JPH05310931A - Thermosetting polyimide resin composition, thermoset product and its production - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific polyfunctional unsaturated imide and a specific thermoplastic resin, having excellent heat- resistance, toughness, flexibility, adhesiveness and mechanical properties and useful as structural material, sealing material, film, etc. CONSTITUTION:The objective composition contains, as essential components, (A) 100 pts.wt. of a polyfunctional unsaturated imide of formula I (D is bivalent group containing C-C double bond; R<1> is >=2-functional organic group; X1 is >=2) and (B) preferably 10-50 pts.wt. of one or more components having compatible range with the component A, a glass transition temperature of >=180 deg.C and a number-average molecular weight of >=10,000 and selected from a polyether imide of formula II (n1 is positive integer), a polyarylate of formula III (n2 is positive integer) and a polyamide imide of formula IV (n3 and n4 are positive integers). A thermoset product having a structure composed of continuously and regularly entangled components A and B can be produced from the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has high heat resistance and excellent mechanical properties such as toughness, flexibility, and adhesiveness, and has structural materials, adhesive materials, molding materials, sealing materials, films, The present invention relates to a thermosetting polyimide resin composition used for laminated plates and the like, a thermosetting product thereof, and a method for producing the thermosetting product.

[0002]

2. Description of the Related Art Conventionally, polyimide has been widely used in applications requiring heat resistance. This polyimide is roughly classified into the first type obtained by shaping at the stage of the precursor polyamic acid and then heat-treating the imide ring and the oligomer having the imide ring. There is a second type obtained by crosslinking.

The first type includes Vespel, Kapton, Upilex, Pyralin (both are registered trademarks) and the like. Although these have extremely high heat resistance, they become insoluble and infusible during molding, and therefore, handling such as molding is difficult. On the other hand, various polymers in which the molecular structure is devised so as to have thermoplasticity have been proposed. However, according to this approach, the molded product is in a molten state at a molding temperature or higher, and the heat resistance is significantly reduced, so that the application to the application utilizing the heat resistance inherent to polyimide is limited.

In that respect, the thermosetting polyimide of the second type obtained by heat-crosslinking an oligomer having an imide ring can be freely molded, and the molded product is insoluble and infusible and has high heat resistance. It is used in large quantities in fields requiring high reliability in harsh environments, such as multi-layer printed circuit boards for large computers, functional components inside and outside automobile engines, parts for space and aeronautical applications. There is.

For example, a polyfunctional unsaturated imide represented by the following general formula 9 can be obtained by polymerizing and crosslinking it to obtain a cured product having a very high crosslinking density.

[0006]

[Chemical 9]

(Wherein D represents a divalent group containing a carbon-carbon double bond, R ¹ represents a bifunctional or higher functional organic group,
x ₁ represents an integer of 2 or more. ) A typical example of this polyfunctional unsaturated imide is represented by the following formula:
Is a bismaleimide.

[0008]

[Chemical 10]

However, since the composition using this bismaleimide has the drawback of being very brittle, it has a problem in toughness, workability and impact resistance. Therefore, although the heat resistance is somewhat inferior, the bismaleimide monomer modified with various crosslinking agents is used. A typical example thereof is a polyamino bismaleimide resin obtained by using a diamine as a cross-linking agent, and kelimide, quinel (both are registered trademarks) and the like belong to this group. Specifically, these are obtained by using an oligomer of bismaleimide and diamine by Michael addition and heating the oligomer to simultaneously increase the molecular weight and crosslink. Other examples include a polyimide obtained by using a polycyanate compound instead of the diamine as a crosslinking agent.

[0010]

However, all of the above-mentioned polyimides obtained by modifying the bismaleimide monomer with various crosslinking agents have a toughness and flexibility that are higher than those of bismaleimide alone. Although it has been improved slightly, it has not reached a sufficient level. Generally, in order to improve the toughness and flexibility of a thermosetting resin, a method of adding a flexible component typified by an elastomer to a thermosetting resin composition has been investigated. For example, in a composition in which a liquid nitrile rubber having a carboxyl group at both ends [Hycar CTBN (registered trademark)] is mixed with bismaleimide,
Spherical domain (island) of rubber is imide matrix (sea)
It forms a so-called sea-island phase separation structure dispersed therein. However, toughness and flexibility are not significantly improved by this method.

As a method for improving the toughness and flexibility of a thermosetting polyimide resin composition, a method of introducing a thermoplastic resin into the composition has been proposed (JP-A-2-58569).
And Japanese Patent Laid-Open No. 2-305860). However, since the thermoplastic resin used in the thermosetting polyimide resin composition described in JP-A-2-58569 is polyarylsulfone, there is a problem in terms of machinability, and the above-mentioned special feature Since the thermoplastic resin used in the thermosetting polyimide resin composition described in Kaihei 2-305860 is a low molecular weight siloxane oligomer, there is a problem that heat resistance is insufficient.

Therefore, the present invention provides a thermosetting polyimide resin composition excellent in mechanical properties such as toughness, flexibility and adhesiveness while maintaining excellent properties such as high heat resistance, and its heat resistance. An object of the present invention is to provide a cured product and a method for producing this thermosetting product.

[0013]

In order to solve the above problems, the inventors have made various studies. As a result, if the thermoplastic resin to be introduced into the thermosetting polyimide resin composition is selected from the following specific ones, while maintaining excellent properties such as high heat resistance, toughness, flexibility, and adhesiveness The present invention has been completed by confirming through experiments that it is possible to improve mechanical properties such as the above to a sufficient level.

Therefore, the thermosetting polyimide resin composition according to the present invention is a thermosetting polyimide resin composition containing, as essential components, a polyfunctional unsaturated imide represented by the following general formula 11 and a thermoplastic resin. , The thermoplastic resin has a compatibility region with the polyfunctional unsaturated imide, a glass transition temperature of 180 ℃ or more, and a number average molecular weight of 10,000 or more, polyetherimide, polyarylate and polyamide It is characterized by being at least one selected from the group consisting of imides.

[0015]

[Chemical 11]

(In Formula 11, D represents a divalent group containing a carbon-carbon double bond, R ¹ represents a bifunctional or higher functional organic group, and x ₁ represents an integer of 2 or more. ) A thermosetting product (product) according to the present invention is a thermosetting product of the thermosetting polyimide resin composition, wherein a phase having a composition mainly composed of polyimide and a phase having a composition mainly composed of a thermoplastic resin are separated. Both of these separated phases continuously and regularly form an intertwined structure.

In the method for producing a thermosetting product according to the present invention, the above-mentioned thermosetting polyimide resin composition is used as a raw material, the polyfunctional unsaturated imide and the thermoplastic resin are made compatible with each other, and By heat-curing the unsaturated imide, the polyimide is separated into a phase having a main composition and a phase having a thermoplastic resin as a main composition, and both of these separated phases continuously form a regularly entangled structure. This is a method of obtaining a thermoset product.

The polyfunctional unsaturated imide represented by the general formula 11 (hereinafter, simply referred to as "polyfunctional unsaturated imide") is not particularly limited, but for example,
Maleic acid N, N'-ethylene-bis-imide, maleic acid N, N'-hexamethylene-bis-imide, maleic acid N, N'-metaphenylene-bis-imide, maleic acid N, N'-paraphenylene -Bis-imide, maleic acid N, N'-4,4'-diphenylmethane-bis-imide [also referred to as the above formula 10, N, N'-methylenebis (N-phenylmaleimide)]. ], Maleic acid N, N'-4,4'-diphenylether-bis-imide, maleic acid N, N'-4,4'-diphenylsulfone-bis-imide, maleic acid N, N'-4,
4'-dicyclohexylmethane-bis-imide, maleic acid N, N'-α, α'-4,4'-dimethylenecyclohexane-bis-imide, maleic acid N, N'-metaxylylene-bis-imide and maleic acid N, N'-diphenylcyclohexane-bis-imide and the like can be mentioned. These are polyfunctional unsaturated imides obtained by reacting maleic anhydride with various diamines to form an amic acid, and then subjecting this amic acid to a dehydration ring-closing reaction. Other acid anhydrides,
For example, it may be a citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, nadic anhydride, or a polyfunctional unsaturated imide obtained by using a halogen-substituted product or an alkyl-substituted product thereof. Examples of other polyfunctional unsaturated imides include compounds represented by the following formulas 12 to 1
4 and the like.

