JPH02302416A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having high melt viscosity, excellent heat distortion temperature, flexural strength, impact strength, etc., comprising a diallyl phthalate-based prepolymer and a terminal allyl-based oligomer. CONSTITUTION:The aimed composition comprising 10 to 90wt.%, preferably 30 to 70wt.% diallyl phthalate-based prepolymer, 90 to 10wt.%, preferably 70 to 30wt.% terminal allyl-based oligomer and preferably <=1/2 based on total amounts of the two substances of a reactive vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel diallylphthalate thermosetting resin composition.

[Conventional technology]

DAP resin, which is obtained using diallyl phthalate (DAP) as a monomer, is widely used in molding materials, decorative laminates, laminates, etc., and is trusted because its electrical properties do not deteriorate over a long period of time under high temperature and high humidity conditions. Collecting books.

However, as the performance of the machines and electrical parts used has improved, there has been an increasing demand for resins that maintain their excellent properties and have even higher heat resistance.

In addition, as is the case with thermosetting resins in general, they are brittle and
It has the disadvantage of insufficient toughness and is weak against impact. Particularly in recent years, with the miniaturization of molded products, the problem of cracking or chipping in thin parts or small protrusions of the molded products has become a major problem.

When diallyl terephthalate (DAT), which has excellent symmetry, is used as a monomer, it can be expected to improve heat resistance, but currently, the secondary cured product of DAT has inferior mechanical properties, such as being more brittle than DAP resin. This is known and has not yet been put into practical use.

By the way, JP-A-59-80409 discloses that by copolymerizing DAT with an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position, such as toluene or xylene, it has excellent heat resistance and mechanical properties. It is described that a prepolymer that provides a cured product with high strength can be synthesized. Further, JP-A-59-135246 describes a method of obtaining a highly impact-resistant resin composition by blending these resins with a diallyl phthalate resin. However, in order to synthesize such a copolymer, many innovations have been made to the polymerization method and reaction equipment, such as the need to blow out the monomer, initiator, and aromatic hydrocarbon through a special nozzle while stirring at high speed. is necessary. Moreover, this method requires the use of a large amount of initiator, and since it involves radical copolymerization, it is not impossible to recover the two monomers and control the polymerization reaction with good reproducibility. However, it has the disadvantage of being extremely difficult.

In addition, diallylisophthalate resin is also known as a resin with high heat resistance and is produced industrially, but because the monomer price is extremely high, it is only used for some limited applications. do not have.

Further, resins obtained using special monomers such as naphthalene dicarboxylic acid diallyl ester are also known, but these are also expensive monomers and have not been put to practical use.

On the other hand, many methods have been used to improve the heat resistance and mechanical properties of diallyl phthalate resins, not only by improving the resin itself but also by devising formulations and polymer blends. For example, methods of reinforcing with fillers such as glass fibers, and methods of modifying with flexible polyester or rubber-like polymers are known.

However, although these methods have attempted to impart toughness to diallylphthalate resins without impairing their excellent properties, it cannot be said that they have achieved their objectives. That is, for example, in the method using the filler described above, it is necessary to leave the long fiber filler in the molded product, but this extremely limits the kneading method and molding method, which is not practical. Furthermore, in the method of modifying with other polymers, etc., the dimensional stability, heat resistance, moisture resistance, mechanical strength, electrical properties, or moldability is usually unduly reduced.

[Problem to be solved by the invention]

As described above, the conventionally proposed methods have not yet been able to sufficiently improve the properties of diallyl phthalate resins. Therefore, the present invention seeks to provide a means for sufficiently improving the properties of diallyl phthalate resins. It is something to do.

That is, as a result of various studies aimed at improving the properties of diallylphthalate resin, the present inventors found that
The inventors completed the present invention by discovering that when a terminal allyl oligomer is blended with the resin, it improves the heat-resistant brittleness, which is a drawback of the resin, without impairing the inherently desirable properties of the diallyl phthalate resin. This is what I did.

[Means to solve the problem]

According to the present invention, there is provided a thermosetting resin composition comprising 10 to 90% by weight of a diallyl phthalate prepolymer and 90 to 10% by weight of a terminal allyl oligomer.

