JPH0641302A - Thermosetting type polyimide resin composition, thermally cured product and its production - Google Patents

Abstract

PURPOSE:To provide a thermosetting type polyimide resin composition having excellent mechanical characteristics and adhesiveness while maintaining high heat resistance, comprising a polyfunctional unsaturated imide, a specific thermoplastic resin and a specific plasticizer as essential components. CONSTITUTION:A thermosetting type polyimide resin composition comprises (A) a polyfunctional unsaturated imide of formula I (D is a divalent carbon-carbon double bond-containing group; R<1> is a bi- or polyfunctional organic group; X1 is an integer of two or more), (B) a thermoplastic resin having compatibility with the component A, containing sulfone group, such as a polyether sulfone of formula II (n1 is a positive integer) or a polysulfone of formula III (n2 is a positive integer) and (C) one or more of a polyamine of formula IV (R<2> is a di- or polyfunctional organic group; X2 is as shown for X1) and a polycyanic ester compound of formula V (R<3> is an aromatic ring-containing di- or polyfunctional organic group; X3 is as shown for X1) as a crosslinking agent for the component A, as essential components. A thermally cured product of the composition forms a structure wherein a phase consisting essentially of the component A and a phase consisting essentially of the component B are separated and these phase are continuously and regularly entangled.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent adhesiveness as well as mechanical properties such as toughness and flexibility while maintaining high heat resistance derived from polyimide. Thermosetting products used for materials, encapsulating materials, films, laminated plates, etc., thermosetting polyimide resin composition as a raw material for the thermosetting products, and the thermosetting products using the composition Regarding the method.

[0002]

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

The first type includes Vespel, Kapton, Upilex, Pyralin (all registered trademarks) and the like. Although these have extremely high heat resistance, they are 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 lowered, 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 thermally cross-linking the 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 6 can be obtained by polymerizing and crosslinking it to obtain a cured product having a very high crosslinking density.

[0006]

[Chemical 6]

(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 the polyfunctional unsaturated imide is bismaleimide represented by the following formula 7.

[0008]

[Chemical 7]

However, the cured product of this bismaleimide is
It has the disadvantage of being very brittle, so it has toughness, workability,
There is a problem with 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. They are,
Specifically, using an oligomer of bismaleimide and diamine by Michael addition, heating this oligomer,
It is obtained by simultaneously increasing the molecular weight and crosslinking. Another example is a polyimide obtained by using a polycyanate compound instead of the diamine as a crosslinking agent.

However, all of the above polyimides obtained by modifying the bismaleimide monomer with various crosslinking agents have slightly improved toughness and flexibility as compared with the case of using bismaleimide alone. However, 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 carboxyl groups at both ends [Hycar CTBN (registered trademark)] is mixed with bismaleimide, so-called spherical domains (islands) of rubber are dispersed in an imide matrix (sea). It forms a sea-island phase separation structure. However, toughness and flexibility are not significantly improved by this method.

As a method for improving the toughness and flexibility of a thermosetting product of a thermosetting polyimide resin composition, a method of introducing a thermoplastic resin into the composition is disclosed in JP-A-2-58569 and JP-A-2-305860. It is proposed in each publication of the issue.

[0012]

However, the conventional thermosetting polyimide resin composition containing a thermoplastic resin does not contain a crosslinking agent, or does not contain a crosslinking agent. Since the agent is allylphenol, there is a problem in adhesiveness. Therefore, the present invention is a thermosetting product which is superior in adhesiveness as well as mechanical properties such as toughness and flexibility while maintaining excellent properties such as high heat resistance derived from polyimide, as compared with conventional products. It is an object of the present invention to provide a thermosetting polyimide resin composition which is a raw material of this thermosetting product, and a method for producing the thermosetting product using this composition.

[0013]

In order to solve the above problems, the inventors have made various studies. As a result, if the thermoplastic resin and the cross-linking agent to be introduced into the thermosetting polyimide resin composition, respectively, to use the following specific ones, while maintaining excellent properties such as high heat resistance, toughness,
We confirmed by experiments that it is possible to improve the adhesiveness to a sufficient level along with mechanical properties such as flexibility.
Completed this invention.

