Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/58—[b]- or [c]-condensed
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines

Definitions

• the present invention relates to an amino group-containing compound having a specific structure, a curable resin composition containing the compound, a cured product, and a laminate containing a layer made of the cured product.
• the cured products obtained from epoxy resins have excellent heat resistance, mechanical strength, electrical properties, and adhesive properties, making them indispensable materials in a variety of fields, including electrical and electronics, paints, and adhesives.
• thermosetting resins such as epoxy resins
• cured products made from thermosetting resins have low long-term reliability.
• a cured epoxy resin deteriorates due to oxidation, cracks may occur.
• thermosetting resins such as epoxy resins cannot be dissolved in solvents (is insoluble) and does not melt even at high temperatures (is infusible). This means that they are poorly recyclable and reusable, and the hardened product becomes waste after use. For this reason, reducing waste and mitigating the burden on the environment is an issue.
• a method has been disclosed in which a thermally decomposable compound is blended into the reactive adhesive component in advance, and then after use, a certain amount of heat is applied to reduce the adhesive strength, making the adhesive dismantlable (see, for example, Patent Document 1).
• the object of the present invention is to provide a compound that is a curable resin but can easily achieve repairability and remolding in the cured product, and a curable resin composition and a cured product thereof made using the same.
• An amino group-containing compound having a molecular weight of less than 1,000 represented by the following general formula:
• m is an integer of 1 to 10.
• Z1 's are each independently a hydrogen atom, an amino group, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and at least one of Z1 's is an amino group or a group having an amino group as a substituent.
• Z3 is any of the structures represented by the following formula (2).
• R' is a divalent hydrocarbon group having 2 to 12 carbon atoms
• R 1 , R 2 and R'' are each independently a hydrogen atom, a methyl group or an ethyl group
• n1 is an integer from 1 to 30
• n2 is the average number of repetitions and is 0.5 to 8
• * represents a bonding point.
• a curable resin composition comprising, as essential components, the amino group-containing compound according to [1] above and a compound (I) reactive with the amino group-containing compound.
• the curable resin composition according to [2] wherein the concentration of reversible bonds in the amino group-containing compound relative to the total mass of the curable components in the curable resin composition is 0.10 mmol/g or more.
• the curable resin composition according to [2] or [3], wherein the compound (I) reactive with the amino group-containing compound is an epoxy resin.
• each Ar is independently a structure having an unsubstituted or substituted aromatic ring
• X' is a structural unit represented by the following general formula (3-1)
• Y' is a structural unit represented by the following general formula (3-2):
• R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group
• R' is a divalent hydrocarbon group having 2 to 12 carbon atoms
• R 3 , R 4 , R 7 and R 8 each independently represent a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group
• R 5 , R 6 , R 9 , and R 10 each independently represent a hydrogen atom or a methyl group
• n1 is an integer from 4 to 16
• n2 is the average number of repeating units and is from 2 to 30.
• R 11 and R 12 each independently represent a glycidyl ether group or a 2-methylglycidyl ether group
• R 13 and R 14 each independently represent a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group
• R 15 and R 16 each represent a hydrogen atom or a methyl group
• m3, m4, p1, p2, and q are the average values of the repetitions, m3 and m4 each independently represent 0 to 25, and m3+m4 ⁇ 1
• p1 and p2 each independently represent 0 to 5; q is 0.5 to 5.
• the bond between X' represented by the general formula (3-2) and Y' represented by the general formula (3-2) may be random or block, and the total numbers of the structural units X' and Y' present in one molecule are m3 and m4, respectively.
• a method for producing an amino group-containing compound comprising synthesizing the amino group-containing compound represented by the formula (1) in situ during a process of curing the compound with a compound (I) reactive with the amino group-containing compound, using a diene-philic intermediate represented by the following general formula (1)': [13] A cured product obtained by curing reaction of the above formula (1)', anthracene having an amino group, and compound (I) reactive with the amino group-containing compound described in [1] above as essential raw materials.
• the present invention makes it possible to impart repairability and remoldability to a cured product made from a curable resin composition, thereby contributing to extending the life of the cured product itself and reducing waste.
• the amino group-containing compound according to one embodiment of the present invention is a compound represented by the following general formula and having a molecular weight of less than 1,000.
• m is an integer of 1 to 10.
• Z1 's are each independently a hydrogen atom, an amino group, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and at least one of Z1 's is an amino group or a group having an amino group as a substituent.
• Z3 is any of the structures represented by the following formula (2).
• R' is a divalent hydrocarbon group having 2 to 12 carbon atoms
• R 1 , R 2 and R'' are each independently a hydrogen atom, a methyl group or an ethyl group
• n1 is an integer from 1 to 30
• n2 is the average number of repetitions and is 0.5 to 8
• * represents a bonding point.
• the general formula (1) has a reversible bond formed by an anthracene structure and a maleimide structure at the molecular end.
• the terminal anthracene structure in the general formula (1) has one or more Z 1s , and this amino group contributes to the curing reaction in the curable resin composition described below.
• m is the number of Z 1s in the anthracene-derived structure and is an integer of 1 to 10, but from the viewpoints of industrial availability of raw materials and ease of control of the curing reaction, it is preferably in the range of 1 to 4, and more preferably 1 or 2.
• Z1 is preferably one having the following structural formula:
• the site that links the maleimide-derived structure is Z3, which is any of the structures represented by the general formula (2).
• n1 is an integer from 1 to 30, preferably in the range of 1 to 12.
• n2 is the average number of repeats, preferably in the range of 0.5 to 8, and 2 to 3.
• n3 is the average number of repeats, preferably in the range of 0.5 to 6, and 2 to 4.
• amino group-containing compound of the present invention examples include, but are not limited to, those shown below.
• the method for producing an amino group-containing compound which is one embodiment of the present invention, is not particularly limited, and may be produced stepwise using known reactions depending on the desired structure, and may also be obtained by appropriately combining commercially available raw materials.
• a representative synthesis method is described below.
• the general formula (1) has two Diels-Alder reaction units in the molecule.
• the Diels-Alder reaction unit is an addition reaction part formed by a Diels-Alder reaction consisting of an anthracene structure and a maleimide structure as a reversible bond.
• the general formula (1) can be obtained by using an anthracene compound having the structure Z1 .
• Diels-Alder reaction in which a conjugated diene such as an anthracene structure and a parent diene such as a maleimide structure undergo an addition reaction to form a six-membered ring, is an equilibrium reaction. At temperatures higher than the temperature at which the above addition reaction proceeds, the addition reaction site dissociates, and a retro-Diels-Alder reaction takes place, which is a reverse reaction returning to the original conjugated diene and parent diene.
• Examples of the anthracene compound having the structure of Z1 include any of the compounds listed in the following formulas. Among these, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene are preferred because of their good curability, and 1-aminoanthracene and 2-aminoanthracene are particularly preferred in terms of the balance between reactivity, cured product properties, and repairability and reshapeability.
