JPH02187413A - Molding composition of diacetylene compound - Google Patents

Abstract

PURPOSE:To obtain the title composition useful in the field of precision machine and electronics, providing molded articles having excellent rigidity, hardness, coefficient of linear expansion, thermal conductivity, etc., comprising a specific diacetylene compound and a specific filler. CONSTITUTION:The aimed composition comprising a diacetylene compound containing a double bond wherein one or more constituent units of a diacetylene group-containing hydrocarbon group shown by formula I or formula II (R is H or monofunctional molecular weight group; R<1>-R<3> are bifunctional organic group; ether bond, ester bond, amino bond, imino bond or urethane bond may be cited as bonding group) are linked through one or more bonding groups to constituent units of C-C double bond-containing hydrocarbon group and a filler (e.g. glass fiber, carbon fiber, stainless steel fiber or SiC whisker) having <=0.2mm length of minimum direction and >=1w/m.k thermal conductivity.

Description

Detailed Description of the Invention (Technical Application of the Invention!l!F) The present invention provides a molded product with excellent rigidity, hardness, coefficient of linear expansion, thermal conductivity, etc. that can be used in precision machinery and electronics fields. The present invention relates to an acetylene compound molding composition.

(Prior art) In recent years, the synthesis of single-crystalline polymers using topochemical reactions through dopant polymerization has attracted attention, and attempts have been made to develop various highly crystalline polymers with high elastic modulus using this method. There is. (For example, "Organic Nonlinear Optical Materials", CMC (I985), Macromolecular Chemistry Vol. 134, p. 219 (I970), Journal of Bolymer Science Vol. 89, p. 133 (I97
1), Journal of Bolimar° Science Bolimar Physics Edition, Volume 12, Page 1511 (I9
74). ) In the field of thermosetting resins, various materials with crosslinking groups such as acetylene groups, norbornene rings, and combinations of maleimide and cyanate have been developed with the intention of improving heat resistance.

However, these new crosslinking groups have drawbacks such as high reaction temperature and long molding time.

Therefore, severe molding conditions are required in order to sufficiently carry out the crosslinking reaction and obtain a good molded product. The present inventors focused on diacetylene groups as highly reactive functional groups,
We have investigated its properties as a crosslinking group. As a result, they found that a material containing a diacetylene group and a double bond in one molecule has excellent curing reactivity. However, when molding this material, crosslinking and decomposition may occur at the same time depending on the heating conditions, and molding alone is extremely unstable in terms of moldability, as it requires heating slowly below room temperature. Ta. Therefore, by mixing a filler with a certain yield size and a certain heat conductivity, the filler exhibits a heat dissipation effect for the reaction heat during molding, and if the diacetylene compound alone is used, it will decompose. We discovered the possibility of molding products without decomposing even under conditions that would cause them to decompose, and as a result of further intensive study, we arrived at the present invention.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide a molding method that can be stably molded without decomposition during molding, is less prone to structural defects such as cracks, and has excellent rigidity, coefficient of linear expansion, thermal conductivity, etc. The object of the present invention is to provide a diacetylene compound molding composition that can provide a molding composition.

(Means for Solving the Problems) That is, the present invention provides one or more constituent units of a diacetylene group-containing hydrocarbon group represented by formula (+) or (II), and a carbon-carbon double A diacetylene compound having a double bond in which one or more structural units of a hydrocarbon group having a bond are connected via one or more connecting groups, and a length in the minimum direction. diacetylene compound molding composition R-c=c-c=c-
R'-・・・・・・(I)-R''-C=C-C=C-R
ff-...(II) (Here, R is a hydrogen atom or a monovalent organic group, R1゜R2, R3 are divalent organic groups, and the linking group is an ether bond, ester bond, or amino bond. , imino bond, and urethane bond).

In the present invention, R in formula (I) is a hydrogen atom or 1
is a valent organic group, for example, CH3-1C2H3-1
C,H.

Then, the hydrogen atom or hydrocarbon group in R may be substituted with another bond, and the bond may be an ether bond,
Ester bond, amide bond, imide bond, amino bond,
Examples include imino bonds and urethane bonds. R at that time
Some of the hydrogen atoms of R in et al. are nitro groups,
It may be substituted with a hydroxyl group, a cyano group, a carboxyl group, an amine group, a halogen atom, or the like.

