JPS59135246A - Highly impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent flexural strength and resistance to impact and heat, by blending a specified diallyl terephthalate copolymer with a diallyl phthalate resin. CONSTITUTION:A dially terephthalate of formula I and an arom. hydrocarbon contg. at least one H at the benzyl position and having formula II (wherein R<1>, R<2> are H, lower alkyl; n is 1-3) are copolymerized in the presence of an org. peroxide or an azo compd. to obtain a diallyl terephthalate copolymer (B) having an iodine value of 40-85, a true specific gravity of 1.20-1.25 (30 deg.C), a softening point of 50-120 deg.C, a viscosity of 80-300cPs in 50% methyl ethyl ketone soln. (30 deg.C), a number-average MW of 4,000-10,000 in terms of polystyrene and a weight-average MW of 70,000-200,000. A diallyl phthalate resin (A) having a number-average MW of 2,000-20,000 is blended with 1-90wt% component B.

Description

[Detailed description of the invention] The present invention relates to a resin composition having particularly excellent impact resistance.

More specifically, the present invention provides a diallyl phthalate resin containing terephthalic acid diallyl ester and the following formula (I) (wherein R1 and R2 are each selected from the group consisting of a hydrogen atom and a lower alkyl group). T
L=an integer of 1 to 3. The present invention relates to a highly impact-resistant resin composition characterized by blending a copolymer of an aromatic hydrocarbon having at least one hydrogen atom at the benzylic position represented by the following formula.

Conventionally, Diary-based resin Sea 1-based resin has excellent mechanical properties such as dimensional stability and rigidity under heat, and electrical properties, and has been widely used in fields that require high reliability. , the resin is brittle and has insufficient toughness, and in recent years, as the amount of molding has become smaller, the molding and shape of the resin has increased, +N
,,1. ．． .

Part 2) Cracks and chips on small protrusions occur.The problem with □ is thick. . . , 111:'-,
,-.

Formulated with the aim of overcoming this technical hurdle.

Diaryl phthalate through improved technology and polymer blends
Many proposals have been made to improve the i-kickness of 1-based resins. For example, reinforcement with fillers such as glass fiber,
A method of modifying with flexible polyester or rubber-like polymer is known. However, all of these methods do not impair the excellent properties of the siali-based resin Sea 1~-based resin, and despite the fact that the first publication was ``f\J'', the purpose was It's hard to say that I've achieved this yet.

For example, in the above-mentioned filler-based method, it is necessary to leave the long fiber filler in the molded product, but this requires a kneading method and a molding method.

In addition, the above-mentioned method of modifying with polymers, etc. has great limitations in terms of dimensional stability,
Usually, any one of heat resistance, moisture resistance, mechanical strength, electrical properties, and moldability is unduly reduced. In this way, the conventionally proposed methods have reached their limits of improvement.
I'm satisfied. In order to achieve improvements (311), the current situation is that much cannot be expected from the previously proposed methods.

On the other hand, polybutylene ethylene terephthalate +-'<'p B-
The progress of thermoplastic resins, starting with R> and polyphenylene nalphide (PPS), has been remarkable, and resins with excellent heat resistance and electrical properties, as well as polymerization technology, have been developed. If so, C could be adopted in a wide range of fields, including fields where thermosetting resins are used. However, since it is only a heat sink, there are troubles due to creep due to the heat resistance of the deformed stone, especially when used for a long period of time under high temperature and high humidity.
There is no cure or resin.

The present inventors conducted various tests with the aim of improving the properties of such dinofuryl phthalate i-based resins. ) at least 1 at the benzylic position
When blending a copolymer consisting of an aromatic hydrocarbon having hydrogen atoms (hereinafter referred to as terephthalic acid di-allyl ester copolymer), the inherently favorable properties of the diallylphthalate h-based resin will be lost in any way. It has been found that the brittleness, which has conventionally been a drawback of the resin, is significantly improved, and a resin composition having a high tV shock value can be obtained. Furthermore, by blending the copolymer, the heat resistance of diallyl orthophthalate resins, which were conventionally considered to be inferior to diallyl phthalate resins; It was also discovered at the same time that the bending strength of Resin Sea 1-based resins was significantly improved compared to conventional resins.