• the structures of the maleimide compounds and anthracene compounds mentioned above each include those having, independently of one another, a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent.
• the alkoxy group, the aralkyloxy group, the aryloxy group, the carboxy group, the alkyloxycarbonyl group, the aryloxycarbonyl group, the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group also include those having various substituents bonded to the carbon atoms they have.
• the Diels-Alder reaction can be carried out by using known methods. For example, a conjugated diene compound and a parent diene compound are mixed in equimolar amounts, and in some cases one of the components is mixed in excess. The mixture is then heated to melt or dissolved in a solvent and stirred at room temperature to 200°C for 1 to 24 hours. The product can then be obtained by filtration or solvent distillation without purification. Alternatively, the product can be obtained by commonly used isolation and purification methods such as recrystallization, reprecipitation, and chromatography.
• Synthesis of sites other than the reversible bond can be performed by known methods.
• a compound having a maleimide group at the end can be obtained by reacting a diglycidyl ether of a dihydroxy compound or a divinyl compound with hydroxyphenylmaleimide. Then, by carrying out a Diels-Alder reaction with an anthracene compound having an amino group as described above, the compound represented by the general formula (1) can be obtained.
• a compound having a maleimide group at the end can be obtained by reacting hydroxyphenylmaleimide or the like with a dihalogenated alkylene compound or a dihalogenated aralkyl compound. Then, as described above, a Diels-Alder reaction can be carried out with an anthracene compound having an amino group to obtain the compound represented by the general formula (1).
• the diglycidyl ether of the aliphatic dihydroxy compound is not particularly limited, and examples thereof include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, Examples of such glycidyl ethers include 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl
• diglycidyl ethers may be used alone or in combination of two or more.
• examples of diglycidyl ethers of aromatic dihydroxy compounds include diglycidyl ethers of dihydroxybenzenes such as hydroquinone, resorcin, and catechol; diglycidyl ethers of dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; bis(4-hydroxyphenyl)methane, 2,2- Diglycidyl ethers of bisphenols such as bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxy
• compounds having a structure in which glycidyl groups are linked via ether groups to both ends of an alkylene chain having 4 to 12 carbon atoms are preferred because they provide an excellent balance between the flexibility and heat resistance of the resulting cured product, and it is most preferred to use 1,6-hexanediol diglycidyl ether or 1,10-decanediol diglycidyl ether.
• diglycidyl ethers of dihydroxybenzenes such as hydroquinone, resorcinol, and catechol are preferred because they provide an excellent balance between the rigidity and heat resistance of the resulting cured product.
• the divinyl compound is not particularly limited, and examples thereof include linear alkylene group divinyl ethers such as polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, and 1,10-decanediol divinyl ether, and branched alkylene group divinyl ethers such as neopentyl glycol divinyl ether.
• linear alkylene group divinyl ethers such as polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanediol divinyl
• vinyl ethers examples include divinyl ethers containing a cycloalkane structure, such as 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, and pentacyclopentadecanediol divinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroquinone divinyl ether, and divinylbenzene, which may be used alone or in combination of two or more.
• divinyl ethers containing a cycloalkane structure such as 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl
• divinyl ethers with a polyether structure or a linear alkylene chain having 9 to 10 carbon atoms are preferred because they provide an excellent balance between the flexibility and toughness of the resulting cured product, and it is most preferred to use polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, or 1,14-tetradecanediol diglycidyl ether.
• hydroquinone divinyl ether, divinylbenzene, etc. because they provide an excellent balance between the rigidity and heat resistance of the resulting cured product.
• the aromatic hydroxy compound is not particularly limited, and examples thereof include dihydroxybenzenes such as hydroquinone, resorcin, and catechol, trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene, triphenylmethane-type phenols such as 4,4',4"-trihydroxytriphenylmethane, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.
• dihydroxybenzenes such as hydroquinone, resorcin, and catechol
• trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene
• triphenylmethane-type phenols such as
• dihydroxynaphthalenes such as hydroxynaphthalene; tetrafunctional phenols such as 1,1'-methylenebis-(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetraol, and 1,1'-oxybis-(2,7-naphthalenediol) obtained by coupling reaction of dihydroxynaphthalenes; bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)cyclohexane.
• tetrafunctional phenols such as 1,1'-methylenebis-(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetraol, and 1,1'
• bisphenols such as bis(4-hydroxyphenyl)sulfone, 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl)-3,4-diol, 3,3'-dimethyl-(1,1'-biphenyl)-4,4'-diol, 3-methyl-(1,1'-biphenyl)-4,4'-diol, 3,3',5,5'-tetramethylbiphenyl-2,2'-diol, 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 5-methyl-(1,1'-biphenyl)-3,4'diol, 3'-methyl-(1,1' Examples of such phenols include biphenols such as 4'-methyl-(1,1'-biphenyl)-3,4'diol and 4'-methyl-(1,1'-biphenyl)-3,4'dio
• bifunctional phenolic compounds having a structure in which a methyl group, a t-butyl group, or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds may also be used.
• the alicyclic structure-containing phenols and the Zylok-type phenolic resins may contain not only bifunctional components but also trifunctional or higher components at the same time, and may be used as is, or may be subjected to a purification process such as a column to extract only the bifunctional components.
• dihydroxybenzenes and bisphenols are preferred because they provide an excellent balance between flexibility and toughness when cured, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferred because of their outstanding toughness-imparting properties.
• phenols that contain an alicyclic structure.
• the reaction ratio of the diglycidyl ether of the dihydroxy compound to the aromatic hydroxy compound is preferably in the range of 1.0/1.01 to 1.0/5.0 (molar ratio) of the former/latter.
• (a1)/(a2) is 1.0/1.1 to 1.0/3.0 (molar ratio).
• the reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the hydroxyphenylmaleimide is preferably carried out in the presence of a catalyst.
• a catalyst various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, etc., alkali metal carbonates such as sodium carbonate, potassium carbonate, etc., phosphorus compounds such as triphenylphosphine, etc., chlorides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, bromides, iodides, quaternary ammonium salts such as chlorides such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium
• Two or more of these catalysts may be used in combination.
• sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds quickly and the amount of impurities is highly reduced.
• the amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 moles per mole of the phenolic hydroxyl group of the hydroxyphenylmaleimide.
• the form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.
• the reaction between the diglycidyl ether of the dihydroxy compound and the hydroxyphenylmaleimide can be carried out without a solvent or in the presence of an organic solvent.
• organic solvents that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol.
• the amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination. In order to carry out the reaction quickly, it is preferable to use no solvent, while the use of dimethyl sulfoxide is preferable in terms of reducing impurities in the final product.
• the reaction temperature for the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. In terms of reducing impurities in the final product, a reaction temperature of 100 to 160°C is preferable.
