JPS6250312A - Heat-resistant thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent moldability and a short molding cycle time, comprising a specified polyfunctional polymerizable monomer and a polyallylated polyhydric phenol. CONSTITUTION:98-65mol% polyfunctional polymerizable monomer (A) having at least 2.0 ethylenically unsaturated groups in the molecule, a MW of 150-400, a volatility of as low as 0.1Torr/150 deg.C or below and a viscosity at 25 deg.C <=100P is mixed with 2-35mol% polyallylated polyhydric phenol (B) having at least 2.0, per molecule, of aromatic ring-bonded allyloxy groups, at least 1.0, per molecule, of aromatic ring-bonded allyl group and an unreacted phenolic hydroxyl group content <=2.0X10<-4>eq/g.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to a novel resin composition based on a polyfunctional polymer finishing agent, more specifically, a polyarylated polyhydric phenol as a polymerization rate regulator and crosslinking agent. The present invention relates to a heat-resistant thermosetting resin composition containing a polyfunctional polymerizable monomer.

[Prior art]

Conventionally, when obtaining a molded product by polymerizing a monofunctional polymer columnar polymer such as styrene or methyl methacrylate with a radical polymerization initiator, the heat of polymerization is likely to be generated rapidly (1: in large quantities);
The key point in technology has been how to control this polymerization heat to stabilize the temperature of the system. If this is not done, the so-called runaway polymerization reaction will occur, and the temperature of the system will rise rapidly, making it impossible to adjust the polymerization rate. 1. The molded product will generate heat and foam and have defects such as cracks and voids. 1. The catalyst will lose its original good physical properties. Select the type of material and gradually polymerize it over several to tens of hours at a low temperature range from room temperature to 60°C (=
Measures have been taken to appropriately suppress self-heating associated with polymerization. In liquid resin composition 1, which is mainly composed of a so-called polyfunctional polymerizable monomer having 2.0 or more ethylenically unsaturated groups per molecule, it is even more difficult to adjust the polymerization rate; Large amount of filler for casting (up to 50% volume)
Although measures have been taken such as introducing heat and pressure molding in a mold for a molding cycle of several to several minutes, it still prevents internal strain, that is, thermal polymerization of polyfunctional polymerizable materials ( = At.

Although it has been desired to achieve both moldability that provides good molded products and an efficient molding cycle, it has been an extremely difficult problem.

[Purpose of the invention]

The present invention is the result of research aimed at shortening the molding time of polyfunctional monomers, for which it has been extremely difficult to adjust the polymerization rate, and eliminating defects in molded products.

He discovered that adding polyallylated polyhydric phenols to the system adjusts the polymerization rate of the system and suppresses the runaway curing reaction, but does not interfere with the crosslinking reaction. We have now completed the present invention.The purpose of this invention is to provide a thermosetting resin composition based on a polyfunctional polymerizable monomer that has both good moldability and a fast molding cycle. be.

[Structure of the invention]

The present invention consists of 98 to 65% (mol) of polyfunctional polymerizable monomers having 2.0 or more ethylenically unsaturated groups/molecule and 2 to 35% (mol) of polyallylated polyhydric phenols. Formability characterized by

It is a heat-resistant thermosetting resin composition with excellent molding cycles.

The polyfunctional monomers used in the present invention (;

It has at least 2.0 ethylenically unsaturated groups/molecule, and may be either a single substance or a fused form.

However, even if monofunctional polymerizable monomers have only 7 molecules of ethylenically unsaturated groups, if the mixed monomer system satisfies the conditions of an average of 2.0 or more ethylenically unsaturated groups/molecule. They may be used together as appropriate.

The polyfunctional polymerizable monomer used in the present invention is particularly one having 2 to 3 ethylenically unsaturated groups per molecule. Diacrylates and dimethacrylates of polyols consisting of alcohols and diezequin compounds.

C3) Methylenebisacrylamide, methylenebismethacrylamide, (C1 divinylbenzene, ■) Polymerizable monomers having 2 unsaturated groups/molecule such as bismale and (midos) ■) Trihydric or higher polyhydric alcohols and triacrylates, trimethacrylates, ψ゛) of polyols consisting of triepoxy compounds, triallyl esters of trivalent or higher polybasic carboxylic acids, and diallyl esters of α, β unsaturated dibasic acids. 01) Lismaleimides, polymerizable upper polymers having 3 unsaturated groups/molecule, such as 01) lismaleimides.

Also, ■ polyacrylates and polymethacrylates of polyols consisting of polyhydric alcohols such as polyglycerin and polypentaerythritol, and evoquinated novolak.

(I) Aniline resin-based polymaleimides, (J
) Tetraallyl pyromellitate, etc. (= polyfunctional heptamers having 4 or more ethylenically unsaturated groups per molecule) can also be used in combination as appropriate.

and (d) α, β unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, etc. or mixtures thereof with saturated dibasic acids, mono to tetraethylene glycol, mono to tetrapropylene glycol.