According to the present invention, 10 to 90% by weight of diallyl phthalate prepolymer, 90 to 10% by weight of terminal allyl oligomer, and 1/2 of the total weight of these two types.
A thermosetting resin composition is provided comprising the following weights of reactive vinyl monomer:

According to the present invention, 10 to 90% by weight of a diallyl phthalate prepolymer, 90 to 10% by weight of a terminal allylic oligomer, and 30% by weight of the total weight of these two types.
% or less of unsaturated polyester resin is provided.

In the present invention, a diallyl phthalate prepolymer is a solvent-soluble and heat-flexible prepolymer obtained by polymerizing diallyl orthophthalate, diallyl isophthalate, or diallyl terephthalate, and usually has a molecular weight of 2,000 to 30,000. refers to a prepolymer that can be post-polymerized. Such prepolymers also include copolymerized prepolymers such as those described in JP-A-59-80409 mentioned above.

The terminal allylic oligomer useful in the present invention is as follows (1)
Or it may be as defined in (2).

(1) The following structural formula, CIIZ = C) 1cH, -0+CO-8r-Coo-
R-0-)-y-CO-Ar-Coo-CIIzCH=
CHz [In the above formula, R is a divalent organic residue derived from a diol having 1 to 20 carbon atoms, and Ar is 1.4-.

1.3- or 1.2-phenylene group, n is 1-
100], which has a degree of unsaturation expressed as an iodine value according to the Rice (Wijs) method of 20-100.

(2) Allyl ester group (C1lz=CHCH
! 0CO-), and has the following formulas A and B, ÷Co-Ar-Coo-R-0÷ AA
-CO-Ar-COO→-y-R' -0-CO-Ar
-COO-B [In the above formula, X is an integer from 2 to IO, and R
' is an organic residue derived from a polyol having X+1 hydroxyl groups, and R and Ar are the same as defined above.] A terminal allylic oligomer having a repeating unit represented by:

In the oligomer (2) above, the mole fraction of structure A in the oligomer structure excluding the terminal allyl ester group is preferably in the range of 10 to 98%, and the remainder is preferably structure B. It is preferable that the degree of unsaturation expressed by the iodine value according to the method is 2O-1oo.

Examples of diols from which R is derived include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexane dimetatool, 1゜3-butanediol. , neopentyl glycol, 1,3-cyclohexanediol, p-xylene glycol, styrene glycol, and other aliphatic or aromatic ring-containing diols.

Examples of the polyol from which R' is derived include aliphatic trihydric alcohols such as glycerin and trimethylolpropane; and aliphatic tetravalent or higher alcohols such as pentaerythritol and sorbitol.

That is, the above oligomer is diallyl terephthalate (D
AT), diallyl isophthalate, and diallyl phthalate can be produced by reacting the above-mentioned polyol. The method for producing such oligomers is as disclosed in detail in Japanese Patent Application No. 63-262217.

Regarding the blending amount in the composition of the present invention, if the amount of the terminal allyl oligomer is small, the heat resistance will not improve, such as a decrease in heating weight compared to a system containing diallyl phthalate prepolymer alone, and it will not be blended. meaningless. In addition, if the amount is too large, problems such as the melt viscosity becoming too low often occur, so it should be blended within an appropriate mixing ratio. The actual blending amount is 10% by weight of the terminal allyl oligomer based on the total weight of the diallyl phthalate prepolymer and the terminal allyl oligomer.
In order to improve the physical properties of the composition, the content is preferably within 90% by weight, preferably within 20% by weight and 80% by weight, and more preferably within 30% by weight and 70% by weight.

When this blended composition is used, the melt viscosity is moderately increased, making injection molding easier to perform, and surprisingly, the heat distortion temperature is improved, compared to a system using allyl oligomer alone. Furthermore, compared to a system in which a diallyl phthalate prepolymer is used alone, there is less decrease in heating weight, and mechanical strengths such as heat deformation temperature, bending strength, and impact resistance are dramatically improved.

Reactive vinyl monomers useful in the present invention include, for example, unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, unsaturated dibasic acids and their derivatives, vinyl saturated aliphatic or aromatic carboxylic acids, etc. Examples include esters and their derivatives, vinyl cyanide compounds such as (meth)acrylonitrile, and the like.

Examples of unsaturated fatty acid esters include various esters of acrylic acid and methacrylic acid. Aromatic vinyl compounds include styrene or substituted styrene. Unsaturated fatty acids and their derivatives include acrylic acid and methacrylic acid and amides thereof. As unsaturated dibasic acids and derivatives thereof, mention may be made of maleic acid, maleic anhydride, fumaric acid and N-substituted maleimides. Furthermore, examples of vinyl esters of saturated aliphatic or aromatic carboxylic acids include vinyl acetate, vinyl propionate, vinyl benzoate, and the like.