• an antioxidant or reducing agent may be added to suppress this.
• the antioxidant is not particularly limited, but examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom.
• the reducing agent is not particularly limited, but examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.
• the reaction mixture can be neutralized or washed until its pH value reaches 3 to 7, preferably 5 to 7.
• the neutralization and washing can be carried out according to conventional methods.
• an acidic substance such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, or oxalic acid can be used as a neutralizing agent.
• the solvent can be distilled off under reduced pressure and heating to concentrate the product, and the compound can be obtained.
• the reaction ratio of the aliphatic divinyl ether and the hydroxyphenylmaleimide is preferably in the range of 1.0/1.01 to 1.0/5.0 (molar ratio) for the former/the latter, and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance of the resulting cured product, it is preferable that (a1)/(a2) is 1.0/1.02 to 1.0/3.0 (molar ratio).
• the reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently without the use of a catalyst, but it can be used appropriately in terms of the selection of raw materials and increasing the reaction rate.
• catalysts that can be used here include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid, and Lewis acids such as aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, and boron trifluoride phenol complex.
• the amount of catalyst used is usually in the range of 10 ppm to 1% by weight based on the mass of the divinyl ether compound. In this case, it is preferable to select the type and amount of catalyst to be used so as not to cause a nuclear addition reaction of the vinyl group to the aromatic ring.
• the reaction between the divinyl compound and the hydroxyphenylmaleimide can be carried out without a solvent or in the presence of an organic solvent.
• organic solvent include aromatic organic solvents such as benzene, toluene, and xylene; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol.
• the amount of the organic solvent used is usually 50 to 300% by mass, and preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.
• the reaction temperature for the above reaction is usually 50 to 150°C, and the reaction time is usually 0.5 to 10 hours. In this case, it is preferable to carry out the reaction in an oxygen atmosphere to prevent self-polymerization of vinyl.
• the dihalogenated alkylene compound is not particularly limited, and examples thereof include 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane, 1,11-dibromoundecane, and 1,12-dibromododecane. These compounds may be used alone or in combination of two or more.
• the dihalogenated aralkyl compound is not particularly limited, and examples thereof include dichloroxylene, dichloromethylbiphenyl, dibromoxylene, dibromomethylbiphenyl, etc., and may be used alone or in combination of two or more kinds.
• the reaction ratio of the hydroxyphenylmaleimide to the dihalogenated alkylene compound or dihalogenated aralkyl compound is preferably in the range of 1.0/1.01 to 1.0/5.0 (molar ratio) of the former/the latter, and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance of the resulting cured product, it is preferable that (a1)/(a2) is 1.0/1.02 to 1.0/3.0 (molar ratio).
• the reaction of the hydroxyphenylmaleimide with the dihalogenated alkylene compound or dihalogenated aralkyl compound is preferably carried out in the presence of a catalyst.
• a catalyst various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Two or more of these catalysts may be used in combination. Among them, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred because the reaction proceeds quickly and they are highly effective in reducing the amount of impurities.
• the amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 10 moles per mole of the phenolic hydroxyl group of the hydroxyphenylmaleimide.
• the form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.
• the reaction of the hydroxyphenylmaleimide with the dihalogenated alkylene compound or dihalogenated aralkyl compound can be carried out without a solvent or in the presence of an organic solvent.
• organic solvents examples include toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, and dimethylformamide.
• the amount of organic solvent used is usually 50 to 300% by mass, preferably 100 to 1000% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.
• the reaction temperature for the above reaction is usually room temperature to 150°C, and the reaction time is usually 1 to 24 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably room temperature to 100°C.
• the parent diene intermediate before the Diels-Alder reaction can be represented by the following general formula (1)'.
• the amino group-containing compound of the present invention can be used in combination with a compound (I) that is reactive with the amino group-containing compound to form a curable resin composition.
• the curable resin composition can be suitably used in various electrical and electronic component applications, such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials.
• the curable resin composition of the present invention is a curable resin composition that contains, as essential components, the amino group-containing compound of the present invention and a compound (I) that is reactive with the amino group-containing compound.
• Examples of the compound (I) that is reactive with the amino group-containing compound include melamine compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, hexamethylenetetramine and its modified products, and oxazoline compounds.
• Examples of the melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated, etc.
• guanamine compounds examples include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, and compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated.
• glycoluril compound examples include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.
• urea compound examples include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.
• the resol resin is, for example, a polymer obtained by reacting a phenolic hydroxyl group-containing compound, such as phenol, alkylphenol such as cresol or xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, naphthol, or dihydroxynaphthalene, with an aldehyde compound under alkaline catalytic conditions.
• a phenolic hydroxyl group-containing compound such as phenol, alkylphenol such as cresol or xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, naphthol, or dihydroxynaphthalene
• the epoxy resins include, for example, liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins; brominated epoxy resins such as brominated phenol novolac type epoxy resins; solid bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, and tetraphenylethane type epoxy resins.
• liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type
• dicyclopentadiene-phenol addition reaction type epoxy resins may be used alone or in combination of two or more kinds, and it is preferable to select and use various types depending on the intended use and physical properties of the cured product.
• isocyanate compound examples include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.
• azide compound examples include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.
• Examples of compounds containing a double bond such as the alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.
• the acid anhydride examples include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'-(isopropylidene)diphthalic anhydride, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.
• aromatic acid anhydrides such as phthalic anhydride, trimellitic an
• the concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol/g or more relative to the total mass of the curable components in the curable resin composition. With this configuration, both the repairability and reshapeability of the cured product obtained from the curable resin composition are further improved.
• the concentration of the reversible bond is more preferably 0.10 to 3.00 mmol/g, and even more preferably 0.15 to 2.00 mmol/g.
• the concentration of the reversible bond in the present invention can be appropriately selected based on the glass transition temperature of the target cured product defined by the tan ⁇ peak top of a dynamic viscoelasticity measuring device (DMA).
• DMA dynamic viscoelasticity measuring device
• the glass transition temperature of the cured product when used as a guideline, if the glass transition temperature of the cured product is near room temperature, sufficient repairability and reshapeability functions are likely to be expressed even at the low concentration side of the preferred range.
• the glass transition temperature of the target cured product exceeds 100°C as a guideline, the functions are likely to be expressed at the high concentration side of the preferred range.
• molecular mobility is generally high, and sufficient repairability and reshapeability functions are easily expressed even if the concentration of the amino group-containing compound is low.
• the effect of expressing the repairability and reshapeability functions can be adjusted by appropriately adjusting the aging temperature for repair and the heating temperature for reshaping.
• the relationship between the glass transition temperature of the cured product and the concentration of reversible bonds is not limited to these.
• the compound (I) that is reactive with the amino group-containing compound it is particularly preferable to use an epoxy resin, since this results in a curable resin composition that is excellent in curability, mechanical strength, heat resistance, etc., of the cured product.