Therefore, the thermosetting polyimide resin composition according to the present invention has a polyfunctional unsaturated imide represented by the following general formula 8 and a compatible region of the polyfunctional unsaturated imide, and is a sulfone. In a thermosetting polyimide resin composition containing, as an essential component, a thermoplastic resin having a group and a cross-linking agent that cross-links the polyfunctional unsaturated imide, the cross-linking agent is a polyamine represented by the following general formula 9 It is characterized in that it is at least one kind of polycyanate compound represented by the following general formula 10.

[0015]

[Chemical 8]

(In Formula 8, 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. )

[0017]

[Chemical 9]

(In Formula 9, R ² represents a bifunctional or more organic group, and x ₂ represents an integer of 2 or more.)

[0019]

[Chemical 10]

(In the formula 10, 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.) The thermosetting product according to the present invention is as described above. A thermosetting product of a thermosetting polyimide resin composition, in which a phase having a main composition of polyimide and a phase having a main composition of thermoplastic resin are separated, and both of these separated phases are continuously and regularly formed. It forms an intertwined structure.

In the method for producing a thermosetting product according to the present invention, the polyfunctional unsaturated imide and the thermoplastic resin are made compatible with each other by using the thermosetting polyimide resin composition as a raw material, Reacting the unsaturated imide with a crosslinking agent,
By thermosetting, a phase having a main composition of polyimide and a phase having a main composition of thermoplastic resin are separated, and both of these separated phases form a continuous and regularly entangled structure. Is a way to get.

The polyfunctional unsaturated imide represented by the general formula (8) (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 compound represented by the above formula 7, 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 generate amic acid, and then subjecting this amic acid to a dehydration ring-closing reaction. In addition, other acid anhydrides, for example, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, nadic acid anhydride, and polyfunctional unsaturated compounds obtained by using these halogen-substituted compounds, alkyl-substituted compounds and the like. It may be an imide. Examples of other polyfunctional unsaturated imides include those represented by the following formulas 11 to 13.

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

(In formulas 11 to 13, 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 polyamine represented by the general formula 9 and the general formula 1 used as a crosslinking agent in the present invention.
The polycyanate compound represented by 0 is a compound that crosslinks by reacting with the carbon-carbon double bond in the polyfunctional unsaturated imide, and one or more of these crosslinking agents are crosslinked. Is selected and used. Specific examples of the polyamine represented by the general formula 9 are not particularly limited, but include, for example, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine and metaphenylenediamine. , Paraphenylenediamine, 4,4'-diamino-diphenylmethane, 2,2-bis- (4-aminophenyl) propane, benzidine, 4,4'-diaminophenyloxide, 4,4'-diaminodiphenylsulfide, 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)
Examples include phenylamine, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis- (paraaminophenyl) phthalane, hexamethylenediamine, and polyamines represented by the following formulas 14 to 15. .

[0028]

[Chemical 14]

[0029]

[Chemical 15]

(In formulas 14 to 15, n represents a positive integer.) Specific examples of the polycyanate compound represented by the general formula 10 are not particularly limited. Examples include those represented by 16 to 30.

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[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]

(In the formula 30, 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, Alkyl-substituted compounds and the like may be used. The thermoplastic resin used in the present invention has a compatibility region with the polyfunctional unsaturated imide and has a sulfone group. Here, that the thermoplastic resin has a compatible region with the polyfunctional unsaturated imide, depending on the selection of temperature and composition,
This means that it is possible to compatibilize the polyfunctional unsaturated imide and the thermoplastic resin. The thermoplastic resin that can be used is not particularly limited, and examples thereof include polyether sulfone and polysulfone. More specifically, a polyether sulfone represented by the following formula 31 and a polysulfone represented by the following formula 32 may be mentioned.
The thermoplastic resins may be used alone or in combination of two or more.

