JPH01311113A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition giving a cured product having excellent mechanical properties and heat-resistance and mutually intermeshed network structure by compounding a polyimide having diacetylene group as a crosslinkable functional group and a thermosetting resin containing ethylenic functional group. CONSTITUTION:The objective composition can be produced by compounding (A) a polyimide having a structural unit of formula -CidenticalC-CidenticalC-R- (R is 7-40C bivalent organic group containing imide group) and (B) a thermosetting resin containing ethylenic functional group (preferably N,N-4,4'- diphenylmethanebismaleimide, etc.) preferably at a ratio to give a component A content of 2-90wt.%. The component A can be produced, e.g., by carrying out the polycondensation of a diamine monomer containing diacetylene group (e.g., 4,4'-diaminodiphenylbutadiyne) and a tetracarboxylic acid dianhydride in an amide solvent and subjecting the produced polyamic acid containing diacetylene group to dehydrative cyclization.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a curable resin composition, specifically, a curable resin composition comprising a polyimide having a diacetylene group in the polymer main chain and a thermosetting resin. Regarding the curable resin composition: The cured molded article obtained by curing the curable resin composition of the present invention has excellent mechanical properties and heat resistance.

[Conventional technology]

Thermosetting resins with ethylenic functional groups, for example, maleimide resins with maleimide groups obtained by the reaction of polyvalent amino compounds and maleic anhydride as polymerizable functional groups, exhibit excellent heat resistance due to the contribution of imide groups. Not only that, but since the polymerization and curing reaction is an addition reaction, it is attracting attention because it does not generate volatile components (Japanese Patent Publication No. 44-20
625 Publication).

However, because maleimide resin undergoes a three-dimensional crosslinking reaction through radical polymerization to form a high-density network structure, it suffers from large thermal contraction during curing, and the cured molded product is brittle.
Therefore, due to poor mechanical properties such as easy cracking due to heating and cooling, various improvements have been studied.
By forming a curable composition of bismaleimide resin and diamine, mechanical properties are improved without reducing heat resistance (French patent m1.555.56).
4 specification), and compositions such as epoxy resins and polyfunctional allyl ester resins (JP-A-53-2190, 54-
10595.53-2191.52-19598.52
-19599.48-19238.49-12600), compositions of polymeric substances such as polysulfone and bismaleimide resin (Japanese Patent Application Laid-Open No. 1983-5037), and the like have also been studied.

On the other hand, certain diacetylene compounds are exposed to heat and T in a crystalline state.
It is well known that polymerization occurs with high-energy rays such as VA or ultraviolet light (topochemical polymerization).The present inventors focused on this unique property of diacetylene groups, and have In order to obtain molded products with excellent properties, we investigated new polymers containing diacetylene groups, and by compression molding these polymers under high pressure conditions in the solid state below their decomposition temperature or below their melting temperature. It has been found that a polymer molded article having mechanical properties can be obtained (Japanese Patent Application Laid-Open No. 177212/1983).

[Problem to be solved by the invention]

Polymers containing diacetylene groups (polyurethane, polyester, polyamide, polyimide, etc.) can be molded with high rigidity by high-pressure molding in a solid state, but since high pressure is used in the molding conditions, molding equipment, molding molds, and molding conditions are required. There were restrictions on body shape, etc. The present invention enables the diacetylene polymer to have high rigidity, heat resistance, etc.
The present invention aims to provide a composition with even higher mechanical properties and improved moldability.

[Means to solve the problem]

In recent years, in the field of thermosetting resins, IPN (Inte
rpenetrating Polymer Netw
Composite materials with an orks (interpenetrating network) structure are attracting attention. Unlike conventional polymer blends and graft polymers, this is characterized by the fact that two types of polymer main chains intertwine and form an entangled network structure. By adopting an IPM structure, mutual compatibility between polymers increases, resulting in an increase in crosslinking density, a finer phase U weave, and an increase in correlated adhesive strength, resulting in excellent mechanical properties and durability that cannot be obtained with a single polymer. Demonstrates chemical resistance and heat resistance. The present inventor has developed a curable resin that provides a cured product having a JPN structure, which comprises a polyimide having a diacetylene group as a crosslinkable functional group in the polymer main chain and a thermosetting resin having an ethylenic functional group. They discovered a composition and completed the present invention.

