WO2002051905A1 - Generateurs de photobase, compositions durcissables preparees au moyen de ces generateurs et procede de durcissement - Google Patents

Generateurs de photobase, compositions durcissables preparees au moyen de ces generateurs et procede de durcissement Download PDF

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WO2002051905A1
WO2002051905A1 PCT/JP2001/011528 JP0111528W WO02051905A1 WO 2002051905 A1 WO2002051905 A1 WO 2002051905A1 JP 0111528 W JP0111528 W JP 0111528W WO 02051905 A1 WO02051905 A1 WO 02051905A1
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group
carbon atoms
atom
compound
electron
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PCT/JP2001/011528
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WO2002051905A8 (fr
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Shigeki Katogi
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Hitachi Chemical Co., Ltd.
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Priority to AU2002225369A priority Critical patent/AU2002225369A1/en
Priority to KR1020037007865A priority patent/KR100566792B1/ko
Priority to CNB018213545A priority patent/CN1326904C/zh
Priority to JP2002553391A priority patent/JP3912287B2/ja
Publication of WO2002051905A1 publication Critical patent/WO2002051905A1/fr
Publication of WO2002051905A8 publication Critical patent/WO2002051905A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/40—Hydrazines having nitrogen atoms of hydrazine groups being quaternised

Definitions

  • the present invention relates to a photobase generator that generates a base upon irradiation with light of 150 to 700 nm, a curable composition using the same, and a curing method.
  • Light curing technology is being applied to coatings, resists, etc. by utilizing the features of low-temperature curing, shortening of processes, short-time curing, and micromachining, compared to conventional thermal curing technology.
  • Curing systems mainly used in light curing are broadly divided into radical curing and cationic curing.
  • a photo-radical generator and a (meth) acrylate resin are the main components, and upon irradiation with light, the photo-radical generator generates radicals through processes such as cleavage and hydrogen abstraction, resulting in a (meth) acrylate tree. It is a system that cures fats and is characterized by the ability to cure quickly.
  • cation curing In the case of cation curing, it consists of a photoacid generator and an epoxy resin, oxetane resin, vinyl ether resin, etc., which have cationic polymerizability. This is a curing system that has low curing shrinkage during curing. In addition, these photo-curing systems have the feature of being excellent in pot life by shielding light.
  • the radical curing system there is a problem that corrosion is caused when using an adherend made of a metal or an inorganic material since a strong acid remains in the system in the case of a radical curing system and a strong acid remains in the system.
  • a thermal latent catalyst having a tertiary amino group such as imidazole dicyandiamide and an epoxy resin, or a lipoxyl reactive with the thermal latent catalyst and an epoxy resin or an epoxy resin.
  • a thermosetting system that combines a group, a mercapto group, an amino group, and a phenolic hydroxyl group is used.
  • This system has high adhesion to adherends such as inorganic, metallic, and organic materials, and has excellent moisture resistance, weather resistance, and heat resistance. It is used in a wide range of applications from gas-electronic materials to semiconductor materials.
  • a curing temperature of 170 ° C. or higher is generally required, and when curing at a temperature of 170 ° C. or lower, a curing system having both pot life has to be constructed. difficult.
  • photobase generators that generate basic compounds by light irradiation have been studied in recent years.
  • photobase generators include, for example, Chemistry & Technology of UV & EB Format s for Co at ngs, Inks & Paints, Ed. By G. Brad The leubamate derivative oxime ester derivative described in Ley, John Wiley and Sons Ltd. (1998), p. 479-p.545, is generally known.
  • most of these compounds have low generation efficiency, and have low basicity because the basic compounds generated by light irradiation are primary or secondary amines, and have a low catalytic activity for curing epoxy resins sufficiently. There is a problem of not having.
  • An object of the present invention is to provide a photobase generator exhibiting excellent catalytic activity at the time of curing at a low temperature and having excellent storage stability, and a curable composition and a curing method using the same. Disclosure of the invention As a result of intensive studies to improve the above-mentioned problems, the present invention has found that the amide imide compound has excellent storage stability and has a curable composition at a low temperature of 170 ° C. or less due to generation of tertiary amine by light irradiation. It was found that the object could be cured. It is described in Japanese Patent Application Laid-Open No. H10-139798 that the amide imide compound generates tertiary amine by heating. However, tertiary amine is obtained by light irradiation which is excellent in low-temperature curability and storage stability. Is not described.
