JPH06107945A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, consisting of a specific polycarbo diimide compound and a specified phenyl ether derivative, having a short curing time, excellent in heat resistance and flow stability and useful as moldings, etc. CONSTITUTION:The objective composition consists essentially of (A) a polycarbodiimide compound such as a carbodiimide copolymer, having >=2 carbodiimide bonds in the molecule and the terminal of the polymer molecule blocked with an aromatic group and <=10000 weight-average molecular weight and containing 5-95 (equiv.) pts. group having a structural unit of formula I and 95-5 (equiv.) pts. group having a structural unit of formula II and (B) a phenyl ether derivative such as 1,3-diallyloxybenzene having >=2 allyloxy groups of the formula OCH2CH=CH2 in the molecule. Furthermore, the components (A) and (B) are preferably blended at a weight ratio of the components [(A)/(B)] within the range of (90/10) to (50/50).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermosetting resin composition having excellent heat resistance.

[0002]

2. Description of the Related Art Generally, a high molecular weight aromatic polycarbodiimide resin is known as a resin having high heat resistance.
However, it is difficult to dissolve in various solvents and has poor thermal fluidity, which makes practical molding difficult. Further, polycarbodiimide undergoes self-crosslinking between carbodiimide bonds upon heating to be cured, but the curing speed is slow, which makes practical molding as a cured resin more difficult. Therefore, LM Alberino et al. (JA
ppl.Polym.Sci., vol.21,1999 [1977]) is a reaction between an aromatic diisocyanate and an organic monoisocyanate as a molecular weight modifier in the presence of a carbodiimide-forming catalyst in order to improve the above problems. As a result, a polycarbodiimide having fluidity under heat and pressure is obtained. The polycarbimide obtained by this method has improved fluidity by controlling the molecular weight, but it takes a significantly long time to cure and is not practical. On the other hand, in JP-A-61-235414 and 61-235415,
In order to shorten the curing time, a crosslinking agent having an active hydrogen group such as aminotriazine and 4,4′-diaminodiphenylmethane is mixed with polycarbodiimide having a controlled molecular weight, and the composition is thermally cured to obtain a thermosetting resin. Is proposing a way to get. However, since the active hydrogen group is used, the heat resistance is lowered, the excellent heat resistance of the carbodiimide bond cannot be utilized, and the fluidity under heating is also lowered, which is still satisfactory. It has not reached the state.

[0003]

The object of the present invention is to improve the above-mentioned drawbacks as a thermosetting resin having a carbodiimide bond, that is, it has excellent heat resistance and good fluidity when melted, Another object of the present invention is to provide a composition for obtaining a thermosetting resin having a short curing time.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a composition of a compound having a carbodiimide bond and a compound having a phenyl ether derivative has the above-mentioned object. Therefore, the present invention has been reached, and the present invention has been reached.

That is, the present invention provides (A) a polycarbodiimide compound having two or more carbodiimide bonds in the molecule, and (B) at least two -OCH in the molecule.
_The present invention provides a thermosetting resin composition containing an phenyl ether derivative having an allyloxy group represented by the formula: CH = CH ₂ as an essential component.

Preferably, the polycarbodiimide compound is
A group having 5 to 95 equivalent parts of a group having a structural unit represented by the following formula (1) and 95 to 5 equivalent parts of a group having a structural unit represented by the following formula (2) is contained, and the terminal of the molecule of the polymer is aromatic. It is a carbodiimide copolymer which is sealed with a group and has a weight average molecular weight of 10,000 or less.

[0007]

[Chemical 4]

The aromatic group at the molecular end of the polycarbodiimide compound is preferably a phenyl group, an orthosultryl group,
At least one selected from the group consisting of meta-tolyl group, para-tolyl group, dimethylphenyl group, chlorophenyl group, trifluoromethylphenyl group, naphthyl group, isopropylphenyl group and diisopropylphenyl group. More preferably, the polycarbodiimide compound is a compound represented by the following formula (3) and having a weight average molecular weight of 20,000 or less.

[0009]

[Chemical 5]

The phenyl ether derivative is preferably represented by the following formula (4).

[Chemical 6]

The configuration will be described in detail below. Any organic compound having two or more carbodiimide bonds in the molecule used in the present invention can be used as long as it has the structure of formula (5) in the molecular chain, but polycarbodiimide is particularly preferable. . -N = C = N- (5) Polycarbodiimide is a polymer compound having a large number of carbodiimide bonds in its molecular chain, and this compound itself is known, and accelerates carbodiimidization of isocyanate from organic polyisocyanate. It is produced in the presence of a catalyst and can be obtained as a varnish or powder.