[0047]

[Chemical 31]

[0048]

[Chemical 32]

In the above formulas 31 to 32, the number of repetitions n ₁ to
Each n ₂ may be a positive integer, but in order to improve the compatibility with the polyfunctional unsaturated imide or the heat resistance of the thermosetting product, n ₂ is preferably 30 to 1000, It is more preferably 50 to 300.
The compounding ratio of the thermoplastic resin is not particularly limited, but for example, the thermoplastic resin is preferably 5 to 100 parts by weight, and 10 to 50 parts by weight with respect to 100 parts by weight of the polyfunctional unsaturated imide. More preferably. 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 9 is used as the crosslinking agent, the compounding ratio of polyfunctional unsaturated imide (r ₁ : equivalent of unsaturated imide group) and polyamine (r ₂ : equivalent of amino group). Is preferably in the range of 1.2 or more in terms of equivalent ratio (r ₁ / r ₂ ). If the compounding ratio is 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 thermosetting product and it becomes difficult to form the thermosetting 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 10 is used as the crosslinking agent, a polyfunctional unsaturated imide (r ₁ : equivalent amount of unsaturated imide group) and a polycyanate ester compound (r ₃ : cyanate group) are used. The compounding ratio with
The equivalent ratio (r ₁ / r ₃ ) is preferably in the range of 0.5 or more. If the compounding ratio is 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 Glass transition temperature T
This is because g is low and heat resistance is low.

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, 2-undecylimidazole, 2-phenylimidazole, 2
-Tertiary amines such as methyl imidazole, 2-ethyl-4-methyl imidazole, benzyl dimethyl amine imidazoles, benzimidazoles and their ammonium salts; phosphorus compounds such as triphenylphosphine; phenol, cresol, xylenol , Phenols such as resorcin, phloroglucin; lead naphthenate,
Organic metal 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 greatly depending on the type of catalyst used, the use of the thermosetting 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 thermosetting product may become coarse or irregular, In that case, it is effective to use a curing accelerator. 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 contains, if necessary, a mold release agent, various additives such as pigments, fillers, etc. which are usually used in conventional resin compositions. You may stay. Further, it may be molded in the form of a prepreg obtained by impregnating a base material such as glass cloth in the form of a varnish dissolved in a solvent for use as a laminated plate, SMC, FRP or the like.

Next, the principle of development of the phase-separated structure in the thermosetting product of the present invention and the means for confirming the phase-separated structure will be described. Generally, when two different kinds of organic substances A and B are mixed, a diagram called a "phase diagram" can be drawn with respect to their composition ratios and temperatures. In some cases, they are compatible with each other in all practical regions, and in other cases, they are not compatible with each other in some regions. This phenomenon is determined by whether the free energy in the case of compatibility is lower than the total of the free energies in the two incompatible phases, that is, the composition dependence of ΔG _mix .

An example of the phase diagram is shown in FIG. This phase diagram is LC
It is called ST type, and is an example in which the same composition is likely to be compatible with each other at low temperatures. However, on the contrary, there are cases where they are compatible with each other on the high temperature side, and in that case, it is called UCST phase diagram. Such a curve on the phase diagram that distinguishes the incompatible region and the compatible region is called a binodal curve (see FIG. 10). Another one in the phase diagram shown in Fig. 10, ∂ΔG
_By combining the points of _mix / ∂φ ² = 0, 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 ∂ΔG _mix / ∂φ ² > 0 on the outside
Has become.

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 a particular theory, as seen in FIG. 11, once the temperatures T ₁
The temperature of the mixed system that is uniformly compatible in the stable compatible region is T
_When it rapidly rises to ₂ and comes into the unstable region, it rapidly starts phase separation into coexisting compositions φ ₁ and φ ₂ . At that time, as shown in FIG. 12, 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. 13 can be obtained by observing such a structure two-dimensionally with a microscope. Actually, such a structure has been confirmed in various systems.