The diaryl resin Sea 1-based resin used in the present invention refers to the polymerization of the ortho, iso, and tele monomers of diallylphthale=1-resin, and usually has a number average molecular weight of 2,000 to 20. .000, solvent-soluble, heat-fusible, post-polymerizable sialyl phthalate brebolymer having an allyl group in the molecule alone, or reacting with the bripoly7- /or unsatiable I [1
A general term for mixtures with polynisdel.

Examples of the above-mentioned reactive osseous heptads include diallylnotare 1-heptadymers consisting of ortho, iso, and tele isomers, styrene heptamers such as subuurene, and α-talolosmethine;
To methyl (meth)acryle-j~, butyl (meth)acryle-1-, ethylene glycol di(meth)acrylate, prepylene glycol di(meth)acryle-1, ]
Examples include acrylic acid-L ster type monomers such as 1-pan-1-di(meth)acrylate. It is preferable that the amount of the reactive hexamer is 70% by weight or less based on the total resin content of the composition of the present invention. If the content exceeds 70% by weight, undesirable effects such as an undue delay in the curing speed and an increase in the internal distortion of the molded product due to an increase in the curing shrinkage rate will occur. For example, by a conventional method using a polybasic unsaturated acid such as maleic acid or fumaric acid, a polybasic saturated acid such as phthalic anhydride, isophthalic acid, or terephthalic acid, and a polyhydric alcohol such as diethylene glycol or propylene glycol. There are products that have an acid value of 5 to 100 culm and are viscous and liquid at room temperature, and solids that have a softening point of 150° C. or less. The amount of unsaturated polynisder added is preferably 80% by weight or less based on the total resin content of the composition of the present invention. If the amount exceeds 80% by weight, the properties of the conventional diallyl phthalate resin will be deteriorated and the moisture resistance of the obtained molded product will be lowered, which is not preferable.

The terephthalic acid diallyl ester copolymer blended into the composition of the present invention is a 7j polymer newly developed by the present applicant, and is composed of prephthalic acid diallyl ester and the following formula (
an aromatic hydrocarbon represented by I);
A copolymer obtained by polymerization in the presence of an azo compound. In the present invention, ( is particularly preferable as a modification site that gives a high impact value to a terephthalic acid diallyl ester copolymer or composition as described below. Namely, the following formula (I>) However, in the above formula (I), R1 and R2 each represent a base selected from the group consisting of a hydrogen atom and a lower alkyl group, and are integers of 11-1 to 3.

A copolymer of an aromatic hydrocarbon having at least one hydrogen atom at the benzylic position represented by the following formula (II) and a terephthalic acid diallyl ester represented by the following formula (II), the copolymer having the following formula (II): One monomer unit has a structure in which one carbon-carbon bond of formula (I) is formed at the end of one monomer unit.
Ru. Furthermore, (+1>, the number of monomer units of formula (I) in the carbon-carbon bond molecular chain portion formed by the allyl group of one unit of formula (I) IE non of the copolymer is 3 to 11, preferably It is a copolymer having a structural feature of 3 to 10 atoms.

The structure of the copolymer may be, for example, a compound of formula (I) such as 1 to
When expressed in the Iζ case using luene (R'=R2=1-1, TL=1), it is expressed by the following formula (III).

(χ-3~11) In the above formula (]III, R represents an unreacted allyl group and/
Or -Q (represents 2-0(-12-) derived from the allyl group constituting the molecular chain portion of the copolymer. Examples of such embodiments include the following: formula(
IV) -[,+(2-Q(--Q(2-Of-)).

