JP2717265B2 - Thermosetting resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a diallyl methyltetrahydrophthalate prepolymer-based thermosetting resin composition having excellent moldability and good dimensional stability. The term "prepolymer" as used herein means an initial polymer having an average degree of polymerization of 10 to 30 and which can be further polymerized (cured).

"Problems to be solved by conventional technology and invention" Conventionally, diallyl phthalate resin, which is a thermosetting resin, is excellent in dimensional stability, mechanical properties such as rigidity when heated, heat resistance, electrical properties, etc. and high reliability Is widely used in the field where the resin is required, but on the other hand, there is a problem that the resin is brittle and has insufficient toughness. The problems of cracking and chipping have become significant.

With the aim of overcoming such technical problems, many proposals have been made to improve the compounding technique and to improve the brittleness of the diallyl phthalate resin by polymer blending. For example, a method of reinforcing with a filler such as glass fiber and a method of modifying with a polyester or rubber-like polymer having flexibility are known. However, even though all of these methods intend to impart toughness without impairing the excellent properties of the diallyl phthalate resin, it is difficult to say that the purpose has been achieved.

On the other hand, the progress of thermoplastic resins such as polybutylene terephthalate and polyphenylene sulfide has been remarkable, and resins and compounding techniques with excellent heat resistance and electrical properties have been developed. It has been adopted in a wide range of fields, including fields where curable resins are used. However, since it is thermoplastic, there is a problem in terms of deformation due to creep and heat resistance. In particular, the reliability in long-term use under high temperature and high humidity is lower than that of thermosetting resin.

"Means and Actions for Solving the Problems" The present inventors have diligently studied the improvement of the diallyl phthalate resin from a new angle to achieve the above object, and have completed the present invention. Average degree of polymerization 10-30
A diallyl dibasic acid thermosetting resin composition comprising a diallyl methyl tetrahydrophthalate prepolymer, a radical initiator and a filler, and a diallyl methyl tetrahydrophthalate prepolymer added to the composition Thermosetting resin composition.

The dibasic acid diallyl ester and its prepolymer have the same molecular weight as the conventional diallyl phthalate prepolymer by changing the rigid benzene skeleton of the conventional diallyl phthalate resin to a flexible skeleton. Having a low viscosity, and having properties comparable to diallyl phthalate prepolymer, and in addition, an extremely useful thermosetting resin exhibiting improved high flexibility after curing. That is what I found.

In the production of the diallyl dibasic acid ester in the present invention, the dibasic acid anhydride as a raw material includes, for example, methyltetrahydrophthalic anhydride, and a known method can be used for producing the monomer. However, in consideration of use in the field of electric and electronic components, it is preferable to use allyl alcohol as an allyl source in order to reduce the chlorine content derived from allyl chloride.

The dibasic acid diallyl ester prepolymer of the present invention,
For example, it can be produced by reacting in the presence of a known organic peroxide or azo compound catalyst. Examples of usable organic peroxide catalysts and azo compound catalysts include the following compounds.

Di-tert-butyl peroxide, di-sec-butyl peroxide,
Dialkyl peroxides and diaryl peroxides such as tert-butyl-sec-butyl peroxide and dicumyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3,3,5 Peroxyketals such as trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; diaroyl peroxides and diacyl peroxides such as benzoyl peroxide, lauroyl peroxide and 2,4-dichlorobenzoyl peroxide; peroxy acids such as diisopropylperoxydicarbonate. Carbonate; tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyoctoate, tert
Peroxyesters such as -butylperoxybenzoate can be exemplified, and azo compounds such as azobisisobutyronitrile other than the above-mentioned organic peroxides can be used in the same manner.

After the polymerization, the prepolymer is separated using, for example, aliphatic hydrocarbons or alcohols, and dried to obtain a thermosetting thermosetting and improved flexibility diallyl dibasic acid ester of the present invention. A prepolymer can be obtained.

Examples of the aliphatic hydrocarbons used include hexane,
Heptane and the like can be exemplified, and examples of the alcohols include methanol, ethanol, isopropyl alcohol, tert-butyl alcohol and the like.

