JP5644471B2 - Method for producing phenolic resin molding material - Google Patents

Description

  The present invention relates to a phenol resin composition and a phenol resin molding material.

Phenolic resins are excellent in various points such as heat resistance, strength, and electrical characteristics among thermosetting resins, and are used in various applications such as molding materials, laminates, and various binders. For example, when used as a molding material, the molded product characteristics are generally good, but the strength and toughness may be insufficient.
In order to obtain a molded article having high strength and high heat resistance, modification using a thermoplastic resin is well known. When vinyl acetate and NBR, which are elastomers, are used as the thermoplastic resin, the strength of the molded product is improved, but the heat resistance is greatly reduced because the softening point of the elastomer is low. Therefore, in order to obtain a molded product having high strength and high heat resistance, modification using engineering plastics can be mentioned.
Modification of phenol resin using polyethersulfone as an engineering plastic has been reported. In Patent Document 1, a polyether sulfone modified resin is prepared by a method in which polyether sulfone is melt-mixed in a phenol resin, and in Patent Document 2, a polyether sulfone is dissolved in phenol and reacted with formaldehyde. ing. In both patent documents, the mechanical strength of a molded product is improved by using a modified resin, but no mention is made of the chemical structure of polyethersulfone. In the present invention, paying attention to the structure of polyethersulfone, a further increase in strength is achieved.

JP-A-6-128457 JP-A-8-157692

The present invention has been made to solve such problems of conventional phenolic resin cured products, and its purpose is to provide mechanical strength without deteriorating the moldability and other properties of the phenolic resin. An object of the present invention is to provide a resin composition that provides an excellent molding material.

Such an object is achieved by the following present inventions (1) to (3).
(1) A method for producing a phenol resin molding material obtained by heating and kneading a raw material containing a phenol resin composition, wherein a reaction is performed using a raw material in which polyether sulfone having a hydroxyl group is dissolved in phenols. A method for producing a phenol resin molding material , comprising a step of synthesizing the phenol resin composition .
(2) The manufacturing method of the phenol resin molding material as described in said (1) which contains the said polyether sulfone 1-20 weight% with respect to the said whole phenol resin composition.
(3) The method for producing a phenol resin molding material according to (1) or (2), wherein the polyether sulfone is uniformly dispersed in a phenol resin.

  According to the present invention, the mechanical strength, which is a conventional problem of a cured phenol resin, can be improved, and thus it is useful as a material such as a molding material.

Hereinafter, the phenol resin composition of the present invention will be described.
The phenol resin composition of the present invention is characterized by containing a novolak-type phenol resin and polyethersulfone containing a hydroxyl group as essential components.

Although it does not specifically limit as a novolak type phenol resin used for the phenol resin composition of this invention, In general, what made phenols and aldehydes react using an acidic substance as a catalyst is used preferably. Although it does not specifically limit as phenols used as the raw material of a novolak-type phenol resin, For example, cresol, such as phenol, o-cresol, m-cresol, and p-cresol, 2,3-xylenol, 2,4-xylenol, 2, 5-xylenol, 2,6-xylenol, 3,4-xylenol, xylenol such as 3,5-xylenol, ethylphenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol, isopropylphenol, butylphenol, p -Alkylphenols such as butylphenol such as tert-butylphenol, p-tert-amylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, fluorophenol, chlorophenol, bromophenol, Halogenated phenols such as dephenol, monovalent phenol substitutes such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol, and monovalent phenols such as 1-naphthol and 2-naphthol, resorcin And polyhydric phenols such as alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and dihydroxynaphthalene. Although these can be used individually or in combination of 2 or more types, generally phenol and cresol are often used.

  Next, the aldehydes used as a raw material for the novolak type phenol resin are not particularly limited. For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n- Examples include butyraldehyde, caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, and salicylaldehyde. These can be used alone or in combination of two or more, but usually formaldehydes such as formaldehyde and paraformaldehyde are often used.

  Although it does not specifically limit as reaction molar ratio [F / P] at the time of making the said phenols (P) and aldehydes (F) react, It is preferable to set it as 0.5-0.9. Thereby, a resin having a suitable molecular weight can be synthesized without the resin gelling during the reaction. When the reaction molar ratio is smaller than the lower limit, the amount of unreacted phenols contained in the obtained resin may be increased. Moreover, when reaction molar ratio exceeds the said upper limit, resin may gelatinize depending on reaction conditions.

  Next, as an acidic substance that serves as a catalyst for the novolak-type phenol resin, for example, organic acids such as oxalic acid, mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, paratoluenesulfonic acid, paraphenolsulfonic acid, and the like can be used. it can. Moreover, these can be used individually or in combination of 2 or more types.