In addition, in the structural part of the above formula (I), the formula (■) of the carbon-carbon bond molecular chain part formed by the allyl group in the middle of the monomer is 3 to 11 as shown in formula (I[), but this carbon-carbon bond molecular chain portion has a head-to-tail bond shown in formula (II[), that is, in addition to the following formula (V), It can have a head-custom bond moiety as shown in formula (VI) below.

One unit of the formula (I) monomer in the above structural subformula (TI7) connects two formulas (V) and (V
It constitutes a branching point that connects the structural parts of I).

In addition, when R is an unreacted allyl group, the following formula % Formula % The above formula (V[l) structural part (Y) is a part that becomes a crosslinking point during curing of the terephthalic acid diallyl ester copolymer.

The terephthalic acid diallyl ester copolymer used in the present invention is preferably a copolymer having the following properties.

(C) Iodine value 40 due to the enactment of the Rice (Wijs) Act
~85°(d) True specific gravity at 30°C is 1.20~1.25(e
) Softening range to 50/approximately 120°C.

(f) 50% methyl ethyl solution viscosity 80-30
0 centiboise (30℃).

(o) The polystyrene equivalent number average molecular group (day TL) measured by GPC (gel permeation chroma 1-graphie) method is 4,000 to 10,000, and the weight average molecular m (Rw) is 70,000 to 200. .00Or,
In addition, the ratio of plTL to 8W is MIV/8'', where the molecular weight distribution expressed as TI is 10 to 40° (h), and the Brabender melt viscosity measured with a Brabender plastograph is 250 to 2.
600m-Q, processing time 5-65 minutes.

In producing the terephthalic acid diallyl ester copolymer of the present invention, the aromatic hydrocarbon of formula (I), which is a raw material monomer, and the prephthalic acid diallyl ester of formula (II) are combined in the presence of an organic peroxide or an azo compound catalyst. Preferably, in the presence of structures (a) and (b) and (C) to 1
It is produced by carrying out a copolymerization reaction by setting reaction conditions to obtain a copolymer having the properties listed in 1).

R1 and R2 of the aromatic hydrocarbon in the above formula (I) are each selected from the group consisting of a hydrogen atom and a lower alkyl group, and examples of the lower alkyl group include C1 to C5 alkyl groups. Examples of such compounds of formula (I) include, for example, toluene, edylbenzene, 9-propylbenzene, isopropylbenzene, 1-butylbenzene, isoamylbenzene, 5eC-butylbenzene, 1-amylbenzene, 5eC- amylbenzene, isoamylbenzene, 2-methylbutyl)-benzene,
O-xylene, m-xylene, p-xylene, xylene isomer mixture, pseudocumene, 1,2-diedylbenzene, 1,3-diedylbenzene, 1,4-diedylbenzene, 1,2-dipropylbenzene, 1,3 -dibu[1-pyrubenzene, 1,4-dipropylbenpine, diisopropylbengenes, p-cymene, 1,2-dibdelbenzene, 1,3-dibdelbenzene, 1,4-dibdelbenzene, 1 .2-Shiicyamylbenzene, 1.3-
Examples include diisoamylbenzene, 1,4-diisoamylbenzene, and 1,2,3-1-rimedylbenzene.

In addition, examples of organic peroxide catalysts and azo compound catalysts include:
The following compounds can be exemplified.

Dialkyl peroxides and diaryl peroxides such as di-tert-butyl peroxide, di-5ec-butyl peroxide, tert-butyl-5ec-butyl peroxide, and dicumyl peroxide.

Sialyl peroxides and diacyl peroxides such as benzoyl peroxide.