  • the present invention relates to a photobase generator which generates a base upon irradiation with light of 150 to 700 nm, and comprises an amine imine represented by the following general formula (I) or ( ⁇ ) It is a photobase generator composed of a compound.
  • R l, scales 2 and 13 are each independently a hydrogen atom, a carbon atom number: an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, Substituted with cycloalkyl group having 4 to 8 carbon atoms, cycloalkenyl group having 4 to 8 carbon atoms, phenoxyalkyl group having 1 to 6 carbon atoms, phenyl group, electron-donating group and Z or electron-withdrawing group Represents a substituted phenyl group, a benzyl group, or an electron-donating group and a benzyl group substituted by Z or an electron-withdrawing group;
  • R 4 is independently an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a carbon atom having 4 carbon atoms; Represents a cycloalkyl group, an alkoxy group having 1 to 5 carbon
  • R 5 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a carbon atom Alkylidene group having 1 to 8 carbon atoms, cycloalkyl group having 4 to 8 carbon atoms, cycloalkenyl group having 4 to 8 carbon atoms, amino group, alkylamino group having 1 to 6 carbon atoms, 1 to 3 carbon atoms Dialkylamino group, morpholino group, mercapto group, hydroxyl group, hydroxyalkyl group having 1 to 6 carbon atoms, halogen atom, ester group having 1 to 6 carbon atoms, alkylcarbonyl group having 1 to 6 carbon atoms, aldehyde group , Cyan, trifluoromethyl group, Cyan group, nitro Group, phenyl group, benzoyl group, benzyl group,
  • X1 to X9 are each independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a carbonyl group; and Ar2 is any one of the following formulas (17) to (26). Is an aromatic group of
  • R34 to R45 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and a carbon atom having 1 to 8 carbon atoms.
  • alkylidene groups cycloalkyl group having 4 to 8 carbon atoms, 4 to 8 carbon atoms
  • XI 0 is a carbon atom
  • the present invention is a curable composition essentially comprising a compound having two or more epoxy groups in a molecule and a photobase generator which is the amide imide compound according to the above (1).
  • the present invention further provides a compound having two or more epoxy groups in the molecule, a photobase generator which is the amide imide compound according to the above (1), a compound having two or more epoxy groups in the molecule. It is a curable composition essentially containing a compound having two or more reactive functional groups in a molecule.
  • the functional group reactive with the compound having two or more epoxy groups in the molecule is a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group.
  • the curable composition according to the above (3) is a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group.
  • the present invention provides a compound having two or more isocyanate groups in the molecule, a photobase generator which is the amide imide compound according to the above (1), and a compound having two or more hydroxyl groups in the molecule. It is a curable composition containing a compound having the same as an essential component.
  • FIG. 1 is a spectrum diagram showing (a)! H-NMR and (b) 13 C-NMR of the compound obtained in Synthesis 1 of amide imide.
  • FIG. 2 is a spectrum diagram showing FT-IR of the compound obtained in Synthesis 1 of amide imide.
  • Figure 3 is a compound obtained in Synthesis 2 of Amin'imido (a) 1 "-.! ! A spectrum diagram showing the NMR and (b) 13 C- NMR.
  • FIG. 4 is a spectrum diagram showing FT-IR of the compound obtained in Synthesis 2 of amide imido.
  • the amine imide as a photobase generator used in the present invention is represented by the above general formula (I) or ( ⁇ ), wherein Rl, 12 and 13 are each independently a hydrogen atom, a carbon atom number.
  • alkyl group having 1 to 8 carbon atoms examples include an isopropyl group, an isobutyl group, a t-butyl group and the like in addition to a linear alkyl group.
  • alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 6 to 8 carbon atoms, and cycloalkyl groups having 1 to 6 carbon atoms are preferred in view of simplicity of synthesis, solubility of the amide imide, and the like. Phenoxyalkyl groups are preferred.
  • a phenyl group In order to increase the sensitivity of light irradiation, it is preferable to introduce a phenyl group, a benzyl group, or a phenoxyalkyl group having 1 to 3 carbon atoms.
  • these aromatic rings include an amino group, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a thioalkyl group having 1 to 3 carbon atoms, and an alkoxy having 1 to 6 carbon atoms.
  • a hydroxyl group an electron donating group such as an alkyl group having 1 to 8 carbon atoms, a halogen atom, an aldehyde group, an alkylcarbonyl group having 1 to 6 carbon atoms, a carbonyl group, an ester group having 1 to 6 carbon atoms,
  • the sensitivity can be further increased by introducing an electron-withdrawing group such as a cyano group, a trifluoromethyl group, or a nitro group.