When polycarbodiimide is used as a varnish of an aprotic organic solvent such as toluene or xylene, 2,4 as an organic polyisocyanate as a raw material is used.
It is preferable to use a mixture of -TDI and 2,6-TDI and have a weight average molecular weight of 10,000 or less (average degree of polymerization: about 1 to 20). If the weight average molecular weight is too high, the solvent becomes difficult to dissolve and the storage stability of the solution also deteriorates. 2,4
-Use ratio of TDI and 2,6-TDI is 100
When the molar parts are used, it is preferable to use 2,4-TDI 5 to 95 molar parts and 2,6-TDI 95 to 5 molar parts, and further, 2,4-TDI 60 to 90 molar parts and 2,6
It is more preferable to use 40 to 10 mol parts of -TDI, and in this case, a higher concentration solution containing 30% by weight or more of the carbodiimide copolymer can be obtained. On the other hand, when the addition ratio of 2,6-TDI is 5 mol parts or less, the storage stability of the varnish is deteriorated, for example, a part of the solution is precipitated after several days.

When polycarbodiimide is used as a powder, various organic polyisocyanates can be used as raw materials, but when performing melt molding, diphenylmethane-4,4'-diisocyanate is used as the organic polyisocyanate, The weight average molecular weight is preferably 20,000 or less (average degree of polymerization: about 1 to 20). When used as a varnish, examples of the organic polyisocyanate as a raw material include the above 2,4-TDI (tolylene-2,4-
Diisocyanate) and 2,6-TDI (tolylene-2,
6-diisocyanate) and 1-methoxybenzene-
2,4-diisocyanate, 1-chlorophenylene diisocyanate and the like can be mentioned.

When used as a powder, examples of the organic polyisocyanate as a raw material include phenylene-1,3-diisocyanate and phenylene-1,4 in addition to the above diphenylmethane-4,4'-diisocyanate.
-Diisocyanate, tetrachlorophenylene diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, diphenyl sulfide-4,
4'-diisocyanate, diphenyl sulfone-4,
4'-diisocyanate, diphenyl ether-4,
4'-diisocyanate, diphenyl ether-3
4'-diisocyanate, diphenylketone-4,4 '
-Diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 2,4'-biphenyldiisocyanate, 4,4'-biphenyldiisocyanate, 3,3'-methoxy- 4,4'-biphenyl diisocyanate, anthraquinone-2,6-diisocyanate, triphenylmethane-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate and polynuclear compounds of dimers or higher of these organic polyisocyanates, Examples thereof include a terminal isocyanate prepolymer obtained by using an organic polyisocyanate in a stoichiometric excess with respect to a polyfunctional active hydrogen compound.

In the present invention, it is preferable to use a polycarbodiimide whose molecular weight is regulated because the heat fluidity becomes better. This polycarbodiimide whose molecular weight is regulated can be produced from the above organic polyisocyanate and an organic monoisocyanate as a molecular weight modifier in the presence of a catalyst that promotes carbodiimidization of isocyanate.

Examples of the organic monoisocyanate used as a molecular weight regulator include phenyl isocyanate, (ortho, meta, para) -tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, methyl isocyanate, butyl isocyanate, chlorophenyl isocyanate, trifluoromethylphenyl. Isocyanate, naphthyl isocyanate, etc. can be illustrated, and 5 to 50 mol parts can be used with respect to 100 mol parts of organic polyisocyanate.

Although various catalysts can be used as the catalyst for promoting the carbodiimidization of isocyanate, 1-phenyl-2-phosphorene-1-oxide, 3-methyl-
1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-2-phosphorene-1-oxide, 1-ethyl-3-methyl-2-phosphorene-1- Oxides and their corresponding isomers, 3-phosphorenes, are good. The catalyst amount can be used in the range of 0.01 to 1% based on the total amount of isocyanate.

In the present invention, as the phenyl ether derivative having two or more allyloxy groups in the molecule, for example, a compound represented by the general formula (6) can be used. R ₁ -(-O-CH ₂ CH = CH ₂ ) _n (6) (In the formula, R ₁ is an aromatic polyvalent organic group, and the allyloxy group is directly bonded to the aromatic ring of the organic group R _1. And n represents an integer of 2 or more, usually 10 or less.)