Di-tert-butyl persulfate, tert-perbenzoate
- Alkyl esters of percarboxylic acids such as butyl etc. E1
:2.2'-azobisisobutyrodi]helyl, 2,2
--Azohis-(2-methyl)thi[]2[~nor), 2
, 2-Azobis-(2-medylhebutani-1-lyl),
1.1'-Azohis-1-cyclohexylcarbonitrile 2,2'-Azohisisomethyl methyl acetate, 4.4
Azo compounds such as --azobis-(4-cyanopentanoic acid), acibibenzene, etc.; tert-butyl hydroperoxide, sec-butyl human 1] peroxide, te 1-laryl hydroperoxide, cumyl hydroperoxide, benzyl hydroperoxide , benzhydryl hydroperoxide, decalyl hydroperoxide, ・
Hydroperoxides such as acetyl peroxide, cyclohexyl hydroperoxide, and 1-decyl hydroperoxide;・Compounds that are easily oxidized by molecular oxygen, in the present invention, prephthalic acid diallyl ester, and the formula (1) At least 1 in the benzyl position represented
Aromatic hydrocarbons having 5 hydrogen atoms or the small polymer of the present invention 1 are equivalent, but if these are oxidized with air or oxygen in advance or during the copolymerization reaction to produce peroxides, the present invention can be applied. It can be used satisfactorily as a catalyst for cohandy reactions.

Regarding the above-mentioned terephthalic acid diallyl ester copolymer, the patent application filed by the present applicant in 1977-
1 8.9 Detailed information is provided in No. 81.・The composition of the present invention [Za5 1 terephthalic acid cyano].

The blending amount of the ester copolymer is 1% by weight or more, preferably 5% by weight or more, and more preferably 20% by weight or more, based on the resin gold of the diallylphthalate resin and the copolymer. This is preferable in order to improve the impact resistance of the composition.

There is no particular restriction on the upper limit of the amount to be blended, and when heat resistance is particularly required, the blending ratio of the copolymer may be increased. In particular, in order to obtain excellent bending strength when diallyl orthophthalate resin is used, it is preferable to blend the symbiotic polymer in an amount of 2.90% by weight based on the resin content.

As already mentioned, it is often pointed out that conventional diallylphthalate resins lack toughness, and if a molded product is dropped while being handled, it is prone to chips, cracks, and damage to protruding parts such as ribs. When used as a connector for electronic circuits, there have been various complaints in practical use, such as the contact surface with the wiring board being easily damaged and the screw being easily cracked when tapped. Furthermore, in recent years, with the miniaturization of electronic devices and components, for example, the spacing between connector bins has become narrower, and wiring methods using pressure bonding and soldering, which require heat resistance, have become widespread. ,・Although thermoplastic resins have become increasingly popular, thermosetting resins are still often used due to requirements for dimensional stability, heat resistance, creep resistance, etc. Therefore, there has been a strong demand in the industry to improve the toughness and impact resistance of diallylphthale I-based resins.

Conventionally, impact resistance has been compared to Charpy and Iso 1 based on impact resistance, but although these can be used for thick walls, the situation often changes when walls are thin. Therefore, the wood inventors decided to mainly use the drop test using thin plates, taking into account the trend toward smaller products.

As a result of this test, the falling weight impact value of the resin composition of the present invention was approximately 80 m'in at most, while that of the conventional diallylphthalate resin, A composition containing 5% by weight of terephthalic acid diallyl ester copolymer in the resin content reaches about 180 mm, and a composition containing 20% by weight reaches a value similar to that of the copolymer, such as about 90 + nm. It was found to have unexpectedly and significantly improved impact resistance. In addition, the bending strength of diallylphtasy 1-based resin alone and diallyl terephthalate 1 sprue copolymer alone is about 8 kq/
mm2, whereas the latter is about 7 to 9/ml+2,
In the compositions of the present invention, those containing 2 to 90% by weight of terephthalic acid diallyl ester copolymer in the resin content have a bending strength of about 10 to 9/mn12, which is much larger than that of each resin alone. I found out that it shows. Furthermore, when measuring the heat resistance of a molded article made of diallyl orthophthalate resin as its sole resin component by exposing it to an air oven at 200°C and measuring its weight loss, it was found that 10% of the initial weight decreased in 260 to 288 hours. However, in the present invention,
For the above-mentioned resin containing 20% diallyl terephthalate 1 sprue copolymer, the time required to reduce the initial weight by 10% is about 1000 hours, and the copolymer
It was found that those containing % by weight showed a remarkable effect of improving heat resistance, requiring about 1600 hours.