• the epoxy resin may be an epoxy resin represented by the following formula (3) and having an epoxy equivalent of 500 to 10,000 g/eq.
• each Ar is independently a structure having an unsubstituted or substituted aromatic ring
• X' is a structural unit represented by the following general formula (3-1)
• Y' is a structural unit represented by the following general formula (3-2):
• R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group
• R' is a divalent hydrocarbon group having 2 to 12 carbon atoms
• R 3 , R 4 , R 7 and R 8 each independently represent a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group
• R 5 , R 6 , R 9 , and R 10 each independently represent a hydrogen atom or a methyl group
• n1 is an integer from 2 to 16
• n2 is the average number of repeating units and is from 2 to 30.
• R 11 and R 12 each independently represent a glycidyl ether group or a 2-methylglycidyl ether group
• R 13 and R 14 each independently represent a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group
• R 15 and R 16 each represent a hydrogen atom or a methyl group
• m3, m4, p1, p2, and q are the average values of the repetitions, m3 and m4 each independently represent 0 to 25, and m3+m4 ⁇ 1
• p1 and p2 each independently represent 0 to 5; q is 0.5 to 5.
• the bond between X' represented by the general formula (3-1) and Y' represented by the general formula (3-2) may be random or block, and the total numbers of the structural units X' and Y' present in one molecule are m3 and m4, respectively.
• an epoxy resin represented by the following formula (4) may be used as the epoxy resin.
• the repairability and remoldability of the cured epoxy resin are improved, and a good balance between flexibility and toughness is achieved.
• the epoxy resin represented by the general formula (3) or (4) may be used alone in combination with the amino group-containing compound of the present invention to form a curable resin.
• an epoxy resin having an epoxy equivalent of 100 to 300 g/eq in combination it is also preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g/eq in combination.
• the epoxy resins that can be used in combination as described above may have an epoxy equivalent in the range of 100 to 300 g/eq, and there are no limitations on their structure.
• liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins, brominated epoxy resins such as brominated phenol novolac type epoxy resins, solid bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclohexyl ether type epoxy resins, and the like.
• epoxy resins examples include butadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resins, biphenyl modified novolac type epoxy resins, and the like. These may be used alone or in combination of two or more kinds, and it is preferable to select and use various types depending on the intended use and physical properties of the cured product.
• liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, and tetramethylbiphenyl type epoxy resin, with an epoxy equivalent of 100 to 300 g/eq. It is particularly preferable to use liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD type epoxy resin, with an epoxy equivalent of 100 to 300 g/eq.
• the ratio of the epoxy resin represented by the general formula (3) or (4) to the epoxy resin having an epoxy equivalent of 100 to 300 g/eq is not particularly limited, but from the viewpoint of ease of phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 90:10 to 10:90, and particularly preferably 80:20 to 20:80.
• Phase separation in the cured product results in a sea-island structure, which balances the adhesiveness and stress relaxation ability of the cured product, exerts high adhesive strength over a particularly wide temperature range, and has the effect of reducing the molding shrinkage rate before and after heat curing of the resin composition.
• a curing agent for epoxy resins other than the amino group-containing compound of the present invention may be blended.
• Curing agents that can be used here include various known curing agents for epoxy resins, such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid compounds, and thiol compounds.
• the amine compounds include, for example, trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetramethylhexamethylenediamine ...
• Aliphatic amine compounds such as triethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, and ⁇ -methylbenzylmethylamine;
• Alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N',N"-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU);
• DBU 1,8-diazabicyclo-[5.4.0]-undecene
• Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, picoline, etc.;
• modified amine compounds such as epoxy compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, aminimides, boron trifluoride-piperidine complexes, and boron trifluoride-monoethylamine complexes.
• modified amine compounds such as epoxy compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, aminimides, boron trifluoride-piperidine complexes, and boron trifluoride-monoethylamine complexes.
• acid anhydrides examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic polypropylene glycol anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
• the phenolic hydroxyl group-containing compounds include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol adduct resins, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, and trimethylolmethane resins.
• bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphen
• tetraphenylolethane resin naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenolic resin (a polyhydric phenol compound in which the phenol nucleus is linked by a bismethylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which the phenol nucleus is linked by a bismethylene group), aminotriazine-modified phenolic resin (a polyhydric phenol compound in which the phenol nucleus is linked by melamine, benzoguanamine, etc.), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which the phenol nucleus and the alkoxy group-containing aromatic ring are linked by formaldehyde).
• biphenyl-modified phenolic resin a polyhydric phenol compound in which the phenol
• Examples of the amide-based compounds include dicyandiamide and polyamidoamine.
• Examples of the polyamidoamine include those obtained by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid, or a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.
• carboxylic acid compound examples include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.
• the thiol compound preferably contains two or more thiol groups in one molecule.
• Examples include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)g
• amine compounds particularly dicyandiamide
• solid phenol compounds are preferred in terms of the heat resistance of the cured product.
• aliphatic amines and thiol compounds are preferred in terms of low-temperature curing.
• the amounts of epoxy resin and curing agent used are not particularly limited, but in terms of the good mechanical properties of the resulting cured product, it is preferable to use an amount that provides 0.4 to 1.5 equivalents of active groups that can react with epoxy groups, including the amino group-containing compound of the present invention, per 1 equivalent of epoxy groups in the resin composition.
• a curing accelerator may be included.
• Various types of curing accelerators can be used, including urea compounds, phosphorus compounds, tertiary amines, imidazole, imidazoline, organic acid metal salts, Lewis acids, and amine complex salts.
• urea compounds particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred because of their excellent workability and low-temperature curing properties.
• triphenylphosphine When used as a semiconductor encapsulation material, triphenylphosphine is a phosphorus compound, and 1,8-diazabicyclo-[5.4.0]-undecene is a tertiary amine, and these compounds are preferred because of their excellent curing properties, heat resistance, electrical properties, and moisture resistance reliability.
• Examples of the phosphorus compound include alkyl phosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine, dialkyl phosphines such as dimethylphosphine and dipropylphosphine, secondary phosphines such as diphenylphosphine and methylethylphosphine, and tertiary phosphines such as trimethylphosphine, triethylphosphine, and triphenylphosphine.
• alkyl phosphines such as ethylphosphine and butylphosphine
• primary phosphines such as phenylphosphine
• dialkyl phosphines such as dimethylphosphine and dipropylphosphine
• secondary phosphines such as diphenylphosphine and methylethy
• the imidazole may, for example, be imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2- Isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-e
• imidazoline compound examples include 2-methylimidazoline and 2-phenylimidazoline.
• urea compounds examples include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, and N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea.
• the curable resin composition of the present invention may also be used in combination with other thermosetting resins or thermoplastic resins to the extent that the effects of the present invention are not impaired.