Such a dibasic acid diallyl ester of the present invention and a prepolymer thereof can be easily cured by a radical polymerization initiator such as an organic peroxide, and the obtained dibasic acid diallyl ester of the present invention and a prepolymer thereof can be obtained. The cured product containing as the main component retains the performance comparable to the conventional diallyl phthalate resin, and becomes a flexible three-dimensional crosslinked product, so it can be used for molding materials, powder coatings, various binders, and optical materials. It is suitable.

The dibasic acid diallyl ester prepolymer of the present invention can be applied to various molding and casting methods by taking advantage of its properties, and can be molded with a low resin content unlike the conventional diallyl phthalate resin. The material can be prepared and has excellent moldability and good dimensional stability. The molded product is excellent in impact resistance, water / moisture resistance, chemical resistance, adhesion, and has little change over time. Therefore, the mechanical strength and electrical characteristics are outstanding, and the reliability is extremely high.

 Hereinafter, the present invention will be described in detail based on examples.

"Examples and Comparative Examples" Reference Example 1 A 1-separable flask equipped with an oil-water separator was charged with 332 g of methyltetrahydrophthalic anhydride (hereinafter, MTHPA), 290.5 g of allyl alcohol, 234 g of benzene, and 9.0 g of 65% sulfuric acid, and stirred. The temperature was raised to 90 ° C. After the start of reflux, the reaction water generated by the esterification reaction was removed to the outside while removing the reaction water.
The reaction was continued for an additional time to complete the allylic esterification reaction. Subsequently, excess allyl alcohol and benzene as a solvent were recovered under reduced pressure (120 ° C., 5 mmHg), and the crude monomer (diallyl methyltetrahydrophthalate) as a dark brown liquid was obtained.
8 g were obtained.

When the obtained crude monomer was purified by distillation, 445 g of a pale yellow transparent monomer was obtained, and the acid value of this monomer was 2.0 m.
It was gKOH / g.

Add the same amount of toluene as the monomer and heat to 70 ° C,
The mixture was neutralized by adding 14.4 g of a 1% aqueous solution of NaOH. After washing with water, toluene was recovered under reduced pressure (120 ° C, 5 mmHg) and purified monomer
420 g were obtained.

 Table 1 shows the quality of the obtained monomers.

Reference Example 2 MTHP in one separable flask with reflux condenser
A 199.2 g, sodium carbonate 144.0 g, sodium iodide 4.
8g, 5.2g of triethylamine and 120ml of xylene were charged all at once and heated. 2.4 g of water when the internal temperature reaches 140 ° C,
Allyl chloride 218.4 g was added dropwise. However, the dropping of water was completed in about 15 minutes as the initial stage of the reaction, and the dropping of allyl chloride required 6.5 hours.

After cooling to 40 ° C., 450 g of water was added, and the mixture was stirred and separated. The organic layer was passed through, and excess allyl alcohol and xylene were recovered under reduced pressure (100 ° C., 3 mmHg). The precipitated salt was removed by filtration to obtain 274.2 g of a crude black-brown monomer.

The resulting crude monomer was purified by distillation to obtain 219 g of a pale yellow purified monomer.

 Table 1 shows the quality of the obtained monomers.

Example 1 The methyl tetrahydrodiallyl phthalate 55 obtained in Reference Example 1 was placed in a one-separable flask equipped with a catalyst supply tube.
After charging 0 g, the mixture was stirred and heated to 120 ° C. When the temperature reached 120 ° C., tert-butyl peroxybenzoate and methyl tetrahydrodiallyl phthalate were previously added in a molar ratio of 0.01.
What was mixed so as to be 4: 1 was supplied at a rate of 0.6 g / min. The reaction temperature was maintained at 150 ° C., and when the refractive index of the polymerization solution reached 1.4995 (30 ° C.), the supply of the catalyst was stopped and the system was cooled.

To the obtained polymerization solution, 3 times the amount of methanol was added and stirred to precipitate a prepolymer. The precipitated prepolymer was thoroughly washed with the same amount of methanol, dried, and pulverized to obtain a white powdery prepolymer.

 Table 2 shows the yield and physical properties of the prepolymer.