Usually, 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 becomes a sea-island structure, so it is practical. On the contrary, 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, a sea-island structure is formed from the initial stage, so the effect of the present invention cannot be obtained. As described above, the present invention has a polyfunctional unsaturated imide, a specific cross-linking agent and a specific thermoplastic resin as essential components, and at the time of heat curing,
A thermosetting polyimide that forms a modulation structure, that is, a structure in which these two separated phases are continuously and regularly intertwined with each other by phase separation into a phase having a main composition of polyimide and a phase having a main composition of thermoplastic resin. A resin composition and a thermosetting product thereof. 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 proof that it has a regular phase-separated structure with a certain period. The period Λ _m is the irradiation light wavelength λ of the light scattering, the refractive index N of the cured product, and the scattering. It can be calculated by the following equation using the scattering angle θ _m that gives the maximum.

[Lambda] _m = ([lambda] / 2N) / sin ([theta] _m / 2) Usually, [Lambda] _{m in} the case where the modulation structure of spinodal decomposition can be fixed is in the range of 0.01 to 10 [mu] _m , and 10 [mu] _m.
It is suspected that the structures exceeding the size of the sea island structure are enlarged. The structure as shown in FIG. 13 should be observed by optical microscope observation.

On the other hand, in the sea-island structure, a structure in which one component is spherically dispersed is observed. Furthermore, in addition to the above-mentioned direct confirmation, the composition is once completely compatible before curing, and remains when the thermosetting product is surface-etched with a solvent that dissolves the thermoplastic resin. It is also useful to confirm that a coral-like structure with a complex 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. 14, and its three-dimensional schematic diagram is shown in FIG. The thermosetting polyimide resin composition according to the present invention and the curing process and manufacturing method of the thermosetting product thereof are not particularly limited. However, as described in the above expression mechanism, it is premised that they are once compatibilized before curing, and for example,
When the components of the composition are mixed in powder form, it is necessary to leave them at a temperature at which they do not harden until they are compatible. However, if the casting method is used in which the components are once mixed in a common solvent in a uniform molecular order and the solvent is removed, in the compatible region, they are instantly and uniformly compatible, so all manufacturing conditions are No limitation is necessary. In addition, the curing speed is adjusted by, for example, 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, the thermosetting product preparation conditions such that the phase mainly composed of polyimide and both the separated phases of the phase mainly composed of the thermoplastic resin can have a mutually continuous structure. It should be taken. A typical example of conditions for producing a thermosetting product will be described below, but these conditions are not limited and vary depending on the composition of the system and the like.

First, one or more polar solvents such as halogenated hydrocarbons such as chloroform, trichloroethylene, trichloroethane, methylene chloride, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, methylcellosolve, etc. are used. All components are mixed and dissolved to prepare a solution having a concentration of 5 to 60% by weight.

The solution obtained is formed into a casting film and the solvent is removed. The obtained film is
The structure is fixed by curing at 0 to 250 ° C. for 1 minute to 5 hours. Furthermore, at a high temperature of 200 to 300 ° C., 1 to 3
Post cure for a time. Of course, when producing a film-shaped molded product, the uncured casting film may be roughly crushed and molded and cured, or without using a solvent,
Temperatures at which powders are mixed and compatible with each other, for example, 70 to 150 ° C
Alternatively, a method of heating to the molding temperature may be performed after leaving it to stand for compatibility.

[0069]

The composition is constituted by including the polyfunctional unsaturated imide, the specific cross-linking agent, and the specific thermoplastic resin as essential components, and the composition is used as a raw material.
After making the polyfunctional unsaturated imide and the thermoplastic resin compatible with each other, the polyfunctional unsaturated imide is reacted with a cross-linking agent, and when thermosetting is performed, the phase of the composition mainly containing polyimide and the composition mainly containing the thermoplastic resin (2) and the two separated phases form a thermosetting product in which both separated phases continuously and regularly form an intertwined structure. Since this thermosetting product has the above-mentioned structure, mechanical properties such as toughness and flexibility derived from the thermoplastic resin are maintained while maintaining excellent properties such as high heat resistance derived from the polyimide. At the same time, it has excellent adhesiveness.

As the thermoplastic resin, one having a compatible region with the polyfunctional unsaturated imide is used. If a thermoplastic resin having no compatible region with the polyfunctional unsaturated imide is used, it becomes impossible to obtain a thermosetting product having the above-mentioned modulation structure. As the cross-linking agent, a polyamine and / or polycyanate compound is used. If you do not use a cross-linking agent, or if you use a cross-linking agent other than polyamine and polycyanate ester compounds, such as allylphenol,
Adhesion is reduced.

