epoxy crosslinking agent include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy. Resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, epoxy resin of aliphatic epoxy resin; resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol Polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, ethylene / polyethylene Glycol diglycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, epoxy compounds such as trimethylolpropane triglycidyl ether; and the like.

  Examples of the benzoxazine crosslinking agent include compounds described in JP-A No. 2006-335671, JP-A 2008-195907, JP-A 2012-036318, and JP-A 2009-001755.

  Examples of the active methylene crosslinking agent include compounds described in JP-A Nos. 6-180501, 2006-178059, and 2012-226297. Specifically, melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5,5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5,5] undecane A compound obtained by methylolating guanamine, etc .; and all of active methylol groups in the compound Or guanamine-based crosslinking agent such as compounds obtained by alkyl etherification or acetoxylation part; and the like.

  Examples of the oxetane cross-linking agent include compounds described in JP 2010-197996 A. Specifically, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (trade name “OXT-121”, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[ (3-Ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name “OXT-221”, manufactured by Toagosei Co., Ltd.), 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (Ube Industries, trade name “ETERNACOLL OXBP”), bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [(3-Ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl Nyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and tetra [(3-ethyl-3- Oxetanylmethoxy) methyl] benzene.

  As said isocyanate crosslinking agent, the compound as described in Unexamined-Japanese-Patent No. 2005-298724 and Unexamined-Japanese-Patent No. 2012-128099 is mentioned, for example. Specific examples include tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.

  Examples of the oxazoline crosslinking agent include 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), and 2,2′-bis (4-ethyl-2-). Oxazoline), 2,2′-bis (5-methyl-2-oxazoline), 2,2′-bis (4,4-dimethyl-2-oxazoline), 2,2′-bis (5,5-diethyl-) 2-oxazoline), 2,2′-bis (4-propyl-2-oxazoline), 2,2′-bis (4-phenyl-2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ) Ethane, 1,2-bis (4-methyl-2-oxazolin-2-yl) ethane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,4-bis (4,4-dimethyl) -2-oxazolin-2-yl) cyclohexane, 1 3-bis (2-oxazolin-2-yl) benzene, 1,2-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,3-bis (4-methyl-2-oxazolin-2-yl) Yl) benzene, 1,3-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,3-bis (4,4-dimethyl-2-oxazolin-2-yl) benzene, 1,4- Bis (4,4-dimethyl-2-oxazolin-2-yl) naphthalene, 2,2′-bis (2-oxazolin-2-yl) biphenyl, 2,6-bis (4,4-dimethyl-2-oxazoline) -2-yl) pyridine and 2,2′-9,9′-diphenoxyethanebis (2-oxazoline).

  Among the crosslinking agents (D), an epoxy crosslinking agent is preferable from the viewpoint of adhesive strength, and among the epoxy crosslinking agents, a bisphenol-type epoxy resin is preferable.

  A crosslinking agent (D) may be used individually by 1 type, and may be used in combination of 2 or more types.

Content of a crosslinking agent (D) is 10-2000 mass parts normally with respect to 100 mass parts of said polymers (A), Preferably it is 100-1500 mass parts, More preferably, it is 150-1000 mass parts. When the usage-amount of a crosslinking agent (D) is the said range, the hardened | cured material which has the outstanding adhesive strength can be obtained.
<2-4> Other components In the composition of the present invention, the polymer (A), the solvent (B), the curing accelerator (C) and the crosslinking agent (within a range not impairing the identification of the composition of the present invention). Components other than D) (hereinafter also referred to as “other components”) can be contained.

Examples of other components include, for example, γ-methacryloxypropyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate, and 1,2, Adhesion aids such as 3-benzotriazole; flame retardants such as phosphazene compounds and bromides for improving the flame retardancy of cured products; rubbers, rubber particles, etc. for imparting flexibility to the cured products Elasticity imparting agent; inorganic particles such as silica and titanium oxide; colorants such as dyes and pigments for imparting color to the cured product; fibers such as carbon fiber, glass fiber and synthetic resin fiber; polyethylene, polystyrene, And thermoplastic resins such as polyurethane.
<2-5> Production of Composition The composition of the present invention comprises the polymer (A) and the solvent (B) as essential components, and, if necessary, the curing accelerator (C) and the crosslinking agent ( It can be produced by mixing D) and the other components. Moreover, you may remove the dust contained in a composition with a filter etc. after mixing.
<3> Cured Product The cured product of the present invention is a cured product obtained by heat curing the polymer of the present invention or the composition of the present invention. The cured product of the present invention can be used, for example, as a matrix for FRP.

