JPH01201314A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in mechanical properties and moldability without detriment to its rigidity and heat resistance, by mixing a diacetylenic polymeric substance with a specified thermosetting resin. CONSTITUTION:100pts.wt. diacetylenic polymeric substance of formula I [wherein Ar1-3 are each a 6-24C bivalent aromatic hydrocarbon group (except for the para isomer), R1-2 are each H or a 1-12C monovalent hydrocarbon group, and n>=2] is mixed with 5-900pts.wt. thermosetting resin of formula II (wherein R5 is an m-valent 6-18C hydrocarbon group, R3-4 are each R1, and m>=2), e.g., bismaleimide resin such as N,N'-ethylenebismaleimide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable resin composition comprising a polymer substance having a diacetylene group as a crosslinkable functional group and a thermosetting resin. The cured molded article obtained by curing the composition of the present invention has excellent mechanical properties and heat resistance.

[Conventional technology]

Cured thermosetting resin molded products with maleimide groups as polymerizable functional groups obtained by the reaction of amines and maleic anhydride not only exhibit excellent heat resistance due to the contribution of imide groups, but also exhibit an addition reaction in the polymerization curing reaction. Therefore, it is attracting attention because it does not generate volatile components (Special Publication Publication No. 44-2).
Publication No. 0625).

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, it has poor mechanical properties such as easy cracking due to heating and cooling, and various improvements have been made. For example, by creating a curable composition of bismaleimide resin and diamine, mechanical properties have been improved without reducing heat resistance (French patent m1.555.564).
No. Specification). Further, compositions such as epoxy resins and polyfunctional allyl ester resins have also been studied (Japanese Patent Application Laid-Open No. 53-2190.54-10595.53-2191
．． 52-19598.52-19599.48-192
38.49-12600). Furthermore, compositions of polymeric substances such as polysulfone and bismaleimide resins have also been studied (Japanese Patent Application Laid-Open No. 47-5037).

On the other hand, certain diacetylene compounds are exposed to heat and T in a crystalline state.
It is well known that polymerization can be effected by high-energy radiation such as radiation or ultraviolet radiation (topochemical polymerization). The present inventors focused on this unique property of diacetylene groups, and synthesized new polymers containing diacetylene groups for the purpose of obtaining molded products with excellent mechanical properties. Hereinafter, we have investigated polymer molded articles having high mechanical properties by high-pressure molding in a solid state below the melting temperature.

[Problem to be solved by the invention]

Although maleimide resin has a high degree of heat resistance and excellent moldability, its cured molded product is fragile.

In addition, 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, the molding equipment and molding mold There were also restrictions on the shape of the molded product, etc.

[Means to solve the problem]

In recent years, in the field of thermosetting resins, IPN (Inte
rpenetratingPolymer Netwo
Composite materials with a rks (interpenetrating network) structure are attracting attention.

This is different from conventional polymer blends and graft polymers, in which two types of polymer main chains intertwine with each other.
The intertwined network structure increases the crosslink density, refines the phase structure, and increases interlayer adhesion, resulting in excellent mechanical properties, chemical resistance, and chemical resistance that cannot be obtained with a single polymer. Develops heat resistance. The present inventors have discovered that without impairing the high rigidity and heat resistance of the diacetylene polymer,
As a result of intensive research aimed at further improving mechanical properties and moldability, we succeeded in further improving mechanical properties and moldability by combining a polymer substance containing diacetylene groups and a thermosetting resin. , arrived at the present invention.

That is, the present invention provides a curable resin composition comprising a polymeric substance having a diacetylene group represented by the following general formula +11 and a thermosetting resin represented by the following general formula (2). be.

(In the formula, Ar+, Arz, Ar3 have a carbon number of 6 to 2
4 divalent aromatic hydrocarbon group (but not a para bond)
shows. R1 and R2 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. n represents an integer of 2 or more. ) (In the formula, Ara represents an m-valent hydrocarbon group having 6 to 18 carbon atoms. R3 and R4 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. m is 2 or more. (represents an integer.) In the polymeric substance represented by the general formula fl), Ar
The divalent aromatic hydrocarbon groups represented by l-, Ar2, and Ar3 have the following structure, and these aromatic hydrocarbon groups mutually form an aliphatic hydrocarbon group, an ether group,
It may be bonded with a 1,000-onythyl 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. The bonding state of these divalent aromatic hydrocarbon groups is a meta bond, ortho bond, etc., but not a para bond, in view of the ease of reaction of the diacetylene group. Polyamides containing diacetylene groups produced using diamines containing diacetylene groups consisting of para bonds have a high polymerization temperature of 380°C or higher, but polyamides containing diacetylene groups using meta-based diamines have a high polymerization temperature of 380°C or higher. The meta-based polyamide is ~300
Polymerization can be carried out under relatively mild conditions at °C.

Examples of structures connected by other bonding groups include the following structures (excluding para-bonds at both ends).

Note that the internal bonds described below may be para bonds.

Examples of R,,R, are H, -C1h, -CzHs,
-C) IzCl, -CHz-CH=Ctl□, -CH
, -C, C)I, etc.

In the thermosetting resin represented by the general formula (2), R
3 is an m-valent organic group having 1 to 24 carbon atoms, and m is an integer of 2 or more, but is preferably 2 to 5 from the viewpoint of the thermal properties and mechanical properties of the cured product.

