JPH10338795A - Phenol resin molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material capable of manifesting excellent antibacterial activities by formulating a specific proportion of a specific amide-based wax and/or a higher alcohol, and an antibacterial agent with a phenolic resin composition. SOLUTION: This material comprises (A) a phenol resin comprising (i) 100 pts.wt. novolak type phenol resin and (ii) 50-150 pts.wt. organic substrate, and, based on 100 pts.wt. component (i), (B) 0.3-1.5 pts.wt. amide-based wax having 40-80 deg.C melting point and/or (C) 0.1-0.7 pts.wt. higher alcohol having 50-70 deg.C melting point (e.g. stearyl alcohol) and (D) 0.1-2 pts.wt. antimicrobial agent. The component D is preferably the one obtained by using silica, alumina, etc., as the inorganic compound carrier and allowing silver, zinc, copper, etc., to be supported thereon. As the result, the phenol resin molding material good in moldability, hardenability, filling properties, antimicrobial activities, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a phenol which is excellent in moldability, that is, excellent in curability and filling property, and excellent in gloss, paint adhesion and antibacterial property under normal conditions and after long-term boiling, and particularly suitable for compression molding. It is a resin molding material.

[0002]

2. Description of the Related Art Phenolic resin molding materials are used in various fields. However, in the kitchen and lacquerware fields, the phenol resin molding materials are usually used under normal conditions of use and the smoothness and gloss of the molded products after boiling. In particular, properties and paint adhesion are required. In addition, the molding method of molded articles in these fields is
Compression molding is mainly performed regardless of the size of the molded product.
Curability for high cycle and thermal stability for continuous molding are particularly required.

Conventionally, a large amount of an inorganic base material is blended to improve the smoothness and gloss of a molded product, but there are problems such as an increase in specific gravity. In addition, regarding the coating adhesion, when stearic acid is usually used, the amount of the release agent incorporated is reduced and molding is performed, but at the time of molding, the release of the molded product from the mold is poor. In this case, the release agent floats, and the coating film peels off. In addition, in the case of extremely large molded products or molded products with extremely steep side surfaces, the lack of thermal stability reduces the fluidity and makes it difficult to fill the material. Tend to cause poor blistering. In addition, phenolic resins used in the kitchen field and lacquerware base field have been given antibacterial properties in view of the problem of food poisoning in the summer of 1996, and the demand has been increasing.

[0004]

SUMMARY OF THE INVENTION The present invention has been made as a result of various studies to solve problems such as low antibacterial properties, and aims at smoothness, glossiness, and the like.
An object of the present invention is to provide a molding material having excellent antibacterial properties without lowering coating adhesion and curability.

[0005]

According to the present invention, an organic base material 50 to 100 parts by weight of a novolak type phenol resin is used.
A phenol resin composition comprising 150 parts by weight has a melting point of 40 with respect to 100 parts by weight of a novolak type phenol resin.
0.3 to 1.5 parts by weight of an amide wax having a melting point of 50 to 70 ° C.
It is a phenolic resin molding material characterized by being mixed with 0.1 to 2 parts by weight of an antibacterial agent.

The novolak-type phenolic resin of the present invention preferably has a ratio of ortho to para bonds in the methylene bond bonded to the phenol nucleus of from 0.7 to 1.0.
And a ratio of ortho-bonds to para-bonds of novolak-type phenol resin (a) having a number average molecular weight of 700 to 950 is 1.7 to 2.7, and a number average molecular weight is 850 to 1200.
Of the phenolic resin (b) as a component, and the mixing ratio thereof is preferably 10 to 35 parts by weight of the phenolic resin (b) per 100 parts by weight of the phenolic resin (a). When the number average molecular weight of the phenolic resins (a) and (b) is less than the above range, the melting point of the resin is low, handling is inconvenient, and the curability tends to decrease. If it exceeds the above range, it may not be possible to stably produce the resin. If the phenolic resin (b) is added in an amount of more than 35 parts by weight with respect to 100 parts by weight of the phenolic resin (a), the curability is too fast, and the surface of the molded article tends to be uneven at the time of molding. The molding may be slow and the molding time may be long, and the viscosity of the molding material may be low.