The curing conditions of the cured product of the present invention are usually 100 ° C. or higher, preferably 100 to 300 ° C., more preferably 150 to 250 ° C., and 0.1 to 10 hours, preferably 0.5 to 5 hours. Prior to the heat curing, heating may be performed at a temperature lower than 50 ° C. as preliminary curing.
<4> Film adhesive The film adhesive of the present invention is a film obtained by thermosetting the thermosetting resin composition of the present invention so that the degree of curing is in a semi-cured state (B stage). Semi-cured product. Alternatively, a semi-cured product can be produced by impregnating a thermosetting resin composition into fibers such as non-woven cloth. The curing conditions are usually 50 ° C. or higher and 0.1 to 2 hours. Further, curing may be performed while pressing the polymer or composition at a pressure of about 0.01 to 1 MPa during curing. Prior to the heat curing, heating may be performed at a temperature lower than 150 ° C. as preliminary curing. Moreover, the film adhesive of this invention can also be manufactured by thermosetting the thermosetting resin composition of this invention on a peeling film.

Since the film adhesive of this invention is manufactured using the thermosetting resin composition of this invention, it is excellent in shear strength and peel strength. Furthermore, the film adhesive of the present invention is excellent in heat resistance.
<5> Laminate The laminate of the present invention is a laminate including the film adhesive of the present invention. The laminate of the present invention is produced by, for example, laminating and curing other layered members such as metal members and fiber reinforced plastics through the film adhesive of the present invention. Since the laminate of the present invention uses the thermosetting resin composition of the present invention, the laminate has characteristics of high shear strength and difficulty in delamination.

  Since the laminate of the present invention has the characteristics of high shear strength and resistance to delamination, it can be suitably used for ships, automobiles, aircraft, building materials, sports equipment, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.
[1] Measuring method of physical properties [1-1] Measuring method of weight average molecular weight (Mw) of polymer The weight average molecular weight (Mw) was measured by gel permeation chromatography under the following conditions.
Column: Tosoh column TSK-M and TSK2500 connected in series Solvent: Tetrahydrofuran Temperature: 40 ° C
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8220-GPC”
[1-2] Identification method of polymer (A) The polymer was identified by ¹ H-NMR and infrared spectroscopic analysis. Infrared spectroscopic analysis was measured by the following method.

The polymer was dissolved in 2-methylethanol to prepare a solution having a solid concentration of 20% by mass. The solution was applied onto a substrate made of polyethylene terephthalate by a doctor blade method, and heated at 70 ° C. for 30 minutes and at 120 ° C. for 30 minutes to obtain a coating film. The coating film was peeled off from the substrate, fixed to a metal frame with an adhesive tape, and then vacuum dried at 120 ° C. for 2 hours to obtain an infrared evaluation film having a thickness of 20 μm. This infrared evaluation film was subjected to infrared spectroscopic analysis with an infrared spectroscope.
[2] Synthesis of Polymer According to the synthesis scheme shown in the following formula (5), a polymer (A1), a polymer (A2), and a polymer (A3) were synthesized.

[Synthesis Example 1] Synthesis of polymer (a1) In a flask under nitrogen atmosphere, 2,6-dihydroxynaphthalene (20.00 g, 0.125 mol), di-μ-hydroxo-bis [(N, N, While stirring a mixture of N ′, N′-tetramethylethylenediamine) copper (II)] chloride (0.58 g, 0.125 mmol) and 380 mL of 2-methoxyethanol at 25 ° C., 31% by mass was added to this mixture. % Hydrogen peroxide solution (13.7 g) was added dropwise over 2 hours, and the mixture was stirred at 25 ° C. for 3 hours. Thereafter, 1000 ml of water was added to the mixture. The precipitated solid was separated by filtration, and the filtrate was vacuum dried at 80 ° C. to obtain a powdery polymer (a1).