Unsaturated polyesters produced by reaction with dihydric alcohols such as neopentyl glycol and polyols such as dievoquine compounds may also be used in combination with the above-mentioned polyfunctional polymers as appropriate.

In addition, the breakdown of one molecule in the above-mentioned nanatsuma is 150-400,
0. ITorr/150℃ (preferably 0.1 Torr
It is preferable to have a low volatility of 100 voids/25° C. or less (preferably 30 voids/25° C. or less).

The polyallylated polyhydric phenols used in the present invention (= have at least 2.0 aromatic rings/molecule: directly bonded allyloxy groups and at least 1.0 molecules/molecule allyl groups directly bonded to the aromatic rings). However, the unreacted phenolic OH group is 2.OX
It is necessary that it is 10″el-/i or less.

If unreacted phenolic OH groups remain, it is undesirable because it significantly interferes with radical polymerization, and 2.0xlO
-' ey must be less than or equal to 711. Therefore, it is necessary that almost all phenolic OH groups be etherified and covered with allyl groups.

Therefore, when dihydric phenols are used as the starting material (- means 2 allyloxy groups directly connected to the aromatic ring, which means 2 per molecule).
In the case of polyhydric phenols having a valence higher than that of the phenol, it is necessary that the number of phenols be 2 or more, which is the same number as the valence of the phenol. Furthermore, it is not enough that all the phenolic OH groups of polyhydric phenols are etherified with allyl groups;
: It is necessary to have 1 or more (preferably 2 or more) directly bonded allyl groups.

The reason for this is that the allyloxy group and allyl group directly linked to the aroma FJ+ have the effect of reacting with radicals and stabilizing them, and this is the reason why they exhibit a polymerization rate adjusting effect in radical polymerization.) However, this is because an allyl group directly bonded to an aromatic ring has an even greater effect.

When the total number of allyloxy groups and allyl groups directly bonded to the aromatic ring is less than 3.0'/molecule, 12 is preferable because although it has a polymerization rate adjusting effect, it significantly suppresses crosslinking and deteriorates the physical properties of the cured product. do not have.

Incidentally, monohydric phenols can be used in almost the same manner as long as the total number of allyloxy groups and allyl groups is 3.0 or more per molecule.

In the method of the present invention (=), the addition ratio of polyallylated polyhydric phenols to polyfunctional polymerizable upper C: is from 2/98 to 35/65 (preferably 5/95-2
0/80).

If the amount of polyallylated polyhydric phenols is less than this, the polymerization 4'' and W'M regulating effect will be significantly reduced, which is undesirable.If it is more than this, the crosslinking suppressing effect will appear and the physical properties of the molded product will be insufficient. Undesirable.

Within the range of the addition ratio of the polyallylated polyhydric phenols of the present invention, the physical properties of the obtained molded product mainly depend on the structure, functionality, and mixing ratio of the polyfunctional polymerizable monomer used (=
The moldability and moldability mainly depend on the type and amount of polyarylated polyhydric phenols added.

That is, the effects of the polyallylated polyhydric phenols used in the present invention are as follows.

■Improve moldability, making it possible to manufacture molded products with fewer defects such as lipoids and cracks, and improving heat resistance as a general physical property inherent in cured products of functional polymerizable monomers. C: To fully demonstrate the advantages such as properties, especially physical properties at high temperatures and chemical resistance.

■It is possible to manufacture defect-free products (1' products) in a short curing cycle.

If you simply want to adjust the polymerization rate, you can use ■ polyhydric phenols such as hydroquinone and catechol, ■ sulfur-containing compounds such as mercaptan and thiophenol, and ■ chlorine-containing compounds such as carbon tetrachloride and chloroform. None of these methods is suitable for the purpose of the present invention because they have the effect of significantly suppressing crosslinking and cannot provide molded products with good physical properties.

The present invention (= The radical polymerization initiator used is 1) ordinary organic peroxides, azo compounds such as azobisisobutyronitrile, etc. Among them, benzoyl peroxide, lacroyl peroxide, chlorhequinanone peroxide, etc. medium-temperature products such as hydride, methyl ethyl ketone peroxide, t-budelperbenzoate, and dicumyl peroxide.

Di-t-butylperoquinide, bis(toptylperoquine) p-isopropylbenzene, 2.5 dimethyl 2.
5-di(t-butylperoxy)hexene, 2-5-dimethyl-2-5-di(dobutyloxy)hexene, and mixtures thereof can all be used, but for the purpose of the present invention. is particularly preferred.

In addition, in the present invention, it is also possible to add a polyfunctional polymer finisher and a polyallylated polyhydric phenol (nifiller), and the effect of adding a filler can also be expected.

Furthermore, in the present invention, the polymerization rate is not affected (= the pot You can only improve your life.