In the present invention, R1, RZ, and R3 are the same or different divalent organic groups, examples of which are CH7 -CZ+t, - -C3H.

CI! - C- CH, - and some of the hydrogen atoms in these RI, R2, R3 are halogen atoms, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, amino groups, amide groups, ester groups, carbonyl It may be substituted with a group, an ether bond, etc.

In addition, the organic group may include an ether bond, a sulfonyl bond,
It may be an organic group connected by an ester bond, a carbonyl bond, etc., and specific examples include a complex group of an Hz-L- group, an aliphatic group, and an alicyclic group. Among R2 and R3, preferred is a carbonized carbon having a carbon-carbon double bond in the present invention, which is composed of a carbon-carbon double bond and an aromatic group such as -CI+2-, from the viewpoint of ease of synthesis and good heat resistance. The hydrogen group is generally a monovalent, divalent or more hydrocarbon group having 1 to 2 carbon atoms, and examples thereof include 112C= Cal CH=
C1 11□C= C1l -C11□= IIC-C1l Cl1=CII Clh
Examples include a group comprised of a combination of a carbon-carbon double bond and a hydrogen atom or an aliphatic group, such as IIC=llCClh, in which the ring structure contains the following.

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

Among these hydrocarbon groups having a carbon-carbon double bond, those having a +1. C=CH-H,
C=-C-II□C= Cal C1l z-CH3 -IIC=CH--CIl□=IC= C1l C1
lz-The diacetylene compound of the present invention contains a connecting group that connects a diacetylene group-containing hydrocarbon group and a hydrocarbon group having a carbon-carbon double bond as a structural unit. As the linking group, the oxygen atom constituting the ether bond (-0-) or ester bond may be substituted with a sulfur atom. Any of these linking groups may be used, and not only one type but also two or more types may be combined. Furthermore, in addition to these linking groups, the diacetylene compound of the present invention has an amide bond, a sulfonyl bond (-SO□-), a carbonyl bond, a diacetylene group-containing hydrocarbon group, and a carbon-carbon double bond as described above. It is a compound in which hydrocarbon groups are bonded into one molecule by the above-mentioned linking group, but - there is no limit to the number of diacetylene group-containing hydrocarbons present in the molecule, and it is a low-molecular compound containing only one diacetylene group-containing hydrocarbon. However, it may also be an oligomer or polymer containing two or more repeating units, and when it is included as a repeating unit, the diacetylene group-containing hydrocarbon group is
They may be of the same species or different species.

In the diacetylene compound of the present invention, in addition to a diacetylene group-containing hydrocarbon group and a hydrocarbon group having a carbon-carbon double bond, the constituent unit is an organic group in which a hydrocarbon group other than the constituent elements is connected by a linking group. may be partially included.

Examples of hydrocarbon groups other than constituent elements include CH:l
There is no particular restriction on the ratio of hydrocarbon groups having two or more bonds (CHz, (e-Hz)-(m), but the preferred range is a molar ratio of 0.2 to 5 at which curing reactivity is significant. It is.

Furthermore, when the ratio is 0.5 to 2, the most minute effect is seen, which is particularly preferable.

Examples of the diacetylene compounds of the present invention include the following.

etc., and furthermore, some of these hydrocarbon groups may be substituted with a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an amino group, a halogen atom, etc. Hydrocarbons other than these constituent requirements Introducing a group may have an effect in balancing curing reactivity and moldability.

In the diacetylene compound of the present invention, a diacetylene group-containing hydrocarbon group and a carbon-carbon double C1l 2- HC=
C1l C1l ]-+IC= C1l□tic=CH(CI*)! Ic -C1l z -〇CIC=CII COClI2 CECCmiI
I II 2C-CI(□ 0→- ]111 -C-11C=CHC0-CH2CEC-CEC-CI
1□20-Ci C-CI+□ C-HC=CH2 Furthermore, oligomer polymers having the following repeating units are exemplified.

-f CH2-CIl = CH CHz OC82C=C C=C- C11□ C-CIl□-C-0-C)+2-C,=CC11□-
〇+ CI+□-〇+ mi c-cut-o-c÷ -o-c +- The filling according to the present invention is defined as having a length in the minimum direction of 0.2 cylinders or less and a thermal conductivity of 1 W/m.・K or higher.