The polyether sulfone used in the present invention is a polyether sulfone having a hydroxyl group. Although it does not specifically limit as polyethersulfone which has a hydroxyl group, For example, Sumika Excel 5003PS and 5003P by Sumitomo Chemical Co., Ltd. which are commercial products are mentioned, It can use individually or in combination. Compared with polyethersulfone having no hydroxyl group, having a hydroxyl group improves the affinity with the phenol resin and improves the mechanical strength of the resulting molded product.

The polyether sulfone used in the present invention is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight, based on the total phenol resin composition. If the amount of polyethersulfone is below the lower limit value, the effect of polyethersulfone cannot be exhibited, so the mechanical properties of the molded product cannot be improved, and if the upper limit value is exceeded, the curability decreases, This is because the molding material is poorly cured and the molded product has poor appearance and dimensional accuracy.

The phenol resin composition of the present invention comprises a polyether sulfone and a novolac type phenol resin, but it is preferable to uniformly disperse the phenol resin composition. Uniform dispersion means that it is completely compatible with the novolac type phenolic resin, and the mechanical strength of the molded product is improved as compared with the material dispersed non-uniformly.

In the present invention, a method for producing a phenol resin composition in which polyether sulfone is uniformly dispersed in a phenol resin is not particularly limited. For example, a reaction is performed using a raw material in which polyether sulfone is dissolved in phenols, and phenol is obtained. A method of synthesizing a resin composition (hereinafter abbreviated as reaction mixing), a method of melting a novolac-type phenol resin and polyethersulfone to obtain a phenol resin composition (hereinafter abbreviated as melt mixing), a phenol resin and a polyether Examples include a method of dissolving a sulfone in a co-solvent and removing the solvent to obtain a phenol resin composition (hereinafter abbreviated as solution mixing).

As the phenols, aldehydes, reaction molar ratio [F / P], and acidic substance used as a catalyst used in the reaction mixture, the same materials as the respective raw materials described in paragraphs 0008 to 0011 can be used.

  The method of adding polyether sulfone in the melt mixing is not particularly limited. For example, there is a method of melting a novolak type phenol resin and adding polyether sulfone thereto, and a method of adding a polyether sulfone to a novolac type phenol resin and melting it. is there. The melting temperature is preferably 200 ° C to 350 ° C. When the melting temperature is 200 ° C. or lower, polyethersulfone does not melt into the novolac type phenol resin and cannot be uniformly dispersed. When the melting temperature is 350 ° C. or higher, the phenol resin is decomposed.

Although the solvent used for solution mixing is not specifically limited, What is necessary is just a solvent in which a novolak-type phenol resin and polyethersulfone dissolve. For example, nonpolar solvents such as dichloromethane and chloroform, polar solvents such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, phenol, o-cresol, m-cresol And cresols such as p-cresol. These can be used alone or in combination of two or more, but usually dichloromethane, N, N-dimethylformamide and phenol are often used.

In the phenolic resin molding material of the present invention, the content of the phenolic resin composition of the present invention is not particularly limited, but when hexamethylenetetramine is used, it is 20 to 50% by weight with respect to the entire molding material. Preferably there is. More preferably, it is 30 to 45% by weight. When the content of the phenol resin composition is less than the above lower limit value, it may be difficult to produce a molding material, or the fluidity at the time of molding may be reduced, which may make molding difficult. When the upper limit is exceeded, dimensional changes due to molding shrinkage and post-shrinkage increase, and it may be difficult to maintain a predetermined molded product dimension depending on the type and application of the molded product.

The phenolic resin molding material of the present invention can further contain an inorganic filler. The inorganic filler used in the present invention is not particularly limited. For example, glass fiber, glass bead, carbon fiber, clay, calcium carbonate, talc, aluminum hydroxide, magnesium hydroxide, silica, wollastonite, rock wool, Mica can be used, and these can be used alone or in combination of two or more.

In the molding material of the present invention, the content of the inorganic filler is not particularly limited, but is preferably 45 to 75% by weight, more preferably 50 to 60% by weight with respect to the entire molding material. If the content of the inorganic filler is below the lower limit, dimensional changes due to molding shrinkage and post-shrinkage increase, and depending on the type and use of the molded product, it may be difficult to maintain a predetermined molded product size. is there. Moreover, when the said upper limit is exceeded, since production of a molding material becomes difficult or the fluidity | liquidity at the time of shaping | molding falls, shaping | molding may become difficult.

  In addition to the raw materials described above, a colorant, a release agent, a curing aid, and the like can be blended with the molding material of the present invention as necessary.