• thermosetting resins include, for example, cyanate ester resins, resins having a benzoxazine structure, active ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc.
• the amount used there are no particular restrictions on the amount used as long as it does not inhibit the effects of the present invention, but it is preferable for the amount to be in the range of 1 to 50 parts by mass per 100 parts by mass of the curable resin composition.
• cyanate ester resin examples include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenyl ether type cyanate ester resin, phenyl ...
• cyanate ester resin examples include phenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac type cyanate ester resin, naphthol-cresol co-condensed novolac type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolac type cyanate ester resin, anthracene type cyanate ester resin, etc. These may be used alone or in combination of two or more.
• cyanate ester resins it is preferable to use bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, and novolac type cyanate ester resin, in that they provide a cured product with excellent heat resistance, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that they provide a cured product with excellent dielectric properties.
• resins having a benzoxazine structure include reaction products of bisphenol F, formalin, and aniline (F-a type benzoxazine resin), reaction products of diaminodiphenylmethane, formalin, and phenol (P-d type benzoxazine resin), reaction products of bisphenol A, formalin, and aniline, reaction products of dihydroxydiphenyl ether, formalin, and aniline, reaction products of diaminodiphenyl ether, formalin, and phenol, reaction products of dicyclopentadiene-phenol adduct resin, formalin, and aniline, reaction products of phenolphthalein, formalin, and aniline, and reaction products of diphenyl sulfide, formalin, and aniline. These may be used alone or in combination of two or more.
• the active ester resin is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used.
• the active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
• an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and/or a naphthol compound is more preferred.
• the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or halides thereof.
• phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-phenol adduct resins.
• active ester resins that are preferred include active ester resins containing a dicyclopentadiene-phenol adduct structure, active ester resins containing a naphthalene structure, active ester resins which are acetylated phenol novolac, and active ester resins which are benzoylated phenol novolac.
• active ester resins containing a dicyclopentadiene-phenol adduct structure and active ester resins containing a naphthalene structure are more preferred because of their excellent ability to improve peel strength.
• novolak resins addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and various vinyl polymers may be used in combination.
• novolak resins include polymers obtained by reacting phenolic hydroxyl group-containing compounds such as phenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene with aldehyde compounds under acid catalyst conditions.
• the various vinyl polymers mentioned above include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly(meth)acrylate, or copolymers thereof.
• vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly(meth)acrylate, or copolymers thereof.
• Thermoplastic resins are resins that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether
• the blending ratio of the amino group-containing compound of the present invention to the other resins can be set as desired depending on the application.
• the curable resin composition of the present invention may also be used in combination with a curing accelerator.
• curing accelerators include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride and boron trifluoride amine complexes such as boron trifluoride monoethylamine complex; organic acid compounds such as thiodipropionic acid; benzoxazine compounds such as thiodiphenolbenzoxazine and sulfonylbenzoxazine; and sulfonyl compounds. These may be used alone or in combination of two or more.
• the amount of these catalysts added is preferably in the range of 0.001 to 15 parts by mass per 100 parts by mass of the curable resin composition.
• a non-halogen flame retardant that contains substantially no halogen atoms may be blended.
• non-halogen flame retardants examples include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. There are no limitations on their use, and they may be used alone or in combination with multiple flame retardants of the same type.
• the phosphorus-based flame retardant may be either inorganic or organic.
• inorganic compounds include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.
• the red phosphorus is preferably surface-treated to prevent hydrolysis or the like.
• the surface treatment method include the following methods (i) to (iii): (i) A method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. (ii) A method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc., and a thermosetting resin such as a phenolic resin. (iii) A method in which a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide or the like is coated twice with a thermosetting resin such as a phenolic resin.
• the organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as cyclic organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives of these compounds reacted with compounds such as epoxy resins and phenolic resins.
• general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus
• the amount of these phosphorus-based flame retardants to be blended is appropriately selected depending on the type of phosphorus-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy.
• red phosphorus when used as a non-halogen flame retardant, it is preferably blended in the range of 0.1 to 2.0 parts by mass per 100 parts by mass of the resin composition containing all of the non-halogen flame retardants and other fillers and additives.
• an organic phosphorus compound is used, it is similarly preferably blended in the range of 0.1 to 10.0 parts by mass, and more preferably in the range of 0.5 to 6.0 parts by mass.
• the phosphorus-based flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc.
• the nitrogen-based flame retardant may, for example, be a triazine compound, a cyanuric acid compound, an isocyanuric acid compound, or a phenothiazine, with triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds being preferred.
• the triazine compounds include, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, etc., as well as (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate, (2) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, and formguanamine and formaldehyde, (3) mixtures of the co-condensates of (2) with phenolic resins such as phenol formaldehyde condensates, and (4) compounds obtained by further modifying (2) and (3) with tung oil, isomerized linseed oil, etc.
• cyanuric acid compound examples include cyanuric acid, melamine cyanurate, etc.
• the amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the type of nitrogen-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin composition containing the non-halogen flame retardant and all other fillers and additives.
• metal hydroxides, molybdenum compounds, etc. may also be used in combination.
• the silicone-based flame retardant can be any organic compound containing silicon atoms, and examples of such compounds include silicone oil, silicone rubber, and silicone resin.
• the amount of silicone-based flame retardant to be used is appropriately selected depending on the type of silicone-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy. It is preferable to use 0.05 to 20 parts by mass of the silicone-based flame retardant in 100 parts by mass of the resin composition containing the non-halogen flame retardant and all other fillers and additives.
• a molybdenum compound, alumina, etc. may also be used in combination.
• inorganic flame retardant examples include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.
• metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, etc.
• metal oxide examples include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide.
• metal carbonate compounds examples include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
• metal powder examples include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
• Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
• low melting point glass examples include glassy compounds such as Seapley (Boxy Brown), hydrated glass SiO 2 -MgO-H 2 O, PbO-B 2 O 3 , ZnO-P 2 O 5 -MgO, P 2 O 5 -B 2 O 3 -PbO-MgO, P-Sn-O-F, PbO-V 2 O 5 -TeO 2 , Al 2 O 3 -H 2 O, and lead borosilicate.
• glassy compounds such as Seapley (Boxy Brown), hydrated glass SiO 2 -MgO-H 2 O, PbO-B 2 O 3 , ZnO-P 2 O 5 -MgO, P 2 O 5 -B 2 O 3 -PbO-MgO, P-Sn-O-F, PbO-V 2 O 5 -TeO 2 , Al 2 O 3 -H 2 O, and lead borosilicate.
• the amount of inorganic flame retardant to be blended is appropriately selected depending on the type of inorganic flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.05 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the resin composition containing the non-halogen flame retardant and all other fillers and additives.
• organometallic salt flame retardants examples include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organocobalt salt compounds, organosulfonic acid metal salts, and compounds in which a metal atom is ionic- or coordinate-bonded to an aromatic compound or heterocyclic compound.