In this way, the composition of the present invention is similar to conventional diallylphthalate.
It has significantly improved the brittleness that was considered a drawback of 1-based resins, and in addition has improved bending strength and heat resistance.
It exhibits characteristic properties such as dimensional stability, chemical resistance, moisture resistance, electrical properties, etc., which are considered to be excellent characteristics of conventional Diary-based resin Sea 1-based resins.

In addition, it has excellent molding processability and curing speed comparable to conventional diallylphthalate-1 resins.

As the curing agent of the present defense composition, peroxides commonly used in diallyl phthalate resins, such as dicumyl peroxylide, tertiary butyl perbenzye-1, benzoyl peroxyl node, etc., can be used as is. be done. The appropriate blending amount is 0.1 to 6% based on the resin content.

The composition of the present invention may contain as desired, as in the case of conventional diallyl phthalate resin compositions, such as fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, etc.
Pigments, flame release agents, and other additives can be blended within a range that does not impair the properties of the composition to improve the physical properties of the molded product.

Examples of fillers that can be used include inorganic and/or organic fillers, and these can be used singly or in combination. The amount used is based on the weight of the resin.
Examples include amounts of about 1 to about 300% by weight.

Specific examples of these fillers include talc, mineral fillers, ashest, glass powder, silica, clay, shirasu, titanium oxide, magnesium oxide,
rAM calcium, alumina, asbestos fiber, silica fiber, glass 48 hlt, silicate glass fiber, alumina 1lli fiber, carbon fiber, boron fiber, beryllium fiber, steel fiber, whisker, etc.; Examples of organic fillers include cellulose, etc. Examples include natural fibers, pulp, acrylic 41m, polyester fibers such as polyethylene terephthalate 1, cotton, rayon, vinylon, and the like.

Examples of polymerization accelerators include metal stones such as cobalt salts, vanadium salts, and mankan salts of naphthenic acid or Al-1-technical acid (plums, aromatic tertiary amines such as dimedylaniline, and cyedylaniline). Examples include:

The usage ω is approximately 0.0% based on the heavy use of the resin of the present invention.
Examples include amounts such as 0.005% to about 6% by weight.

Furthermore, examples of polymerization-inhibiting IL agents include quinones such as p-henzoquinone and nano-1-quinone, polyhydric phenols such as hydroquinone, D-tert-butylcatechol, hydroquinone monomethyl ether, and p-cresol; Examples include quaternary ammonium salts such as trimethylammonium. The amount of potato to be used is, for example, about 0', O'O'1 to about 0.1% by weight based on the weight of the resin of the present invention.
Examples of Q include metal salts of stearic acid such as stearic acid calciudate, stearic acid 1', and magnesium stearate. The amount used is about 0.1 to about 5% based on the weight of the resin of the present invention.
In addition, examples of coupling agents and □L'U can be traced to indicate the i column of r-methacryloxypropyl 1 to rimeallyl h rimethoxysilane, etc. Tegiru. The amount used can be 1J based on a single woody resin, for example, about 0, 1 to about 3 times 196 times. '□Face)'
For example, pigments such as carbon black, iron black, cadmi yellow, benzidine yellow, cadmi orange, pen color, cadmi red, copal h blue, anthraquinone puru] are exemplified in one row of 31. The amount used is approximately "0" per 1 coat of Komyo Resin.
．． Examples of flame retardants include andymon oxide; inorganic compounds such as aluminum hydroxide; tris(chloroedyl) phosphate; - Tsu O knee 3 - U D. A., Length) Approximately 7. -11, □ Phosphorous compounds such as polyphosphoric acid and ammonium, chlorinated paraffins, diary) ref [ ] rendates, etc., □ decaproic acid and nil 1
Among the diallylphthalate resins, there are known red ones such as bromine compounds such as Nithyl, de-1-rathromo anhydride and lataric acid. The formulation m is C based on the weight of the resin of the present invention.
A suitable range is from about 1% to about 30%. □ is a method for molding the composition of the present invention.
The same known molding methods and molding conditions as those for =-type resins can be used as they are.In other words, the casting method involves injecting the composition of the present invention into a mold and hardening it, and heating the composition to form a fluidized state. The composition is placed in a mold and cured by heating under pressure, such as the extrusion molding method or the transfer molding method. A laminate, a molding method, a fine powder or a solution of the composition, which is dissolved in a solvent, impregnated into a fibrous sheet, dried and, if necessary, under pressure conditions, cures the resin in the fibrous sheet. Examples of forming methods include a coating method in which the composition is applied to a substrate and cured on the substrate, and a decorative board forming method in which a printing paper or the like is impregnated with the composition solution and, after drying, is cured by heating and pressing on the substrate. . During molding, the heating temperature for curing is approximately 12
Examples include temperatures such as 0 to about 190°C. In addition, when using pressurized conditions, the pressure is about 5 to about 1000 k.
An example may be a pressure such as g'/cnt.