The phenyl ether derivative is generally prepared by a known method in which the corresponding polyhydric phenolic compound is reacted with an allyl halide. Specific examples of phenyl ether derivatives include 1,3- or
1,4-Diaryloxybenzene, 1,3,5-triaryloxybenzene, 1,3-, 1,4-, 1,6-, 1,
8-, 2,6- or 2,7-diaryloxynaphthalene, 1,3,6-triaryloxynaphthalene, 2,2 '
-Or 4,4'-diaryloxybiphenyl, bis (4-allyloxyphenyl) methane, 2,2-bis (allyloxyphenyl) propane, 2,2-bis (3,5-
Dichloro-4-allyloxyphenyl) propane, bis (4-allyloxyphenyl) ether, bis (4-allyloxyphenyl) thioether, bis (4-allyloxyphenyl) sulfone, tris (4-allyloxyphenyl) phosphite , Tris (4-allyloxyphenyl)
Examples thereof include phosphate, and a polyallyloxy compound of a benzene polynuclear body obtained by a reaction of a phenol resin and an allyl halide. A divalent phenyl ether derivative derived from a dihydric phenol such as 2,2-bis (4-hydroxyphenyl) propane, from the standpoints of being readily available and imparting good properties to the moldability and final resin. Is particularly preferably used. Also,
A phenyl ether derivative obtained by reacting an allyl halide with an initial condensate of phenol and formaldehyde is also useful. In the composition of the present invention, the above phenyl ether derivative may be used alone, or may be mixed and used.

The compounding ratio of the polycarbodiimide compound of the present invention and the phenyl ether derivative is preferably in a wide range of 95: 5 to 40:60 by weight,
Particularly preferably, it can be used in the range of 90:10 to 50:50, and it is preferable to determine the composition ratio of the both components depending on the intended use and the required properties of the final cured resin. When the polycarbodiimide content is 40% by weight or more, the excellent heat resistance originally possessed by the polycarbodiimide is sufficiently exerted, and when it is used in an amount of 95% by weight or less, it is the object of the present invention to improve the flow stability during melting and the curing time. The effect of shortening is particularly good.

The composition of the present invention is easily cured by heating from the outside, but a curing catalyst and a curing accelerator are added if desired, and the molding temperature or molding time is adjusted depending on the molding method and the shape of the molded product. Can be controlled. At this time, as the curing catalyst and the curing accelerator used, for example, tertiary amines such as triethylenediamine, N, N-dimethylbenzylamine and N-methylmorpholine, 2-methylimidazole, 2-phenylimidazole, 2-phenylimidazole Examples thereof include imidazoles such as ethyl-4-methylimidazole, azo compounds such as azobisisobutyronitrile, and organic peroxides such as t-butylperbenzoate, dicumylperoxide and benzoylperoxide.

The composition of the present invention can also be used as a varnish by dissolving or suspending it in a suitable solvent such as chloroform, perkrene, THF, toluene, xylene, NMP and the like.

If desired, inorganic fillers and reinforcing fibers,
For example, crushed silica, synthetic silica, alumina powder, mica,
Titania, or glass fiber, carbon fiber, aramid fiber, boron fiber, etc. can be added, and further, natural wax, synthetic wax, organic fatty acid, internal release agent such as metal salt of organic fatty acid, halogen compound, oxidation and the like. A flame retardant such as antimony and a coloring agent such as carbon black can be added depending on the purpose.

The thermosetting resin of the present invention can be used for injection molding, transfer molding, extrusion molding, compression molding, etc.
It is molded by a known molding method and put into practical use. Further, when a thermosetting resin is used as a varnish, it can be applied to the production of a known laminate.

[0025]

EXAMPLES Examples will be shown below to specifically describe the embodiments of the present invention. The physical properties of the polymers obtained in the examples and comparative examples were measured by the following methods. 5% decomposition temperature: A 5% weight loss temperature of the polymer was measured at a temperature rising rate of 10 ° C./min in air using a thermogravimetric analyzer (TGA). Glass transition temperature: The glass transition temperature was measured by an expansion method using a thermomechanical analyzer (TMA) at a heating rate of 5 ° C / min. Kinematic viscosity: 1 using a Koka type flow tester (made by Shimadzu)
After preheating at 50 ° C. for a predetermined time, a load of 100 kgf / cm ² was applied and measurement was performed. Pencil hardness: The surface hardness of the cured film was measured according to JIS K5400.

Examples 1-5 Diphenylmethane-4,4'-diisocyanate and phenylisocyanate were combined with 3-methyl-1-phenyl-2-
A powdery polycarbodiimide with a controlled molecular weight (hereinafter abbreviated as PCI, weight average molecular weight of about 8000) synthesized by heating in xylene in the presence of a phosphorene-1-oxide catalyst was added to a phenyl ether derivative (BA).
PP, DABP, BAPS) were added and mixed well to obtain a powdery resin composition. The kinematic viscosity was measured in order to evaluate the melt flow stability of these powdery resin compositions. Next, these resin compositions were pressure-molded at 250 ° C. for a predetermined time to obtain a reddish-brown transparent resin molded product and a cured film. Table 1 shows the respective physical properties of the obtained molded products.