The weight average molecular weight of the polymer (a1) was 48,000. An infrared spectrum of the polymer (a1) is shown in FIG.
[Example 1] Synthesis of polymer (A1) Sodium hydroxide (3.80 g) was dissolved in water (250 g) in a flask to prepare a sodium hydroxide solution. Polymer (a1) (6.00 g) was added to an aqueous sodium hydroxide solution, and the mixture was stirred at 25 ° C. While stirring at 25 ° C., a solution of allyl bromide (13.8 g) dissolved in ethanol (30 ml) was dropped into the flask over 30 minutes, and then stirred at 25 ° C. for 12 hours. The solid precipitated in the flask was filtered off, and the residue was washed with water and vacuum dried at 50 ° C. to obtain a powdery polymer (A1). The results of ¹ H-NMR measurement of the polymer (A1) are shown below.

¹ H-NMR (solvent: CDCl ₃₎ chemical shifts σ: 7.8~6.9ppm (benzene ring on _{hydrogen, 4H), 6.0~5.6ppm (CH 2} = C H -CH 2 -O, 2H _{), 5.3~4.8ppm (CH 2 = CH} -C H 2 -O, 4H), 4.8~4.3ppm (CH 2 = CH-C H 2 -O, 4H)
Example 2 Synthesis of Polymer (A2) Polymer (A1) (6.88 g) was dissolved in tetrahydrofuran (200 g) in a flask to prepare a solution. This solution was cooled to 0 ° C., 69% by mass of m-chloroperbenzoic acid aqueous solution (36.5 g) was added dropwise over 30 minutes, and the solution was added at 0 ° C. for 1 hour and at 25 ° C. for 1 hour. , And stirred at 50 ° C. for 8 hours. Subsequently, the volatile matter in the solution was distilled off. The residue after evaporation was dissolved in tetrahydrofuran (30 g), and then reprecipitated using methanol (500 ml) as a poor solvent. The precipitated solid was separated by filtration, and the residue was washed with methanol and vacuum dried at 50 ° C. to obtain a powdery polymer (A2).

The result of NMR measurement of the polymer (A2) is shown below.
¹ H-NMR (solvent: CDCl ₃₎ chemical shifts σ: 7.8~6.9ppm (benzene ring on _{hydrogen, 4H), 6.0~5.6ppm (CH 2} = C H -CH 2 -O, XH _{), 5.3~4.8ppm (C H 2 =} CH-CH 2 -O, 2XH), 4.8~4.3ppm (CH 2 = CH-C H 2 -O, 2XH), 4.4~ _{4.0ppm (CH 2 ▽ CH-C} H 2 -O, 4YH), 3.2~1.8ppm (C H 2 ▽ C H -CH 2 -O, 6YH)
When the X and Y values were calculated, X = 0.58 and Y = 0.42. In the synthesis of the polymer (A2), it was revealed that 42 mol% of allyl groups out of all allyl groups of the polymer (A1) were epoxidized.
[Example 3] Synthesis of polymer (A3) The same operation as in Example 2 was carried out except that the amount of m-chloroperbenzoic acid aqueous solution used was changed, and 20 of all allyl groups of polymer (A1). A polymer (A3) in which mol% of the allyl group was epoxidized was obtained.
Synthesis Example 2 Synthesis of Polymer (D4) n-Butylamine (29.3 g) was stirred at 35 ° C. in a solution (270 g) in which polyhydroxystyrene (24 g) in the flask was dissolved in butyl acetate. Was dripped. Then, an aqueous paraformaldehyde (24 g) solution was added dropwise. After dropping, the inside of the flask was replaced with nitrogen, and heated at 23 ° C. for 30 minutes, 50 ° C. for 1 hour, 75 ° C. for 1 hour, and 110 ° C. for 9 hours. The heated solution was washed twice with an aqueous NaOH solution (concentration: 3% by mass), three times with acetic acid (concentration: 10% by mass), and further twice with water, and then volatile components such as butyl acetate were reduced in pressure. The polymer (D4) (Mw: 5,000) was obtained by removing with a distiller. The polymer (D4) was a polymer composed of 95 mol% of structural units represented by the following formula (d4) and 5 mol% of structural units represented by the following formula (d4 ′).

[3] Production of composition [Example 4]
In a paint shaker (using 2.5 mmφ zirconia beads), 10 parts of the polymer (A2), “jER828” (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 190 g / eq) 50 Part, "jER834" (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 230-270 g / eq), 10 parts, "Kane Ace MX-153" (trade name, manufactured by Kaneka Corporation, 10 parts of a composition in which 33% by mass of core-shell rubber particles were dispersed in a bisphenol A type liquid epoxy resin, 10 parts of dicyandiamide, and 60 parts of cyclopentanone were mixed to obtain the composition of Example 4. A cured product was produced using the obtained composition, and predetermined evaluation was performed.