The composition of the present invention can be used for molding in a wide range of fields as listed below.

For example, connectors, motor commutators, governors, coil bobbins, 1 relays, switches, terminal boards, ignitions, breakers, ukes, 1 binders for learning resistors, printed helding, typed parts, and Element sealing material; Coil encapsulation and other light electrical insulation (Aa'4, etc.) in the electrical and electronic fields, such as ・Plus deck brake □-key screws 1- and others: Category: For example, tableware and other utensils Category: For example, disinfection with chemicals or steam is required.
It is used for W as a molding material in one field.

Furthermore, the composition is impregnated or coated on a fibrous sheet such as paper, non-woven fabric, glass cloth, etc. in the presence or absence of a solvent, and applied to wood, paper, metal, and other inorganic substrates. Press and cure, but pre-cured materials can be pasted on the moon and plated with a decorative board for construction materials such as platform scales, furniture, interiors, sharpening nets, Meigetsu equipment, axles, and ship interiors. It is useful for wood and other fields.Also, if the composition is directly impregnated into wood and cured, it becomes a wood-plastic composite (so-called wPc), which can be used as flooring materials, edge decks, roof decks, and architectural structural materials. It can be used in fields such as sports equipment, etc., and can be used as a laminated board made of 3 immersed and laminated sheets of rough, glass cloth, etc., in fields that require high bulk and opening ↑ at high humidity, for example. , terminal play 1-, rotating machine related fields such as motor wedges, insulation collars, slot armors, coil separators, etc., tough 1-piece,
It is useful for stationary related fields such as Vari ~7~, terminal play ~1~, operation boards, panels such as switchboards, printed wiring boards, variable condenser insulation supports, etc., and is also useful for temperature and
Fields that require excellent mowing stability and good mechanical strength even under severe humidity changes, such as laser dome/millimeter blades, rocket nozzles, air ducts for diene machines, etc. In addition, areas that require chemical resistance such as parts of various chemical devices, fields that require toughness, rust resistance, and mechanical strength such as antennas, skis, ski poles, fishing rods, etc. Other paints, molding materials for other resins, hot stamping resins, UV curing inks, lenses and other optical applications such as phase 4 and A, glass fibers, carbon fibers, navy blue binders, light, electron beams. Or resin for resist film in Ringerafite using X-rays, etc.
It can be used for a wide range of purposes.

A more detailed explanation will be given below with reference to Examples.

Production example 1 of prephthalic acid diallyl ester copolymer? Internal diameter 600mm with Tahin vane type variable stirrer, 7-tube and double tube feed nozzle for catalyst feed, nitrogen persil, leak valve, sampling port, temperature gauge and pressure gauge.
A polymerization tank made of 5US304 with di(-kerato) having a content of 112Of2 was used.