That is, the present invention provides a curable resin composition comprising a polyimide containing a structural unit represented by the following general formula Tl) and a thermosetting resin having an ethylenic functional group.

-C≡C-CmiC-R-... (1) (In the formula, R represents a divalent organic group having 7 to 40 carbon atoms and containing an imide group.

) As the thermosetting resin having an ethylenic functional group, one represented by the following general formula (2) is particularly preferable.

(In the formula, R+ and Rz are hydrogen atoms or carbon atoms 1 to 1
2 represents a monovalent hydrocarbon group. R1 has 1 to 24 carbon atoms
represents a polyvalent organic group. (m represents an integer of 2 or more) The divalent organic group containing an imide group represented by R in the above general formula +1) generally has the following general formula (3) containing two imide groups, (4) ) can be shown.

(In the formula, A+, A!, and A are divalent organic groups, At is a tetravalent organic group, and A4 and A are trivalent aromatic groups.

) Note that since R is a divalent organic group having 7 to 40 carbon atoms, the imide group is excluded <A, ~A, or A4~A.

The total number of carbon atoms in the organic groups is 3 to 36.

In the formula (31, T4), A+, A:l, A
Examples of the divalent organic group represented by s include the following aromatic hydrocarbon groups and aliphatic hydrocarbon groups.

Incidentally, these aromatic hydrocarbon groups may be bonded to each other with an aliphatic hydrocarbon group, an ether group, a thioether group, a carbonyl group, a sulfone group, an ester group, an amide group, a urethane group, an azomethine group, or the like. Further, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a halogen group, a hydrocarbon group, or the like.

-CHl-, 4CH2+y, 4CLh-1@C
HaT, -(CHz)r5(CHr)r.

l CH3C! Examples of the tetravalent organic group represented by 115A are the following aromatic hydrocarbon groups or aliphatic groups.

A4. Examples of the trivalent aromatic group represented by A6 include the following aromatic hydrocarbon groups.

Incidentally, these aromatic hydrocarbon groups may be bonded to each other with an aliphatic hydrocarbon group, an ether group, a thioether group, a carbonyl group, a sulfone group, an ester group, an amide group, a urethane group, an azomethine group, or the like. Further, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a halogen group, a hydrocarbon group, or the like.

Specific examples of polyimides having diacetylene groups include polyimides having the following structural units.

1;1 The polyimide containing diacetylene groups, which is the first component of the present calling number composition, is produced by the following two methods.

The first method is a diamine monomer containing a diacetylene group and an equimolar amount of tetracarboxylic acid 2-anhydride 7mer-2 or a diacetylene group-containing diamine monomer.
A polyamic acid containing a diacetylene group is produced by polycondensing an anhydride monomer and an equimolar amount of a diamine monomer in an amide solvent, followed by dehydration and ring closure using heat or a chemical cyclizing agent. This is a method for producing polyimide containing an acetylene group (Formula 11, Formula 1).

...... (Formula I) (In the formula, A represents any corresponding organic group of A1 to A.) The second method is to oxidize a bisacetylene compound in the presence of a catalyst. This is a method for producing a diacetylene group-containing polyimide by polymerizing by campling reaction (2), formula (2).

・・・・・・・・・(2■) ・・・・・・・・・(2■) (In the formula, A represents any organic group corresponding to A or ~A) Above In the case of method 1, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl is used as the solvent for polymerizing diacetylene group-containing polyamic acid from diamine monomer and tetracarboxylic acid dianhydride monomer. Aprotic polar solvents such as acetamide, hexamethylphosphoramide, dimethyl sulfoxide are preferred.
There are no particular restrictions on the polymerization temperature, but from 0°C to 100°C.
It can be carried out at ℃. In addition, there is no particular restriction on the polymerization time, but it can be carried out in the range of 1 hour to 24 hours. After the polymerization reaction is completed, the polymerization solvent is poured into a poor solvent of polyamic acid to precipitate the polymer, and after filtration and washing, the pressure is reduced. The desired diacetylene group-containing polyamic acid can be obtained by drying under the same conditions.