• the amount of the organometallic salt flame retardant to be blended is appropriately selected depending on the type of organometallic salt flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.005 to 10 parts by mass per 100 parts by mass of the resin composition containing the non-halogen flame retardant and all other fillers, additives, etc.
• the curable resin composition of the present invention may contain a filler.
• the filler include inorganic fillers and organic fillers.
• examples of the inorganic filler include inorganic fine particles.
• Inorganic fine particles include, for example, those with excellent heat resistance, such as alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.); those with excellent thermal conductivity, such as boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, and diamond; those with excellent electrical conductivity, such as metal fillers and/or metal-coated fillers using simple metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.), tin oxide, and indium oxide; and those with excellent barrier properties, such as minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, and titanate.
• silica fine particles such as powdered silica and colloidal silica can be used without any particular limitation.
• powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Co., Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd.
• colloidal silica includes, for example, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL manufactured by Nissan Chemical Industries, Ltd.
• silica particles may also be used, for example, silica particles that have been surface-treated with a reactive silane coupling agent having a hydrophobic group, or silica particles that have been modified with a compound having a (meth)acryloyl group.
• a reactive silane coupling agent having a hydrophobic group or silica particles that have been modified with a compound having a (meth)acryloyl group.
• Commercially available powdered silica modified with a compound having a (meth)acryloyl group includes Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd.
• commercially available colloidal silica modified with a compound having a (meth)acryloyl group includes MIBK-SD manufactured by Nissan Chemical Industries, Ltd.
• the shape of the silica microparticles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous shapes can be used.
• the primary particle size is preferably in the range of 5 to 200 nm.
• Titanium oxide fine particles can be used not only as extender pigments but also as ultraviolet light responsive photocatalysts, such as anatase type titanium oxide, rutile type titanium oxide, and brookite type titanium oxide. Furthermore, particles designed to respond to visible light by doping different elements into the crystal structure of titanium oxide can also be used. Anionic elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cationic elements such as chromium, iron, cobalt, and manganese are preferably used as elements to be doped into titanium oxide.
• the form that can be used can be a powder, a sol dispersed in an organic solvent or water, or a slurry.
• Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by Teika Co., Ltd.
• Examples of commercially available slurry-type titanium oxide fine particles include TKD-701 manufactured by Teika Co., Ltd.
• the curable resin composition of the present invention may further contain a fibrous substrate.
• the fibrous substrate is not particularly limited, but is preferably one used in fiber-reinforced resins, such as inorganic fibers and organic fibers.
• Inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, as well as carbon fiber, activated carbon fiber, graphite fiber, tungsten carbide fiber, silicon carbide fiber (silicon carbide fiber), ceramic fiber, natural fiber, mineral fibers such as basalt, boron nitride fiber, boron carbide fiber, and metal fibers.
• the metal fibers include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.
• organic fibers examples include synthetic fibers made from resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as proteins, polypeptides, and alginic acid.
• resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate
• natural fibers such as cellulose, pulp, cotton, wool, and silk
• regenerated fibers such as proteins, polypeptides, and alginic acid.
• carbon fiber and glass fiber are preferred because they have a wide range of industrial applications. Of these, only one type may be used, or multiple types may be used simultaneously.
• the fibrous substrate may be an assembly of fibers, with either continuous or discontinuous fibers, and in the form of either a woven or nonwoven fabric. It may also be a fiber bundle in which the fibers are aligned in one direction, or in the form of a sheet in which fiber bundles are arranged. It may also be a three-dimensional shape in which the fiber assembly has thickness.
• the curable resin composition of the present invention may contain a dispersion medium for the purpose of adjusting the solid content and viscosity of the resin composition.
• the dispersion medium may be any liquid medium that does not impair the effects of the present invention, and examples of the dispersion medium include various organic solvents and liquid organic polymers.
• the organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether.
• ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK)
• cyclic ethers such as tetrahydrofuran (THF) and dioxolane
• esters such as methyl acetate, ethyl acetate, and butyl acetate
• the liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples include acrylic polymer (Floren WK-20: Kyoeisha), amine salt of special modified phosphate ester (HIPLAAD ED-251: Kusumoto Chemical), modified acrylic block copolymer (DISPERBYK2000; BYK-Chemie), etc.
• the resin composition of the present invention may contain other compounds, such as catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow control agents, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, and reactive diluents.
• the resin composition of the present invention may be a curable resin composition that is a self-repairing composition or a remolding material composition.
• the resin composition of the present invention can be cured to obtain a cured product.
• Curing can be performed at room temperature or by heating.
• curing can be performed by a single heating step or by going through a multi-stage heating process.
• the curable resin composition of the present invention can also be cured with active energy rays.
• a photocationic polymerization initiator can be used as the polymerization initiator.
• active energy rays include visible light, ultraviolet light, X-rays, and electron beams.
• photocationic polymerization initiators include aryl-sulfonium salts and aryl-iodonium salts. Specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetrakis(pentafluoro)borate, tri(alkylphenyl)sulfonium hexafluorophosphate, etc. can be used.
• the photocationic polymerization initiators may be used alone or in combination of two or more kinds.
• the curable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned components, and the method for doing so is not particularly limited.
• it can be prepared by uniformly mixing the components using a pot mill, ball mill, bead mill, roll mill, homogenizer, super mill, homodisper, universal mixer, Banbury mixer, kneader, etc.
• the curable resin composition of the present invention is prepared by dissolving the amino group-containing compound of the present invention and the compound (I) reactive with the amino group-containing compound, as well as the curing agent, filler, fibrous substrate, dispersion medium, and resin other than the various compounds described above, which can be used in combination, in a dispersion medium such as the organic solvent described above, as necessary. After dissolution, the solvent is distilled off, and the curable resin composition can be obtained by drying under reduced pressure using a vacuum oven or the like.
• the curable resin composition of the present invention may also be in a state in which the above-mentioned constituent materials are uniformly mixed. In this case, it is preferable to mix the materials uniformly using a mixer or the like.
• the mixing ratio of each constituent material can be appropriately adjusted depending on the desired characteristics of the cured product, such as mechanical strength, heat resistance, repairability, and remoldability.
• the order in which the constituent materials are mixed is not particularly limited in the preparation of the curable resin composition.
• the cured product of the present invention is obtained by curing a compound (I) reactive with the amino group-containing compound of the present invention with the amino group-containing compound of the present invention.
• the curing method can be appropriately selected from known methods depending on the properties of the compound (I) reactive with the amino group-containing compound used.
• the cured product of the present invention is cured by the amino group-containing compound of the present invention as described above, and therefore can maintain good mechanical strength by exhibiting an appropriate crosslinking density.
• mechanical energy such as scratches or external force is applied to the cured product of the present invention, the reversible bonds are broken, but the equilibrium shifts in the direction of the bonds, so that an adduct is formed again, which is thought to enable the damage to be repaired and the product to be reshaped.