  • R 4 independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group.
  • Ar 1 in the general formula (I) is an aromatic group represented by any of the general formulas (1) to (16),
  • R 5 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms.
  • X 1 to X 9 are each independently a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a carbonyl group.
  • Ar 2 in the general formula ( ⁇ ) is an aromatic group represented by any of the following formulas (17) to (26);
  • R 34 to R 45 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms.
  • XI 0 is a carbon atom, a nitrogen atom, a nitrogen atom substituted by an alkyl group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group
  • X11 to X14 are each independently , A carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a carbonyl group.
  • Known methods can be used for the synthesis of the amine imide.
  • Encyc opediaof Polimer Sci enc e and Engine eri ng John Wiley & S ons Ltd., (1985), vol. 1, p. 740 they can be obtained from the reaction of the corresponding carboxylic carboxylic esters with hydrazine and epoxy compounds.
  • a synthesis method from the corresponding carboxylic acid ester and hydrazine or epoxy compound is particularly preferable.
  • the synthesis temperature and the synthesis time are not particularly limited as long as the starting material used is not decomposed, but generally the desired amide imide compound is obtained by stirring at a temperature of 0 to 100 for 30 minutes to 7 days. Obtainable.
  • the compound (epoxy resin) having two or more epoxy groups in a molecule used in the present invention is not particularly limited as long as it has two or more epoxy groups in a molecule, and a known compound can be used. Can.
  • the compound having two epoxy groups in one molecule includes a compound represented by the general formula (27).
  • the broken line indicates a methylene group.
  • R46 is a divalent organic group shown below
  • c is an integer from 0 to 20
  • R51 and R52 are independently hydrogen or an alkyl group having 1 to 12 carbons, h and i are independently an integer of 1 to 20
  • j is an integer from 0 to 20
  • R53 is an alkyl group having 1 to 12 carbon atoms
  • k is an integer from 0 to 20
  • n are independently integers from 0 to 5
  • R54 and R55 are independently an alkyl group, an alkoxy group,
  • 0 is an integer from 1 to 20
  • the compounds having an epoxy group used in the present invention include the following compounds.
  • the broken line indicates a methylene group.
  • R56 is hydrogen, methyl or ethyl
  • p is an integer from 0 to 20
  • examples of the compound having an epoxy group used in the present invention include the following compounds.
  • r is an integer from 0 to 20
  • R 57 to R 60 each independently represent a hydrogen atom, a halogen atom, or a monovalent group.
  • the monovalent group include an ester group such as an amino group and a carbomethoxy group, an amide group such as a carpoaminomethyl group, a carbamino group such as an aminocarboxymethyl group, a methyl group, an ethyl group, a propyl group, and a butyl group. , Hexyl, heptyl, etc. alkyl or substituted or unsubstituted phenyl, vinyl, 1-propenyl, 1-butenyl, etc. Examples include a alkenyl group and a silyl group.
  • those containing 2 to 4 epoxy groups in the molecule are preferable because the polymer has an appropriate crosslinking density. If the number of epoxy groups exceeds 5, the crosslink density of the polymer is too high and it is difficult to handle, and the intramolecular reaction tends to occur simultaneously.
  • a compound having an epoxy group having an epoxy equivalent of about 43 to 10,000 may be used as the compound having an epoxy group in the present invention. If the epoxy equivalent is 43 or less, a compound having an epoxy group cannot be formed, and if it is more than 10,000, the reaction rate tends to decrease.
  • the epoxy equivalent is 43 or less, a compound having an epoxy group cannot be formed, and if it is more than 10,000, the reaction rate tends to decrease.
  • the crystallinity of the composition is reduced, and the storage stability is excellent. . Therefore, 0 ⁇ (s ⁇ x) is preferable, 0.5 ⁇ (s ⁇ x) is more preferable, and 1 ⁇ (s ⁇ x) is most preferable.
  • u is an integer from 0 to 10
  • V is an integer from 0 to 50
  • X is an integer from 0 to 10
  • Examples of such a compound having two or more epoxy groups in a molecule include an epoxy resin, and examples thereof include bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol nopolak-type epoxy resin, cresol nopolak-type epoxy resin, bisphenol A-nopolak-type epoxy resin, bisphenol F-nopolak-type epoxy resin, alicyclic epoxy resin, glycidyl Examples thereof include an ester type epoxy resin, a glycidylamine type epoxy resin, a hydantoin type epoxy resin, an isocyanurate type epoxy resin, and an aliphatic chain epoxy resin. These epoxy resins may be octogenated or hydrogenated. Two or more of these epoxy resins may be used in combination. Among them, bisphenol-type epoxy resins are preferable because, compared with other various epoxy compounds, grades having different molecular weights are widely available and adhesiveness and reactivity can be arbitrarily set.
  • the amine imide can be generally used as a curing catalyst for a compound (epoxy resin) having two or more epoxy groups in a molecule.
  • the amount of the amine imide used is two or more epoxy groups in the molecule.
  • the amount is preferably from 0.01 to 50 parts by weight, more preferably from 0.1 to 30 parts by weight, based on 100 parts by weight of the compound (epoxy resin). If the amount is less than 0.01 part by weight, the effect of promoting the curing tends to be insufficient, and if it exceeds 50 parts by weight, the compatibility tends to decrease.
  • the compound having two or more epoxy groups in the molecule (epoxy resin) and an amide imide compound are used in combination with a compound having two or more functional groups reactive with an epoxy resin in the molecule.
  • the functional group reactive with the epoxy resin means a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group that is known to react with the epoxy resin. Can be.
  • a polymer having a functional group introduced into a polymer side chain having a weight average molecular weight of 10,000 or more may be used.
  • the amount of the compound having two or more functional groups having reactivity with the compound having two or more epoxy groups in the molecule is calculated as follows: the total amount of functional groups / epoxy based on the epoxy resin. It is preferable that the total amount of the groups (equivalent ratio) be 0.5 / 1.5 to 1.5 / 0.5, and 0.8 Z 1.2 to 1.2. More preferably, the ratio is /0.8. If the ratio is less than 0.5 / 1.5 or exceeds 1.5 / 0.5, a large amount of unreacted epoxy groups and functional groups will remain in the cured product, It tends to degrade mechanical properties.
  • the compound having an isocyanate group used in the present invention (hereinafter referred to as “isocyanate resin”) is not particularly limited as long as it has two or more isocyanate groups in the molecule. Can be used. Such compounds include p-phenylene diisocyanate, 2
  • a polymer having a weight average molecular weight of 3,000 or more having an isocyanate group at the side chain or terminal thereof may be used.
  • the compound having an isocyanate group is usually used in combination with a compound having a hydroxyl group in the molecule.
  • a resin having two or more hydroxyl groups in a molecule is not particularly limited, and a known resin may be used.
  • hydroxyl groups are present on the side chains or terminals of polymers having a weight average molecular weight of 3,000 or more. A thing may be used.
  • the amount of the compound having two or more hydroxyl groups in the molecule is from 0.5 / 1 to 5 to 1.5 in terms of the total amount of hydroxyl groups and the total amount of noisocyanate groups (equivalent ratio) based on the isocyanate resin.
  • the ratio is preferably set to a ratio of /0.5, more preferably 0.8 / 1.2 to 1.2Z0.8. If this ratio is less than 0.5 / 1.5 or exceeds 1.5 / 0.5, a large amount of unreacted epoxy groups and functional groups will remain in the cured product, and Tends to degrade the mechanical properties of objects.
  • the amount of the amineimide compound used as a curing catalyst for the isocyanate resin and the compound having a hydroxyl group is 0.01 to 50 parts by weight based on 100 parts by weight of the total amount of the compound having an isocyanate group and the compound having a hydroxyl group. Preferably, 0. More preferably, it is 1 to 30 parts by weight. If the amount is less than 0.01 part by weight, the effect of promoting curing tends to be insufficient, and if it exceeds 50 parts by weight, the compatibility tends to decrease.
  • a sensitizer may be used in combination for the purpose of increasing the absorption of irradiation light and increasing the sensitivity.
  • known singlet sensitizers and triplet sensitizers can be used as long as they do not adversely affect the curable composition.
  • aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carboxylic acid derivatives, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are suitably used.
  • the amount of the sensitizer to be used should be referred to the absorption wavelength and the molar extinction coefficient of the sensitizer, but is generally 0.01 to 5 parts by weight per 1 part by weight of the amide imide compound. 0.1 to 2 parts by weight is particularly preferred. When the amount of the sensitizer is less than 0.01 part by weight, the efficiency of light absorption is lowered. When the amount is more than 5 parts by weight, light may not reach the entire curable composition.
  • the curable composition of the present invention may optionally contain additives such as an adhesion improver such as a coupling agent, a leveling agent, and an organic or inorganic filler.
  • an adhesion improver such as a coupling agent, a leveling agent, and an organic or inorganic filler.