Comparative Example 1 Ortho diallyl phthalate (600 g) was charged into a 1-separable flask and heated with stirring. 30c when the temperature reaches 150 ° C
Air was supplied at a rate of c / min and maintained at 170 ° C. When the refractive index of the polymerization reaction reached 1.5264, the supply of air was stopped and the system was cooled.

To the obtained polymerization solution, 3 times the amount of methanol was added and stirred to precipitate a prepolymer. The precipitated prepolymer was thoroughly washed with the same amount of methanol, dried, and pulverized to obtain a white powdery prepolymer.

 Table 2 shows the yield and physical properties of the prepolymer.

Examples 2 and 3 and Comparative Example 2 a) Preparation of Full Compound The prepolymers obtained in Example 1 and Comparative Example 1 were blended as shown below to prepare a full compound.

b) Compression molding of full compound Take 20 to 40 g of the full compound obtained above, make a nearly disk-shaped tablet with a diameter of 50 mm and a thickness of 10 mm by manual pressing using a mold, and apply a high frequency preheater to about 80 ° C. Immediately after being preheated, place it in the center of the cavity of the compression molding die that has been adjusted to the prescribed temperature, and press the
g / cm ² at a molding predetermined time, the diameter after 100 mm, a thickness of about 2~4m
m-shaped disc-shaped product was obtained.

Table 4 summarizes the compression molding temperature, time, and physical properties of the molded product. The method for measuring the physical properties of the molded product is as described after Table 4.

Method for Testing Physical Properties of Molded Product (1) Rockwell Hardness Measured at room temperature using a Rockwell hardness tester (M scale) and expressed as an arithmetic average of three measured values.

(2) Thickness of test piece The thickness of the test piece is measured at the center of the sample using a micrometer.

(3) Dimensional Shrinkage Rate The diameter of a molded product sample is actually measured using a micrometer, the difference from the mold cavity diameter (100 mm) is determined, the result is divided by the mold cavity diameter, and multiplied by 100.

(4) Bending strength Test piece: Nine test pieces of about 10 mm width cut out from three molded articles with a diamond cutter are used.

Testing machine: AUTOGRAPH DCS-5000 (manufactured by Shimadzu Corporation) Measurement conditions: 50 kg of load cell, support width of 60 mm, crosshead speed of 2 mm / min The calculation is shown by the arithmetic mean of 6 points according to the formula described in JISK6918.

(5) DSC reaction rate The calorific value of each of the test sample obtained by pulverizing the molded product sample and the full compound before molding was measured using a differential scanning calorimeter (910 DSC system manufactured by DuPont). It is calculated by the formula.

In the formula, A is the calorific value of the full compound (J / g) B is the calorific value of the finely pulverized molded product (J / g) (6) Boiling water absorption The test piece is a disk sample with a diameter of 100 mm and a thickness of 2 mm. Others are determined according to JISK 6918.

(7) Electrical properties Volume resistivity, dielectric constant, dielectric loss tangent, arc resistance are JISK 6
918, dielectric breakdown strength (step method) is performed according to JISK6911.

[Effects of the Invention] According to the present invention, by changing the benzene skeleton of the conventional diallyl phthalate resin to another skeleton, methyl having excellent fluidity and flexibility and retaining the characteristics of the conventional diallyl phthalate resin is obtained. A diallyl tetrahydrophthalic acid prepolymer is obtained, and its cured product is an improvement over the disadvantages of the conventional diallyl phthalate resin, and is of great industrial value.

 ────────────────────────────────────────────────── ─── Continued on the front page (56) References USSR Patent Invention 499284 (SU, A) “Kauch. Rezina” (6), p. 42-44, 1981 ("Chem. Abstr." No. 95: 151935) "Deposited Doc.", 1980, SPSTL 57lkhp-D80, 5pp. Avail. (“Chem. A bstr.” No. 95: 188671)

Claims (2)

(57) [Claims] 1. A thermosetting resin composition comprising a diallyl dibasic acid ester, comprising a diallyl methyl tetrahydrophthalate prepolymer having an average degree of polymerization of 10 to 30, a radical initiator and a filler. 2. A diallyl dibasic acid thermoset comprising a diallyl methyltetrahydrophthalate prepolymer having an average degree of polymerization of 10 to 30, a diallyl methyltetrahydrophthalate monomer, a radical initiator and a filler. Resin composition.