[0071]

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-phenylmaleimide) represented by the above formula 7 [Mitsui Toatsu Chemicals, Inc., BMI-
S] 100 parts by weight, polyether sulfone represented by the above formula 31 [Sumitomo Chemical Co., Ltd., Victrex (Vict
rex) (registered trademark) 4100P, glass transition temperature 225 ° C,
A polymerization degree of about 200, a number average molecular weight of 17,700] and 30 parts by weight of 2,4′-diaminodiphenylmethane represented by the following formula 36 (reagent manufactured by Tokyo Kasei Co., Ltd.) and 27.7 parts by weight of methylene chloride were added. A 10 wt% solution was prepared. This solution (resin composition) 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 sample.

This sample was cured at 200 ° 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 by using the manufactured GP-5.
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 cured product of the sample has an ordered phase-separated structure having a constant period (the same applies hereinafter).

FIG. 2 shows that when the sample of Example 1 was cured,
6 is a graph showing the results of observing the change over time of the structural period Λ _m obtained from the angle indicating the scattering maximum. As shown in this figure, it was confirmed that the phase separation structure became larger (structure grew) with the passage of time, and the phase separation structure was fixed after a certain period of time. FIG. 1 shows the results of observing the phase-separated structure of the final cured product of the sample of Example 1 with an optical microscope. However, in this figure, the length of 12 mm actually corresponds to the length of 20 μm (magnification 600). As shown in this figure, a periodic structure corresponding to the result of the light scattering (see FIG. 2) was observed.

Example 2 A thin film-like sample obtained in the same manner as in Example 1 was heated to 150 ° C.
It was cured with and the light scattering was measured. 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 is shown in Table 1 below.

Example 3 A thin film-like sample obtained in the same manner as in Example 1 was heated to 170 ° C.
It was cured with and the light scattering was measured. 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 is shown in Table 1 below.

-Examples 4 to 17-In the same manner as in Example 1 except that 10% by weight solution of methylene chloride was prepared by mixing the components as shown in Tables 1 to 3 below. A thin film sample was obtained. The obtained sample was cured at the temperatures shown in Tables 1 to 3 below, and light scattering measurement was performed.

Light scattering measurements revealed a scattering maximum for all samples 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 in each case. The structural period of the final cured product of the sample of each example is shown in Tables 1 to 3 below.

-Example 18- N, N'-methylenebis (N-phenylmaleimide) represented by the above formula 7 [BMI-, manufactured by Mitsui Toatsu Chemicals, Inc.]
S] 100 parts by weight, 30 parts by weight of the polyether sulfone used in Example 1 and 2,2-
Bis (cyanate phenyl) propane [Tokyo Kasei Co., Ltd.
Manufacturing] 52 parts by weight were mixed to obtain a 10% by weight solution of methylene chloride. Using this solution, a thin film sample obtained in the same manner as in Example 1 was cured at 140 ° C., and light scattering measurement was performed.

Light scattering measurements revealed a scattering maximum in the profile. -Example 19- A 10 wt% solution of methylene chloride was prepared by the same formulation as in Example 18, and a thin film sample was obtained in the same manner as in Example 1 using this solution. The sample was cured at 170 ° C,
Light scattering measurements were performed.

Light scattering measurements revealed a scattering maximum in the profile. -Example 20- A 10 wt% methylene chloride solution was obtained by the same formulation as in Example 18, and a thin film sample was obtained in the same manner as in Example 1 using this solution. This sample was cured at 200 ° C,
Light scattering measurements were performed.

Light scattering measurements showed a scattering maximum in the profile. FIG. 3 is a graph together with the results of observing the change over time of the structural period Λ _m obtained from the angle showing the scattering maximum when curing the samples of Examples 18 to 20. However, the curing temperature of each sample is
Is 140 ° C., Example 19 is 170 ° C., Example 20 is 20 ° C.
It was 0 ° C. As shown in this figure, both samples
It was confirmed that the phase separation structure became larger with the passage of time, and the phase separation structure was fixed after a certain time.