Furthermore, other crosslinkable polyfunctional monomers such as difunctional, trifunctional, and tetrafunctional monomers can also be used as the reactive vinyl monomer.

Among the above-mentioned reactive vinyl monomers, aromatic allyl esters such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, ( Preferred are meth)acrylic esters, vinyl acetate, and the like.

The amount of the reactive vinyl monomer is 1/2 or less of the total weight of the diallyl phthalate prepolymer and diallyl terephthalate oligomer, preferably 10% by weight.
It is better if it is below. If it exceeds 1/2, the curing rate will be unduly delayed, the curing shrinkage rate will increase, and the internal distortion of the molded product will increase significantly, which is not preferable.

The unsaturated polyester resins useful in the present invention may be those commonly known, such as polybasic unsaturated acids such as maleic acid and fumaric acid, phthalic anhydride, isophthalic acid,
From a viscous liquid at room temperature with an acid value of about 5 to 100, manufactured using a polybasic saturated acid such as terephthalic acid and a polyhydric alcohol such as diethylene glycol or propylene glycol, to a softening point of 150°C or less. There are solid ones and vinyl esters obtained by reacting diglycidyl ether of bisphenol-A with (meth)acrylic acid.

The amount of unsaturated polyester resin blended is preferably 30% or less, preferably 20% or less of the total weight of the diallyl phthalate prepolymer and the terminal allyl oligomer. A blend exceeding 30% by weight is not preferable because the inherent electrical properties and other properties of the diallyl phthalate resin are significantly deteriorated.

The composition of the present invention can be used as a molding material for various products in the same way as conventional diallylphthalate resin compositions. It is necessary to use a curing agent during molding, and any radical polymerization initiator that can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays can be used as such curing agent. It can be selected as appropriate depending on the use, purpose, blending ratio of components, method of curing the curable composition, etc. of the curable composition. Particularly preferred curing agents include peroxides such as dicumyl peroxide, t-butyl peroxybenzoate, and benzoyl peroxide. The amount of curing agent used is generally 0.1 to 6% by weight based on the resin solid content.
It is appropriate that

When molding the composition of the present invention, as in the case of conventional diallylphthalate resin compositions, for example, fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, pigments, etc. , flame retardants, and other additives may be blended and used within a range that does not impair the properties of the composition,
Thereby, moldability or physical properties of the molded article can be improved.

As for the molding method, known molding methods and molding conditions similar to those for conventional diallyl phthalate resins can be applied as they are. That is, a casting method in which the composition of the present invention is injected into a mold and cured, an injection molding method or a transfer molding method in which the composition is heated to a fluid state, and then placed in a mold and cured by heating; A compression molding method in which an object is heated and pressurized in a mold to harden it.
A laminate molding method in which the composition is dissolved in a suitable organic solvent, impregnated into a fibrous sheet, and the resin is cured in the fibrous sheet in a dryer or under pressure if necessary. A coating method in which a powder or solution is applied to a substrate and cured on the substrate, a printing paper etc. is impregnated with the composition solution, and after drying,
Examples of molding methods include a decorative board molding method in which the material is cured by heating and pressing on a substrate. The heating temperature for curing during molding is preferably about 40 to about 220°C. In addition, when using pressurized conditions, the pressure is as follows:
A pressure of about 5 to 1000 kg/c+a can be exemplified.

The composition of the present invention can be used as a molding material in the following wide range of fields. For example, connectors, motor commutators, governors, coil bobbins, relays, switches, terminal boards, ignitions, breakers, sockets, binders for sliding resistors, printed wiring boards, sealing materials for electronic parts and elements, coil encapsulation, etc. Electrical and electronic fields such as insulating materials in light electrical to heavy electrical fields.

It is also useful as a molding material in, for example, the field of machinery such as plastic brake pistons, the field of tableware and other daily necessities, and the field of medical materials such as trays and containers that require chemical or steam sterilization.

Furthermore, the composition is impregnated or applied to a fibrous sheet such as paper, nonwoven fabric, glass cloth, etc. in the presence or absence of a solvent, and the composition is pressed and cured to a wood, paper, metal, or other inorganic substrate, or it is precured. By adhering it to the above-mentioned base material, it can be used in the form of a decorative board for various building materials, furniture, interiors, cabinets, kitchen equipment, axles, ship interior materials, and other fields.