[0019]

[Chemical formula 12]

[0020]

[Chemical 13]

[0021]

[Chemical 14]

(In formulas 12 to 14, m and n each represent a positive integer.) As the polyfunctional unsaturated imide, only one type may be used, or 2
You may use together 1 or more types. In the present invention, a thermosetting resin other than the polyfunctional unsaturated imide may be used in combination with the polyfunctional unsaturated imide, if necessary. The thermosetting resin other than the polyfunctional unsaturated imide is not particularly limited as long as it does not hinder the achievement of the object of the present invention, and for example, an epoxy resin or the like can be used. The content of polyfunctional unsaturated imide is 3 with respect to the whole thermosetting resin component.
It is preferably 5% by weight or more. This is because if the polyfunctional unsaturated imide content is lower than this range, the heat resistance is reduced.

The thermosetting polyimide resin composition according to the present invention may optionally contain a crosslinking agent. The cross-linking agent is not particularly limited, but for example, a polyamine represented by the following general formula 15, a polycyanate compound represented by the following general formula 16, and a polyfunctional non-functional compound represented by the following general formula 17 Examples thereof include saturated compounds and polyfunctional unsaturated compounds represented by the following general formula 18.

[0024]

[Chemical 15]

(In Formula 15, R ² represents an organic group having two or more functional groups, and x ₂ represents an integer of 2 or more.)

[0026]

[Chemical 16]

(In the formula 16, R ³ represents a bifunctional or more organic group having at least one aromatic ring, and x ₃ represents an integer of 2 or more.)

[0028]

[Chemical 17]

(In Formula 17, R ⁴ represents an H or CH ₃ group, R ⁵ represents a bifunctional or more organic group having at least one aromatic ring, and x ₄ represents an integer of 2 or more. )

[0030]

[Chemical 18]

(In the formula 18, R ⁶ represents a —CH ₂ — group or a —CH ₂ —O— group, and R ⁷ represents a bifunctional or higher functional organic group having at least one aromatic ring or triazine ring. , X ₅ represents an integer of 2 or more.) All of these cross-linking agents cross-link by reacting with the carbon-carbon double bond in the polyfunctional unsaturated imide, and are used alone. Or both may be used together.

The polyamine represented by the general formula 15 is not particularly limited, but for example,
4,4'-diaminodicyclohexylmethane, 1,4-
Diaminocyclohexane, 2,6-diaminopyridine,
Meta-phenylenediamine, para-phenylenediamine,
4,4'-diamino-diphenylmethane, 2,2-bis- (4-aminophenyl) propane, benzidine, 4,
4'-diaminophenyl oxide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) methylphosphine oxide, bis -(3-aminophenyl) methylphosphine oxide, bis- (4-aminophenyl) phenylphosphine oxide, bis- (4-
Aminophenyl) phenylamine, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis- (paraaminophenyl) phthalane, hexamethylenediamine, and polyamines represented by the following formulas 19 to 20. Is mentioned. These may use only 1 type and may use 2 or more types together.

[0033]

[Chemical 19]

[0034]

[Chemical 20]

(In the formulas 19 to 20, n represents a positive integer.) Specific examples of the polycyanate compound represented by the general formula 16 are not particularly limited. 21-35, etc. are mentioned.

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

[0039]

[Chemical formula 24]

[0040]

[Chemical 25]

[0041]

[Chemical formula 26]

[0042]

[Chemical 27]

[0043]

[Chemical 28]

[0044]

[Chemical 29]

[0045]

[Chemical 30]

[0046]

[Chemical 31]

[0047]

[Chemical 32]

[0048]

[Chemical 33]

[0049]

[Chemical 34]

[0050]

[Chemical 35]

(In the formula 35, n represents a positive integer.) However, the polycyanate compound is not limited to the above compounds, and analogs of these compounds, for example, compounds having more functional groups, You may use an alkyl substitution product. As the polycyanate compound, only one kind may be used, or two or more kinds may be used in combination.

Specific examples of the polyfunctional unsaturated compound represented by the above general formula 17 are not particularly limited, but examples thereof include those represented by the following general formulas 36 to 41. These may use only 1 type and may use 2 or more types together.

[0053]

[Chemical 36]

[0054]

[Chemical 37]

[0055]

[Chemical 38]

[0056]

[Chemical Formula 39]

[0057]

[Chemical 40]

[0058]

[Chemical 41]

(In the formulas 40 to 41, n represents an integer of 2 or more.) Specific examples of the polyfunctional unsaturated compound represented by the general formula 18 are not particularly limited, but for example, Formulas 42 to 45, allyl etherified o-cresol novolac represented by Formula 46 below, and Formula 47 below
An allyl etherified novolak represented by the following formula, an allylated phenol novolak represented by the following formula 48, a polyfunctional allyl phenol represented by the following formula 49, and an o, o′-diallyl represented by the following formula 50 -Bisphenol A, the following formula 5
Allyl etherified bisphenol A represented by 1 and triallyl isocyanurate represented by the following formula 52 (TAI
C), triallyl trimellilate (TAT) represented by the following formula 53, diallyl phthalate (DAP) represented by the following formula 54, and the like. These may use only 1 type and may use 2 or more types together.

[0060]

[Chemical 42]

[0061]

[Chemical 43]

[0062]

[Chemical 44]

[0063]

[Chemical 45]

[0064]

[Chemical 46]

[0065]

[Chemical 47]

[0066]

[Chemical 48]

(In the formulas 46 to 48, m represents a positive integer and n represents an integer of 2 or more.)

[0068]

[Chemical 49]

(In the formula 49, n represents a positive integer.)

[0070]

[Chemical 50]

[0071]

[Chemical 51]

[0072]

[Chemical 52]

[0073]

[Chemical 53]

[0074]

[Chemical 54]

The thermoplastic resin used in the present invention is at least one selected from the group consisting of polyetherimide, polyarylate and polyamideimide, and has a compatibility region with the polyfunctional unsaturated imide. With
It has a glass transition temperature (Tg) of 180 ° C. or higher and a number average molecular weight of 10,000 or higher. Here, that the thermoplastic resin has a compatible region with the polyfunctional unsaturated imide,
This means that the polyfunctional unsaturated imide and the thermoplastic resin can be compatibilized by selecting the temperature and the composition. Specific examples of the thermoplastic resin that can be used are not particularly limited, but include, for example, polyetherimide represented by the following formula 55, polyarylate represented by the following formula 56 and formula 57 below. Polyamideimide etc. are mentioned.

[0076]

[Chemical 55]

[0077]

[Chemical 56]

[0078]

[Chemical 57]

In the above formulas 55 to 57, the number of repetitions n ₁ to
n ₄ may be any positive integer, but in order to improve the compatibility with the polyfunctional unsaturated imide or the heat resistance of the cured product, each is preferably 30 to 1000, and 50 to 50 It is more preferably 300. The blending ratio of the thermoplastic resin is not particularly limited, but for example, the thermoplastic resin is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polyfunctional unsaturated imide,
It is more preferably 10 to 50 parts by weight. If,
This is because if the blending ratio of the thermoplastic resin is out of the above range, it becomes difficult to effectively control the phase separation structure.

When the polyamine represented by the above formula 15 is used as the crosslinking agent, polyfunctional unsaturated imide (r ₁ : equivalent of unsaturated imide group) and polyamine (r ₂ : equivalent of amino group)
It is preferable that the compounding ratio thereof is within the range of 1.2 or more in terms of equivalent ratio (r ₁ / r ₂ ). If these compounding ratios are smaller than the above range (the amount of polyamine is too large), the curing time is shortened during curing, and as a result, the phase separation structure effective for improving the toughness is improved. This is because it becomes difficult to form the resin, and it becomes difficult to form a cured product.