For example, glass fiber, carbon fiber, stainless fiber, Si
C whiskers, potassium titanate whiskers, organic and inorganic short fibers and long fibers such as glass fibers, sheet-like, paper-like, woven, cotton-like, etc., or silica, alumina, magnesium oxide, titanium oxide , talc, clay, copper powder, silver powder, gold powder, Affi powder, carbon powder, glass powder, aramid powder, diamond powder, barium titanate, boron carbide, boron nitride, silicon nitride (Si
3N4), mica, calcium carbonate, glass peas, aluminum sulfate, barium sulfate, calcium sulfate, molybdenum disulfide, glass flakes, mica, and other organic and inorganic powders, granules, flakes, rods, tubes, sheets, It is an object formed into a plate shape. In particular, it is effective to use a heat-resistant material that can maintain a solid state at a high temperature of 250° C. or higher. In addition, if the size of the filler is large, the uniformity with the diacetylene compound will be poor (and the contact area will also be small, which will cause problems in terms of heat dissipation of reaction heat during molding. It was found that a length of 0.2 length or less is preferable.

On the other hand, the thermal conductivity of the filler itself is preferably 1 W/m·K or more in terms of heat dissipation of reaction heat during molding. If these requirements are not met, depending on the conditions, it may decompose during molding, which is not desirable in terms of safety during molding.

In the composition of the present invention, if the ratio of the diacetylene compound is high, decomposition cannot be suppressed, and if the ratio of the filler is high, it is difficult to integrate, so the composition contains 5 parts of the filler per 100 parts of the diacetylene compound. ~400 parts, preferably 10 parts to 3
00 parts were mixed. Additionally, thermosetting resins, thermoplastic resins, heat stabilizers, light stabilizers, flow control agents, plasticizers, colorants, curing accelerators/inhibitors, etc. can be mixed and used as required.

The composition of the present invention can be prepared in the form of a powder, a tube, A composition in the form of a sheet, fiber, plate, or rod is produced. Then 190”0~4
It is cured and molded at a temperature of 50°C for several seconds to several hours. At that time, the conditions may be reduced pressure or increased pressure.

In some cases, after molding, after-curing is performed at a temperature of 200 to 400°C. Examples of solvents that can be used include ether, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, ethyl acetate, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexafluoroisopropanol, and the like.

Applications include not only reinforced molded products, but also adhesive bonding of the composition to other organic insulating materials, such as imide, amide, amide-imide, ester-based organic polymer films, mica foil, laminated mica foil, metal foil, etc. It can also be used as Furthermore, these compositions can be stacked in multiple layers and pressed together to form a laminate. At this time, a copper foil is also crimped at the same time, so that a copper-clad laminate can be used as a substrate for printed wiring.

(Effects of the Invention) The diacetylene compound molding composition of the present invention does not decompose (can be stably molded) by adding a specific filler, and structural defects such as cracks are less likely to occur during curing and molding. Rapid heating is also possible, and productivity is greatly improved.The physical properties of the molded product obtained are good, which cannot be obtained with existing resin molded products, especially in terms of rigidity, hardness, coefficient of linear expansion, and thermal properties. Very good conductivity.

The diacetylene compound molding composition of the present invention can be used in precision mechanical parts and electronics fields by taking advantage of these advanced physical properties.

(Examples) Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

(Example 1) Tetrahydrofuran? Yong? PAN-based carbon fiber (fiber diameter 7-8μm, thermal conductivity 7W/m-K)
) was impregnated with 4 cm x 10 cm cloth, stacked with 10 sheets, air-dried, and then heated to 200 kg/c at 200°C.
Molding was carried out for 60 minutes at a pressure of J.

At that time, the resin content of the molded article obtained was 23%.

The molded product could be molded without decomposition during molding, and the physical properties of the obtained molded product were good, with a flexural modulus of 8 GPa, and good hardness, coefficient of linear expansion, and thermal conductivity.

(Example 2) -f-OC-C)1=CIl-COO-CH, -C:C
-C11=C--CHz-0-i 40% hexafluoroisopropanol? Glass chopped strand (Asahi fiberglass, 03MA429)
, fiber diameter 13 μm, thermal conductivity 1.1 W/m ・
K) and then remove the hexafluoroisopropanol with a rotary evaporator until the resin amount is 3.
A 5% mixture was obtained.

The mixture was preformed at room temperature at 150 kg/ctM and then molded at 200°C under a hydrostatic pressure of 2.000 kg/eIII for 120 minutes.The mixture could be molded without decomposition, and its physical properties were as follows: Rate is 15.6G
Pa, and the hardness, coefficient of linear expansion, and thermal conductivity were also good.