  • various polymers may be appropriately added for the purpose of increasing the viscosity and improving the film forming property.
  • the polymer used is not particularly limited, but it is essential that the curability is not adversely affected.
  • Such polymers include, for example, general-purpose phenoxy resins such as polyimide resins, polyamide resins, bisphenol A-type phenoxy resins, bisphenol F-type phenoxy resins, bisphenol A / bisphenol F copolymerized phenoxy resins, and the like.
  • Methacrylate resins polyacrylate resins, polyimide resins, polyurethane resins, polyester resins, polyvinyl butyral resins, modified SBS resins and their epoxy resins, SEBS resins and their modified products, and the like can be used. These can be used alone or in combination of two or more. Further, these polymers may contain a siloxane bond or a fluorine substituent. Any of these can be suitably used as long as the resins to be mixed are completely compatible with each other or are in a state where cloudy phase separation occurs and cloudiness occurs.
  • the molecular weight is not particularly limited, but a general weight average molecular weight of 50,000 to 150,000 is preferable. Particularly preferably, 100,000 to 800,000 is particularly preferable.
  • the amount used is preferably from 20 to 32 parts by weight based on 100 parts by weight of a compound having at least two or more epoxy groups in the molecule (epoxy resin) or 100 parts by weight of the isocyanate resin.
  • the curable composition of the present invention can be used in the form of a paste when it is liquid at normal temperature. When it is solid at room temperature (25 ° C), it may be used by heating or pasting using a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the curability and show sufficient solubility, but those having a boiling point at normal pressure of 50 to 150 ° C. Is preferred. If the boiling point is less than 50 ° C, it may volatilize if left at room temperature, which limits its use in open systems. If the boiling point is more than 150 ° C, it may be difficult to remove the solvent.
  • the curable composition of the present invention can be used in the form of a film.
  • a solution obtained by adding a solvent or the like to the curable composition, if necessary, is applied to a releasable substrate such as a fluororesin film, a polyethylene terephthalate film, release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. Then, it is placed on a peelable substrate, and the solvent or the like is removed, and the film can be used as a film.
  • a releasable substrate such as a fluororesin film, a polyethylene terephthalate film, release paper, or a substrate such as a nonwoven fabric is impregnated with the solution.
  • a releasable substrate such as a fluororesin film, a polyethylene terephthalate film, release paper, or a substrate such as a nonwoven fabric is impregnated with the solution.
  • the solvent or the like is removed, and the film
  • the curable composition of the present invention can be cured by simultaneous light irradiation and heating, or by heating after light irradiation.
  • Light irradiation is preferably performed in the wavelength range of 150 to 750 nm. It can be cured with an irradiation amount of 1 to 100 J / cm 2 .
  • the heating temperature is such that the compound has at least two epoxy groups in the molecule (epoxy resin) and a compound having at least two epoxy groups in the molecule (epoxy resin) and has a functional group reactive with the compound. There is no particular limitation as long as it is below the decomposition point of the compound, but a temperature of 30 to 200 ° C is preferred, and a temperature of 50 to 170 ° C is more preferred.
  • the heating time is from 1 second to 3 hours, preferably from 30 seconds to 1 hour, in order to sufficiently perform the curing.
  • the curable composition of the present invention includes paints, adhesives, inks, photoresists, It can be applied to a wide variety of applications such as packaging materials, various automotive parts, electrical and electronic materials, semiconductor materials, optical materials, optical fibers, adhesives for optical fibers, and optical waveguide materials.
  • anisotropic conductive adhesives in addition to bonding wood, building materials, plastics, leather, etc., anisotropic conductive adhesives, circuit connection materials represented by silver paste, silver films, etc., and semiconductor devices such as flip chips, etc. It can be used as an adhesive material for a semiconductor element such as an anisotropic conductive material for a flip chip for connection to a wiring board.
  • the curable composition of the present invention can be bonded by heating after light irradiation. Therefore, it can be suitably used.
  • the melting point and the onset of thermal decomposition in an oxygen atmosphere were measured by TG-DTA.
  • the melting point was 147 ° C and the onset of decomposition was 201 ° C.
  • an epoxy resin (DER 736; trade name of Dow Chemical Co., Ltd., epoxy equivalent: 172) 1.00 g, at least 2
  • phenol erythritol tetra (mercaptoacetate) (manufactured by Tokyo Chemical Industry Co., Ltd., SH group
  • An equivalent amount of 108, the reactive functional group was a mercapto group (0.614 g) and 0.016 g of the amide imide compound of Example 1 were mixed at room temperature to obtain a uniform solution.