The polyfunctional unsaturated imide and the polyamine may each be used in the form of a single monomer, or may be prepolymerized by reacting both in a polar solvent. When such a prepolymerization reaction is carried out in advance, it is preferable to carry out prepolymerization at a temperature of 60 to 95 ° C in order to prevent the formation of a homopolymer of a polyfunctional unsaturated imide. Further, if this prepolymerization reaction is carried out for a long time, the molecular weight of the obtained prepolymer becomes too large, and as a result, the compatibility with the thermoplastic resin is impaired, which is not preferable. Therefore, it is preferable to stop the reaction in a state where the content of the component having a molecular weight of more than 10,000 is within 10%.

When the polycyanate ester compound represented by the above formula 16 is used as a cross-linking agent, a polyfunctional unsaturated imide (r ₁ : equivalent of unsaturated imide group) and a polycyanate ester compound (r ₃ : cyanate group The compounding ratio with
The equivalent ratio (r ₁ / r ₃ ) is preferably in the range of 0.5 or more. If these compounding ratios are smaller than the above range (the amount of the polycyanic acid ester compound is too large), it becomes difficult to form an effective phase-separated structure during curing, and the base cured product This is because the glass transition temperature Tg becomes low and the heat resistance becomes low.

As the cross-linking agent, the compound represented by the general formula 17 or 18
The compounding ratio of the cross-linking agent in the case of using a polyfunctional unsaturated compound represented by is not particularly limited, but polyfunctional unsaturated imide (r ₁ : equivalent amount of unsaturated imide group) and cross-linking agent (r ₄ : The equivalent ratio (r ₁ / r ₄ ) to the equivalent of the unsaturated group in the polyfunctional unsaturated compound is preferably 0.1 to 10, and more preferably 0.25 to 1. More preferable.
If the ratio is less than 0.1, the effect of adding the crosslinking agent cannot be obtained, and if it is more than 10, the heat resistance of the cured product is lowered.

The thermosetting polyimide resin composition of the present invention may optionally contain a catalyst for the purpose of promoting the curing reaction. The catalyst that can be used is not particularly limited, but examples thereof include those listed below. Organic bases such as N, N-dimethylaniline, N, N-dimethyltoluidine, N, N
-Dimethyl-p-anisidine, p-halogeno-N, N-
Dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N
-Methylmorpholine, triethanolamine, tertiary amines such as 2-undecylimidazole, 2-ethyl-4-methylimidazole, benzyldimethylamineimidazoles, benzimidazoles and their ammonium salts; triphenylphosphine, etc. Phosphorus compounds; phenols such as phenol, cresol, xylenol, resorcin, phloroglucin; lead naphthenate,
Organometallic salts such as lead stearate, zinc naphthenate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate; SnCl ₂ , ZnCl ₂ , A
chlorides such as lCl ₃ ; ion catalysts such as alkali metal compounds; radical catalysts such as azobisisobutyronitrile and organic peroxides such as dicumyl peroxide; catalysts such as acetylacetonate and its transition metal salts; Is.

The amount of these catalysts used varies significantly depending on the type of catalyst used, the use of the cured product, the curing conditions, etc., and cannot be specified unconditionally, but the amount of the catalyst in a general sense, for example, It is preferably 5% by weight or less with respect to the thermosetting resin component. Incidentally, depending on the combination of the curing system and the curing temperature, the curing speed is too slow, the phase separation cannot be fixed, and the phase separation structure of the cured product may become coarse or irregular. In this case, the use of a curing accelerator is effective. However, the use of this curing accelerator is merely an auxiliary means used for adjusting the curing rate for achieving a good balance between phase separation and curing, and is not an essential requirement of the present invention.

The thermosetting polyimide resin composition of the present invention may contain, if necessary, a releasing agent, various additives such as pigments, fillers, etc. which are usually used. In addition, a laminated plate, SMC, in the form of a prepreg obtained by impregnating a substrate such as glass cloth in the form of a varnish dissolved in a solvent.
It may be molded for applications such as FRP. Next, the principle of manifestation of the phase separation structure in the thermosetting product of the present invention and the means for confirming the phase separation structure will be described.

In general, when two different kinds of organic substances A and B are mixed, a diagram called "phase diagram" can be drawn with respect to their composition ratio and temperature. In some cases, they are compatible with each other in all practical areas, or in other cases, they are not compatible with each other in some areas. This phenomenon is determined by whether or not the free energy when they are compatible is lower than the total of the free energies in the two phases that are not compatible, that is, what composition dependence ΔG _mix has.

An example of the phase diagram is shown in FIG. This phase diagram is L
This is called the CST type, and is an example in which the same composition facilitates compatibility at low temperatures. However, on the contrary,
In some cases, they are compatible with each other on the high temperature side, in which case they are called UCST phase diagrams. Such a curve on the phase diagram that distinguishes the incompatible region and the compatible region is called a binodal curve (see FIG. 26). In the phase diagram shown in Fig. 26, another one, ∂
If the points of ΔG _mix / ∂φ ² = 0 are combined, the spinodal curve (indicated by the broken line in the figure) in which the apex coincides with the binodal curve and enters the incompatible region side can be drawn. .. Inside the spinodal curve, ∂ΔG
_mix / ∂φ ² <0, and on the outside, ∂ΔG _mix / ∂φ
² > 0.

Among the incompatible regions, the inside of the spinodal curve is called the unstable region, and the region between the spinodal curve and the binodal curve is called the metastable region. According to the detailed theory, as shown in FIG. 27, once the temperature T ₁
The temperature of the mixed system that is uniformly compatible in the stable compatible region is T
_When it is rapidly raised to ₂ and comes into the unstable region, the phase separation rapidly starts in the coexisting compositions φ ₁ and φ ₂ . At that time, as shown in FIG. 28, the concentration has a constant wavelength Λ _m (structural period), and a structure in which both separated phases are continuous and regularly entangled is formed. Such a structure is called a “modulation structure”, and the period Λ _m of this modulation structure is thermodynamically defined by the following equation by the position (φ, T ₂ ) on the phase diagram.

Λ _m ≈2πL [3 | T _S −T ₂ | / T _S ] ^−1/2 Here, L is the interaction distance between molecules and is usually 3
It takes a value around 0 nm. It has been clarified by computer simulation that the arabesque pattern as shown in FIG. 29 can be obtained by observing such a structure two-dimensionally with a microscope. Actually, such a structure has been confirmed in various systems.

Normally, this process is an early phenomenon called spinodal decomposition, and at the end stage, similar structural enlargement occurs, and finally the sea-island structure is not the structure shown in FIG. It will be detected. In order to fix the mutual continuous structure by spinodal decomposition, it is effective to fix one or both components in a short time by rapid cooling, etc., but when the temperature is raised again, it changes to a sea-island structure, and it becomes practical. On the other hand, it was not very meaningful.

However, it has recently been shown that when one component is a thermosetting component, the thermosetting phase cannot move freely due to the reaction at the initial stage of spinodal decomposition, so that structural fixation permanently occurs. .. An example in which an epoxy resin is used as a thermosetting resin and a modulation structure with a thermoplastic resin is fixed is already known [Reference (1): K. Yamana
ka, et al., Polymer, 30 , 662 (1989); and reference (2):
Yamamoto et al., Proc. 40th Annual Polymer Conference II-11-05 (199
1) etc.].

However, an example in which a polyimide resin is used as the thermosetting resin and the modulation structure with the thermoplastic resin is fixed is as follows:
It has not yet been reported in the academic literature. On the other hand, FIG.
In the metastable region in the middle, since the sea-island structure is formed from the initial stage, the effect of the present invention cannot be obtained. As described above, the present invention has a polyfunctional unsaturated imide and a specific thermoplastic resin as essential components, and at the time of curing, from the phase decomposition of the polyfunctional unsaturated imide and the thermoplastic resin, a modulation structure, that is, these A composition and a thermosetting product thereof, in which two separate phases are continuous together to form a regularly entangled structure. In order to confirm such a structure, the following two points are important.