Subsequently, in the reaction of dehydrating and ring-closing the diacetylene group-containing polyamic acid to form a diacetylene group-containing polyimide, heat or a chemical ring agent can be used. Although it is preferable to produce a curable resin composition using isolated and purified polyamic acid containing diacetylene groups as the polyimide used in the present invention, it is preferable to produce a curable resin composition using isolated and purified polyamic acid containing diacetylene groups. It is also possible to use a modified version. As the chemical cyclizing agent, aliphatic acid anhydrides such as acetic anhydride and propionic anhydride are suitable.

The amount of the chemical cyclizing agent used is 1 to 20 times the amount of amic acid equivalent, preferably 2 to 10 times. In this cyclization reaction, an organic base such as pyridine, 3-methylpyridine, 3.5-lutidine, or quinoline may be used as a catalyst. There are no particular restrictions on the amount of catalyst. Moreover, other organic solvents can also be used as diluents during the chemical cyclization reaction.

The chemical cyclization reaction is carried out at a temperature of 10°C to 150°C and a time of 1
It can be carried out in a range of 0 minutes to 1 day.

After the cyclization reaction is completed, the desired diacetylene group-containing polyimide can be obtained by filtering the reaction solution as it is, or by pouring it into a poor solvent to precipitate it, filtering it, washing it, and then drying it under reduced pressure. can.

In the case of method 2, the catalyst used for polymerizing the bisacetylene compound by oxidative camping reaction is copper salts, manganese salts, cobalt salts, etc., and the co-catalyst can be amines or alkaline compounds.

Preferred catalyst systems include cuprous chloride/pyridine, cupric chloride/pyridine, eleventh chloride/N, N,N,N-tetramethylethylenediamine, manganese chloride/α-benzoin oxime, and the like. The amount of catalyst is 0.0% based on the monomer.
Polymerization can be carried out in a range of 1% to 100%.

The polymerization solvent is a good solvent for the bisacetylene monomer and diacetylene group-containing polyimide, and is not particularly limited as long as it is inert to the catalyst. Preferred solvents include chlorobenzene, dichlorobenzene, trichlorobenzene, N
-Methylpyrrolidone, N,N-dimethylacetamide,
1,4-dioxane, tetrahydrofuran, etc.

Oxygen used in oxidative coupling polymerization can be used as is or diluted with an inert gas such as nitrogen, and air can also be used. It is preferably carried out under an oxygen stream.

The polymerization temperature is at most 100℃, usually from 40℃ to 8℃.
Although carried out in the 0° C. range, polymerization at elevated temperatures should be avoided in order to prevent undesirable side reactions.

Termination of the polymerization is carried out by pouring the polymerization reactants into a poor solvent for the polymerization product to precipitate the polymerization product, or by adding an acid or base capable of reacting with the catalyst to destroy the catalyst. Subsequently, the produced polymer is filtered and washed,
By drying under reduced pressure, the desired polyimide containing diacetylene groups is obtained.

As the thermosetting resin having an ethylenic functional group used as the second component in the composition of the present invention, various types can be used, but a maleimide compound represented by the above general formula (2) is preferable.

Examples of the hydrocarbon groups R+ and Rz in the general formula (2) include CHI -CJs, CzHt, C
4H9゜CHz CH≡CHz, CHz C≡CH
1st prize is mentioned.

Examples of R3 include the following polyvalent organic groups having 1 to 24 carbon atoms, and m is an integer of 2 or more, but it is preferable from the thermal and mechanical properties of the cured product. 2
5.

CHz, CHz C) 12-, -CHz
Chz Chz Chz.

-(-CHz+s+fcoz.

Specifically, the thermosetting resin represented by (2) is:
For example, N,N'-ethylene bismaleimide, N,N
”-hexamethylene bismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-m-xylylene bismaleimide, N,N'-p-xylylene bismaleimide, N,N'-1,3- Bismethylene cyclohexane bismaleimide, N, N'-1,4-bismethylene cyclohexane bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N'-2,6=tolylene bismaleimide, N , N'-3,3''-diphenylmethane bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N''-3°3'-diphenylsulfone bismaleimide, N,N'-4,4 ”-diphenylsulfone bismaleimide, N, N'-4,
4'-diphenyl sulfide bismaleimide, N, N'
-1)-benzophenone bismaleimi)', N, N'-
Diphenylether bismaleimide, It, N'-diphenylether bismaleimide, N.