  • Example 3 DSC measurement was performed in the same manner as in Example 3 except that the amide imide compound was changed to the compound of Example 2 and light irradiation was changed to 6 J / cm 2 .
  • Example 2 (Comparative Example 2) Except for not performing the light irradiation, the measurement results of Example 4 and c Example 3 DSC measurements were carried out in the same manner, 4 and Comparative Example 1, 2 shown in Table 1.
  • the curing reaction proceeds at a low temperature of 20 to 60 ° C as compared with Comparative Examples 1 and 2, and has a maximum exothermic peak temperature at a temperature lower than the decomposition temperature of the amine imide compound. Indicated. This result indicates that the amine imide generated a basic compound upon irradiation with light, enabling low-temperature curing.
  • epoxy resin As a compound having an epoxy group (epoxy resin), 50 g of bisphenol A-type epoxy resin (Epicoat 828; trade name of Yuka Shell Epoxy Co., Ltd., epoxy equivalent 184) is dissolved in methyl ethyl ketone. A solution having a solid content of 40% by weight was used. As the polythiol, 13.5 g of Penyu erythritol (SH equivalent: 50) was used. As the photobase generator, 2.0 g of the amine imide of Example 1 was used.
  • bisphenol A, bisphenol F (1/1) and epichlorohydrin are used as c-phenoxy resins using 1.5 g of an epoxy silane compound (A-187; trade name of Nippon Tunicer Co., Ltd.) as a silane coupling agent.
  • Bisphenol A, F copolymerized phenoxy resin (average molecular weight: 20,000) 50 g was prepared from phosphorus by a general method, and this was The resulting solution was dissolved in ketone and used as a solution having a solid content of 40% by weight.
  • a 0.2 m-thick nickel layer is provided on the surface of the particles having polystyrene as a core, and a metal having a thickness of 02 / zm is provided outside the nickel layer to have an average particle diameter of 10 / zm.
  • Particles having a specific gravity of 2.0 were prepared and used.
  • a solution containing the above components without conductive particles (50 g epoxy resin, 13.5 g polythiol, 2.0 g amide imide compound, 1.5 g silane coupling agent, 50 g phenoxy resin in solid content) 3% by volume of conductive particles are mixed and dispersed, applied to a 80 / xm-thick fluororesin film using a coating device, and dried with hot air at 70 ° C for 10 minutes to form a 25 im thick circuit on the fluororesin film. A film made of the composition for connection was formed.
  • a flexible circuit board having 500 copper circuits with a line width of 50 / m, a pitch of 100 Aim and a thickness of 18 xm, and a 0.2 m indium oxide U
  • a thin layer of TO (thickness: 1 lmm, surface resistance: 20 ⁇ / port) was connected by heating and pressing at 150 ° (:, 4 MPa for 60 seconds) over a width of 2 mm.
  • the adhesive surface of the film-like circuit connection material was heated and pressurized at 70 ⁇ , 0.5 MPa for 5 seconds and temporarily connected, then the fluororesin film was peeled off, and the film surface made of the circuit connection composition was removed.
  • connection body was measured and evaluated by a 90-degree peeling method according to JIS_Z0237.
  • the adhesive strength was measured using Tensilon UTM-4 manufactured by Toyo Paul Douin Co., Ltd. (with a peeling speed of 50 mmZ at 25).
  • the bonding strength of the connector performed as described above was 700 N / m, indicating a sufficient bonding strength.
  • Hexamethylene diisocyanate (Kanto Chemical) A uniform varnish consisting of 0.672 g of polytetrahydrofuran (manufactured by BAS F Japan, trade name: polytetrahydrofuran 250) as a resin having a hydroxyl group, and 1.00 g of a resin having a hydroxyl group, and 0.016 g of the amide imide compound of Example 1 as a photobase generator was prepared. . This was sampled in a DSC sample pan so as to be 1 Omg, and 3 J / mg was measured using an AEL 1 B / M (365 nm illuminance: 21.5 mW / cm 2 ) ultraviolet ray irradiator manufactured by Fujitsu Limited.