[Examples 5 to 7, Comparative Example 1]
A composition was prepared in the same manner as in Example 4 except that the types and amounts of the ingredients were changed as shown in Table 1. A cured product was produced using the obtained composition, and predetermined evaluation was performed.

Details of each component in Table 1 are as follows.
(A2): Polymer synthesized in Example 2 (A2)
(A3): Polymer synthesized in Example 3 (A3)
(RA1): Novolac type epoxy resin (Mw = 10000)
(B1): cyclopentanone (C1): dicyandiamide (C2): cyclohexyl p-toluenesulfonate (D1): “jER828” (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 190 g / Eq)
(D2): “jER834” (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent of 230 to 270 g / eq)
(D3): “Kane Ace MX-153” (trade name, manufactured by Kaneka Corporation, a composition in which 33% by mass of core-shell rubber particles are dispersed in a bisphenol A liquid epoxy resin)
(D4): Polymer synthesized in Synthesis Example 2 (D4)
(D5): Trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX321L”)
[4] Production and Evaluation of Cured Product A production method and an evaluation method of the cured product are as follows.
[4-1] Production of cured product The composition was dip-coated on a nonwoven fabric (nylon nonwoven fabric manufactured by Nippon Vilene Co., Ltd., film thickness 40 um, basis weight 13 g / m ² ), heated at 80 ° C. for 10 minutes, and 0.04 MPa. While pressing, the film was heated at 100 ° C. for 30 minutes to obtain a film adhesive comprising a cured product and a nonwoven fabric.
[4-2] Adhesive strength Adhesive strength was evaluated by shear strength. After the film-like adhesive obtained in “[4-1] Production of cured product” was cut into a size of 25 mm × 12.5 mm, two aluminum plates (size: 25 mm × 100 mm, thickness: 2 mm) ) And heated at 180 ° C. for 2 hours to prepare a shear strength evaluation sample. The sample was pulled in the 180 degree direction with an Instron tester, and the maximum load was evaluated as the shear strength. The evaluation results are shown in Table 1.
[4-3] Heat resistance The heat resistance of the cured product was evaluated at a 5% by mass thermal weight reduction temperature (° C). The film adhesive obtained in the above-mentioned “[4-1] Production of cured product” was heated at 180 ° C. for 2 hours to prepare a sample for evaluation. With a TG / DTA measuring device, the 5% weight reduction temperature of the sample for evaluation was measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere.

Claims (9)

A polymer having a polynaphthylene structure containing at least one structural unit selected from the following formula (1) and the following formula (2).

(In the formulas (1) and (2), R ¹ and R ³ each represent a group bonded to the naphthalene ring via an oxygen atom, a group having an epoxy group or an ethylenically unsaturated group, or —CH ₂ represents a group represented by OR ⁵ , R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group, and when a plurality of R ¹ and R ³ are present, R ¹ and R ³ may be the same as or different from each other, and R ² and R ⁴ each represent a group bonded to a naphthalene ring and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. When a plurality of R ² and R ⁴ are present, R ² and R ⁴ may be the same or different from each other, a and c each represent an integer of 1 to 6; d represents an integer of 0 to 5, and a + b = 6 And c + d = 6, and m and n each represents an integer of 2 or more.)   The polymer according to claim 1, wherein the polymer has a structural unit represented by the formula (1). The polymer according to claim 2, wherein the structural unit represented by the formula (1) is represented by the following formula (3).

(In the formula, R ¹ and m are the same as R ¹ and m in the formula (1), respectively.)   A composition comprising the polymer according to claim 1 and a solvent.   Furthermore, the composition of Claim 4 containing a hardening accelerator and a crosslinking agent.   Hardened | cured material obtained by hardening | curing the polymer in any one of Claims 1-3.   A cured product obtained by curing the composition according to claim 4 or 5.   A film-like adhesive obtained by impregnating at least a composition according to claim 4 or 5 into a fiber and semi-curing the fiber.   The laminated body formed by laminating | stacking a layered member through the film adhesive of Claim 8.

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