4 to 6 show Examples 18 to 20, respectively.
The result of having observed the phase separation structure of the final hardened | cured material of the sample of this invention by an optical microscope is shown. However, in these figures, 12
A length of 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. 3) was observed. FIG. 7 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 18 to 20 and the curing temperature. As shown in this figure, it was confirmed that the higher the curing temperature, the larger the structural period.

The final cured product of the sample of Example 19 was
After cooling completely with liquid nitrogen, it fractured. The polyethersulfone phase was removed by etching the fractured surface of this sample with methylene chloride, which is a solvent that readily dissolves polyethersulfone, at room temperature for 24 hours. The surface of the sample thus etched was observed with a scanning electron microscope (SEM), and the results are shown in FIG. 8 (magnification 2000). As seen in this figure, a connected particle structure was observed.

-Examples 21 to 25-In the same manner as in Example 1 except that each component was blended as shown in Tables 4 and 5 below to prepare a 10% by weight solution of methylene chloride. A thin film sample was obtained.
The obtained sample was cured at the temperatures shown in Tables 4 and 5 below, and the light scattering measurement was performed.

Light scattering measurements showed a scattering maximum in the profile for all samples. 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 in each case. The structural periods of the final cured products of the samples of each example are shown in Tables 4 and 5 below.

-Comparative Example 1-N, N'-methylenebis (N-phenylmaleimide) represented by the above formula 7 [BMI-, manufactured by Mitsui Toatsu Chemicals, Inc.]
S] 100 parts by weight and 30 parts by weight of the polyether sulfone used in Example 1 were mixed to obtain a 10% by weight solution of methylene chloride. Using this solution, a thin film sample was obtained in the same manner as in Example 1. This sample was cured at 170 ° C. and light scattering measurement was performed.

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 5 below. -Comparative Example 2-N, N'-methylenebis (N-phenylmaleimide) represented by the above formula 7 [Mitsui Toatsu Chemicals, Inc., BMI-
S] 100 parts by weight, 30 parts by weight of the polyether sulfone used in Example 1, o, o'-diallyl-bisphenol A represented by the following formula 41 (BP, manufactured by Mitsui Toatsu Chemicals, Inc., BP
A-CA] 75 parts by weight and 2-phenylimidazole [Tokyo Kasei Co., Ltd. reagent] 1.75 parts by weight were mixed to prepare a 10% by weight solution of methylene chloride. Using this solution, a thin film sample was obtained in the same manner as in Example 1. This sample is 17
It was cured at 0 ° C. and light scattering measurement was performed.

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 5 below. -Example 26- A methylene chloride solution (resin composition) was obtained by the same formulation as in Example 3. However, the solution concentration was changed to 20% by weight. This resin composition was applied to a glass cloth made of E glass (94
g / m ² ) and then dried at 50 ° C. for 7 minutes to remove methylene chloride, which is a volatile component, to obtain a prepreg.

After four prepregs were superposed, copper foil having a thickness of 18 μm was laminated on and under the prepreg. The obtained laminated body is sandwiched between stainless steel plates, and is molded and cured under the same curing conditions as in Example 3 using a pressing machine.
A copper foil-clad laminate was obtained. -Example 27- By the same formulation as in Example 11, a methylene chloride solution (resin composition) was obtained. However, the solution concentration was changed to 20% by weight. Using this resin composition, the same operation as in Example 26 was performed to obtain a copper foil-clad laminate. However, the curing conditions are the same as in Example 11.

-Comparative Example 3-A methylene chloride solution (resin composition) was obtained by the same formulation as in Comparative Example 1. However, the solution concentration was changed to 20% by weight. Using this resin composition, the same operation as in Example 26 was performed to obtain a copper foil-clad laminate. However, the curing conditions are the same as in Comparative Example 1.

-Comparative Example 4-A methylene chloride solution (resin composition) was obtained with the same composition as in Comparative Example 2. However, the solution concentration was changed to 20% by weight. Using this resin composition, the same operation as in Example 26 was performed to obtain a copper foil-clad laminate. However, the curing conditions are the same as in Comparative Example 2.

