JPH0651802B2 - Method for producing high-modulus molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has a high elastic modulus using a double bond-containing diacetylene compound that has a high degree of rigidity and can be used as a material in the field of precision machinery and electronics. The present invention relates to a method for manufacturing a molded body.

[Prior art]

In recent years, various studies have been carried out, such as the discovery of a compound capable of obtaining a polymer having extremely good crystallinity by topochemical polymerization among diacetylene compounds. The elastic modulus of the polymer produced as an example is measured, and it is known that a high elastic modulus of 50 to 60 GPa is developed in the one-dimensional direction.

However, no attempts have been made so far to develop a high elastic modulus isotropically using a diacetylene compound.
The present inventors have molded various diacetylene compounds for the purpose of obtaining an isotropic high elastic modulus material by crosslinking. As a result, it has succeeded in obtaining a molded product having an elastic modulus of 10 GPa or more by forming a material containing a diacetylene group and a double bond in one molecule (Japanese Patent Laid-Open Publication No. 6-58242).
3-145337).

[Problems to be solved by the invention]

However, although these molded products show extremely high elastic modulus as a single organic material, so-called composite materials, for example, the elastic modulus is always higher than that of carbon fiber-based composite materials and aramid-based composite materials, It is necessary to further increase the elastic modulus.

An object of the present invention is to provide a method for producing a molded product having a modulus of elasticity comparable to or superior to those composite materials.

[Means for Solving the Problems]

Therefore, the present inventors have conducted research for the purpose of dramatically improving the elastic modulus of a molded article using a diacetylene compound having a double bond. Although the elastic modulus is slightly improved by increasing the molding temperature and pressure, these methods are not necessarily the best measures because it is essential to increase the manufacturing cost and improve the performance of the manufacturing apparatus. However, it is recognized that the elastic modulus may be significantly improved only by irradiating the molded body obtained according to JP-A-63-145337 with high energy light, and further, the material, the molding conditions, the type of high energy light and the like. As a result of various studies on the irradiation dose, the amide type diacetylene compound was found to have a remarkable improvement in elastic modulus, and the present invention was reached.

That is, the present invention provides one or more kinds of diacetylene group-containing hydrocarbon groups represented by the general formula (I) and one or more kinds of hydrocarbon groups having a carbon-carbon double bond, Method for producing a high elastic modulus molded body in which a molded body of a diacetylene compound linked via an amide group is irradiated with γ-rays —R ¹ —C≡CC≡C—R ² —... Formula (I) (here) And R ¹ and R ^{2 each} represent a divalent organic group).

In the present invention, the diacetylene compound is typically R ³ -X ¹ -R ¹ -C≡CC≡CR ² -X ² -R ⁴ (wherein R ¹ and R ² are divalent organic groups. , R ³ , R
⁴ is a monovalent organic group having a carbon-carbon double bond,
X ¹ and X ² are amide groups. ) Gives a molded body with a high elastic modulus.

Further, as a diacetylene compound, X ¹ -R ¹ -C≡CC≡CR ² -X ² -R ⁵ (wherein R ¹ and R ² are divalent organic groups, and X ¹ and X
² is an amide group, and R ⁵ is a divalent organic group having a carbon-carbon double bond. And a polymer (oligomer or polymer) having a repeating unit of

R ¹ in the diacetylene compound as the raw material of the present invention,
R ² is the same or different divalent organic group. For example, And a group in which an aromatic group and an aliphatic group are combined. Among these divalent organic groups, an organic group having a carbon number of 1 to 13 is particularly preferable. Furthermore, some hydrogen atoms of these organic groups may be substituted with a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, a halogen atom or the like.

Further, this organic group may be an organic group linked by an ether bond, a sulfonyl bond, an ester bond, or a carbonyl bond, for example, Etc.

R ¹ and R ² may be any of those described above, but in view of curing reactivity and easiness of synthesis, —CH ₂ —, Is preferred.

In the present invention, R in the above diacetylene compound is
³ , R ⁴ is a monovalent organic group having a carbon-carbon double bond, and examples thereof include: Is mentioned.

Some of the hydrogen atoms of these hydrocarbon groups are nitro group, hydroxyl group, cyano group, carboxyl group, amino group,
It may be substituted with a halogen atom or the like.

Among these double bonds, preferred ones are H ₂ C═CH—, because of curing reactivity. And especially H ₂ C = CH−, Is.

In the present invention, X ¹ and X ² in the diacetylene compound are amide groups, and the amide groups include
It may be a secondary amide group or a tertiary amide group.

In the present invention, R ⁵ in the diacetylene compound is
Is a divalent organic group containing a carbon-carbon double bond, and examples thereof include -CH = CH-, Etc.

Some of hydrogen atoms in R ⁵ may be substituted with a halogen atom, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, an amide group, an ester group, a carbonyl group, an alkoxy group or the like. Further, the organic group may be bound by an alkoxy group, a sulfonyl group, a carbonyl group, a carboxyl group, an amide group, or the like, and specific examples thereof include: Etc.

Among these organic groups having a carbon-carbon double bond, since the easiness of synthesis and the reactivity of the diacetylene group are increased, -CH = CH-, -CH = CH-CH = CH-, Are preferred, and -CH = CH- is particularly preferred.

