JPS5948009B2 - Curable resin composition - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cured polyimide composition having excellent heat resistance and good mechanical properties. Conventionally, as polyimide or polyamide imide, US Pat.
Publication No. 0 describes a bisimide-diamine-based cured product, which is mainly used as a heat-resistant material in fields such as varnish, engineering, and plastics. Although a cured product with excellent heat resistance can be obtained by crosslinking bisimide with diamines, it also has the drawback of lacking impact resistance and adhesiveness. In order to improve such defects, epoxy resin is replaced with polyimide/
It has been proposed to use it in combination with a diamine curing system (Japanese Patent Publication No. 47-42160), but although adhesion and impact resistance can be improved by using an epoxy resin in combination, there is generally a tendency for heat resistance to decrease. Therefore, in engineering applications that require a high degree of heat resistance, adhesion, and impact resistance, conventional bismaleimide/diamine or When bismaleimide/diamine/epoxy cured products are applied, accuracy, safety, stability, and reliability are not necessarily sufficient. However, in order to satisfy these points, the present invention aims to improve heat resistance, impact resistance in a wide temperature range, mechanical properties, and adhesiveness, and in particular improves the network structure of the cured product. The crosslinking method is unique in order to form it densely and impart toughness. That is, the composition of the present invention contains (I) as an essential component.
An unsaturated polyimide obtained from a dicarboxylic acid having an ethylenic carbon-carbon double bond and a polyamine or a reactive derivative thereof; Partial structural formula CH2C

[() Iris...one (()・]

and (m-polyamine (however, as described later, two of the above three components may be partially or completely reacted before being mixed with other components). A preferred unsaturated polyimide obtained from a polyamine and a dicarboxylic acid having an ethylenic carbon-carbon double bond, which is an essential component of the composition of the invention, has the general formula 8 (where D represents an unsaturated double bond). A divalent organic group having A
indicates the removal of a divalent organic compound). Such bisimides include, for example, N,N'-ethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, and the general formula ( The unsaturated bisimide represented by 1) is composed of an unsaturated dicarboxylic acid anhydride represented by the general formula (wherein D is the same as defined in the general formula (1)),
It can be obtained by a conventional method from a diamine represented by the general formula (where A is the same as defined in general formula (1)). Examples of the unsaturated dicarboxylic anhydride represented by the above general formula (2) include maleic anhydride, citraconic anhydride,
α,β-monounsaturated dicarboxylic acid anhydrides such as itaconic anhydride, pyrosinconic anhydride, dichloromaleic anhydride or one of these anhydrides and an acyclic, alicyclic or heterocyclic diene such as cyclopentadiene, etc. Examples include Diels-Alder reaction products. Also, examples of the diamine represented by the general formula (3) include fats.
Diamines having a cyclic structure in the molecule can be used to improve heat resistance, which is the purpose of the present invention. It is preferable from that point of view. Preferred diamines containing such a ring include metaphenylenediamine, paraphenylenediamine, and 2,2-bis(
4-aminophenyl)propane), 4,4'-diaminodiphenylmethane, benzidine, 1,4-diaminocyclohexane, 1,3,5-triaminobenzene, 4,4
'-dicyclohexylmethane, bis-(4-aminophenyl)diphenylsilane, bis-(4-aminophenyl)methylphosphine oxide, bis-(
3-aminophenyl)methylphosphine oxide,
Bis-(4-aminophenyl) phenylphosphine oxide, bis-(4-aminophenyl) phenylamine, metaxylylene diamine, para-xylylene diamine, 1,1-bis(p-aminophenyl) putalan, 6
, 6'-diamino-2,2'-dipyridyl, 4,4'-
Diaminobenzophenone, 4,4'-diaminoazobenzene, bis(4-aminophenyl)phenylmethane, 1
, 1-bis(4-aminophenyl)cyclohexane, 1
, 1-bis(4-amino-3-methylphenyl)cyclohexane, 2,5-bis(m-aminophenyl)-1,
3,4-oxadiazole, 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5
-bis(m-aminophenyl)thiazolo(4,5-α)
Thiazole, 5,5'-di(m-aminophenyl)-
2,2'-bis(1,3,4-oxadiazolyl)diphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4
'-Diaminodiphenyl ether, 2,6-diaminopyridine, tris(4-aminophenyl)phosphine oxide, bis(4-aminophenyl)-N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,5-diamino-1,3,4-oxadiazole, melamine, benzoguanamine, 2,4-bis(β-amino-tert-butyl ) Toluene, bis(p
-β-amino-tert-butylphenyl)ether,
Bis(p-β-methyl-α-aminophenyl)benzene, bis-p-(1,1-dimethyl-5-aminobentyl)benzene, 1-isopropyl-2,4-m-phenyldiamine, 4,4 '-bis(p-aminophenyl)