〔Effect of the invention〕

The composition of the present invention can fully exhibit the excellent physical properties such as heat resistance inherent in molded products of polyfunctional polymerizable monomers, and also has the disadvantages of long molding cycles and difficult moldability. can be shortened and improved to a practical stage by improving the process, and is extremely useful industrially as a heat-resistant thermosetting resin composition.

Therefore, it is especially suitable for use in the electrical industry, where heat resistance is required, such as molding materials, laminated products, paints, adhesives, cast products, etc.

〔Example〕

Example 1 The above composition was mixed and uniformly dissolved. This product hardly thickened even after being left at room temperature for 3 months.

This material was injected into a 15 x 10 x O,8 (CIL) silicone resin mold, cured at 110°C for 10 minutes, then cured at 130°C for 20 minutes, and then post-cured at 160°C for 20 minutes.

The cast cured product obtained was transparent and free of defects such as voids, cracks, and birefringence.

The physical properties of the obtained cast cured product are shown in Table 1.

Comparative Example 1 The above composition was mixed and uniformly dissolved. When this product was injected into the silicone resin mold of Example 1 and cured at 110°C, it foamed significantly in 8 minutes, and C nivoids and cracks occurred on one side, making it impossible to obtain a good molded product.

Example 2 The above compositions were mixed and uniformly dissolved. This product hardly thickened even after being left at room temperature for 3 months.

This was poured into a silicone resin mold having the same shape as in Example 1, cured at 100°C for 20 minutes, then post-cured at 130°C for 20 minutes, and then at 1:160°C for 20 minutes. The cast cured product obtained was transparent and free of defects such as voids, cracks, and birefringence.

The physical properties of the obtained cast cured product are shown in Table 1.

Comparative Example 2 The above composition was mixed uniformly (dissolved). This was injected into the V9 cone resin mold of Example 1 and cured at 100°C, resulting in remarkable heat generation and foaming in 18 minutes, resulting in good casting. Further, when cured at 70° C., gelation began in 5 hours and cured in 8 hours.

When this was further cured at 90°C for 10 hours and 130°C for 10 hours, a translucent and uniform cast plate with no cracks or voids was obtained.The properties are shown in Table 1.

Comparative Example 3 The above composition was mixed uniformly (=dissolved). This was injected into the silicone mold of Example 1 and cured at 100°C. It cured in about 35 minutes, and was further cured at 130°C for 40 minutes. 1:, 1
Post-curing was performed at 60° C. for 40 minutes. Although the cast cured product obtained was transparent and free of defects such as voids and clutter, it was not possible to obtain a cast cured product with satisfactory physical properties due to incomplete rehabilitation. The physical properties of the cast cured product obtained are shown in Table 1 f-2.

Example 3 Trimethylolpropane triacrylate 3
9.2 g of the above composition was mixed and uniformly dissolved. This product hardly thickened even after being left at room temperature for 2 months.

Silicone resin mold C used in Example 1: Casting 1
00'C for 16 minutes, then 130℃ for 12 minutes (:1
It was post-cured at 60°C for 20 minutes.

The cast cured product obtained was transparent and free of voids, cracks, and birefringence. The physical properties of this product are shown in Table 1.

Comparative Example 4 The composition of Example 3 except for tetraallyl bisphenol S dicrine diyl ether was cured in the same manner as in Example 1 at 100°C using the resin mold, and intense exothermic foaming occurred in 14 minutes. death.

Good cast-cured products were not observed.

Example 4 The above composition was mixed with two rolls at room temperature to form a uniform putty-like molding material. This molding material does not harden even if stored at room temperature for 3 months, and can be similarly molded under heat and pressure. This molding material was molded in a mold at 180°C for 5 minutes,
A compacted molded product was obtained.

The physical properties of the obtained molded article are shown in Table 2.

Comparative Example 5 The composition of Example 4, except for tetraallyl bisphenol S diallyl ether, was used as a molding material and molded in the same manner as in Example 4, but the molding contained many minute racks and voids and had satisfactory physical properties. I couldn't get the item. The physical properties of the obtained molded article are shown in Table 2.

Table 1! 142 Normal load 1i2.5Kp Temperature increase rate 5℃/min Needle speed 0.25
M10 Mine 2 Thermal Expansion Measurement Method (: Depends.

Claims (2)

[Claims] (1) Consisting of 98-65% (mol) of polyfunctional polymerizable monomers having 2.0 or more ethylenically unsaturated groups/molecule and 2-35% (mol) of polyallylated polyhydric phenols. A heat-resistant thermosetting resin composition. (2) Polyallylated polyhydric phenols have allyloxy groups directly connected to aromatic rings of 2.0 or more molecules/molecule and 1.0 molecules/molecule or more of allyloxy groups
The heat-resistant thermosetting resin according to claim (1), which has an allyl group directly connected to an aromatic ring of a molecule or more, and has an unreacted phenolic OH group of 2 x 10^-^4 eg/g or less. Resin composition.