In the present invention, if a diacetylene compound as a forming raw material is exemplified, Furthermore, oligomers, polymers, etc. having the following repeating units can be mentioned.

Etc.

A method for synthesizing a diacetylene compound which is a raw material for the molded article of the present invention has already been disclosed (for example, JP-A-63-961).
No. 44) In order to produce a molded article having a high elastic modulus, which the present invention aims to achieve, the molded article produced in JP-A-63-145337 is irradiated with γ-rays.

γ-rays are preferred because of their high energy and excellent permeability.

The irradiation dose is not particularly limited, but if it is too large, decomposition occurs, so 5-500 MRad, preferably 10-1
It is 00 MRad.

The irradiation temperature is not limited, but is preferably 10 ° C to 150 ° C.

In the molded article of the present invention, the diacetylene compound may be used alone, or in addition to the diacetylene compound, a thermosetting resin, a thermoplastic resin, an inorganic substance, a metal, a carbon material, a stabilizer, a flow control agent, a release agent. It is also possible to mix a mold material, a coloring material, an ultraviolet absorber, a curing accelerator / inhibitor, and the like. If necessary, their shape is a sheet shape, a paper shape, a woven shape, a cotton shape, a fibrous shape, a granular shape, a flaky shape, a plate shape, a rod shape, a tubular shape, or the like.

A molded article using the diacetylene compound obtained by the present invention has excellent mechanical properties, for example, an elastic modulus of 18.5.
GPa or higher, generally 19 GPa or higher, elastic modulus of 20 GPa or higher depending on compound selection and molding conditions, and further 22
An elastic modulus of GPa or more can be expressed.

The elastic modulus can be measured by a bending elastic modulus, a tensile elastic modulus or other elastic modulus depending on the shape of the molded article. The bending elastic modulus is measured according to ASTM-D7 as a standard method.
90-66 can be used. However, the molded article of the present invention may not always produce a large (long) molded article that can be measured by the ASTM measurement method. Therefore, the following method was used as the method for measuring the flexural modulus of the small molded article.

That is, as a method of measuring the flexural modulus, the test piece is 15 mm or more in length, 4 mm in width, and 2 mm in height, the fulcrum bending distance is 10 mm, the fulcrum tip radius is 2R, and the pressure wedge tip radius is 5R.
The test speed was set to 5 mm / min for measurement. In this case AS
Although the flexural elasticity method was slightly smaller than the TM method, the values were almost the same.

〔The invention's effect〕

The molded product obtained by the present invention has excellent mechanical properties,
For example, the flexural modulus of a general organic polymer is 1 to 3 GPa, whereas that of the cured molded article according to the present invention is 18. GPa or higher, generally 19-21 GPa, depending on compound selection 22
It also exhibits an elastic modulus of GPa or higher.

As described above, the molded product of the present invention has good mechanical properties,
For example, it is extremely useful in the fields of electronic materials and precision machine parts.

〔Example〕

Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, but the scope of the present invention is not limited to these examples.

Example 1 Manufactured according to Example 1 of JP-A-63-95233, 3 gamma rays with cobalt 60 as a radiation source at room temperature
It was irradiated with 5M Rad. The elastic modulus was significantly improved before and after irradiation for all the molded bodies (Table 1). Also, heat resistance and dimensional stability were improved by γ-ray irradiation.

Example 2 Manufactured according to Example 2 of JP-A-63-95323. 4 gamma rays with cobalt 60 as a radiation source at room temperature
Irradiated with 0 MRad. The elastic modulus was significantly improved before and after irradiation for any of the molded bodies (Table 2). Also, heat resistance and dimensional stability were improved by γ-ray irradiation.

Example 3 The diacetylene compound shown below was treated at 800 MPa and 200 ° C.
Compress for 1 hour, then use cobalt 60 as the source γ
The line was irradiated with 40 MRad.

Table 3 shows the flexural modulus before and after irradiation.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // C08L 49:00

Claims (3)

[Claims] 1. A diacetylene group-containing hydrocarbon group represented by the general formula (I), or two or more thereof, and one or more hydrocarbon groups having a carbon-carbon double bond, A method for producing a high elastic modulus molded body, which comprises irradiating a molded body of a diacetylene compound linked via an amide group with γ-rays. -R ¹ -C≡CC≡C-R ² - ...... formula (I) ^(wherein, R 1, ^{R 2} represents a divalent organic group) 2. The structural formula of the diacetylene compound is represented by R ³ -X ¹ -R ¹ -C≡CC≡CR ² -X ² -R ⁴ (wherein R ¹ and R ² are divalent organic groups). Yes, R ³ , R
⁴ is a monovalent organic group having a carbon-carbon double bond, and X ¹ and X ² are amide groups. ] The manufacturing method of the molded object of Claim 1 which is these. 3. A diacetylene compound is X ¹ -R ¹ -C≡CC≡CR ² -X ² -R ⁵ (wherein R ¹ and R ² are divalent organic groups, and X ¹ and X
² is an amide group, and R ⁵ is a divalent organic group having a carbon-carbon double bond. The method for producing a molded article according to claim 1, which is a polymer having the following repeating unit: