JP3176808B2 - Phenolic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder used for obtaining a molded article excellent in heat resistance and toughness, and relates to a phenol resin composition excellent in heat resistance and toughness.

[0002]

2. Description of the Related Art A phenol resin is a material having excellent mechanical properties, electrical properties, adhesiveness, and the like, but a molded article using the phenol resin has a drawback that it is hard and brittle. An elastomer modification method is considered to be effective as a method for improving the brittleness of a phenol resin and increasing its toughness, and many studies have been made. A typical example is carboxy-terminated liquid NBR
There is an elastomer-modified phenol resin modified by (CTBN) or the like. The toughening of the phenolic resin by the modification of the elastomer is manifested by the fact that the phenolic resin in which the elastomer is dissolved and the curing agent are mixed and the phenolic resin is cured, whereby the elastomer phase is separated into spherical phases. This method has the disadvantage that only liquid elastomers can be used because they need to be dissolved in the phenolic resin. In addition, since the phase separation at the time of curing is used, there is a problem that the characteristics of the cured product are greatly changed depending on the type of the curing agent and the curing conditions (temperature, time).
Further, there is a disadvantage that the heat resistance of the phenol resin is greatly impaired by modification with the elastomer.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have focused on elastomers as a compounding agent for improving the toughness of a phenolic resin without deteriorating the heat resistance of the phenolic resin, without reducing the heat resistance of the phenolic resin. As a result of the study, they have found that an ethylene-acrylate copolymer elastomer is excellent as a compounding agent, and have further advanced various studies based on this finding to complete the present invention.

[0004]

SUMMARY OF THE INVENTION The present invention provides an ethylene-
Phenolic copolymer
Phenols and aldehydes
A method for producing a phenolic resin composition
Ethylene-acryl contained in the phenolic resin composition
The content of the acid ester copolymer elastomer is 2 to 50% by weight.
% Of a phenolic resin composition characterized in that
It is about the method. Phenols used for producing the phenolic resin composition of the present invention include phenol, cresol, xylenol, ethylphenol,
There are propyl phenol, catechol, resorcin, hydroquinone, bisphenol A, and other various alkyl phenols, as well as by-products when producing these phenols. These may be used alone or in combination of two or more. Is also good. On the other hand, aldehydes include formaldehyde, paraformaldehyde,
Benzaldehyde and the like can be used.

[0005] Catalysts for the addition condensation reaction of phenols and aldehydes include acids such as oxalic acid, hydrochloric acid and sulfuric acid, metal salts such as zinc acetate, sodium hydroxide and potassium hydroxide, depending on the type of resin. And alkalis such as barium hydroxide and calcium hydroxide, and amines such as ammonia and triethylamine can be used alone or in combination of two or more. In the case of producing a liquid phenol resin, as a solvent, in addition to alcohols such as methanol and ethanol, glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, ethers, esters, ether esters, ketones and the like Various types can be used alone or in combination of two or more types.

On the other hand, the ethylene-acrylate copolymer elastomer used in the present invention is a copolymer elastomer synthesized from ethylene and an acrylate ester typified by methyl acrylate or the like. Those containing a group or the like can also be used. The content of the ethylene-acrylate copolymer elastomer blended in the phenol resin composition is preferably 2 to 50% by weight. When the content of the ethylene-acrylate copolymer elastomer is less than 2% by weight,
The effect of improving the toughness of the phenolic resin composition is small, and if it exceeds 50% by weight, the curability and heat resistance deteriorate.

As a method of blending the ethylene-acrylic ester copolymer elastomer into the phenol resin, a method is used in which the ethylene-acrylic ester copolymer elastomer is dissolved in phenols in advance and then resinified . This
In the method of the above, ethylene-acrylate copolymer
As the stoma dissolves in phenols, the phenol tree
To improve the toughness without impairing the heat resistance of the fat
The object of the present invention appears most effectively. Ethylene-
Acrylic ester copolymer elastomer is dissolved in solvent
You can also use what you have done.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. “Parts” and “%” described herein all indicate “parts by weight” and “% by weight”.

Example 1 A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 1,000 parts of phenol and 100 parts of an ethylene-acrylate copolymer elastomer "Esprene EMA2152" manufactured by Sumitomo Chemical Co., Ltd., and the internal temperature was lowered. After heating to 100 ° C and the elastomer was completely dissolved, the internal temperature was lowered to 60 ° C or less and 37% formalin 63
After charging 0 parts and 20 parts of oxalic acid, the temperature was gradually increased to 95
After the temperature reached ° C, a reflux reaction was performed for 120 minutes. Then
While dehydrating the system under a vacuum of 650 mmHg, the temperature in the system was raised to 190 ° C. to obtain 1180 parts of a novolak-type solid phenol resin having a melting point of 105 ° C. 100 parts of the obtained solid resin and hexamethylenetetramine 1
0 parts were pulverized with a pulverizer to obtain a powdery modified phenol resin.

