JPS6181461A - Modification of cured resin - Google Patents

Abstract

PURPOSE:To improve the heat-resistance and chemical resistance, etc. of a hardly crosslinkable resin, by compounding the resin with a crosslinkable polymer or a crosslinkable monomer, and crosslinking the mixture by radiation. CONSTITUTION:(A) 10-90pts. (wt.) of a hardly crosslinkable resin (e.g. polystyrene) os compounded with (B) 1-50pts. of a crosslinkable mixture composed of (B1) a crosslinkable polymer (e.g. 1,2-polybutadiene) and/or (B2) a crosslinkable monomer (e.g. ester acrylate) at a ratio (B1/B2) of <=20 and (C) 0.1'n30pts. of an initiator (e.g. benzoin, benzyl, etc.). A molded article produced from said composition is irradiated with beta-ray, gamma-ray, etc. at a dose of 5-70 Mrad.

Description

Detailed Description of the Invention [Technical Field] This invention relates to the improvement of cured resins that improve the heat resistance, chemical resistance, etc. of cured products of resins that do not or are difficult to crosslink, that is, hard-to-crosslink resins. Regarding quality law.

[Background technology]

In recent years, various resins with excellent heat resistance and chemical resistance have been developed. However, in general, thermoplastic resins and the like inherently have low heat resistance, so it is desired to improve this property.

One way to meet these demands is to crosslink resins. Modification of cured resin products by crosslinking is an effective and reliable means. However, depending on the type of resin, it may not be possible to cure the resin using simple treatments such as those used for ordinary thermosetting resins, so in such cases, special catalysts may be used or However, there are limits to what can be done, and it cannot be said to be a general method.

[Purpose of the invention]

In view of the above circumstances, it is an object of the present invention to provide a method for modifying a cured resin product that is versatile and capable of easily and reliably modifying even a hard-to-crosslink cured resin product. shall be.

[Disclosure of the invention]

In order to achieve such an object, the present invention provides a cured resin product in which a crosslinkable polymer and/or a crosslinkable monomer is blended with a hard-to-crosslink resin, and if necessary, an initiator is blended, and the resulting cured resin is crosslinked by radiation. The main point is the modification method.

That is, the hard-to-crosslink resin cured product is improved by crosslinking the hard-to-crosslink resin with a crosslinkable polymer or a crosslinkable monomer by radiation. This will be explained in detail below.

Examples of the hardly crosslinkable resin used in this invention include polystyrene, polyphenylene sulfide,
Polysulfone, polyethersulfone, SB resin, SB
S resin, ABS resin, polyetherimide, polybutylene terephthalate.

Examples include polyethylene terephthalate and aromatic polyester. However, it is not limited to these.

Next, examples of crosslinkable polymers include 1.2 polybutadiene, 1.4 polybutadiene, styrene butadiene copolymer, modified 1, 2 polybutadiene (maleic modified, acrylic modified, epoxy modified), rubbers, etc. It is not particularly limited to these. In addition, examples of crosslinking monomers include (i) ester acrylates;

Acrylic acids such as epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, etc. polyfunctional monomers, ■monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, and polyvaramethylstyrene;
(2) Examples include, but are not limited to, polyfunctional epoxies.

Initiators include benzoin, benzyl, allyldiazonium fluorophosphate, benzyl methyl ketal, 2.
2-Jethoxyacetophenone.

Benzoyl isobutyl ether, p-tert-butyltrichloroacetophenone, benzyl (〇-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, benzophenone, Michler's ketone, tetramethylthiuram sulfide, azobisisobutyronitrile,
Benzoyl peroxide, di-tert-butyl peroxide, l-hydroxycyclohexylphenyl nide, 2-hydroxy-2-methyl-1-phenyl-
Propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,
2-chlorothioxanthone, methyl benzoyl formate 4.4-bisdimethylaminohensiphenone (Michler's ketone), benzoin methyl ether, methyl-
Examples include 〇-henzoylbenzoate α-aziroxime ester. A preferred commercially available initiator is ``Biscumil'' manufactured by NOF Corporation, which is prepared by the following formula. This product has a 1-fraction reduction temperature of 330°C.

CH3Cl-13 The ratio of the above raw materials to be blended is not particularly limited, but the crosslinkable polymer and/or crosslinkable top layer is mixed with 10 to 90 parts by weight (hereinafter abbreviated as parts) of the hardly crosslinked resin. Preferably, the proportion is from 1 to 50 parts, and the proportion of the initiator is from 0.1 to 3 parts. Furthermore, the ratio of the crosslinkable polymer to the crosslinkable monomer is not particularly limited, but
It is preferable that the amount of crosslinkable polymer is 20 or less per 1 of crosslinkable monomer.