[0027]

[Table 1] As is clear from the results in Table 1, the thermosetting resin composition of the present invention has a curing time and a glass transition temperature (related to heat resistance) that are in the conventional level, has a low kinematic viscosity, and is excellent in fluidity. There is.

Comparative Example 1 Fluidity was evaluated by measuring kinematic viscosity in the same manner as in Example 1 except that the phenyl ether derivative was not used.
A molded product was obtained by pressure molding at 30 ° C. for 30 minutes. As shown in Table 2, it can be seen that the PCI powder alone has a significantly higher viscosity than the PCI composition to which the phenyl ether derivative is added. In addition, the thermophysical properties of this molded product were not sufficient for thermosetting resins, such as a low glass transition temperature. Comparative Examples 2 and 3 A composition was prepared in the same manner as in Example 1 except that active hydrogen compounds (MDA, BPA) were used instead of the phenyl ether derivative. The fluidity was evaluated by measuring the kinematic viscosity, and a molded product was obtained by pressure molding at 250 ° C. for 30 minutes. As shown in Table 2, as a result of measuring the kinematic viscosity, the PCI composition to which the active hydrogen compound was added showed no fluidity, and it was found that the fluidity was extremely poor.

[0029]

[Table 2]

Example 6 A mixture of 80 parts by mole of 2,4-TDI and 20 parts by mole of 2,6-TDI (trade name: TDI 80, Mitsui Toatsu Chemicals, Inc.)
Manufactured by K.K.), 92 g of phenyl isocyanate and 9 g of phenyl isocyanate were dissolved in toluene, 0.36 g of 3-methyl-1-phenyl-2-phosphorene-1-oxide catalyst was added, and polymerization was carried out at 110 ° C. A resin varnish was obtained (average molecular weight about 1000, solid content 30 wt%). To this varnish, 19 g of BAPP was added and uniformly dissolved to prepare a composition varnish (weight ratio 80/2).
0). Cast the resulting composition varnish on a glass plate,
It was dried at 120 ° C. for 3 hours to obtain a film. A cured film was obtained by heat-treating this film at 250 ° C. for 30 minutes. The physical properties of this product were as follows. 5% decomposition temperature 473 ° C pencil hardness 4H

Comparative Example 4 A cured film was obtained in the same manner as in Example 6 except that BAPP was not used. The 5% decomposition temperature of this cured film was 488 ° C., it softened at around 40 ° C., and the heat resistance as a thermosetting resin was poor. Moreover, the pencil hardness of the cured film was H, which was inferior in hardness and did not have sufficient physical properties as a thermosetting resin.

[0032]

EFFECT OF THE INVENTION The thermosetting composition of the present invention contains the polycarbodiimide compound and the phenyl ether derivative as described above and is easily cured by heating. The heat resistance of the polymer of the compound having a carbodiimide bond, the curing time, and the flow stability at the time of dissolution in the case of a powder composition are significantly improved, and the industrial utility value is extremely large.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. A polycarbodiimide compound having (A) two or more carbodiimide bonds in the molecule, and (B) at least two aryloxy groups represented by the following formula —OCH ₂ CH═CH ₂ in the molecule. A thermosetting resin composition comprising a phenyl ether derivative as an essential component. 2. The polycarbodiimide compound comprises groups 5 to 95 equivalent parts having a structural unit represented by the following formula (1) and groups 95 to 95 having a structural unit represented by the following formula (2).
The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition contains 5 equivalent parts, and the end of the polymer molecule is sealed with an aromatic group and has a weight average molecular weight of 10,000 or less. . [Chemical 1] 3. The aromatic group at the molecular end of the polycarbodiimide compound is a phenyl group, an orthoritolyl group, a meta-tolyl group, a para-tolyl group, a dimethylphenyl group, a chlorophenyl group, a trifluoromethylphenyl group, a naphthyl group, an isopropyl group. The thermosetting resin composition according to claim 1, which is at least one selected from the group consisting of a phenyl group and a diisopropylphenyl group, which is the carbodiimide copolymer according to claim 2. 4. The thermosetting resin composition according to claim 1, wherein the polycarbodiimide compound has a weight average molecular weight represented by the following formula (3) of 20,000 or less. [Chemical 2] 5. The thermosetting resin composition according to claim 1, wherein the phenyl ether derivative is represented by the following formula (4). [Chemical 3]