Observing a regular periodic structure. This item is usually achieved by optical means. The fact that the scattering maximum appears in the light scattering measurement is a proof that the structure has a regular phase separation structure with a certain period.
_m can be calculated by the following equation using the irradiation light wavelength λ of light scattering, the refractive index N of the cured product, and the scattering angle θ _m that gives the scattering maximum.

[Lambda] _m = ([lambda] / 2N) / sin ([theta] _m / 2) Normally, [Lambda] _m is 0.01 to 10 [mu] _m when the modulation structure of spinodal decomposition can be fixed.
It is suspected that the structure exceeding the size of the sea island structure is enlarged. The structure as shown in FIG. 29 should be observed by optical microscope observation.

On the other hand, in the sea-island structure, a structure in which one component is dispersed spherically is observed. Further, in addition to the above-mentioned direct confirmation, the composition is once completely compatible before curing, and remains when the cured product is surface-etched with a solvent that dissolves the thermoplastic resin. It is also useful to confirm that a coral-shaped structure with intricate imide phase can be observed.

For reference, the epoxy curing phase shown in the above-mentioned document (1) describing the modulation structure in the epoxy system (the surface etched with a solvent dissolving a thermoplastic resin)
A scanning electron microscope (SEM) photograph of the above is shown in FIG. 30, and its three-dimensional schematic diagram is shown in FIG. The present invention is a composition containing a polyfunctional unsaturated imide and a specific thermoplastic resin as essential components, and a cured product that undergoes continuous phase separation with each other, and a thermosetting product thereof. Is not particularly limited. However, as described in the above expression mechanism, it is premised that they are once compatibilized. For example, when powders are mixed, it is necessary to leave them at a temperature at which they do not harden until they become compatible. Will be needed. However, if a casting method is used in which the solvent is uniformly mixed with a common solvent in a molecular order and then the solvent is removed, in the compatibility region, the ingredients are instantly and uniformly compatible, so that no limitation on manufacturing conditions is necessary. Absent. Also, the curing speed is
For example, it is adjusted by adjusting the curing temperature and the presence or absence of the above-mentioned curing accelerator. Adjusting the cure rate provides a means of controlling the structural period of phase separation. In short, within the scope of the present invention, it is necessary to obtain a cured product production condition such that both the phase mainly composed of polyimide and the separated phase composed mainly of the thermoplastic resin can have a mutually continuous structure. It's good. Typical examples of conditions for producing a cured product will be described below, but the conditions differ depending on the composition of the system and are not limited.

First, all components are mixed and dissolved using one or more polar solvents such as methylene chloride, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, methylcellosolve, etc., and the concentration is 5 to 60% by weight. % Solution is prepared. The resulting solution is cast into a film and the solvent is removed.

The obtained film is cured at 140 to 250 ° C. for 1 minute to 5 hours to fix the structure.
Further, post-curing is performed at a high temperature of 200 to 300 ° C. for 1 to 3 hours. Of course, in the case of producing a film-shaped molded product, the uncured casting film may be roughly crushed and molded and cured, or the powder is mixed without using a solvent, and the temperature at which they are compatible, for example, A method may be performed in which the mixture is left at 70 to 150 ° C. for compatibilization and then heated to the molding temperature.

[0100]

A composition is formed by including a polyfunctional unsaturated imide and the above-mentioned specific thermoplastic resin as essential components, and using this composition as a raw material, the polyfunctional unsaturated imide and the thermoplastic resin are combined. When the polyfunctional unsaturated imide is thermally cured after being made compatible, the polyimide is separated into a phase having a main composition and a thermoplastic resin having a main composition, and both of these separated phases are continuous. As a result, a thermoset product having a regularly intertwined structure is produced. Since this thermosetting product has the structure as described above, it has high heat resistance derived from polyimide and mechanical properties such as toughness, flexibility, and adhesiveness derived from thermoplastic resin. ..

In the present invention, the thermoplastic resin has a compatibility region with the polyfunctional unsaturated imide and is 180 ° C.
At least one selected from the group consisting of polyetherimide, polyarylate and polyamideimide having the above glass transition temperature and a number average molecular weight of 10,000 or more is used. If a thermoplastic resin having no compatible region with the polyfunctional unsaturated imide is used, a cured product having the above-mentioned modulation structure cannot be obtained.

When a thermoplastic resin having a glass transition temperature of less than 180 ° C. or a number average molecular weight of less than 10,000 is used, the heat resistance of the cured product decreases. Polyetherimide,
As the thermoplastic resin other than polyarylate and polyamideimide, for example, polyphenylene oxide (PPO), polyvinylidene fluoride (PVDF), polyether ether ketone (PEEK), polyphenylene sulfite (PPS), polyacetal (POM),
Nylon, polycarbonate (PC) and the like are available, but these thermoplastic resins cannot be used in the present invention. This is because these are unsuitable in terms of heat resistance, solvent or compatible region. For example, polyphenylene oxide and polyvinylidene fluoride do not have compatible zones with polyfunctional unsaturated imides. For polyetheretherketone and polyphenylene sulfite, it is difficult to select a preferable solvent. For polyacetal and nylon, it is difficult to select a preferable solvent, and the glass transition temperature is lower than 180 ° C., so that the heat resistance is lowered. Polycarbonate has a compatible region with a polyfunctional unsaturated imide, but its glass transition temperature is lower than 180 ° C., so that it lowers heat resistance.

[0103]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. -Example 1-N, N'-methylenebis (N- represented by Formula 10 above
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight, polyetherimide [made by GE, Ultem (registered trademark) 1000, glass transition temperature Tg21
7 ° C, number average molecular weight 12,000, weight average molecular weight 300
00] 30 parts by weight and diaminodiphenylmethane 2
7.7 parts by weight were mixed to obtain a 10% by weight solution of methylene chloride. This solution was cast on a cover glass and the solvent was removed under reduced pressure at room temperature for 24 hours to obtain a thin film.

This thin film was cured at 150 ° C., and light scattering was measured over time, and observation with an optical microscope was performed. The light scattering measurement is performed by Optec Co., Ltd.
The light scattering of the cast film is 30
The measurement was performed every second (the same applies to the following examples). Light scattering measurements revealed a scattering maximum in the profile. This indicates that the sample has an ordered phase-separated structure having a certain period (the same applies hereinafter).

-Example 2-A thin film obtained in the same manner as in Example 1 was cured at 170 ° C to prepare a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. -Example 3-A thin film obtained in the same manner as in Example 1 was cured at 200 ° C to prepare a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. FIG. 1 is a graph together with the results of observing the change with time of the structural period Λ _m obtained from the angle showing the scattering maximum when the samples of Examples 1 to 3 were cured. However, the curing temperature of each sample was 150 ° C. in Example 1, 170 ° C. in Example 2, and 200 ° C. in Example 3. As shown in this figure, it was confirmed that in all the samples, the phase separation structure increased with the passage of time, and the phase separation structure was fixed after a certain period of time.

2 to 4 show the results of observing the phase-separated structures of the final cured products of the samples of Examples 1 to 3 with an optical microscope, respectively. However, in these figures, the length of 12 mm actually corresponds to the length of 20 μm (magnification 600). As seen in these figures, a periodic structure corresponding to the result of the light scattering (see FIG. 1) was observed. Figure 5
4 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 1 to 3 and the curing temperature. As shown in this figure, it was confirmed that the higher the curing temperature, the longer the structural period.

The final cured product of the sample of Example 2 was completely cooled with liquid nitrogen and then fractured. The polyetherimide phase was removed by etching the fracture surface of this sample using methylene chloride, which is a solvent that readily dissolves polyetherimide, at room temperature for 24 hours. The surface of the sample subjected to such etching was observed with a scanning electron microscope (SEM), and the result is shown in FIG.
(Magnification 2000). As seen in this figure, a connected particle structure was observed.

Example 4-In Example 1, the components were blended as shown in Table 1 below to prepare a 10 wt% solution of dimethylformamide (DMF), and the solution was cast and dried. A thin film was obtained in the same manner as in Example 1 except that the period of time was changed to 72 hours.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural cycle of this final cured product was 1.0 μm. -Examples 5 to 9-A thin film was prepared in the same manner as in Example 1 except that each component was blended as shown in Tables 1 and 2 below to prepare a 10 wt% methylene chloride solution. Obtained.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of the final cured product of each example is shown in Tables 1 and 2 below.