In addition, if the composition is directly impregnated into wood and cured,
It is a wood-plastic composite (so-called WPC) and can be used in fields such as floorboards, decks, roof decks, building structural materials, and sporting goods. Furthermore, as a laminated board impregnated with glass cloth or other fibrous sheet structure and laminated, it can be used in fields that require high-temperature properties, such as terminal plates, wedges such as motors, insulation collars, slot armor, and coils. It is useful for rotating machine-related fields such as separators, stationary machine-related fields such as duct pieces, barriers, terminal plates, operating rods, panels such as switchboards, printed wiring boards, PC insulation supports, etc., and also for temperature and humidity. It has excellent dimensional stability even when the temperature changes rapidly, and is useful in fields that require good mechanical strength, such as laser domes, missile blades, rocket nozzles, and jet aircraft air ducts. It is also useful for parts of various chemical equipment. Fields that require chemical resistance such as antennas,
Fields that require weather resistance, chemical resistance, and mechanical strength such as skis, ski poles, and fishing rods, other paints, mold materials for other resins, hot stamping resins, U
It can be used in a wide range of applications, such as V-curing ink, materials for lenses and other optical applications, binders for glass fibers and carbon fibers, and resins for resist films in phosphorography using light, electron beams, or X-rays.

〔Example〕

The present invention will be further explained below with reference to Examples.

Diallyl terephthalate 2, oligomer 〇L reference example 1~
9 DAT 600 in a 12-three flask with a distillation device
g, 78.4 g of ethylene glycol, and 0.1 g of dibutyltin oxide were charged and heated to 180° C. under a nitrogen stream to distill off the allyl alcohol produced. s
When about 140 g of allyl alcohol had been distilled out, the pressure inside the reaction system was reduced to 50 mmHg to increase the rate of distillation of allyl alcohol. After the theoretical amount of allyl alcohol had distilled off, the reaction was allowed to proceed for an additional hour, and then the reaction mass was cooled.

After the reaction product solidified, it was crushed into small lumps, placed in methanol In, and vigorously stirred for about 1.0 hour while crushing the polymer to obtain a powdered polymer. After separating methanol by filtration, it is dried and crushed to obtain oligomer 49.
6 g was obtained (Reference Example 1).

Table 1 shows the physical properties of the oligomer obtained (Reference Example 1),
Physical properties of oligomers obtained by changing reaction conditions and isolation conditions (
Reference Examples 2 to 9) are also shown.

Examples 1 to 14 and Comparative Examples 1 and 2 ■ Composition Preparation Each composition shown in Table 2 containing the diallyl terephthalate oligomer obtained in the reference example was thoroughly mixed in advance, and the front roll temperature was 100 to 110. Roll temperature after °C1 70~9
The mixture was roll-kneaded at 0°C for 5 minutes, taken out from the rolls into a sheet, left to cool, and then used in a frame.

Further, the roll temperature was slightly changed depending on the properties of the composition.

■ Take a predetermined amount of the unfilled compound obtained through compression molding, put it into a compression mold (100 x 100 x 3 or 15 x 15 x 90 mn+) maintained at 80°C, and apply a press pressure of about 100 kg/cd. 125 over 30 minutes
Raise the temperature to °C and hold at this temperature for 10 minutes. The molded product was taken out of the mold, immediately placed in an oven at 150°C, and left for 10 hours.

Table 3 shows the physical properties of the obtained cured product.

Further, as Comparative Examples 1 and 2, results were shown in which only diallyl phthalate prepolymer and diallyl terephthalate prepolymer were used.

Claims (1)

[Scope of Claims] 1. A thermosetting resin composition comprising 10 to 90% by weight of a diallyl phthalate prepolymer and 90 to 10% by weight of a terminal allyl oligomer. 2. Thermosetting resin consisting of 10 to 90% by weight of a diallyl phthalate prepolymer, 90 to 10% by weight of a terminal allyl oligomer, and a reactive vinyl monomer of 1/2 or less of the total weight of these two types. Composition. 3. Thermosetting resin composition consisting of 10 to 90% by weight of diallyl phthalate prepolymer, 90 to 10% by weight of terminal allyl oligomer, and unsaturated polyester resin of 30% or less of the total weight of these two types. thing.