• IR infrared absorption
• FT-IR Fourier transform infrared spectroscopy
• the cured product which is one embodiment of the present invention, can be obtained by using the amino group-containing compound of the present invention as one component of a curable resin composition. It is also possible to use the aforementioned dienophilic intermediate, which is an intermediate of the amino group-containing compound, in combination with a compound capable of undergoing an addition reaction by Diels-Alder reaction, to form the amino group-containing compound during the curing process (while synthesizing in situ) to produce a cured product.
• the amino group-containing compound represented by the above formula (1) can be obtained during the curing reaction, and a cured product can be obtained as the curing reaction progresses.
• the anthracene having an amino group that can be used in this case is the same as described above.
• the curable resin composition of the present invention and the cured product produced from the curable resin composition have excellent heat resistance and repairability, and are remoldable, making them useful for the following applications:
• the curable resin cured product of the present invention can be laminated with a substrate to form a laminate.
• the substrate of the laminate can be an inorganic material such as metal or glass, or an organic material such as plastic or wood, and can be used as appropriate depending on the application.
• the substrate can be in the shape of a laminate, a flat plate, a sheet, or a three-dimensional structure, or it can be three-dimensional. It can be any shape depending on the purpose, such as one with curvature over the entire surface or part. There is no restriction on the hardness or thickness of the substrate.
• a multi-layer laminate can be formed by laminating a first substrate, a layer made of the cured product of the curable resin composition of the present invention, and a second substrate in this order.
• the curable resin composition of the present embodiment has excellent adhesiveness, and can be suitably used as an adhesive for bonding a first substrate and a second substrate.
• the curable resin cured product of the present invention can be used as a substrate, and the cured product of the present invention can be laminated on top of it.
• the cured product of the curable resin of the present invention can relieve stress, making it particularly suitable for use in bonding dissimilar materials.
• the substrate is a metal and/or metal oxide and the second substrate is a laminate of dissimilar materials such as a plastic layer, the adhesive strength is maintained due to the stress relaxation ability of the cured product of the present invention.
• the layer containing the cured product may be formed by direct coating or molding on the substrate, or an already molded product may be laminated.
• the coating method is not particularly limited, and examples thereof include spraying, spin coating, dip coating, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, screen printing, and inkjet coating.
• directly molding examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, and press molding.
• a precursor that can be a substrate may be coated on the cured product of the present invention and cured, or the precursor that can be a substrate or the composition of the present invention may be adhered in an uncured or semi-cured state and then cured.
• the precursor that can be a substrate and examples thereof include various curable resin compositions.
• the cured product obtained using the curable resin composition of the present invention has particularly high adhesion to metals and/or metal oxides, and can be particularly well used as a primer for metals.
• Metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials of these, while metal oxides include single oxides and/or composite oxides of these metals. Since the composition has particularly excellent adhesion to iron, copper, and aluminum, it can be particularly well used as an adhesive for iron, copper, and aluminum.
• the curable resin composition of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry. Even when used to bond dissimilar materials such as metal and nonmetal, the adhesive can maintain high adhesion without being affected by changes in the temperature environment, and peeling is unlikely to occur.
• the adhesive can also be used as an adhesive for general office use, medical use, carbon fiber, storage battery cells, modules, and cases, and can be used as an adhesive for bonding optical components, bonding optical disks, mounting printed wiring boards, die bonding adhesives, semiconductor adhesives such as underfills, underfills for reinforcing BGAs, anisotropic conductive films, anisotropic conductive pastes, and other mounting adhesives.
• the curable resin composition of the present invention has a fibrous substrate, and the fibrous substrate is a reinforcing fiber
• the curable resin composition containing the fibrous substrate can be used as a fiber-reinforced resin.
• the method of incorporating the fibrous substrate into the composition is not particularly limited as long as it does not impair the effects of the present invention, and examples of the method include a method of combining the fibrous substrate with the composition by kneading, coating, impregnation, injection, compression bonding, etc. These methods can be selected as appropriate depending on the form of the fiber and the application of the fiber-reinforced resin.
• extrusion molding is common, but it can also be made by a flat press.
• Other methods that can be used include extrusion molding, blow molding, compression molding, vacuum molding, and injection molding.
• a film-shaped product is to be manufactured, in addition to melt extrusion, solution casting can be used.
• melt molding method examples include inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding.
• a cured product can be manufactured using various curing methods using active energy rays.
• thermosetting resin when used as the main component of the matrix resin, a molding method in which the molding material is made into a prepreg and pressurized and heated by a press or autoclave can be used.
• Other examples include RTM (Resin Transfer Molding), VaRTM (Vacuum Assist Resin Transfer Molding), laminate molding, and hand layup molding.
• the curable resin composition of the present invention has good heat resistance and repairability, and is also remoldable, so it can be used as a molding material for large cases, motor housings, casting materials for the inside of cases, gears, pulleys, etc. These may be cured products of resin alone, or cured products reinforced with fibers such as glass chips.
• Fiber reinforced resin can form an uncured or semi-cured state known as prepreg. After distributing the product in prepreg state, it may be subjected to final curing to form a cured product. When forming a laminate, it is preferable to form the prepreg, then laminate other layers and then perform final curing, since this allows the formation of a laminate in which each layer is in close contact. There are no particular limitations on the mass ratio of the composition and fibrous substrate used in this case, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60 mass%.
• the cured product of the present invention has good heat resistance and repairability, and is remoldable, and can be used as a heat-resistant material and an electronic material.
• it can be suitably used for semiconductor encapsulation materials, circuit boards, build-up films, build-up boards, adhesives, and resist materials.
• It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a highly heat-resistant prepreg.
• the heat-resistant and electronic components thus obtained can be suitably used for a variety of applications. Examples include industrial machine parts, general machine parts, automobile, railway, and vehicle parts, space and aviation-related parts, electronic and electrical parts, building materials, containers and packaging parts, daily necessities, sports and leisure goods, and housing parts for wind power generation. However, they are not limited to these.
• the adhesive can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry.
• the adhesive of the present invention can maintain high adhesion without being affected by changes in temperature environment, even when used to bond dissimilar materials such as metal and non-metal, and peeling is unlikely to occur.
• the adhesive of the present invention can also be used as an adhesive for general office use, medical use, carbon fiber, storage battery cells, modules, and cases.
• Examples of the adhesive of the present invention include adhesives for bonding optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, adhesives for semiconductors such as underfills, underfills for reinforcing BGAs, and mounting adhesives such as anisotropic conductive films and anisotropic conductive pastes.
• the resin composition, the curing accelerator, and compounding agents such as inorganic fillers are melt-mixed sufficiently until homogeneous using an extruder, kneader, roll, etc. as necessary.
• fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulating material for power transistors and power ICs, it is preferable to use highly filled crystalline silica, alumina, silicon nitride, etc., which have a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc.
• the filling rate is preferably in the range of 30 to 95 mass% per 100 parts by mass of the curable resin composition. Among them, in order to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the linear expansion coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable.
• Examples of semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention include a method in which the semiconductor encapsulating material is molded by casting, or using a transfer molding machine, an injection molding machine, or the like, and then heated at 50 to 250°C for 2 to 10 hours.
• a method for obtaining a printed circuit board from the composition of the present invention includes laminating the above prepreg by a conventional method, appropriately overlaying copper foil, and subjecting the laminate to heat-pressure bonding at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.
• a method for producing a flexible substrate from the crosslinkable resin composition of the present invention includes a method comprising the following three steps.
• the first step is a step of applying a crosslinkable resin composition containing a resin component, an organic solvent, etc., to an electrical insulating film using a coater such as a reverse roll coater or a comma coater.
• the second step is a step of heating the electrically insulating film on which the crosslinkable resin composition has been applied at 60 to 170° C. for 1 to 15 minutes using a heater to volatilize the solvent from the electrically insulating film and B-stage the crosslinkable resin composition.
• the third step is a step of thermocompression bonding (the compression pressure is preferably 2 to 200 N/cm and the compression temperature is preferably 40 to 200° C.) a metal foil to the adhesive of the electrically insulating film in which the crosslinkable resin composition has been B-staged, using a heated roll or the like. If sufficient adhesive performance is obtained by going through the above three steps, the process may be terminated here, but if complete adhesive performance is required, it is preferable to further post-cure the resin composition at 100 to 200° C. for 1 to 24 hours.
• the thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 ⁇ m.
• the method for obtaining a build-up substrate from the composition of the present invention includes, for example, the following steps. First, the composition containing an appropriate amount of rubber, filler, etc. is applied to a circuit board on which a circuit is formed by spray coating, curtain coating, or the like, and then cured (step 1). Thereafter, if necessary, a predetermined through-hole portion or the like is drilled, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and then a metal such as copper is plated (step 2). These operations are repeated as desired to alternately build up resin insulating layers and conductor layers of a predetermined circuit pattern (step 3).
• the build-up substrate of the present invention can be produced by forming a roughened surface by heating and pressing the resin-coated copper foil, which is a copper foil on which the resin composition is semi-cured, onto a wiring board on which a circuit is formed, at 170 to 300° C., thereby omitting the steps of forming a roughened surface and plating.
• a build-up film can be obtained from the composition of the present invention by applying the composition to the surface of a support film (Y) as a substrate, and then drying the organic solvent by heating or blowing hot air thereon to form a layer of the composition (X).
• the organic solvents preferably used here include, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and it is preferable to use them in a proportion that results in a non-volatile content of 30 to 60% by mass.
• ketones such as acetone, methyl ethyl ketone, and cyclohexanone
• acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether
• the thickness of the layer (X) formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 ⁇ m, it is preferable that the resin composition layer has a thickness of 10 to 100 ⁇ m.
• the layer (X) of the composition in the present invention may be protected with a protective film, which will be described later. By protecting the layer with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer and prevent scratches.
• the above-mentioned support film and protective film may be made of polyolefins such as polyethylene, polypropylene, polyvinyl chloride, etc., polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil.
• PET polyethylene terephthalate
• the support film and protective film may be subjected to a matte treatment, corona treatment, or release treatment.
• There are no particular limitations on the thickness of the support film but it is usually 10 to 150 ⁇ m, and preferably 25 to 50 ⁇ m.
• the thickness of the protective film is preferably 1 to 40 ⁇ m.
• the support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film has been heat cured, the adhesion of dirt and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.
• a multilayer printed circuit board can be manufactured using the build-up film obtained as described above.
• the protective film is peeled off, and then the layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method.
• the lamination method may be a batch type or a continuous type using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination.
• the lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C, a pressure bonding pressure of 1 to 11 kgf/cm2 (9.8 x 104 to 107.9 x 104 N/ m2 ), and lamination is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less.
• Conductive Paste As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned.
• the conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.
• GPC Tosoh Corporation "HLC-8320GPC" Column: “TSK-GEL G2000HXL” + “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Measurement condition: 40°C Mobile phase: Tetrahydrofuran Flow rate: 1 ml/min Standard: Tosoh Corporation's "PStQuick A", “PStQuick B", "PStQuick E", and "PStQuick F"
• the epoxy equivalent of the synthesized epoxy resin was measured according to JIS K7236, and the epoxy equivalent (g/eq) was calculated.
• Examples of methods for calculating the number of repeating units include calculations based on the results of various appropriate instrumental analyses such as GPC molecular weight measurement, FD-MS, and NMR.
• Example 5 Synthesis of Diels-Alder reaction product (D-5)"
• D-5 Diels-Alder reaction product
• N-(4-aminophenyl)maleimide was prepared. That is, 5.35 g (49.5 mmol) of p-phenylenediamine and 97 mL of tetrahydrofuran (THF) were added to a 300 mL eggplant flask, and 4.85 g (49.5 mmol) of maleic anhydride dissolved in 36 mL of THF was added dropwise at room temperature over 1 hour while stirring. After completion of the dropwise addition, stirring (rt/12 h) was performed, and the precipitate formed was collected by suction filtration and dried under reduced pressure (rt/12 h) to obtain 9.49 g of APMA (yellow solid).
• a curable resin composition was obtained by mixing each compound uniformly in a mixer (Thinky Corporation's "Thinner Mixer ARV-200”) according to the formulation in Table 1 (the numbers in the table are by weight).
• This curable resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Corporation's "JIS H 4000 A1050P") using a silicone tube as a spacer, and heat curing was performed under specified conditions to obtain a cured product having a thickness of 0.5 mm.
• the prepared cured product was freeze-pulverized. 0.07 g of the pulverized cured product was placed in a mold having a size of 10 mm square and a thickness of 0.5 mm, and vacuum pressing was performed under the specified conditions. The appearance of the obtained cured product was visually observed.
• the evaluation criteria were as follows: A: The seams disappeared and the cured product became integrated. B: Some of the seams were visible to the naked eye, but the cured product was integrated. C: It had a solidified shape and fell apart when light pressure was applied.
• compositions shown in the table are as follows: EPICLON-850S: Bisphenol A type liquid epoxy resin (manufactured by DIC Corporation, epoxy equivalent 188 g/eq) Denacol EX-201: (manufactured by Nagase ChemteX Corporation, epoxy equivalent 117 g/eq) TD-2131: Phenol novolac type phenolic resin (manufactured by DIC Corporation, hydroxyl group equivalent: 104 g/eq) 4,4'-Diaminodiphenylmethane (Kanto Chemical Co., Ltd.) TPP: Triphenylphosphine (Tokyo Chemical Industry Co., Ltd.)

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