  Although the manufacturing method of the phenol resin molding material of this invention is not specifically limited, It knead | mixes and knead | mixes with a power mill etc. the kneaded material heat-melt-kneaded with the pressure kneader, the twin screw extruder, the heating roll, etc. The molding material thus obtained can be applied to any of injection molding, transfer molding, compression molding and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

The raw materials used in the examples and comparative examples are as follows.
(1) Novolac-type phenolic resin A: “PR-HF-3” manufactured by Sumitomo Bakelite Co., Ltd.
(2) Polyethersulfone A: "5003PS" manufactured by Sumitomo Chemical Co., Ltd. (3) Polyethersulfone B: "4800" manufactured by Sumitomo Chemical Co., Ltd. (4) Hexamethylenetetramine: Sumitomo Seika Urotropin (5) Glass fiber: E glass fiber manufactured by Nitto Boseki Co., Ltd. (reference fiber diameter 10 ± 1.5 μm)
(6) Curing aid: Magnesium oxide (7) Release agent: Calcium stearate (8) Colorant: Carbon black

Example 1
After adding 900 parts by weight of novolac-type phenol resin A and 100 parts by weight of polyethersulfone A to a 3 L flask, heating to 230 ° C. and stirring for 1 hour, the contents are taken out and solid phenol resin composition at room temperature. 1000 parts by weight were obtained.

(Example 2)
In Example 1, 1000 parts by weight of a phenolic resin composition was obtained in the same manner as in Example 1 except that 990 parts by weight of the novolak-type phenol resin A and 10 parts by weight of the polyethersulfone A were changed.

Example 3
In Example 1, 1000 parts by weight of a phenolic resin composition was obtained in the same manner as in Example 1 except that 800 parts by weight of the novolac-type phenol resin A and 200 parts by weight of the polyethersulfone A were changed.

Example 4
In Example 1, 1000 parts by weight of a phenol resin composition was obtained in the same manner as in Example 1 except that 995 parts by weight of the novolak type phenol resin A and 5 parts by weight of the polyethersulfone A were changed.

(Example 5)
In Example 1, 1000 parts by weight of a phenolic resin composition was obtained in the same manner as in Example 1 except that 700 parts by weight of the novolac-type phenol resin A and 300 parts by weight of the polyethersulfone A were changed.

(Example 6)
900 parts by weight of powdered novolac-type phenolic resin A and 100 parts by weight of powdered polyethersulfone A were mixed in a laboratory miller (LM-2, manufactured by Osaka Chemical Co., Ltd.), and 975 parts by weight of a phenolic resin composition. Got.

(Comparative Example 1)
In Example 1, 1000 parts by weight of the phenol resin composition was prepared in the same manner as in Example 1 except that the novolac type phenol resin A was changed to 900 parts by weight and the polyether sulfone A was changed to 100 parts by weight of the polyether sulfone B. Obtained.

(Comparative Example 2)
As a phenol resin composition, 1000 parts by weight of novolac type phenol resin A was used.
Next, Table 1 shows these phenol resin compositions, tetramethylenehexamine as a curing agent, glass fiber as a fiber base material, magnesium oxide as a curing aid, calcium stearate as a release agent, and carbon black as a colorant. The mixture was charged at a ratio, melted and kneaded for 3 minutes with a heating roll at 90 ° C., taken out, and pulverized into granules to obtain a molding material.

(Evaluation method)
Using the molding materials obtained in Examples and Comparative Examples, test pieces were produced by transfer molding. The molding conditions were a mold temperature of 175 ° C. and a curing time of 3 minutes.
The obtained test piece was treated in an atmosphere at 180 ° C. for 6 hours, and the bending strength, bending elastic modulus (at room temperature and 150 ° C. when heated), and Charpy impact strength were measured according to JIS K 6911 “General Thermosetting Plastics Test Method”. ”In accordance with the measurement. The results are shown in Table 2.

Examples 1 to 6 are molding materials using the phenolic resin of the present invention. The mechanical strength at room temperature and heat of the molded product obtained from these was better than Comparative Example 1 using polyethersulfone containing no hydroxyl group and Comparative Example 2 containing no polyethersulfone. It was.

The phenol resin molding material of the present invention is a molding material having improved mechanical strength as compared with conventional phenol resin molding materials. For this reason, it can be suitably used for mechanical parts such as automobile parts, general-purpose machine parts, and electric / electronic parts.

Claims (3)

A method for producing a phenol resin molding material obtained by heating and kneading a raw material containing a phenol resin composition,
A method for producing a phenol resin molding material , comprising a step of reacting a raw material obtained by dissolving polyether sulfone having a hydroxyl group in a phenol and synthesizing the phenol resin composition . The manufacturing method of the phenol resin molding material of Claim 1 which contains the said polyether sulfone 1-20 weight% with respect to the said whole phenol resin composition. The method for producing a phenol resin molding material according to claim 1, wherein the polyether sulfone is uniformly dispersed in a phenol resin.