  • AEL 1 B / M 365 nm illuminance: 21.5 mW / cm 2
  • a compound having at least two or more epoxy groups in a molecule (epoxy resin) alone at a low temperature by irradiating light a compound having at least two or more epoxy groups in a molecule (epoxy resin) ), A curing agent, an isocyanate resin, and an alcohol, and a curable composition having excellent storage stability can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Materials For Photolithography (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

L'invention concerne des générateurs de photobase pouvant générer des bases par exposition à des rayons ayant des longueurs d'onde de 150 à 750 nm, ces générateurs étant des composés amine-imide représentés par la formule générale (I) ou (II); des compositions durcissables préparées au moyen de ces générateurs; et un procédé de durcissement au moyen de ces générateurs. Les R1', R2' et R3' représentent chacun individuellement hydrogène, C1-8 alkyle, C1-8 alcoxy, C1-8 alkylidène, C4-8 cycloalkyle, C4-8 cycloalcényle, C1-6 phénoxyalkyle, phényle substitué ou non substitué, ou benzyle substitué ou non substitué; les R4' représentent chacun individuellement C1-5 alkyle, hydroxyle, C4-8 cycloalkyle, C1-5 alcoxy, ou phényle; Ar1 et Ar2 représentant chacun un groupe aromatique.
PCT/JP2001/011528 2000-12-27 2001-12-27 Generateurs de photobase, compositions durcissables preparees au moyen de ces generateurs et procede de durcissement WO2002051905A1 (fr)

Priority Applications (4)

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AU2002225369A AU2002225369A1 (en) 2000-12-27 2001-12-27 Photobase generators, curable compositions prepared by using the same and process of curing
KR1020037007865A KR100566792B1 (ko) 2000-12-27 2001-12-27 광염기발생제 및 이것을 이용한 경화성 조성물 및 경화방법
CNB018213545A CN1326904C (zh) 2000-12-27 2001-12-27 光碱发生剂以及应用它的固化性组合物及固化方法
JP2002553391A JP3912287B2 (ja) 2000-12-27 2001-12-27 光塩基発生剤並びにそれを用いた硬化性組成物及び硬化方法

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US6835513B2 (en) 2002-03-28 2004-12-28 Samsung Electronic Co., Ltd. Carbazole based charge transport compounds
WO2007111092A1 (fr) 2006-03-24 2007-10-04 Konica Minolta Medical & Graphic, Inc. Feuille de barriere transparente et son procede de production
WO2008001637A1 (fr) * 2006-06-26 2008-01-03 Three Bond Co., Ltd. Composé imide d'amine destiné à être activé par irradiation par un rayonnement d'énergie active, composition utilisant celui-ci et procédé servant à faire durcir celui-ci
WO2009084229A1 (fr) * 2007-12-28 2009-07-09 Mitsui Chemicals, Inc. Agents de durcissement latents, composition de résine époxy contenant ceux-ci, matières de scellement et dispositifs d'affichage électroluminescents organiques
WO2010147161A1 (fr) 2009-06-17 2010-12-23 株式会社スリーボンド Générateur de base et de radicaux, composition l'utilisant et procédé pour son durcissement
US8137892B2 (en) 2006-12-14 2012-03-20 Asahi Kasei Chemicals Corporation Photobase generator and photocurable resin composition
WO2013089100A1 (fr) 2011-12-16 2013-06-20 株式会社スリーボンド Composition de résine durcissable
WO2015008709A1 (fr) 2013-07-18 2015-01-22 セメダイン株式会社 Composition photodurcissable
WO2015088021A1 (fr) 2013-12-13 2015-06-18 セメダイン株式会社 Composition photodurcissable présentant des propriétés adhésives
JP2017155204A (ja) * 2016-03-04 2017-09-07 学校法人東京理科大学 光硬化性組成物、化合物及び塩基変換増殖剤
JP2020094060A (ja) * 2020-03-09 2020-06-18 学校法人東京理科大学 塩基変換増殖剤
CN112334562A (zh) * 2018-06-26 2021-02-05 日东电工株式会社 密封剂片
JP2021109924A (ja) * 2020-01-10 2021-08-02 昭和電工マテリアルズ株式会社 光硬化性樹脂組成物及び接着剤
WO2023127800A1 (fr) * 2021-12-28 2023-07-06 旭化成株式会社 Composition de résine époxyde, produit durci, matériau d'étanchéité et adhésif