(Comparative Example 1) (-QC-CIl = CIl -Co O-C11□
-(:=C-(:= CCHz O) alone,
After preforming at room temperature at 150 kg/cdt, it was molded at 200°C under hydrostatic pressure at 2,000 kg/cffl, and it decomposed in about 30 minutes.

(Example 3) Potassium tannate fiber (manufactured by Tenba Kagaku, Tl5MO2 fiber diameter 0.2-0.5 am, thermal conductivity 5.3 W/m-K)
50 parts in a small mill at room temperature to 150k
2,000k at 180°C after preforming with g/c
Molding was carried out for 120 minutes under a hydrostatic pressure of g/cIll.

As a result, the molded product could be molded without decomposition, and the physical properties of the molded product obtained were good, with a flexural modulus of 13.2 GPa, and good hardness, coefficient of linear expansion, and thermal conductivity.

[Example 4] Silica (manufactured by Katayama Chemical, special reagent grade, average particle size 0.01 μm
, thermal conductivity 1.5 W/m-K) 20 parts under reduced pressure, + QCCH=CHCOOC1h CECC MimiC
The mixture was added all at once to a hexafluoroisopropanol solution containing 80 parts of CHzO and mixed. Put this mixture into the mold, 2
When molded for 5 hours at 00kg/c+fl and 200°C, it was molded without decomposition, and its physical properties were good with a flexural modulus of 7.2GPa, hardness, coefficient of linear expansion, and thermal conductivity. The rate was also good.

(Comparative Example 2) -(l-QC-CIl=CIl-CoO-CH
2-(:=C-CEC-Cl+2-0-); 8
0 parts and cured epoxy resin (manufactured by Asahi Kasei Kogyo, AER3
31, crushed and bathed with 200 mesh is 75
After mixing 20 parts of hexafluoroisopropanol (less than .mu.m, thermal conductivity 0.2 W/m-K) in hexafluoroisopropanol, the hexafluoroisopropanol was dried up. When this mixture was put into a mold and molded for 5 hours at 200 kg/CI (200'C), it decomposed and could not be molded.

(Example 5) HC= CH-COOCHz C”i CCmi c-c
ut alumina (Japan Aerosil, aluminum oxide C1 average particle size 0.02μm, thermal conductivity 20W/
m, -K) was added all at once to 40 parts, and after mixing, acetone was removed using a rotary evaporator.

Put the mixture into a mold and press at 250°C120
When molded for 120 minutes at 0 kg/crfl, the molding was possible without decomposition, and its physical properties were that the flexural modulus was 9, O
It had a good G Pa, and its hardness, coefficient of linear expansion, and thermal conductivity were also good.

(Example 6) -(l-QC-C)l = C1(-COO-CIl□
-c=c-c= C-Cl1□-oh 70 parts and E glass pulverized material (average particle size 0.15 mm, thermal conductivity 1.1 W
/m-K) in a small mill, preformed at room temperature at 150 kg/aa, and then heated at 200°C.
Molding was carried out for 60 minutes at 52,000 kg/c+11. The molded product could be molded without decomposition during molding, and the physical properties of the obtained molded product were good, with a flexural modulus of 10.3 GPa, and good hardness, coefficient of linear expansion, and thermal conductivity.

(Comparative Example 3) Instead of the E-glass pulverized product (average particle size 0.15 mm) of Example 6, E-glass pulverized product (average particle size 0.5 mm, thermal conductivity 1.1 W/m-K) was used. Example 6 was repeated except that: As a result, decomposition occurred and a molded article could not be obtained.

Claims (1)

[Scope of Claims] One or more constituent units of a diacetylene group-containing hydrocarbon group represented by general formula (I) or (II) and one hydrocarbon group having a carbon-carbon double bond. A diacetylene compound having a double bond in which the species or two or more structural units are connected via one or more linking groups;
The length in the minimum direction is 0.2 mm or less and the thermal conductivity is 1W.
/m・K or more diacetylene compound molding composition R-C≡C-C≡C-R^1...(I) -R^2-C≡C-C≡C-R^ 3-...(II) (Here, R is a hydrogen atom or a monovalent organic group, R^1R^
2, R^3 represents a divalent organic group, and the linking group represents an ether bond, ester bond, amino bond, imino bond, or urethane bond. )