Example 10 N, N′-methylenebis (N-represented by the above-mentioned formula 10)
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight and 30 parts by weight of the polyetherimide used in Example 1 were blended to obtain a 10% by weight solution of methylene chloride. Using this solution, a thin film obtained in the same manner as in Example 1 was cured at 170 ° C. and used as a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 2 below. -Example 11- The thin film obtained similarly to Example 10 was hardened at 200 degreeC, and it was set as the sample for light-scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase separation structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 2 below. -Example 12-N, N'-methylenebis (N- represented by the above formula 10
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight, 30 parts by weight of the polyetherimide used in Example 1 and 2,2-
Bis (cyanate phenyl) propane [Tokyo Kasei Co., Ltd.
[Production] 52 parts by weight were mixed to obtain a 10% by weight solution of methylene chloride. Using this solution, the thin film obtained in the same manner as in Example 1 was cured at 140 ° C. to prepare a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 2 below. -Example 13- The thin film obtained similarly to Example 12 was hardened at 170 degreeC, and it was set as the sample for light-scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 3 below. -Example 14- The thin film obtained similarly to Example 12 was hardened at 200 degreeC, and it was set as the sample for light-scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 3 below. -Example 15- A thin film was obtained in the same manner as in Example 1 except that each component was blended as shown in Table 3 below to prepare a 10 wt% solution of methylene chloride.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 3 below. -Example 16- In Example 1, each component was mix | blended as shown in the following Table 3, a 10 weight% solution of dimethylformamide (DMF) was prepared, and after casting this solution, the time to dry was set. A thin film was obtained in the same manner as in Example 1 except that the time was changed to 72 hours.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 3 below. -Example 17- A thin film was obtained in the same manner as in Example 1 except that each component was blended as shown in Table 3 below to prepare a 10 wt% solution of methylene chloride.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 3 below. -Example 18- In Example 1, each component was mix | blended as shown in the following Table 3, a 10 weight% solution of dimethylformamide (DMF) was prepared, and after casting this solution, the time to dry was set. A thin film was obtained in the same manner as in Example 1 except that the time was changed to 72 hours.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 3 below. -Examples 19 to 22-A thin film was obtained in the same manner as in Example 1 except that each component was blended as shown in Table 4 below to prepare a 10 wt% solution of methylene chloride. ..

The obtained thin film was cured at the temperature shown in Table 4 below to prepare a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of the final cured product of each example is shown in Table 4 below.

-Comparative Examples 1-3-Each component was blended as shown in Table 5 below to prepare a 10% by weight solution of methylene chloride. To perform a flexion test,
Cast on a tin plate instead of a cover glass,
A thin film was obtained in the same manner as in Example 1. This thin film was cured under the conditions shown in Table 5 below to prepare a sample. However, in Comparative Example 1, a sample could not be prepared because cracking occurred during slow cooling after curing.

[0124] diameter Thus the sample of Comparative Example 2-3 was obtained, and, for samples (cured product) of Example 2, 13 and 10, in accordance with JIS-K5400- ^1979, flex resistance test (bending 10φ) was performed. As a result, the bending angles when cracks occurred were as follows. Example 2 ... 45 ° Comparative Example 2 ... 25 ° Example 13 ... 45 ° Comparative Example 3 ... 25 ° Example 10 ... 20 °

[0125]

[Table 1]

[0126]

[Table 2]

[0127]

[Table 3]

[0128]

[Table 4]

[0129]

[Table 5]

The details of each substance in the column of "blending of thermosetting polyimide resin composition" in the above Tables 1 to 5 are as follows. Polyfunctional unsaturated imide A: N represented by the above formula 10,
N'-methylenebis (N-phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI-S]. Polyfunctional unsaturated imide B: a compound represented by the following formula 58 [BMI-DA manufactured by Mitsui Toatsu Chemicals, Inc.].

[0131]

[Chemical 58]

Polyfunctional unsaturated imide C: a compound represented by the following formula 59 [BMI-MP manufactured by Mitsui Toatsu Chemicals, Inc.].

[0133]

[Chemical 59]

Polyfunctional unsaturated imide D: represented by the following formula 60 (manufactured by Mitsui Toatsu Chemicals, Inc.).

[0135]

[Chemical 60]

Polyamine A: 4,4'-diaminodiphenylmethane represented by the following formula 61 [Tokyo Kasei Co., Ltd.]
Manufacturing reagent].

[0137]

[Chemical formula 61]

Polyamine B: 4,4'-diaminodiphenyl sulfone represented by the following formula 62 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0139]

[Chemical formula 62]

Polyamine C: 4,4'-diaminodiphenyl ether represented by the following formula 63 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0141]

[Chemical 63]

Polyamine D: A compound represented by the following formula 64 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0143]

[Chemical 64]

Polycyanate ester: 2,2-bis (cyanatephenyl) propane represented by the following formula 65 (manufactured by Tokyo Kasei Co., Ltd.).

[0145]

[Chemical 65]

Polyetherimide: manufactured by GE, Ultem (registered trademark) 1000, glass transition temperature Tg of 217 ° C.,
Number average molecular weight 12,000, weight average molecular weight 30,000. Polyarylate: U-Polymer (registered trademark), U100, glass transition temperature Tg of 190 ° C., number average molecular weight of 10,000 or more [confirmed by GPC (gel permeation chromatography; the same applies hereinafter)] manufactured by Unitika.

Polyamideimide: manufactured by Amoco Japan, Torlon (registered trademark) 4000T, glass transition temperature Tg2
89 ° C, number average molecular weight of 10,000 or more [confirmed by GPC]. The annotations in Tables 1 to 5 are as follows. * 1: Curing in each example was carried out at the temperature shown in this column for 3 hours. * 2: In each example, post-curing was performed for 6 hours at the temperature shown in this column (the size of the phase-separated structure did not change during this post-curing).

* 3: The cast film was observed with an optical microscope while raising the temperature, and the minimum temperature at which it became transparent was recorded. -Example 23- N, N'-methylenebis (N- represented by the above formula 10
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight, polyetherimide [made by GE, Ultem (registered trademark) 1000, glass transition temperature Tg21
7 ° C, number average molecular weight 12,000, weight average molecular weight 300
00] 30 parts by weight, allyl etherified o-cresol novolac represented by the above formula 46 [Sumitomo Chemical Co., Ltd.,
A-4L (Part A), m / n = 5/5, allyl equivalent 270-280
g / eq., OH equivalent 270-280 g / eq.] 39 parts by weight and 2-ethyl-4-methylimidazole [Tokyo Kasei Co., Ltd.] 2.78 parts by weight, and 1 part of methylene chloride was added.
A 0 wt% solution was prepared. This solution was cast on a cover glass and the solvent was removed under reduced pressure at room temperature for 24 hours to obtain a thin film. This thin film was cured at 150 ° C. and used as a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. -Example 24-The thin film obtained like Example 23 was hardened at 170 degreeC, and it was set as the sample for light-scattering measurement. Light scattering measurements revealed a scattering maximum in the profile.

-Example 25- A thin film obtained in the same manner as in Example 23 was cured at 200 ° C to prepare a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. Figure 7
6 is a graph showing the results of observing the change with time of the structural period Λ _m when curing the samples of Examples 23 to 25 in the same manner as in Example 1. However, the curing temperature of each sample was 150 ° C. in Example 23, 170 ° C. in Example 24,
Example 25 was 200 ° C. As you can see in this figure,
It was confirmed that, in each of the samples, the phase separation structure increased with the passage of time, and the phase separation structure was fixed after a certain time.

8 to 10 show Examples 23 to 2 respectively.
The result of having observed the phase separation structure of the final hardened | cured material of the sample of 5 with an optical microscope is shown. However, in these figures, 1
A length of 2 mm actually corresponds to a length of 20 μm (magnification 600). As seen in these figures, a periodic structure corresponding to the result of the light scattering (see FIG. 7) was observed.