The double-tube supply nozzle for monomer and catalyst supply is placed below the liquid level in the body of the polymerization layer, and the inner diameter of the outer tube is 1.5 mm before entering the polymerization tank. 2fi inside
The f residence time was made as short as possible. In preparation for nozzle blockage, use 311 such nozzles! ! I installed it. A nitrogen gas tank was also installed in the body of the polymerization tank, and the internal pressure during the polymerization reaction was used to collect the liquid phase.An oil rotary vacuum pump and a nitrogen cylinder were connected to the nitrogen tank. and can be switched as needed.

Eotcg of the formula (I,) aromatic hydrocarbon (+-j C) shown in Table 1 below was added to the above polymerization tank, and the mixture was heated at room temperature.
The operation of reducing the pressure with a vacuum pump and returning it to normal pressure with slag was repeated three times to replace the air in the tank with nitrogen, and then the pressure was reduced again and the polymerization tank was sealed. Start the stirrer 2
4. , while stirring with ORP M, steam was passed through the jacket and the temperature was raised to 140°C.

The stirring speed was set to 20 PPM, and terephthalic acid diallyl ester was added at a predetermined rate from the outer tube of the double tube nozzle, and at the same time, perfermented di-te,r-t-butyl (
[)T'E3PO) and formula (1) aromatic hydrocarbon (T'E3PO)
C) were mixed in advance at a molar ratio of 0, 5:, 1 at a predetermined speed, and the discharge pressure was 7Q kq/ol.
was supplied to the polymerization tank using a pump. During this time, the steam was adjusted so that the temperature of the polymerization tank was maintained at 140°C. The formula to be supplied <In) terephthalic acid diallyl ester (1)
AT) was cooled to 15°C, the mixture of di-tert-butyl peroxide aroma and pre-hydrocarbon was cooled to 5°C, and the piping leading to the polymerization tank was kept cold.

The polymerization tank pressure was 0.3 to 2 M/cn (Q).

Once the supply of a predetermined amount of sialyl terephthalate, aromatic hydrocarbon, and di-tert-butyl peroxide is completed,
- Stop the steam, reduce the stirring speed to 24 ORPM, and cool by passing cooling water through the jacket. After cooling down to around room temperature, open the leak valve and return to normal pressure.
The polymerization reaction was completed.

During the polymerization reaction, samples were taken from the sampling port and the reaction was monitored by refractive index and GPC.

The feed rates and amounts of diallyl terephthalate, aromatic hydrocarbon, and tert-butyl peroxide are shown in Table 1 below.

The volatile components of the polymerization reaction solution obtained above were distilled off using a thin film evaporator, and the unreacted aromatic hydrocarbons in the evaporation residue were removed.
Combination of copolymer and unreacted terephthalic acid diallyl ester
The ratio of 1 to 1 was set to 0.3:1 by weight, and then the evaporated residue was stirred while being dropped into a stirring tank containing 5 times the weight of methanol of the supplied diallyl terephthalate. - was precipitated. The precipitated copolymer was thoroughly washed with the same amount of methanol, filtered, dried, and pulverized to obtain a powdery copolymer.

Table 1 shows the yield and physical properties of the copolymer.

Table 1 In Table 1 above, (1) is the measured value of Gel Permeation Cloa 1 to borisdylene converted by the graph method, manufactured by Waters "1".
I used a 50CGPCJ mounting.

For (2), an rPF61J light transmission automatic melting point measuring device manufactured by Hattler was used.

(3) is a measurement value using Flabender Plastograph manufactured by Rei Brabender (Germany).

Kneading chamber capacity 50cc, rotor model W 5011, sample 5
0g + zinc stearate 0.5g, kneading temperature 130
°C, rotor rotation speed 22RPMT: kneading resistance 5000
Continue until mg is reached, and from the 1-lux curve of the recording paper,
The lowest torque value was defined as the Brabender melt viscosity, and the time from the end of sample loading to 5000 Ill (] was defined as the processing time.