N'-(methylene ditetrahydrophenyl) bismaleimide, N,N'-(3-ethyl)-4,4'-diphenylmethane bismaleimide, N,N'-(3,3"
-dimethyl)-4,4'-diphenylmethane bismaleimide, N,N'-(3,3'-diethyl)-4,4
'-diphenylmethane bismaleimide, N, N'-(3
, 3'-dichloro)-4,4'-diphenylmethane bismaleimide, N, N'-1-lysine bismaleimide, N
, N'-isophorone bismaleimide, N, N''-p, p
-diphenyldimethylsilyl bismaleimide, N, N'
-diphenylpropane bismaleimide, N,N'-naphthalenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N''-4+4'-diphenylmethane-bis-dimethyl In addition to bifunctional maleimide resins such as maleimide, reactions between aniline and formalin, reactions between acidic organisms (polyamine compounds), 3.4.4'-)riaminodiphenylmethane, triaminophenol, etc., and maleic anhydride. Polyfunctional maleimide compounds obtained by the above are representative examples of thermosetting resins particularly suitable for the composition of the present invention.

The maleimide resin represented by the above formula (2), which is preferably used as the second component thermosetting resin, is produced by a known reaction (formula (2)) between a polyvalent amino compound and a maleic anhydride derivative.

〔Production method〕

The method for producing a composition by blending the polyimide containing diacetylene groups of the present invention and a thermosetting resin includes:
- Various methods used in boat fishing can be applied, such as melt blending using an extruder, Brabender, roll, etc., dry blending using a mixer, solution blending using a solvent, etc.

Solution blending is suitable for laborious and uniform blending. That is, this is a method in which a polyimide containing a diacetylene group and a thermosetting resin are dissolved in a common good solvent, and the solution is poured into a common poor solvent to cause co-precipitation. At this time, since polyimide has poor solubility in organic solvents, it is preferable to blend the mixture in the form of polyamic acid, which is a precursor of polyimide, and then perform cyclodehydration to obtain polyimide.

A common good solvent is N-, which is used as a polymerization solvent.
Aprotic polar solvents such as methylpyrrolidone, dimethylacetamide, dimethylformamide, hexamethylphosphoramide, etc. are used.

Furthermore, salts of lithium chloride and calcium chloride may be present in these solvents.

Common poor solvents include alcoholic solvents such as methanol and ethanol, aliphatic solvents such as hexane and heptane, and water. The amount of the poor solvent used is 2 to 10 times the amount of the good solvent.

The precipitated solid is separated by a method such as filtration or centrifugation, and dried to obtain a mixture of polyamic acid containing diacetylene groups and thermosetting fj (fat).

By dehydrating and ring-closing the mixture of the diacetylene group-containing polyamic acid and the thermosetting resin, the curable resin composition of the present invention comprising the diacetylene group-containing polyimide and the thermosetting resin can be obtained.

There is no particular restriction on the composition ratio of the polyimide containing diacetylene groups as the first component of the curable resin composition of the present invention and the thermosetting resin as the second component, but preferably the diacetylene group-containing polyimide as the first component The content of polyimide is from 0.5% to 99% by weight, particularly preferably 2% by weight.
to 90% by weight. If the content of the first component, diacetylene group-containing polyimide, is less than 2% by weight, the cured molded product cannot be expected to exhibit mechanical properties such as toughness, and if it is more than 90% by weight, it is unfavorable in terms of cost.

The curable resin composition of the present invention can be easily molded by filling it into a mold and heating it. The heat curing temperature is in the range of 150°C to 350°C. 1
If it is below 50°C, it takes a long time to cure and is not economical, and if it is above 350°C, the curing reaction becomes too fast and is difficult to control.

The curable resin composition of the present invention can be cured under relatively mild conditions, and the resulting cured product has excellent mechanical properties and is an insoluble and infusible material with excellent heat resistance. It provides a heat-resistant polymer material.

The curable resin composition of the present invention is useful as a molding resin by incorporating inorganic fillers, flame retardants, pigments, etc. Further, the curable resin composition of the present invention is useful as a face for impregnation, lamination, adhesion, and film by making it into an organic solvent solution (face).

〔Example〕

Next, the present invention will be explained in more detail using experimental examples.

