JP5703660B2 - Method for producing phenolic resin composition - 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, mechanical strength, and electrical properties among thermosetting resins, and are used in various applications such as molding materials, laminates, and various binders.
However, although the hardened | cured material characteristic of a phenol resin is generally favorable, it may be inadequate in mechanical strength. As a method for imparting mechanical strength to the thermosetting resin, a composite technique with a thermoplastic resin can be mentioned. However, when an elastomer having low heat resistance is combined, the heat resistance is significantly lowered. By using a high heat resistant engineering plastic as the thermoplastic resin, the mechanical strength can be improved without impairing the heat resistance. For example, by controlling the phase separation rate and curing rate so that the curing reaction between epoxy resin and polyethersulfone does not form a clear co-continuous structure or spherical domain structure, the resulting cured product has a pseudo-homogeneous structure. And can improve strength and impact strength (see, for example, Patent Document 1). Patent Document 1 does not describe a combination of a phenol resin and a polyetherimide.

  In Patent Document 1, since the interaction between the epoxy resin and the polyethersulfone is strong, a cured product having a pseudo-compatible structure is obtained without forming a spherical domain structure and a co-continuous structure. However, although it is very fine, it is difficult to say that the characteristics of polyethersulfone are exhibited to the maximum because of phase separation. If a cured product in which the thermoplastic resin is completely compatible, for example, an IPN structure can be imparted to the cured product, it is considered that the properties of the thermoplastic resin can be exhibited to the maximum and further physical properties can be improved.

Japanese Patent No. 3142425

  The present invention was made in order to solve the problem of insufficient toughness while maintaining the heat resistance of a conventional cured phenol resin, and the object of the present invention is the moldability of phenol resin and other An object of the present invention is to provide a phenol resin composition that provides a phenol resin molding material having excellent impact resistance without deteriorating various properties.

Such an object is achieved by the following present inventions (1) to ( 2 ).
(1) A method for producing a phenol resin composition comprising at least an inorganic filler, used in a phenol resin molding material obtained by heating and melt-kneading, and containing a novolac type phenol resin and a polyetherimide, method of preparing the phenolic resin composition, and this to conduct the reaction using a raw material obtained by dissolving the polyetherimide in phenols, also, was dissolved the polyetherimide and the novolac phenolic resins to the co-solvent after manufacturing method of a phenolic resin composition characterized that you remove solvent.
(2) The manufacturing method of the phenol resin composition as described in (1) which contains the said polyetherimide 1-20 weight% with respect to the said phenol resin composition whole.

  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.

In the evaluation of “uniform solubility” in the examples, a test piece is placed on a paper on which characters are written in black, and an example of “◯” in which characters can be observed, that is, uniformly dispersed is shown. In the evaluation of “uniform solubility” in the examples, a test piece is placed on a paper on which characters are written in black, and an example of “x” in which characters cannot be observed, that is, is not uniformly dispersed is shown.

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 novolac type phenol resin and a polyetherimide 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 polyetherimide used in the present invention is not particularly limited, and examples thereof include Ultem1000, Ultem1040, XH6050, and STM1700, which are commercially available products from SABIC Innovative Plastics. Moreover, these can be used individually or in combination. It is preferable that it is 1 to 20 weight% of the whole phenol resin composition of this invention, More preferably, it is 2 to 15 weight%, More preferably, it is 5 to 10 weight%. If the amount of the polyetherimide is below the lower limit, the effect of the polyetherimide is not exhibited, so that the mechanical properties of the molded product cannot be improved. If the upper limit is exceeded, the curability is lowered, and the molding material This is because of the above-mentioned curing failure and poor appearance and dimensional accuracy of the molded product.

The phenol resin composition of the present invention is obtained by uniformly dispersing polyetherimide in a novolac type phenol resin. Uniform dispersion means that it is completely compatible with the phenol resin, and that the phenol resin composition is uniform by visual observation. If the material is dispersed non-uniformly, the mechanical strength of the molded product is significantly reduced.

In the present invention, a method for producing a phenol resin composition in which polyether imide is uniformly dispersed in a novolak type phenol resin is not particularly limited. For example, the reaction is performed using a raw material in which polyether imide is dissolved in phenol, and phenol is obtained. A method for synthesizing a resin composition (hereinafter abbreviated as reaction mixing), a method for obtaining a phenol resin composition by melting a novolak-type phenol resin and polyetherimide (hereinafter abbreviated as melt mixing), a phenol resin and a polyetherimide Is dissolved in a co-solvent, and the solvent is removed 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 for adding the polyetherimide in the melt mixing is not particularly limited. For example, there are a method in which a novolak-type phenol resin is melted and polyetherimide is added thereto, and a method in which a polyetherimide is added to a novolak-type phenol resin and melted. The melting temperature is preferably 200 ° C to 350 ° C. When the melting temperature is 200 ° C. or lower, the polyetherimide 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 polyetherimide 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) Polyetherimide: SABIC Innovative Plastic
(3) Phenol: Wako Pure Chemical Industries, Ltd. (4) Oxalic acid: Wako Pure Chemical Industries, Ltd. (5) Hexamethylenetetramine: Sumitomo Seika Co., Ltd. Urotropin (6) Glass fiber: Nittobo E glass fiber ( (Standard fiber diameter 10 ± 1.5μm)
(7) Curing aid: Magnesium oxide (8) Release agent: Calcium stearate (9) Colorant: Carbon black