FIG. 11 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 23 to 25 and the curing temperature. As shown in this figure, it was confirmed that the higher the curing temperature, the longer the structural period. In addition, Example 24
The final cured product of the above sample was completely cooled with liquid nitrogen and then fractured. The polyetherimide phase was removed by etching the fracture surface of this sample using methylene chloride, which is a solvent that readily dissolves polyetherimide, at room temperature for 24 hours. The surface of the sample subjected to such etching was observed by a scanning electron microscope (SEM), and the result is shown in FIG. 12 (magnification 350).
0). As seen in this figure, a connected particle structure was observed.

-Examples 26 to 28-In the same manner as in Example 23, except that each component was blended as shown in Tables 6 and 7 below to prepare a 10 wt% solution of methylene chloride. , A thin film was obtained. The obtained thin film was cured at 170 ° C. and used as a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of the final cured product of each example is shown in Tables 6 and 7 below. -Example 29- N, N'-methylenebis (N- represented by the above formula 10
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight, 30 parts by weight of the polyetherimide used in Example 23 and the polyfunctional allylated phenol represented by the above formula 49 (SH150AR, manufactured by Mitsubishi Yuka Co., Ltd., allyl equivalent: 110 to 120 g / eq., OH equivalent 135 to 14
5 g / eq., Softening point 45-55 ° C.] 64 parts by weight,
A 10% by weight solution of methylene chloride was prepared. Using this solution, a thin film obtained in the same manner as in Example 23 was cured at 150 ° C to prepare a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. -Example 30- The thin film obtained similarly to Example 29 was hardened at 170 degreeC, and it was set as the sample for light-scattering measurement. -Example 31- The thin film obtained similarly to Example 29 was hardened at 200 degreeC, and it was set as the sample for light-scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. FIG. 13 shows the results of Examples 29 to 3 above.
6 is a graph showing the results of observation of the temporal change of the structural period Λ _m when curing the sample No. 1 in the same manner as in Example 1. However, the curing temperature of each sample is 15 in Example 29.
The temperature was 0 ° C, 170 ° C in Example 30 and 200 ° C in Example 31. As shown in this figure, it was confirmed that in all the samples, the phase separation structure increased with the passage of time, and the phase separation structure was fixed after a certain period of time.

14 to 16 show Examples 29 to 29, respectively.
The result of having observed the phase separation structure of the final hardened | cured material of the sample of 31 with an optical microscope is shown. However, in these figures,
12mm length is actually 20μm length (magnification 600)
Equivalent to. As seen in these figures, a periodic structure corresponding to the result of the light scattering (see FIG. 13) was observed.

FIG. 17 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 29 to 31 and the curing temperature. As shown in this figure, it was confirmed that the higher the curing temperature, the longer the structural period. In addition, Example 30
The final cured product of the above sample was completely cooled with liquid nitrogen and then fractured. The polyetherimide phase was removed by etching the fracture surface of this sample using methylene chloride, which is a solvent that readily dissolves polyetherimide, at room temperature for 24 hours. The surface of the sample subjected to such etching was observed with a scanning electron microscope (SEM), and the result is shown in FIG.
0). As seen in this figure, a connected particle structure was observed.

-Example 32- A thin film was obtained in the same manner as in Example 23 except that each component was blended as shown in Table 7 below to prepare a 10 wt% solution of methylene chloride. It was The obtained thin film was cured at 170 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile.

As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed.
The structural period of the final cured product was 1.9 μm. -Example 33- A thin film was obtained in the same manner as in Example 23 except that each component was blended as shown in Table 7 below to prepare a 10% by weight solution of methylene chloride.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural cycle of the final cured product is
It was 2.1 μm. -Example 34-N, N'-methylenebis (N- represented by the above formula 10
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight, 30 parts by weight of the polyetherimide used in Example 23, o, o'-represented by the above formula 50.
Diallyl-bisphenol A [Mitsui Toatsu Chemicals, Inc.,
BPA-CA] 75 parts by weight and 2-phenylimidazole [Tokyo Kasei Co., Ltd. reagent] 1.75 parts by weight were mixed to obtain a 10% by weight solution of methylene chloride. Using this solution, a thin film obtained in the same manner as in Example 23 was cured at 150 ° C to prepare a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. -Example 35- The thin film obtained similarly to Example 34 was hardened at 170 degreeC, and it was set as the sample for light-scattering measurement. -Example 36- The thin film obtained similarly to Example 34 was hardened at 200 degreeC, and it was set as the sample for light-scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. FIG. 19 shows the above-mentioned Examples 34 to 3.
9 is a graph showing the results of observation of the structural period Λ _m with time when the sample of No. 6 was cured in the same manner as in Example 1. However, the curing temperature of each sample is 15 in Example 34.
The temperature was 0 ° C., Example 35 was 170 ° C., and Example 36 was 200 ° C. As shown in this figure, it was confirmed that in all the samples, the phase separation structure increased with the passage of time, and the phase separation structure was fixed after a certain period of time.

20 to 22 show Embodiments 34 to 34, respectively.
The result of having observed the phase separation structure of the final hardened | cured material of 36 samples by an optical microscope is shown. However, in these figures,
12mm length is actually 20μm length (magnification 600)
Equivalent to. As seen in these figures, a periodic structure corresponding to the result of the light scattering (see FIG. 19) was observed.

FIG. 23 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 34 to 36 and the curing temperature. As shown in this figure, it was confirmed that the higher the curing temperature, the longer the structural period. In addition, Example 35
The final cured product of the above sample was completely cooled with liquid nitrogen and then fractured. The polyetherimide phase was removed by etching the fracture surface of this sample using methylene chloride, which is a solvent that readily dissolves polyetherimide, at room temperature for 24 hours. The sample surface subjected to such etching was observed by a scanning electron microscope (SEM), and the result is shown in FIG.
0). As seen in this figure, a connected particle structure was observed.

-Examples 37 to 40-A thin film was prepared in the same manner as in Example 23 except that each component was blended as shown in Table 8 below to prepare a 10% by weight solution of methylene chloride. Got The obtained thin film was cured at the temperature shown in Table 8 below to prepare a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of the final cured product of each example is shown in Table 8 below. -Examples 41 to 45-A thin film was obtained in the same manner as in Example 23 except that each component was blended as shown in Table 9 below to prepare a 10 wt% solution of methylene chloride. ..

The obtained thin film was cured at the temperature shown in Table 9 below to prepare a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of the final cured product of each example is shown in Table 9 below.

-Example 46- 100 parts by weight of a polyfunctional unsaturated imide represented by the above formula 12 [BMI-M20 manufactured by Mitsui Toatsu Chemicals, Inc.] and 30 parts by weight of the polyetherimide used in Example 23. Parts were mixed to obtain a 10 wt% methylene chloride solution. Using this solution, a thin film obtained in the same manner as in Example 23 was heated to 150 ° C.
The sample was cured with to prepare a sample for light scattering measurement.

Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of this final cured product is shown in Table 9 below. -Examples 47 to 49-A thin film was prepared in the same manner as in Example 23 except that each component was blended as shown in Tables 9 and 10 below to prepare a 10 wt% methylene chloride solution. Obtained.

The obtained thin film was cured at the temperatures shown in Tables 9 and 10 below to prepare a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural period of the final cured product of each example is shown in Tables 9 and 10 below.

-Example 50- In Example 23, DMF (N, N'-dimethylformamide) was prepared by mixing the components as shown in Table 10 below.
A thin film was obtained in the same manner as in Example 23, except that a 10% by weight solution of the above was prepared, and after casting this solution, the drying time was changed to 72 hours.

The obtained thin film was cured at 200 ° C. and used as a sample for light scattering measurement. Light scattering measurements revealed a scattering maximum in the profile. As a result of observing the final cured product of the sample with an optical microscope, a phase-separated structure having a structural period was confirmed. The structural cycle of this final cured product was 2.7 μm. -Comparative Examples 4 to 7-Each component was blended as shown in Table 10 below to prepare a 10 wt% solution of methylene chloride.