-2,2'-dithiazole, m-bis(4-p-aminophenyl-2-thiazolinolivenzene, 2,2'-bis(rr1aminophenyl)-5,5'-dibenzimidazole, 4,4'-dibenzanilide , 4,4'-diaminophenyl benzoate, N,N'-bis(4-aminobenzyl)-p-phenylenediamine, 3,5-bis(m-aminophenyl)-4-phenyl 1,2,4-triazole, or In addition to these, -f, 1,000 in the molecule
] Mi W-■ Mi”t. Other aliphatic diamines include ethylene diamine, 2,17-diaminoeicosadecane, 1,10-diamino-1,10-dimethyldecane, 1
, 12-diaminooctadecane, hexamethylenediamine, hebutamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylenediamine, 3-methylhebutamethylenediamine, 4,4-dimethylhebutamethylene Diamine, 2,11-diaminododecane, 1,2-bis(3-aminopropoxy)ethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,
Examples include 5-dimethylhebutamethylenediamine. Such an unsaturated dicarboxylic acid and a polyamine such as a diamine are heated and stirred by a known mechanical method, such as adding a solvent that is azeotropic with water, such as xylene, and other solvents if desired, and water produced by condensation is separated. The polyimide according to the present invention can be obtained by a method such as sufficiently removing water and then separating the product. In addition, various polyamines that can be used in the present invention include aliphatic diamines, aromatic diamines, alicyclic diamines, and diamines having a heterocycle, but diamines having a cyclic structure in the molecule, In particular, it is preferable to use a diamine having an amino group directly connected to a ring from the viewpoint of improving heat resistance, which is the objective of the present invention. Preferred diamines containing such a ring include metaphenylenediamine, paraphenylenediamine, 2,2-bis(4-aminophenyl)propane), 4,4'-diaminodiphenylmethane, benzidine, and 1,4-diaminocyclohexane. ,1
, 3,5-triaminobenzene, 4,4'-dicyclohexylmethane, bis(4-aminophenyl)diphenylsilane, bis(4-aminophenyl)methylphosphine oxide, bis(3-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)methylphosphine oxide, -aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)phenylamine, metaxylylenediamine,
Paraxylylenediamine, 1,1-bis(p-aminophenyl)phthalane, 6,6'-diamino-2,2'-dipyridyl, 4,4'-diaminobenzophenone, 4,4
'-Diaminoazobenzene, bis(4-aminophenyl)phenylmethane, 1,1-bis(4-aminophenyl)cyclohexane, 1,1-bis(4-amino-3-methylphenyl)cyclohexane, 2,5-bis(m-aminophenyl) )-1,3,4-oxadiazole, 2,
5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis(m-aminophenyl)thiazolo(4,5-α)thiazole, 5,5'-di(m-aminophenyl) -2,2'-bis(t),3,4-oxadiazolyl)diphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4, diaminodiphenyl ether ,2
, 6-diaminopyridine, tris(4-aminophenyl)phosphine oxide, bis(4-aminophenyl)-
N-methylamine, 1,5-diaminonaphthalene, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 3,
3'-dimethoxybenzidine, 2,5-diamino-1,
3,4-oxadiazole, melamine, benzoguanamine, 2,4-bis(β-amino-tert-butyl)toluene, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl- α-aminophenyl)benzene, bis-p-(1,1-dimethyl-5
-aminopentyl)benzene, 1-isopropyl-2,
4-m-phenyldiamine, 4,4'-bis(p-aminophenino(ha)-2,2'-dithiazole, m-bis(4-p-aminophenyl-2-thiazolyl)benzene, 2,2'- Bis(m-aminophenyl)-5,5'-
dibenzimidazole, 4,4'-dibenzanilide,
4,4/-diaminophenylbenzoate, N,N'-
Bis(4-aminobenzyl)-p-phenylenediamine, 3,5-bis(m-aminophenyl)-4-phenyl-1,2,4-triazo→R range has other groups in the molecule such as and/or diamines containing phenyl groups; other aliphatic diamines include ethylene diamine, 2
, 17-diaminoeicosadecane, 1,10-diamino-1,10-dimethyldecane, 1,12-diaminooctadecane, hexamethylene diamine, hebutamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, diamino Propyltetramethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11
-diaminododecane, 1,2-bis(3-aminopropoxy)ethane, 2,2-dimethylpropylenediamine,
Examples include 3-methoxyhexamethylene diamine, 2,5-dimethylhexamethylene diamine, and 2,5-dimethylhebutamethylene diamine. Other preferred polyamines include condensates of aniline and formalin (in the formula, n represents a number of 0.1 or more on average) and water additives thereof. The epoxy compound used in the present invention is an epoxy compound having at least one terminal epoxy group and one or more partial formulas in the average molecule, and includes, for example, the following compounds. 1) p-isoprobenylphenol dimer 4-methyl-2,4-bis(p-hydroxyphenyl) pent-1
-ene and the general formula of epihalohydrin such as epichlorohydrin, epipromhydrin (X = halogen, 2
= hydrogen atom, methyl group, or ethyl group) by a known method. Epoxy compounds having adjacent epoxy groups (for example, epoxy resins from bisphenol A, epoxy nopolacs, glycidyl ethers or glycidyl esters of polyether polyols, glycidyl ethers of isocyanuric acid-hydantoin compounds, etc.) are exemplified by various so-called epoxy resins. ) and -
4-methyl-2,4-bis(p-hydroxyphenyl)