Specifically, 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-bismethylenecyclohexane bismaleimide, N,N'-1,4-bismethylenecyclohexane bismaleimide, N,N ' −
2,4-tolylenebismaleimide, N,N'-2,6-
) rylene 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'-p-benzophenone bismaleimide, N, N
'-Diphenylethane bismaleimide, N,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'-tolidine bismaleimide, N,N'-isophorone bismaleimide, N,N'-p,p-diphenylmethylsilyl bismaleimide, N,N'-diphenylpropane bismaleimide, N,N'-naphthalene bis Maleimide, N, N'-p-phenylenebismaleimide, N
, N'-m-phenylene bismaleimide, N, N'
In addition to bifunctional maleimide resins such as -4,4'-diphenylmethane-bis-dimethylmaleimide, reaction products of aniline and formalin (polyamine compounds)
, 3,4,4'-triaminodiphenylmethane, triaminophenol, etc., and polyfunctional maleimide compounds obtained by reaction with maleic anhydride are representative examples of maleimide resins particularly suitable for the composition of the present invention.

The diacetylene group-containing polymeric substance represented by the formula -C (11) is produced by the following two methods.

The first method is produced by reaction of diamine monomers containing diacetylene groups with dicarboxylic acid derivatives.

(In the formula, X is a halogen group, a hydroxyl group, or an alkoxy group.) In the second method, a bisacetylene compound is produced by an oxidative camping reaction in the presence of a catalyst.

The second component, maleimide resin, is produced by reacting a polyvalent amine compound and a maleic anhydride derivative.

〔Production method〕

As a method for producing the blended composition of the diacetylene group-containing polymer and maleimide resin of the present invention, various methods used in boat fishing can be applied, such as an extruder, Brabender, roll A melt blending method using a mixer, a dry blending method using a mixer, a solution blending method using a solvent, etc. can be applied. Solution blending is suitable for simple and uniform blending. That is, this is a method in which a diacetylene group-containing polymer and a maleimide resin are dissolved in a common good solvent, and the solution is poured into a common poor solvent to co-precipitate.

As common good solvents, aprotic polar solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and hexamethylphosphoramide are used. Further, salts such as lithium chloride and calcium chloride may be present in these solvents.

Common poor solvents used to precipitate the curable resin composition by introducing the curable resin composition solution 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 the curable resin composition of the present invention.

The blending ratio of the polymeric substance represented by formula fl) and the thermosetting resin represented by formula (2) is 5 to 900 parts by weight of formula (2) to 100 parts by weight of formula (1). , preferably 10 to 500 parts by weight.

[Forming method]

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 festival for 3-dipping, lamination, adhesion, and film by making it into an organic solvent solution (facial).

〔Example〕

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

Reference example Meta-amide diacetylene polymer (PA)
Production of m-APBI/1-PT) 4. A solution of 23.2 parts of 4'-diaminophenylbutadiine dissolved in 200 parts of dry N-methylpyrrolidone was cooled to 0°C, and 20.3 parts of isophthalic acid chloride was dissolved. part was added in powder form.

After reacting at 0°C for 1 hour, the reaction temperature was raised to room temperature and the reaction was continued for an additional 2 hours to form a meta-amide diacetylene polymer (PA
(n+-APBI/1-PT) solution was prepared.

Example 1 36 parts of N,N'-4,4'-diphenylmethane bismaleimide (DDM-BMI) was added to the meta-amide diacetylene polymer solution prepared in Reference Example and thoroughly mixed and stirred. Pour into a large amount of water with vigorous stirring, and add PA (
m-APBI/1-PT) and DDM-8 old were precipitated together. After filtering the precipitate, it was washed twice with water and twice with methanol, and dried under reduced pressure at 60° C. all day and night to produce a curable resin composition.

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 Autograph DSS-500 manufactured by Ichitsu Seisakusho, the bending strength was 123 MPa and the bending modulus was 5.4 GPa.

Example 2 The molded article obtained in Example 1 was further post-cured at 30° C. for 5 hours. The resulting molded body had a bending strength of 87 MPa and a bending modulus of elasticity of 5.5 GPa.

Examples 3 to 5 PA of Example 1 (n+-APBI/1-PT), DD
A cured molded body was obtained by changing the composition ratio of M-BMI and curing conditions. The mechanical properties of the cured molded product are shown in the table.

Comparative Example I N,N'-4,4'-diphenylmethane bismaleimide (DDM-BMI) was heated to 170°C, poured into a molten 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 PA (m-APBI/1-PT) solution prepared in Reference Example was poured into methanol with vigorous stirring, and the PA (m-APBI/1-PT) solution was poured into methanol with vigorous stirring.
BI/1-PT) was isolated. This diacetylene group-containing polymer can be molded under high pressure conditions of 5,000 atmospheres or more, but under normal pressure the polymer powders do not fuse together and are in a disjointed state, making molding impossible.

Claims (1)

[Claims] A polymeric substance represented by the following general formula (1) and the following general formula (
2) A curable resin composition comprising the thermosetting resin shown in item 2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar_1, Ar_2, and Ar_3 represent divalent aromatic hydrocarbon groups having 6 to 24 carbon atoms (but not para bonds). R_1 and R_2 are hydrogen atoms. Alternatively, it represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. n represents an integer of 2 or more.) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_5 is m having 6 to 18 carbon atoms. Represents a valent hydrocarbon group.R_3 and R_4 are hydrogen atoms or carbon atoms of 1 to 1
2 represents a monovalent hydrocarbon group. m represents an integer of 2 or more. )