Example 2 Into the same reactor as in Example 1, 1000 parts of phenol and 300 parts of Baymac G, an ethylene-acrylate copolymer elastomer manufactured by Showa Denko / DuPont, were heated to an internal temperature of 100 ° C. After the elastomer was completely dissolved, the internal temperature was lowered to 60 ° C. or less, 630 parts of 37% formalin and 20 parts of oxalic acid were charged, and the temperature was gradually raised to reach 95 ° C., and the reflux reaction was continued for 120 minutes. went. Next, while dehydrating the system under vacuum of 650 mmHg, the temperature in the system was raised to 190 ° C. to obtain 1350 parts of a novolak type solid phenol resin having a melting point of 115 ° C. 100 parts of the obtained solid resin and 10 parts of hexamethylenetetramine were pulverized with a pulverizer to obtain a powdery modified phenol resin.

Comparative Example 1 A similar reactor as in Example 1 was charged with 1,000 parts of phenol, 630 parts of 37% formalin and 20 parts of oxalic acid, and the temperature was gradually raised to reach 95 ° C. and refluxed for 120 minutes. The reaction was performed. Next, 6
While dehydrating under a vacuum of 50 mmHg, the temperature in the system was raised to 190 ° C. to obtain 1080 parts of a novolak type solid phenol resin having a melting point of 100 ° C. 100 parts of the obtained solid resin and 10 parts of hexamethylenetetramine were pulverized with a pulverizer to obtain a powdery unmodified phenol resin.

Comparative Example 2 In a reactor similar to that of Example 1, 1000 parts of phenol and "HICAR CTBN 130" manufactured by BF Goodrich Co. as carboxy-terminal liquid NBR were used.
0x8 "300 parts, 630 parts of 37% formalin and oxalic acid 2
After charging 0 parts, the temperature was gradually raised and the reflux reaction was carried out for 120 minutes after the internal temperature reached 95 ° C. Next, 650 m inside the system
While dehydrating under a vacuum of mHg, the temperature in the system was reduced to 19
The temperature was raised to 0 ° C. to obtain 1400 parts of a novolak type solid phenol resin having a melting point of 95 ° C. Obtained solid resin 1
00 parts and 10 parts of hexamethylenetetramine were pulverized by a pulverizer to obtain a powdery modified phenol resin.

The powdered resins obtained from the above Examples and Comparative Examples were blended in the following proportions and melt-mixed in a kneader to obtain a molding material. (Mixing) Resin 1000 parts Glass fiber 350 parts Clay 150 parts

The above molding material is molded at a molding pressure of 280 kg / c.
Heat molding was performed at m ² and a molding temperature of 165 ° C. to obtain a molded product.
Table 1 shows characteristic values of the obtained four types of molded articles. The test method is as follows. Bending strength JIS K 7203 Charpy impact strength JIS K 7111

(Table 1) ────────────────────────────────── Example 1 Example 2 Comparative Example 1 Comparative Example 2 曲 げ Room temperature bending strength (MPa) 236 230 232 218 200 ° C Hot bending strength (MPa) 173 171 173 120 Charpy impact strength (kJ / m ² ) 7.2 7.8 6.5 7.3 ──────────────── ──────────────────

As is clear from Table 1, when the powdered resin composition obtained in the example is used, a molded article having excellent heat resistance and toughness can be obtained.

[0017]

The phenolic resin composition of the present invention is excellent in heat resistance and toughness. For example, a molding material, an organic fiber binder, a rubber compounding agent, a grinding stone binder, an inorganic fiber binder, an electronic A product having excellent heat resistance and toughness can be obtained by using it for a component coating agent, a resin for a laminate, a binder for a sliding member, and the like.

Claims (1)

(57) [Claims] 1. An ethylene-acrylate copolymer copolymer
Dissolve the lastmer in phenols in advance and then
Phenolic resin group that reacts phenols and aldehydes
A method of manufacturing a formed product, ethylene contained in the phenolic resin composition - method for producing a phenolic resin composition content of the ester copolymer elastomer acrylic acid is characterized in that 2 to 50 wt%.