An epoxy compound obtained by reacting pent-1-ene with an excess of epoxy groups. 111) An average of more than one adjacent epoxy compound in one molecule obtained by reacting the epoxy compound obtained in 1) above with at least two polyhydric phenols, polycarboxylic acids, isocyanuric acid, and hydantoins. Epoxy compounds containing groups. ! V) Mixtures of the epoxy compounds of i) to Ill). Examples of methods for blending and curing the composition include methods 1 to 3 below. 1 unsaturated polyimides and polyamines,
and a method of simultaneously mixing and curing the above epoxy compounds. 2. A method in which polyamines and the above-mentioned epoxy compound are reacted in advance in a molar ratio such that the polyamine is in excess and active amino hydrogen remains, and the obtained epoxy-added amine compound is mixed with unsaturated polyimide and cured and molded. 3. The unsaturated polyimide and the polyamine may be reacted in advance in excess of the polyamine, and the resulting product may be used as a curing agent for the above-mentioned epoxy compound. Further, although not necessarily essential, a radical polymerization catalyst (for example, peroxide) can also be used for the purpose of improving curability and heat resistance. Peroxides used in the present invention include peroxides of ketones and aldehydes such as methyl ethyl ketone peroxide, cyclohexanone peroxide, bis-(1-oxycyclohexyl) peroxide, acetyl peroxide, caprylyl peroxide, and lauroyl peroxide. peroxide, diacyl peroxides such as stearoyl peroxide, benzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, 2,4,21,4'-tetrachlorobenzoyl peroxide, di-t-butyl peroxide, di-t-acyl peroxide, t-
Dialkyl peroxides such as butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, t
Hydroperoxides such as -butyl hydroperoxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxy-hexane, cumene hydroperoxide, t-butyl peracetate, t-butyl peroxide, Isoptile, t-butylperpivalate, t-butylperbenzoate, di-
t-butyl perphthalate, 2,5-dimethyl (2,5
- Alkyl peroxide esters such as benzoyl peroxy)hexane, t-butyl permale, t-butyl peroxy-isopropyl carbonate, and other peroxides such as succinic peroxide, etc. can be mentioned. The mixture of epoxy compound, polyimide, polyamine and organic peroxide is heated at 130 to 250°C, preferably at 150°C.
Can be cured at temperatures of ~200°C. Further, as a catalyst, an organic peroxide is used alone or in combination with a conventionally known catalyst, and the amount added is preferably 0.5 to 5 parts by weight per 100 parts by weight of the mixture of the epoxy compound, polyimide, and polyamine. is 1 to 3 parts by weight. The above-mentioned mixing methods include mixing powders, such as pulverizing with a ball mill, crusher, etc. to obtain a uniform powder mixture, mixing in a paste or molten state, such as melting for a single hour with a heating roll S at 100 to 150°C; There are a method of kneading and then pulverizing, a method of heating above the softening point and thorough stirring, and a method of mixing as a solution using a solvent. Further, as a method for curing and molding the composition of the present invention, casting, compression molding, etc. may be performed at a curing temperature of 150 to 300°C, preferably 1805 to 230°C. In addition, at this time, curing accelerators, reactive diluents such as monoglycidyl ether, non-reactive diluents, pigments, fillers and other additives such as silica powder, bitumen, white tar, cellulose, glass fiber, etc. , synthetic quaternary fibers, viscosity, sand, rock, mica, aluminum powder, titanium white, Erosil, talc pentonite, calcium carbonate and similar substances may be added, for example by dissolving the composition in a solvent, glass cloth, etc. There are methods such as impregnating or laminating the base material. The effect of the present invention is to provide a curable resin composition that has excellent heat resistance, adhesiveness, mechanical properties, impact resistance, and electrical properties. Examples of the present invention are shown below, and "parts" in the examples indicate parts by weight. Example 1 100 parts of 4-methyl-2,4-bis(p-hydroxyphenyl)benth-1-technique and 1 part of epichlorohydrin
82 parts are placed in a four-way flask equipped with a thermometer, stirrer and reflux.

Claims (1)

[Scope of Claims] 1. As essential constituents: (I) an unsaturated polyimide obtained from a dicarboxylic acid having an ethylenic carbon-carbon double bond and a polyamine or a reactive derivative thereof; and (II) an average A curable resin composition containing an epoxy compound having more than one adjacent epoxy group in one molecule and one or more partial structural formulas (including mathematical formulas, chemical formulas, tables, etc.), and (III) a polyamine ( However, two of the above three components may be partially or completely reacted before being mixed with other components).