Next, the organic substrate will be described. One of the preferred embodiments of the present invention is that coconut husk powder and / or peach husk powder, which is a 200-mesh whole mesh, is used as an organic base material.
It is characterized by mixing laminating board powder and / or plywood powder which is a whole mesh of 00 mesh, and the compounding ratio is the total amount of the laminating board powder and the plywood powder with respect to 100 parts by weight of the total amount of coconut shell powder and peach powder. 20 to 100 parts by weight are preferred. It is preferable to mix 100 to 300 parts by weight of fir tree powder with respect to 100 parts by weight of coconut husk powder, and if it exceeds 300 parts by weight, the specific gravity becomes heavy, and the viscosity of the molding material becomes low, causing flow unevenness in the appearance of the molded product. Sometimes. If the amount is less than 100 parts by weight, the gloss of the molded product may be reduced.
Laminated powder 80-150 per 100 parts by weight of coconut powder
It is preferable to mix the parts by weight. If the amount exceeds 150 parts by weight, the moldability deteriorates and the smoothness of the appearance of the molded product may be lost. When the amount is less than 80 parts by weight, the smoothness of the molded product is improved, but the glossiness of the molded product may be reduced. The plywood powder is preferably 10 to 60 parts by weight with respect to 100 parts by weight of coconut husk powder. If it exceeds 60 parts by weight, the moldability is improved, but the smoothness and gloss of the appearance of the molded product may be deteriorated.
If the amount is less than 10 parts by weight, moldability such as filling property may be deteriorated.

Next, the release agent will be described. The characteristic feature of the amide wax used in the present invention is that the melting point is 4%.
0 to 80 ° C. Another feature of the higher alcohol is that the melting point is 50 to 70 ° C. These release agents can be used alone, but are preferably used in combination in the present invention. The mixing ratio of the higher alcohol is usually 0.2 to 1.4 with respect to 1 part by weight of the amide wax. Parts by weight. The melting points of the amide wax and the higher alcohol are 0.3 to 1.5 parts by weight of the amide wax and 0.1 parts by weight of the higher alcohol with respect to 100 parts by weight of the phenol resin, respectively.
If the amount of the release agent is less than 0.7 parts by weight, the release from the mold during molding becomes worse, and if the amount is more than 0.7 parts by weight, the mold is stained or the appearance of the molded product and the paintability are impaired. Will be able to In the present invention, examples of the higher alcohol having a melting point of 50 to 70 ° C. include stearyl alcohol, heptadecyl alcohol, and nonadecyl alcohol.

Next, the antibacterial agent will be described. The antibacterial agent used in the present invention preferably uses silica, alumina, zeolite, or the like as an inorganic compound carrier, and carries an antibacterial metal such as silver, zinc, or copper thereon. The average particle size of the antibacterial agent is preferably from 0.1 to 100 μm. Evenly dispersing the antibacterial agent is required to develop the antibacterial effect uniformly on the surface of the molded product, but if the particle size is larger than this, the antibacterial effect decreases and the amount of addition needs to be increased significantly. Not preferred. Such an antibacterial agent is uniformly dispersed in the molding material, and its antibacterial effect is long and stable.

[0010] The phenolic resin molding material of the present invention comprises, as an organic base material, coconut shell powder and / or fir tree powder having a total mesh of 200 mesh, and laminated board powder and / or plywood powder having a total mesh of 100 mesh. . By blending these finely divided organic base materials, the dispersion of the mixture becomes better when the phenolic resin, the organic base material, the release agent and the like are mixed. Further, the organic base material used in the present invention has good impregnation of the phenolic resin, and sufficiently penetrates into the inside of the base material due to its fine particle size. These features improve the smoothness and gloss of the molded article. In addition, even after long-term boiling treatment, the phenol resin sufficiently penetrates the organic base material, and there is substantially no organic base material not impregnated with the phenol resin, so that the organic base material does not swell due to moisture absorption. . For this reason, the smoothness and gloss of the surface of the molded article after the long-term boiling treatment are remarkably improved as compared with the conventional one.