The interlayer adhesion (adhesion between prepregs) of the copper foil-clad laminates obtained in Examples 26 to 27 and Comparative Examples 3 to 4 was examined. Adhesion test is JIS standard (sample width 10mm, pulling speed 50mm / min) at 25 ℃
It was carried out according to. As a result, the interlaminar adhesive strength of the laminated board of each example was as follows. Example 26 ... 1.24 kgf / cm Example 27 ... 1.10 kgf / cm Comparative example 3 ... 0.51 kgf / cm Comparative example 4 ... 0.73 kgf / cm As seen from the above results, It was confirmed that the laminates had a higher interlayer adhesion than the laminates of Comparative Examples 3 to 4.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

[0096]

[Table 4]

[0097]

[Table 5]

Details of each substance in the column of "blend of thermosetting polyimide resin composition" in the above Tables 1 to 5 are as follows. Polyfunctional unsaturated imide A: N, N ′ represented by the above formula 7
-Methylenebis (N-phenylmaleimide) [BMI-S manufactured by Mitsui Toatsu Chemicals, Inc.]. Polyfunctional unsaturated imide B: one represented by the following formula 33 [BMI-DA manufactured by Mitsui Toatsu Chemicals, Inc.].

[0099]

[Chemical 33]

Polyfunctional unsaturated imide C: a compound represented by the following formula 34 (BMI-MP manufactured by Mitsui Toatsu Chemicals, Inc.).

[0101]

[Chemical 34]

Polyfunctional unsaturated imide D: represented by the following formula 35 (manufactured by Mitsui Toatsu Chemicals, Inc.).

[0103]

[Chemical 35]

Polyfunctional unsaturated imide E: represented by the above formula 11 [BMI-M2 manufactured by Mitsui Toatsu Chemicals, Inc.]
0]. Polyamine A: 4,4'-diaminodiphenylmethane represented by the following formula 36 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0105]

[Chemical 36]

Polyamine B: 4,4'-diaminodiphenyl sulfone represented by the following formula 37 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0107]

[Chemical 37]

Polyamine C: 4,4'-diaminodiphenyl ether represented by the following formula 38 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0109]

[Chemical 38]

Polyamine D: A compound represented by the following formula 39 (a reagent manufactured by Tokyo Kasei Co., Ltd.).

[0111]

[Chemical Formula 39]

Polycyanate: 2,2-bis (cyanatephenyl) propane represented by the following formula 40 (manufactured by Tokyo Kasei Co., Ltd.).

[0113]

[Chemical 40]

Allylphenol: o, o'-diallyl-bisphenol A represented by the following formula 41 [BPA-CA manufactured by Mitsui Toatsu Chemicals, Inc.].

[0115]

[Chemical 41]

Catalyst: 2-phenylimidazole [Reagent manufactured by Tokyo Kasei Co., Ltd.]. Polyether sulfone: represented by the above formula 31 [manufactured by Sumitomo Chemical Co., Ltd., Victrex (registered trademark) 4100P, glass transition temperature 225 ° C., polymerization degree about 2]
00, number average molecular weight 17700]. Polysulfone: represented by the above formula 32 [Amoco Japan, Udel (registered trademark) P1700, glass transition temperature 189 ° C].

The annotations in Tables 1 to 5 are as follows. * 1: Curing in each example was performed for 3 hours at the temperature shown in this column. * 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 heating, and the minimum temperature at which the film became transparent was recorded.

[0118]

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 has excellent adhesiveness as well as mechanical properties such as flexibility. Therefore, the thermosetting product of the present invention 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 an optical micrograph showing a phase separation structure (particle structure) of a final cured product of a sample of Example 1.

FIG. 2 is a graph showing changes with time in structural period when the sample of Example 1 is cured at 200 ° C.

FIG. 3 is a graph showing the change with time of the structural period when the sample of Example 18 was cured at 140 ° C., the sample of Example 19 at 170 ° C., and the sample of Example 20 at 200 ° C. is there.

FIG. 4 is an optical micrograph showing the phase-separated structure (particle structure) of the final cured product of the sample of Example 18.