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EP2368875B1 (fr) * 2008-12-02 2014-09-03 Wako Pure Chemical Industries, Ltd. Photogénérateur de base
JP7050245B2 (ja) * 2017-05-10 2022-04-08 学校法人東京理科大学 活性エネルギー線硬化型組成物、硬化膜の製造方法及び硬化物
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US6835513B2 (en) 2002-03-28 2004-12-28 Samsung Electronic Co., Ltd. Carbazole based charge transport compounds
WO2007111092A1 (fr) 2006-03-24 2007-10-04 Konica Minolta Medical & Graphic, Inc. Feuille de barriere transparente et son procede de production
WO2008001637A1 (fr) * 2006-06-26 2008-01-03 Three Bond Co., Ltd. Composé imide d'amine destiné à être activé par irradiation par un rayonnement d'énergie active, composition utilisant celui-ci et procédé servant à faire durcir celui-ci
JP2008001857A (ja) * 2006-06-26 2008-01-10 Three Bond Co Ltd 活性エネルギー線の照射により活性化するアミンイミド化合物、それを用いた組成物およびその硬化方法
US8137892B2 (en) 2006-12-14 2012-03-20 Asahi Kasei Chemicals Corporation Photobase generator and photocurable resin composition
US8466238B2 (en) 2007-12-28 2013-06-18 Mitsui Chemicals, Inc. Latent curing agents, epoxy resin compositions containing the same, sealing materials, and organic EL displays
WO2009084229A1 (fr) * 2007-12-28 2009-07-09 Mitsui Chemicals, Inc. Agents de durcissement latents, composition de résine époxy contenant ceux-ci, matières de scellement et dispositifs d'affichage électroluminescents organiques
JP5486927B2 (ja) * 2007-12-28 2014-05-07 三井化学株式会社 潜在性硬化剤、それを含むエポキシ樹脂組成物、シール剤および有機ｅｌディスプレイ
US8686059B2 (en) 2009-06-17 2014-04-01 Three Bond Co., Ltd. Base and radical generator, composition using same and method for curing same
JP5549819B2 (ja) * 2009-06-17 2014-07-16 スリーボンドファインケミカル株式会社 塩基およびラジカル発生剤、およびそれを用いた組成物およびその硬化方法
EP2444391A1 (fr) * 2009-06-17 2012-04-25 Three Bond Co., Ltd. Générateur de base et de radicaux, composition l'utilisant et procédé pour son durcissement
EP2444391A4 (fr) * 2009-06-17 2012-11-14 Three Bond Co Ltd Générateur de base et de radicaux, composition l'utilisant et procédé pour son durcissement
KR20120032484A (ko) 2009-06-17 2012-04-05 가부시끼가이샤 쓰리본드 염기 및 라디칼 발생제, 및 그것을 이용한 조성물 및 그의 경화 방법
WO2010147161A1 (fr) 2009-06-17 2010-12-23 株式会社スリーボンド Générateur de base et de radicaux, composition l'utilisant et procédé pour son durcissement
US9150723B2 (en) 2011-12-16 2015-10-06 Three Bond Fine Chemical Co., Ltd. Curable resin composition
WO2013089100A1 (fr) 2011-12-16 2013-06-20 株式会社スリーボンド Composition de résine durcissable
WO2015008709A1 (fr) 2013-07-18 2015-01-22 セメダイン株式会社 Composition photodurcissable
WO2015088021A1 (fr) 2013-12-13 2015-06-18 セメダイン株式会社 Composition photodurcissable présentant des propriétés adhésives
JP2017155204A (ja) * 2016-03-04 2017-09-07 学校法人東京理科大学 光硬化性組成物、化合物及び塩基変換増殖剤
CN112334562A (zh) * 2018-06-26 2021-02-05 日东电工株式会社 密封剂片
EP3816257A4 (fr) * 2018-06-26 2022-07-06 Nitto Denko Corporation Feuille de scellement
CN112334562B (zh) * 2018-06-26 2024-04-09 日东电工株式会社 密封剂片
JP2021109924A (ja) * 2020-01-10 2021-08-02 昭和電工マテリアルズ株式会社 光硬化性樹脂組成物及び接着剤
JP2020094060A (ja) * 2020-03-09 2020-06-18 学校法人東京理科大学 塩基変換増殖剤
WO2023127800A1 (fr) * 2021-12-28 2023-07-06 旭化成株式会社 Composition de résine époxyde, produit durci, matériau d'étanchéité et adhésif

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CN1531562A (zh) 2004-09-22
KR20030077553A (ko) 2003-10-01
JP3912287B2 (ja) 2007-05-09
JP4555995B2 (ja) 2010-10-06
CN1326904C (zh) 2007-07-18
AU2002225369A1 (en) 2002-07-08
WO2002051905A8 (fr) 2004-05-13
TWI245778B (en) 2005-12-21
JP2006328427A (ja) 2006-12-07
KR100566792B1 (ko) 2006-04-03
JPWO2002051905A1 (ja) 2004-04-22

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