A general phenol resin molding material contains a linear higher fatty acid or an ester wax as a release agent. These release agents have poor compatibility with the phenolic resin, and bleed from the molded article to the surface of the molded article due to moisture in the molded article after molding or by moisture absorption. For this reason, the coating adhesion is deteriorated, and the coating film is peeled off, or the coating material pops out, making it impossible to apply. The amide wax having a melting point of 40 to 80 ° C. and the higher alcohol having a melting point of 50 to 70 ° C. used in the present invention each have a large polarity. Has good compatibility. For this reason, since the release agent does not bleed from the inside of the molded product to the surface of the molded product due to the moisture in the molded product or the moisture due to moisture absorption, it is considered that the coating adhesion is excellent. Further, as described above, the impregnating property of the phenolic resin is improved by blending the fine organic base material,
It is considered that there is no moisture swelling of the organic base material, and therefore, the amount of moisture absorbed in the molded product is small, which is one of the reasons for improving the coating adhesion.

The molding method for obtaining a molded article from the phenolic resin molding material according to the present invention can be applied to any of compression molding, transfer molding, injection molding and the like, and is not limited.

[0013]

EXAMPLES The raw materials and formulations shown in Table 1 were kneaded with a heating roll, and then cooled and pulverized to obtain a novolak-type phenolic resin molding material. The obtained molding material was evaluated for moldability (bulge, filling property), appearance of molded article (normal state, after 2 hours of boiling treatment), coating adhesion (normal state, after 2 hours of boiling treatment), and antibacterial property. The results are shown in the lower column of Table 1.

[0014]

[Table 1] (Note) Novorak resin (a): Ortho bond to para bond ratio of 0.
8, number average molecular weight 800 Novolak resin (b): ortho-to-para bond ratio 2.0,
Number average molecular weight 900

(Measurement Method) (1) Formability: In a mold for bowl molding of about 90 g, a phenol resin molding material was charged into a mold as powder, and
After compression molding under the conditions of 60 ° C./curing time of 70 seconds, blisters and filling properties are visually evaluated. (2) Molded product appearance: In the molded product obtained in (1) above,
The appearance of the molded article under normal conditions and after the boiling for 2 hours is visually evaluated. (3) Coating adhesion: The molded article obtained in the above (1) is coated, and the coating adhesion is evaluated based on the X-cut tape method of JIS K 5400 “Test method for coating film resistance”. (4) Antibacterial property: about φ70 × molded under the conditions of (1) above
Escherichia coli is allowed to stand on a molded article of 2 mm using sterile physiological saline as a medium for 24 hours, and the change in the number of Escherichia coli is evaluated.

[0016]

According to the present invention, the moldability is good,
The resulting molded article has good curability, filling properties, glossiness in normal conditions and after long-term boiling, coating adhesion, and antibacterial properties, and is suitable as an industrial phenolic resin molding material.

Claims (4)

[Claims] 1. A phenolic resin composition comprising 50 to 150 parts by weight of an organic base material per 100 parts by weight of a novolak-type phenolic resin,
0.3 to 1.5 parts by weight of an amide wax having a melting point of 40 to 80 ° C and / or 50 to 70 parts by weight based on 0 part by weight.
A phenolic resin molding material comprising 0.1 to 0.7 parts by weight of a higher alcohol at a temperature of 0.1 ° C. and 0.1 to 2 parts by weight of an antibacterial agent. 2. A novolak-type phenolic resin having a ratio of ortho-bonds to para-bonds in a methylene bond bonded to a phenol nucleus of 0.7 to 1.0 and a number-average molecular weight of 700 to 950. (A) and a novolak-type phenol resin (b) having a ratio of ortho-bond to para-bond of 1.7 to 2.7 and a number average molecular weight of 850 to 1200 as a component; 10 parts by weight of phenolic resin (b)
The phenolic resin molding material according to claim 1, which is blended in an amount of from 35 to 35 parts by weight. 3. An organic base material comprising: coconut shell powder and / or peach powder having a total mesh of 200 mesh, and laminated board powder and / or plywood powder having a total mesh of 100 mesh; The phenolic resin molding material according to claim 1 or 2, wherein the total amount of the laminated board powder and the plywood powder is 20 to 100 parts by weight based on 100 parts by weight of the total amount of the phenolic resin molding material. 4. An antibacterial agent comprising inorganic compound fine particles carrying silver, zinc or copper as an antibacterial metal, and having an average particle size of 1 to 100 μm. Phenolic resin molding material.