FIG. 5 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product of the sample of Example 19.

FIG. 6 is an optical micrograph showing a phase-separated structure (particle structure) of the final cured product of the sample of Example 20.

FIG. 7 is a graph showing the relationship between the structural period Λ _m of the final cured products of the samples of Examples 18 to 20 and the curing temperature.

FIG. 8 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 19 was etched with a solvent.

FIG. 9 is a low temperature dissolution type phase diagram (LCST type phase) 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. 10 is a diagram showing a binodal curve and a spinodal curve in the above phase diagram.

FIG. 11 is a diagram for explaining the process of phase separation when the temperature of the mixed system that is uniformly compatible in the above phase diagram is rapidly raised.

FIG. 12 is a diagram schematically showing a three-dimensional modulation structure having a structural period Λ _m and concentration fluctuation.

FIG. 13 is a diagram schematically showing a two-dimensional modulation structure having a structural period Λ _m .

FIG. 14 is a scanning electron microscope (SEM) photograph of the literature (1) showing the particle structure after solvent etching of the surface of a cured product of a conventional epoxy resin / thermoplastic resin mixed system having a modulation structure. .

FIG. 15 is a three-dimensional schematic diagram showing the particle structure of the epoxy resin part 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

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

An example of the phase diagram is shown in FIG. This phase diagram is LC
It is called ST type, and is an example in which the same composition is likely to be compatible with each other at low temperatures. However, on the contrary, there are cases where they are compatible with each other on the high temperature side, and in that case, it is called UCST phase diagram. Such a curve on the phase diagram that distinguishes the incompatible region and the compatible region is called a binodal curve (see FIG. 10). Another one in the phase diagram shown in Fig. 10, ∂ ² _
When the points of ΔG _mix / ∂φ ² = 0 are combined, a spinodal curve (indicated by a 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, ∂ ² _
ΔG _mix / ∂φ ² <0, and outside, ∂ ² _ΔG
_mix / ∂φ ² > 0.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C08L 67/03 LPK 8933-4J 71/10 LQH 9167-4J LQK 9167-4J 81/06 LRF 7308- 4J 101/00 LTA 7242-4J

Claims (8)

[Claims] 1. A polyfunctional unsaturated imide represented by the following general formula 1, a thermoplastic resin having a compatibility region of the polyfunctional unsaturated imide and having a sulfone group, and the polyfunctional unsaturated imide. In a thermosetting polyimide resin composition containing, as an essential component, a cross-linking agent that cross-links an imide, the cross-linking agent is a polyamine represented by the following general formula 2 and a polycyanate compound represented by the following general formula 3. A thermosetting polyimide resin composition, which is at least one of the above. [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. ) [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. ) 2. 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 whole thermosetting resin component. 3. The thermosetting polyimide according to claim 1 or 2, wherein the thermoplastic resin is at least one selected from the group consisting of polyether sulfone represented by the following formula 4 and polysulfone represented by the following formula 5. Resin composition. [Chemical 4] (In Formula 4, n ₁ represents a positive integer.) (Among formalized 5, n ₂ represents a positive integer.) 4. The thermosetting polyimide resin composition according to claim 1, wherein 5 to 100 parts by weight of the thermoplastic resin is mixed with 100 parts by weight of the polyfunctional unsaturated imide. 5. A thermosetting product of the thermosetting polyimide resin composition according to any one of claims 1 to 4, 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. 6. The thermosetting product according to claim 5, wherein the structure formed by both of the separated phases being continuous and regularly intertwined with each other has a constant period. 7. The thermosetting product according to claim 6, wherein the cycle of the structure can be determined by using the scattering maximum in the light scattering measurement as a parameter. 8. The thermosetting polyimide resin composition according to claim 1, which is used as a raw material, and after the polyfunctional unsaturated imide and the thermoplastic resin are made compatible with each other,
By reacting the polyfunctional unsaturated imide with a cross-linking agent and thermosetting, 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. A method for producing a thermosetting product, which comprises obtaining a thermosetting product having a structure in which a regular and intertwined structure is formed.