To perform the bending test, casting was performed on a tin plate instead of the cover glass, and a thin film was obtained by the same method as in Example 23. This thin film was cured under the conditions shown in Table 10 below to prepare a sample. However, in Comparative Example 7,
Since the film was too fragile, cracks occurred during slow cooling after curing, so a sample could not be prepared. Regarding the samples of Comparative Examples 4 to 6 thus obtained and the samples (cured products) of Examples 24, 30 and 35,
According JIS-K5400- ^1979, it was bending resistance test (bending diameter 10φ). As a result, the bending angles when cracks occurred were as follows.

45 ° Comparative Example 4 ... 25 ° Example 30 ... 45 ° Comparative Example 5 ... 25 ° Example 35 ... 45 ° Comparative Example 6 ... 25 °

[0176]

[Table 6]

[0177]

[Table 7]

[0178]

[Table 8]

[0179]

[Table 9]

[0180]

[Table 10]

Details of each substance in the column of "blend of thermosetting polyimide resin composition" in Tables 6 to 10 are as follows. Polyfunctional unsaturated imide A: N represented by the above formula 10,
N'-methylenebis (N-phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI-S]. Polyfunctional unsaturated imide B: one represented by the above formula 58 [BMI-DA manufactured by Mitsui Toatsu Chemicals, Inc.].

Polyfunctional unsaturated imide C: represented by the above formula 60 [BMI-BAP manufactured by Mitsui Toatsu Chemicals, Inc.]
P]. Polyfunctional unsaturated imide D: represented by the above formula 12 [BMI-M20 manufactured by Mitsui Toatsu Chemicals, Inc.]. Crosslinking agent A: allyl etherification represented by the above formula 46
-Cresol Novolac [Sumitomo Chemical Co., Ltd., A-4L (Pa
rt A), m / n = 5/5, allyl equivalent 270-280 g / eq.,
OH equivalent 270-280 g / eq.].

Crosslinking agent B: Allyl etherified novolak represented by the above formula 47 (manufactured by Sumitomo Chemical Co., Ltd.). Crosslinking agent C: Allylated phenol novolac represented by the above formula 48 (manufactured by Sumitomo Chemical Co., Ltd.). Crosslinking agent D: polyfunctional allylated phenol represented by the above formula 49 [SH150AR, manufactured by Mitsubishi Petrochemical Co., Ltd., allyl equivalent 11
0-120 g / eq., OH equivalent 135-145 g / eq., Softening point 45-55 ° C].

Crosslinking agent E: o represented by the above formula 50,
o'-diallyl-bisphenol A [BPA-CA manufactured by Mitsui Toatsu Chemicals, Inc.]. Crosslinking agent F: Allyl etherified bisphenol A represented by the above formula 51 [BPA-AE manufactured by Mitsui Toatsu Chemicals, Inc.]. Crosslinking agent G: triallyl isocyanurate (TAIC) represented by the above formula 52 (reagent manufactured by Tokyo Kasei Co., Ltd.).

Thermoplastic resin A: Polyetherimide represented by the above formula 55 [made by GE, Ultem (registered trademark) 1
000, glass transition temperature Tg 217 ° C, number average molecular weight 1
2000, weight average molecular weight 30,000]. Thermoplastic resin B: polyarylate represented by the above formula 56 [manufactured by Unitika, U polymer (registered trademark), U100,
Glass transition temperature Tg of 190 ° C., number average molecular weight of 10,000 or more (confirmed by GPC)].

Thermoplastic resin C: Polyamide imide represented by the above-mentioned formula 57 [Amorco Japan, Torlon (registered trademark) 4000T, glass transition temperature Tg 289 ° C., number average molecular weight of 10,000 or more (confirmed by GPC)]. In addition, Tables 6 to 1
The annotation of 0 is as follows. * 1: 2UZ represents 2-undecylimidazole [Tokyo Kasei Co., Ltd. reagent], and 2E4MZ is 2-ethyl-4-.
Represents methyl imidazole [Tokyo Kasei Co., Ltd.], 2P
Z is 2-phenylimidazole [Tokyo Kasei Reagents]
And DCP represents dicumyl peroxide.

* 2: Curing in each example was carried out for 3 hours at the temperature shown in this column. * 3: In each example, at the temperature shown in this column for 2 to 6 hours,
Post-cure was performed (during this post-cure the size of the phase separated structure did not change). * 4: The cast film was observed with an optical microscope while heating, and the minimum temperature at which the film became transparent was recorded.

-Example 51-N, N'-methylenebis (N-
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 52 parts by weight, epoxy resin (Yukaka Shell Co., Ltd.)
Manufactured by EP-828, bifunctional epoxy resin, epoxy equivalent 190 g / eq.) 48 parts by weight, 4,4'-diaminodiphenylmethane represented by the above formula 61 [Tokyo Chemical Industry Co., Ltd.
Reagent made by 26.9 parts by weight and polyetherimide represented by the above formula 55 [made by GE, Ultem (registered trademark) 1
000, glass transition temperature Tg 217 ° C, number average molecular weight 1
2000, weight average molecular weight 30000] 30 parts by weight was mixed to obtain a 10% by weight solution of methylene chloride. Using this solution, a thin film obtained in the same manner as in Example 23 was added to 150
After being cured at 3 ° C. for 3 hours, post-curing was performed at 230 ° C. for 3 hours to obtain a sample (cured product).

Comparative Example 8 In Example 51, N, N'-methylenebis (N-phenylmaleimide) was not used at all, and the epoxy resin and 4,4'-diaminodiphenylmethane were added in an amount of 100% by weight, respectively. Parts were performed in the same manner as in Example 51 except that the amount was changed to 26 parts by weight to obtain a thin film. After curing this thin film at 150 ° C. for 3 hours, 230
Sample (cured product) by post-curing at ℃ for 3 hours
Got

-Comparative Example 9-N, N'-methylenebis (N-
Phenylmaleimide) [Mitsui Toatsu Chemicals, Inc., BMI
-S] 100 parts by weight and 30 parts by weight of polycarbonate [manufactured by Mitsubishi Gas Chemical Co., Inc., H4000, glass transition temperature Tg150 ° C, number average molecular weight 10,000 or more (confirmed by GPC), viscosity average molecular weight 15,000, weight average molecular weight 18,000]. , A 10 wt% solution of methylene chloride. A thin film was obtained by using this solution and performing the same operation as in Example 51. After curing this thin film at 160 ° C. for 3 hours,
A sample (cured product) was obtained by post-curing at 230 ° C. for 3 hours.

The above-mentioned first, tenth, and twelfth embodiments,
The heat resistance of the samples obtained in Example 15, Example 16, Example 23, Example 51, and Comparative Examples 8 to 9 was examined.
Heat resistance is determined by the elastic modulus E ₁ at room temperature and the elastic modulus E at 180 ° C.
₂ was measured and evaluated by these ratios E ₃ (= E ₂ / E ₁ ). The higher the value of E _3, the higher the heat resistance.
As a result, the E ₃ value of each sample was
0, Example 12, Example 15, Example 16 and Example 23 were as high as 1.0, and Example 51 was as high as 0.2, while Comparative Examples 8-9 were high. All were as low as 0.01.

[0192]

EFFECTS OF THE INVENTION The thermosetting product of the thermosetting polyimide resin composition according to the present invention is superior in toughness to conventional polyimide resin cured products while maintaining excellent characteristics such as high heat resistance derived from polyimide. It is also excellent in mechanical properties such as flexibility and adhesiveness. Therefore, this thermosetting product can exhibit excellent performance when used as a structural material, an adhesive material, a molding material, a sealing material, a film, a laminated plate, or the like.

According to the method for producing a thermosetting product of the present invention, the above excellent thermosetting product can be easily obtained.

[Brief description of drawings]

FIG. 1 is a graph showing the changes over time in the structural period when the sample of Example 1 was cured at 150 ° C., the sample of Example 2 at 170 ° C., and the sample of Example 3 at 200 ° C. is there.

FIG. 2 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 1 is cured at 150 ° C.