Examples 1 to 8 Comparative Examples 1 to 6 After adding 2 parts by weight of dicumyl peroxide to each composition shown in Table 2 and mixing well, roll kneading (front roll 90~
After 100°C1 [ ] - 60-80°C, kneading time 6 minutes)
This was crushed to form Comparan 1 by using a Henshi 1 Lumikir.

Take 20 to 30 g of the above compound, make a disk-shaped tablet with a diameter of 501 m and a thickness of 10 mm using a manual press using a mold, preheat it to about 80'C with a high-frequency preheater, and immediately heat it to the specified temperature. The temperature of the mold for compression molding, which had been adjusted to the temperature of
After molding for 1 minute, a disc-shaped molded product with a diameter of about 100 mm and a thickness of 21 volumes is 1 q.

The molded product was subjected to a general test method according to JISK-6911, a hammer impact test method according to JISK-7211, and a heat resistance test, and the results are shown in Table 2.

In addition, among the physical properties of the molded products in Table 2, the falling impact value and heat resistance were measured by the following methods.

Falling Weight Impact Test Thirty-six Des 1 pieces were cut out from two molded products using a tie A7 Mondo cutter and subjected to measurement.

The testing machine used was a DuPont falling ball tester (500g load, flat support, 1/2 inch impact center), and the Dixon mode method was used to determine the 50% fracture height □Reference: JISK -7211),.

Heat Resistance Test Three molded products were left in a constant temperature bath at 150° C. for 2 hours and then allowed to cool in a desiccator.

The initial weight of each molded product test piece was measured, and then the test pieces were left in a constant temperature bath adjusted to 200±2°C for an appropriate period of time. The samples were allowed to cool in a desiccator and their weights were measured. At this time, if the average value of the reduction of the working area of the three test pieces does not reach 10% of the initial value,
Again, these test pieces were left in a constant temperature bath at 2Q'0 ± 2°C for an appropriate period of time, and the mold weight reduction was determined again. The heat resistance was evaluated based on the time required for this test.

Examples 9 to 10 Comparative Examples 7 and -8 Using each resin U compound of Example 1.3 and Comparative Example 1.6 or the resin alone, about 1 kg of a full compound consisting of the compound of -C1-F was prepared as follows. Eight rounds were made using the H method.

Compound resin 100 width m part dicumyl peroxide () 1~2 rr Hyde [J quinone
0.01 Horn methacryloxysilane OLG
=l Calcium stearate 2 JJ crow short fiber * 60CI Charcoal n'J 73 /L/ Shira L, 40 r) *7
In the above formulation manufactured by Asahi Fiberglass Co., Ltd., dicumyl peroxide, hydroquinone J5 and methacryloxysilane were added together with the resin.
The solution was dissolved in 500 q of water and zeuged. This was charged into a crusher with a capacity of 13R, and then calcium stearate and calcium carbonate, which had been well mixed together, were placed on the table for about 5 minutes. Short glass fibers were then added, and the mixture was mixed for another 10 minutes.
ζ. This was left for one day and night to volatilize the residual acetone, and then kneaded for about 10 minutes with a front roll at 100°C and a rear roll at 90°C. The compound taken out in the form of a sheet from the roll was pulverized in a Ferri mill equipped with a screen of 2 mm in diameter to obtain a granicol-like compound.

Each compound was molded in the same manner as in Examples 1 to 8, and the physical properties were tested. The results are shown in Table 3.

Table 3 *Total time until weight loss reaches 5.1% of initial weight 361-

Claims (1)

[Scope of Claims] A highly impact-resistant resin composition characterized by blending a diallylphthalate-1 resin with the following terephthalic acid diallyl ester copolymer. The above terephthalic acid diallyl ester copolymer is a copolymer of terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position represented by the following formula. However, in the above formula, R1 and R2 each represents a group selected from II' consisting of a hydrogen atom and a lower alkyl group, and TL is an integer of 1 to 3.