(Example 1)
980 parts by weight of novolak-type phenol resin A and 20 parts by weight of polyetherimide were charged into a 3 L flask, heated to 230 ° C. and stirred for 1 hour, and then the contents were taken out to obtain 1000 parts by weight of a phenol resin composition solid at room temperature. It was.
The obtained composition, tetramethylenehexamine as a curing agent, aramid fiber as a fiber base material, magnesium oxide as a curing aid, calcium stearate as a release agent, and carbon black as a colorant are charged in a blending ratio shown in Table 2, The mixture was melt kneaded for 3 minutes with a heating roll at 90 ° C. and then taken out and pulverized into granules to obtain a molding material.

(Example 2)
In Example 1, 1000 parts by weight of a phenol 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 polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Example 3)
In Example 1, 995 parts by weight of a phenol resin composition was obtained in the same manner as in Example 1 except that 950 parts by weight of the novolak-type phenol resin A and 50 parts by weight of the polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

Example 4
In Example 1, 995 parts by weight of a phenol resin composition was obtained in the same manner as in Example 1 except that 920 parts by weight of the novolak-type phenol resin A and 80 parts by weight of the polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Example 5)
In Example 1, 995 parts by weight of a phenolic resin composition was obtained in the same manner as in Example 1 except that 900 parts by weight of the novolak type phenol resin A and 100 parts by weight of the polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Example 6)
In Example 1, 990 parts by weight of a phenol resin composition was obtained in the same manner as in Example 1 except that 800 parts by weight of the novolak-type phenol resin A and 200 parts by weight of the polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Example 7)
980 parts by weight of phenol and 20 parts by weight of polyetherimide were placed in a 3 L flask and heated to 100 ° C. After dissolution, 10 parts by weight of oxalic acid was added, 560 parts by weight of 37% formaldehyde aqueous solution was added (F / P ratio = 0.66), and the mixture was refluxed for 1 hour. Then, normal pressure removal of water and vacuum removal were performed, and when the resin temperature reached 180 ° C., the reaction was terminated, and the contents were taken out to obtain 870 parts by weight of a phenol resin composition. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Example 8)
980 parts by weight of novolac type phenol resin A, 20 parts by weight of polyetherimide, and 2000 parts by weight of phenol were placed in a 5 L flask and heated to 100 ° C. to dissolve. Thereafter, phenol was removed in vacuum, and heating was terminated when the resin temperature reached 180 ° C., and the contents were taken out to obtain 1000 parts by weight of a phenol resin composition. A molding material was obtained in the same manner as in Example 1 using this resin composition.

Example 9
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 polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Example 10)
In Example 1, 980 parts by weight of a phenol resin composition was obtained in the same manner as in Example 1 except that 700 parts by weight of the novolak-type phenol resin A and 300 parts by weight of the polyetherimide were changed. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Comparative Example 1)
As a phenol resin composition, 1000 parts by weight of novolac type phenol resin A was used. A molding material was obtained in the same manner as in Example 1 using this resin composition.

(Comparative Example 2)
980 parts by weight of powdered novolac-type phenol resin A and 20 parts by weight of powdered polyetherimide resin are mixed in a lab miller (manufactured by Osaka Chemical Co., Ltd., LM-2) (hereinafter abbreviated as pulverized and mixed) to obtain a phenol resin composition. 990 parts by weight of the product was obtained. A molding material was obtained in the same manner as in Example 1 using this resin composition.

Note to table: Measurement method
Uniform solubility: The phenol resin composition was placed in an arbitrary container with a smooth bottom, heated at a temperature of 150 ° C. for 1 hour, and then cooled to room temperature to obtain a material. A test piece having a flat thickness surface was prepared by cutting and polishing the material so as to have a thickness of 4.0 mm. The test piece was placed on a paper with black letters written, and if the letters were observable, “◯” was indicated as being uniformly dispersed, and if not observable, “○” was indicated.

(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 3.

Examples 1 to 8 are molding materials using the phenolic resin of the present invention, and the mechanical strength at room temperature and heat of molded products obtained therefrom is 0.5% by weight and 30% by weight for polyetherimide. The results were better than the mechanical strength of the molded articles obtained from Comparative Examples 1 and 2 and Comparative Example 3 containing no polyetherimide, and Comparative Example in which uniform dispersion was not achieved by pulverization and mixing.

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 (2)

A method for producing a phenol resin composition comprising at least an inorganic filler, used in a phenol resin molding material obtained by heating and melt-kneading, and containing a novolac type phenol resin and a polyetherimide,
Method of preparing the phenolic resin composition, and this to conduct the reaction using a raw material obtained by dissolving the polyetherimide in phenols, also, was dissolved the polyetherimide and the novolac phenolic resins to the co-solvent after manufacturing method of a phenolic resin composition characterized that you remove solvent. The manufacturing method of the phenol resin composition of Claim 1 which contains the said polyetherimide 1-20 weight% with respect to the said whole phenol resin composition.