A method for obtaining a resin composition by blending the above-mentioned raw materials is usually a method of blending or solution mixing. Blend is 260
Preferably it is carried out at a temperature of -300°C. The means used for blending is not limited, and examples include a Banbury mixer, a single-screw or twin-screw extruder, and a heating kneader. The kneading time in these devices is usually about 2 to 15 minutes. However, the kneading time is not limited to this.

The resulting resin composition is molded into a plate, film, or sheet using injection molding.

Extrusion molding method, transfer molding method, direct pressure molding method, etc.
Any method is fine. It may also be molded using a casting method.

In order to cause radiation crosslinking to the resin molded product obtained as described above, this composition must be exposed to β-rays, γ-rays, etc.
70 Mr a d, preferably 25-60 Mr a d
Just irradiate it. However, since the radiation dose varies somewhat depending on the resin composition, etc., it is not limited to the above range.

Note that before and/or after this radiation irradiation, the molded product may be auxiliary heated or the molded product may be irradiated with ultraviolet rays. In that case, the heating time, heating temperature, and amount of ultraviolet irradiation are appropriately selected.

Examples will be described below along with comparative examples.

The resin compositions obtained with the formulations shown in Table 1 were heated and kneaded at the temperatures listed in Table 1, and molded into a sheet. This sheet-like material has γ
The physical properties of the cured resin obtained by irradiating the resin with 30 Mr ad of radiation are as shown in Table 1.

As shown in the table, all of the Examples had improved physical properties compared to the Comparative Examples.

(Left below) In Table 1, PS stands for polysulfone, PSt stands for polystyrene, PBT stands for polybutylene terephthalate, and PBu stands for polysulfone.
is polybutadiene, DAP is diallylphthalate,
TAIG is triallylisocyanurate, TMPT is trimethylolpropane trimethacrylate, DCP
and dicumyl peroxide respectively.

〔Effect of the invention〕

The present invention can reliably improve the physical properties of various hard-to-crosslink resin cured products using the simple method described above.

Agent Patent Attorney Takehiko Matsumoto Procedural Amendment (Viewed on 2nd and 3rd IO, 1981, Relationship with the case of the person making the amendment Patent Applicant Address 1048 Kadoma, Kadoma City, Osaka Name (583) Matsushita Electric Works Co., Ltd. Representative Iku Kobayashi 4, No agent 6, Specification subject to amendment 7, Contents of amendment + 11 The entire text of the specification is corrected as shown in the attached sheet (including amendments to the name) .

Description 1, Name of the invention, Method for modifying solidified resin material 2, Claims (111i) A crosslinkable polymer and/or a crosslinkable monomer is blended with a crosslinkable resin, and an initiator is blended as necessary. A method for modifying resin-based materials by crosslinking them with radiation.

(2) 1 to 50 parts by weight of crosslinkable polymer and/or crosslinkable monomer to 10 to 90 parts by weight of hardly crosslinkable resin (however, crosslinkable polymer/crosslinkable monomer≦20) and 0 initiator
．． A method for modifying a hemostatic resin according to claim 1, wherein 1 to 31 parts by weight are blended.

3. Detailed Description of the Invention [Technical Field] The present invention relates to a modification of a solidified resin that improves the heat resistance, chemical resistance, etc. of a solidified resin of a resin that does not undergo crosslinking or is difficult to crosslink, that is, a hard-to-crosslink resin. Regarding quality law.

[Background technology]

In recent years, various resins with excellent heat resistance and chemical resistance have been developed. However, in general, thermoplastic resins and the like inherently have low heat resistance, so it is desired to improve this property.

One way to meet these demands is to crosslink resins. Modification of a solidified resin product by crosslinking is an effective and reliable means. However, depending on the type of resin, it may not be possible to crosslink (cure) it by the simple treatment used for ordinary thermosetting resins, so in such cases, special catalysts may be used. There are some things that can be done, but there are limits to what can be done, and it cannot be said to be a general method.

[Purpose of the invention]

In view of the above circumstances, it is an object of the present invention to provide a widely versatile method for modifying solidified resins, which can easily and reliably modify even hard-to-crosslink resin solidified products. shall be.

[Disclosure of the invention]

In order to achieve such an object, the present invention provides a solidified resin product in which a crosslinkable polymer and/or a crosslinkable monomer is blended with a hard-to-crosslink resin, and an initiator is blended as necessary, and the product is crosslinked by radiation. The main topic is the reforming method. That is, the hard-to-crosslink resin is mixed with a cross-linkable polymer or a cross-linkable monomer and subjected to radiation crosslinking to improve the hard-to-crosslink resin solidified product. This will be explained in detail below.

Examples of the hardly crosslinkable resin used in this invention include polystyrene, polyphenylene sulfide,
Polysulfone, polyethersulfone, SB resin, SB
Examples include S resin, ABS resin, polyetherimide, polybutylene terephthalate, polyethylene terephthalate, and aromatic polyester. However, it is not limited to these.