Reference Example Production of diacetylene group-containing polyamic acid and polyimide 4. Into a solution of 23.2 parts of 4'-diaminodiphenylbutadiine dissolved in 200 parts of dry N,N-dimethylformamide, 21 parts of pyromellitic acid dianhydride was added. .8 parts were added in powder form. The reaction was carried out at room temperature for 5 hours to form para diacetylene group-containing polyamic acid (PAA (p-APB I).
/PMDA)) solution was prepared.

Similarly, 3,3'-diaminodiphenylbutadiine was used instead of 4,4'-diaminodiphenylbutadiine, and meta-diacetylene group-containing polyamic acid (FAA
(m-APB I/PMDA) solution was manufactured. In addition, diacetylene group-containing polyamic acid (FAA
(p-PD/TCB I) solution was manufactured.

Furthermore, 10 times the amount of acetic anhydride and a catalytic amount of triethylamine were added to these polyamic acids containing diacetylene groups, and a dehydration ring-closing reaction was carried out at 60°C for one day and night. After the reaction was completed, the mixture was poured into methanol to separate the polymer. , polyimides containing diacetylene groups were produced by drying under reduced pressure.

Example I N was added to the para-diacetylene group-containing polyamic acid (FAA (p-APB r/PMDA) solution produced in Reference Example).
, 20.7 parts of N'-4,4'-diphenylmethane bismaleimide (DDM-BMI) were added, and the mixture was thoroughly mixed and stirred. Add the FAA (p
-APBI/PMDA) and DDM-BMI were precipitated together. After filtering the precipitate, it was dried under reduced pressure at 60"C overnight, and then the dry powder was mixed with 200 parts of acetic anhydride,
A dehydration ring-closing reaction was carried out with 2 parts of triethylamine at 60°C for 1 day and night, and after separation by filtration, it was dried under reduced pressure at 60°C to obtain a curable resin composition (PI (p-APB [/PMDA)/DDM-BM].
I) was produced.

The obtained curable resin composition was filled into a mold, pre-cured at 200°C for 2 hours using a hot press, taken out from the mold, and further post-cured at 250°C for 5 hours. When the cured molded product was subjected to a bending test using an Autograph DSS-500 manufactured by Shimabara Seisakusho at a cross speed of 0 and 5 wm/min, the bending strength was 50 MPa and the bending modulus was 5.20 Pa.

Further, when the coefficient of linear expansion was measured at 2° C./min using TMA manufactured by Rigaku Denki, it was 3.92×10−′/deg.

Example 2 The molded article obtained in Example 1 was further post-cured at 300° C. for 5 hours. The resulting molded body had a bending strength of 30 MPa and a bending modulus of elasticity of 3.80 P.a.

Examples 3 to 4 P r (p-APB I/PMDA)/ of Example 1
A cured molded article was obtained by changing the composition ratio of DDM-BMI to 30/70.70/30 and changing the curing conditions.

Examples 5-8 PI (p-APB I/PMDA) of Examples 1-4
) was changed to PI (m-APB I/PMDA) to obtain a cured molded product.

Examples 9-10 PI (p-APB I/PMDA) of Examples 1-2
) was changed to PI (p-PD/TCB N) to obtain a cured molded product. The mechanical properties of the cured molded products of Examples 1 to 0 are shown in the table. The flexural modulus measured using DDV-1 [Type 1 Pylon manufactured by Toyo Baldwin] is also shown.

Comparative Example 1 N,N'-4,4'-diphenylmethane bismaleimide [DDM-BMI] was heated to 170°C to melt it, poured into a mold, and cured at 200°C for 5 hours.

The cured molded product contained many cranks and could not be used for measuring mechanical properties.

Comparative Example 2 The same heat curing as in Example 1 was attempted using only the diacetylene group-containing polyimide (PI (p-APB I/PMDA)) produced in Reference Example, but the polymer powder was hardly fused. It was in a disjointed state and could not be molded.

Claims (1)

[Scope of Claims] 1) A curable resin composition comprising a polyimide containing a structural unit represented by the following general formula (1) and a thermosetting resin having an ethylenic functional group. -C≡C-C≡C-R-...(1) (In the formula, R represents a divalent organic group having 7 to 40 carbon atoms including an imide group.) 2) The thermosetting resin is as follows. The composition according to claim 1, which is represented by general formula (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (In the formula, R_1 and R_2 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. R_3 represents a monovalent hydrocarbon group having 1 to 24 carbon atoms. Represents a polyvalent organic group. m represents an integer of 2 or more.)