FIG. 3 is an optical micrograph showing a phase separation structure (particle structure) of the final cured product when the sample of Example 2 is cured at 170 ° C.

FIG. 4 is an optical micrograph showing a phase separation structure (particle structure) of the final cured product when the sample of Example 3 is cured at 200 ° C.

FIG. 5: Structural period Λ of the final cured products of the samples of Examples 1 to 3
It is a graph which shows the relationship between _m and a curing temperature.

FIG. 6 is a scanning electron microscope (SEM) photograph showing the particle structure after the fracture surface of the final cured product of the sample of Example 2 was etched with a solvent.

FIG. 7 is a graph showing the change with time of the structural period when curing the sample of Example 23 at 150 ° C., the sample of Example 24 at 170 ° C., and the sample of Example 25 at 200 ° C. is there.

FIG. 8 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 23 is cured at 150 ° C.

FIG. 9 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 24 is cured at 170 ° C.

FIG. 10 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 25 is cured at 200 ° C.

FIG. 11 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 23 to 25 and the curing temperature.

FIG. 12 is a scanning electron microscope (SEM) photograph showing the particle structure after the fracture surface of the final cured product of the sample of Example 24 was etched with a solvent.

FIG. 13: The sample of Example 29 at 150 ° C., Example 30
Of the sample of Example 31 at 200 ° C.,
It is a graph which also shows the time-dependent change of the structural period at the time of hardening, respectively.

FIG. 14 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 29 is cured at 150 ° C.

FIG. 15 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 30 is cured at 170 ° C.

FIG. 16 is an optical microscope photograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 31 is cured at 200 ° C.

FIG. 17 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 29 to 31 and the curing temperature.

FIG. 18 is a scanning electron microscope (SEM) photograph showing the particle structure after the fracture surface of the final cured product of the sample of Example 30 was etched with a solvent.

FIG. 19 shows a sample of Example 34 at 150 ° C., Example 35
Of the sample of Example 36 at 200 ° C.,
It is a graph which also shows the time-dependent change of the structural period at the time of hardening, respectively.

FIG. 20 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 34 is cured at 150 ° C.

FIG. 21 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 35 is cured at 170 ° C.

FIG. 22 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product when the sample of Example 36 is cured at 200 ° C.

FIG. 23 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 34 to 36 and the curing temperature.

FIG. 24 is a scanning electron microscope (SEM) photograph showing the particle structure of the fractured surface of the final cured product of the sample of Example 35, which has been subjected to etching treatment with a solvent.

FIG. 25 is a low temperature dissolution type phase diagram (LCST type phase diagram) showing the correlation between the composition and temperature in a system in which a uniform solution is formed (compatible) at low temperature and separated into two phases by increasing the temperature. Figure).

FIG. 26 is a diagram showing a binodal curve and a spinodal curve in the above phase diagram.

FIG. 27 is a diagram for explaining the process of phase separation when the temperature of the mixed system that is uniformly compatible is rapidly raised in the above phase diagram.

FIG. 28 is a diagram schematically showing a three-dimensional modulation structure having a structural period Λ _m and concentration fluctuation.

FIG. 29 is a diagram schematically showing a two-dimensional modulation structure having a structural period Λ _m .

FIG. 30 is a scanning electron microscope (SEM) photograph of the literature (1) showing the particle structure after solvent etching the surface of a cured product of a conventional epoxy resin / thermoplastic resin mixed system having a modulation structure. .

FIG. 31 is a three-dimensional schematic diagram showing a particle structure of an epoxy resin portion after solvent etching the surface of a cured product of a conventional epoxy resin / thermoplastic resin mixed system having a modulation structure.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 19, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

An example of the phase diagram is shown in FIG. This phase diagram is L
This is called the CST type, and is an example in which the same composition facilitates compatibility at low temperatures. However, on the contrary,
In some cases, they are compatible with each other on the high temperature side, in which case they are called UCST phase diagrams. Such a curve on the phase diagram that distinguishes the incompatible region and the compatible region is called a binodal curve (see FIG. 26). In the phase diagram shown in Fig. 26, another one, ∂
^When the points of ² ΔG _mix / ∂φ ² = 0 are combined, the apex coincides with the binodal curve and a spinodal curve (indicated by a broken line in the figure) that enters the incompatible region side can be drawn. it can. ∂ ² inside the spinodal curve
ΔG _mix / ∂φ ² <0, and outside, ∂ ² ΔG
_mix / ∂φ ² > 0.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C08K 5/17 KAY 7242-4J 5/3415 KBG 7242-4J C08L 67/03 LPK 8933-4J 71/10 LQH 9167 -4J LQK 9167-4J 79/08 LRC 9285-4J 101/00 LTA 7242-4J

Claims (9)

[Claims] 1. A thermosetting polyimide resin composition containing, as essential components, a polyfunctional unsaturated imide represented by the following general formula 1 and a thermoplastic resin, wherein the thermoplastic resin is:
While having a compatible region with the polyfunctional unsaturated imide,
At least one selected from the group consisting of polyetherimide, polyarylate, and polyamideimide having a glass transition temperature of 180 ° C. or higher and a number average molecular weight of 10,000 or higher, which is at least one kind. -Type polyimide resin composition. [Chemical 1] (In Formula 1, D represents a divalent group containing a carbon-carbon double bond, R ¹ represents a bifunctional or higher organic group, and x ₁ represents 2
Represents the above integers. ) 2. The thermosetting polyimide resin composition according to claim 1, further comprising a crosslinking agent. 3. The cross-linking agent is a polyamine represented by the following general formula 2, a polycyanate compound represented by the following general formula 3, a polyfunctional unsaturated compound represented by the following general formula 4, and The thermosetting polyimide resin composition according to claim 2, which is at least one selected from the group consisting of polyfunctional unsaturated compounds represented by the general formula 5. [Chemical 2] (In Formula 2, R ² represents a bifunctional or higher functional organic group, and x ₂ represents an integer of 2 or more.) (In the formula 3, R ³ has at least one aromatic ring 2
It represents a functional or higher organic group, and x ₃ represents an integer of 2 or more. ) [Chemical 4] (In Formula 4, R ⁴ represents an H or CH ₃ group, R ⁵ represents a bifunctional or more organic group having at least one aromatic ring, and x ₄ represents an integer of 2 or more.) 5] (In formula 5, R ⁶ is a —CH ₂ — group or —CH ₂ —O—
Represents a group, R ⁷ represents a bifunctional or more organic group having at least one aromatic ring or triazine ring, and x ₅ represents an integer of 2 or more. ) 4. The thermosetting polyimide resin composition according to claim 1, wherein the content of the polyfunctional unsaturated imide is 35% by weight or more based on the entire thermosetting resin component. 5. The thermosetting polyimide resin composition according to claim 1, wherein the polyetherimide is represented by the following chemical formula 6. [Chemical 6] (Among formalized 6, n ₁ represents a positive integer.) 6. The thermosetting polyimide resin composition according to claim 1, wherein the polyarylate is represented by the following formula 7. [Chemical 7] (Among formalized 7, n ₂ represents a positive integer.) 7. The thermosetting polyimide resin composition according to claim 1, wherein the polyamide-imide is represented by the following formula (8). [Chemical 8] (Among formalized 8, n ₃ and n ₄ represents a positive integer.) 8. A thermosetting product of the thermosetting polyimide resin composition according to any one of claims 1 to 7, wherein a phase having a composition mainly composed of polyimide and a phase having a composition mainly composed of a thermoplastic resin. A thermosetting product in which the two separated phases form a structure in which both separated phases are continuously and regularly intertwined with each other. 9. The thermosetting polyimide resin composition according to claim 1 is used as a raw material, and the polyfunctional unsaturated imide and the thermoplastic resin are made compatible with each other.
By thermosetting the polyfunctional unsaturated imide, the polyimide is separated into a phase having a main composition and a phase having a thermoplastic resin as a main composition, and both of these separated phases have a structure in which both are continuously and regularly entangled. A method for producing a thermosetting product for obtaining a thermosetting product being formed.