Next, examples of crosslinkable polymers include, but are not limited to, 1.2 polybutadiene, 1.
．． 4 polybutadiene, styrene-butadiene copolymer, modified 1.2 polybutadiene (maleic modification, acrylic modification, epoxy modification).

Examples include rubbers, and examples of polymers with particularly excellent radiation crosslinking properties include polyethylene.

polyvinyl acetate, polyacrylate polybutadiene,
Examples include nylon and polyparamethylstyrene.

Among these, when polyparamethylstyrene is used, a substrate for a laminate with excellent characteristics can be obtained.

In addition, examples of crosslinking monomers include (i) ester acrylates;

Acrylic MIfi such as epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, etc. Examples include polyfunctional monomers, (1) monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, and polyparamethylstyrene, and (2) polyfunctional epoxies, but are not particularly limited to these.

Initiators include benzoin, benzyl, allyldiazonium fluorophosphate, benzyl methyl ketal, 2.
2-Jethoxyacetophenone.

Benzoylisobutyl ether, p-tert-butyltrichloroacetophenone, benzyl(〇-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, hensifhenone, Michler's ketone, tetramethylthiuram sulfide, azobisisobutyronitrile,
Benzoyl peroxide, di-tert-butyl peroxide, l-hydroxycyclohexylphenyl edone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 2
-chlorothioxanthone, methyl benzoyl formate, 4,4-bisdimethylaminobenzophenone (Michler's ketone), benzoin methyl ether, methyl-0-benzoyl benzoate, α-aziroxime ester f. A preferred commercially available initiator is "Biscumyl" manufactured by NOF, which is prepared by the following formula:
This has a 1-fraction reduction temperature of 330'C.

CH3CHl CH3CH3 The ratio of blending the above raw materials is not particularly limited, but 10 to 90 parts by weight (hereinafter abbreviated as parts) of the hardly crosslinkable resin to 1 part of the crosslinkable polymer and/or crosslinkable monomer. The ratio of the crosslinkable polymer to the crosslinkable monomer is not particularly limited. On the other hand, it is preferable that the crosslinkable polymer is 2o or less.

A method for obtaining a resin composition by blending the above-mentioned raw materials is usually a method of blending or solution mixing. Blend is 260
Preferably it is carried out at a temperature of -300°C. The means used for blending is not limited, but examples include a Banbury mixer, a l-screw or twin-screw extruder, and a heating kneader. The kneading time in these devices is usually about 2 to 15 minutes. However, the kneading time is not limited to this.

The resulting resin composition is molded into a plate, film, or sheet using injection molding.

Extrusion molding method, transfer molding method, direct pressure molding method, etc.
Any method is fine. It may also be molded using a casting method.

In order to cause radiation crosslinking to the resin molded product obtained as described above, this molded product is exposed to β-rays, γ-rays, etc.
70 Mrad, preferably 25-60 Mrad
Just irradiate it. However, since the radiation dose varies somewhat depending on the resin composition, etc., it is not limited to the above range. Note that before and/or after this radiation irradiation, the molded product may be auxiliary heated or the molded product may be irradiated with ultraviolet rays. In that case, the heating time, heating temperature, and amount of ultraviolet irradiation are appropriately selected.

The C1 example will be described below along with a comparative example.

The resin compositions obtained with the formulations shown in Table 1 were heated and kneaded at the temperatures listed in Table 1, and molded into a sheet. This sheet-like material has γ
The physical properties of the resin solidified by 30 Mrad radiation were as shown in Table 1.

As shown in the table, all of the Examples had improved physical properties compared to the Comparative Examples.

(Left below) In Table 1, PS stands for polysulfone, PSt stands for polystyrene, PBT stands for polybutylene terephthalate, and PBu stands for polysulfone.
DAP is polybutadiene, DAP is diallyl phthalate,
TAIC is triallylisocyanurate, TMPT is trimethylolpropane trimecrylate, DCP
and dicumyl peroxide respectively.

〔Effect of the invention〕

The present invention can reliably improve the physical properties of various hard-to-crosslink resin solidified products using the simple method described above.

Claims (1)

[Scope of Claims] 1) A method for modifying a cured resin product by blending a crosslinking polymer and/or a crosslinking monomer with a hard-to-crosslink resin and, if necessary, blending an initiator with the mixture and crosslinking it with radiation. (2) 1 to 50 parts by weight of crosslinkable polymer and/or crosslinkable monomer to 10 to 90 parts by weight of hardly crosslinkable resin (however, crosslinkable polymer/crosslinkable monomer≦20) and 0 initiator
．． The method for modifying a cured resin product according to claim 1, wherein 1 to 3 parts by weight is blended.