KR20160001476A - Phenol resin molding material - Google Patents

Abstract

Disclosed is a phenolic resin molding material. The disclosed phenolic resin molding material of the present invention comprises: 10-30 wt% of a novolac-type phenolic resin; 25-50 wt% of a resol-type phenolic resin; 5-35 wt% of phenol-cellulose composite powder; and 5-20 wt% of an additive containing a filler. According to the present invention, an amine-based hardening agent is not used in the phenolic resin molding material. Thus, corrosion or damage on a molded product caused by ammonia after molding can be prevented, and durability and heat resistance of the molded product can be improved as well.

Description

{PHENOL RESIN MOLDING MATERIAL}

The present invention relates to a phenolic resin, and more particularly, to a phenolic resin molding material which can be used for phenolic resin molding.

In general, inorganic or organic composite materials such as phenolic resin molding materials are widely used for manufacturing electric and electronic parts having a complicated shape of a minute size by extrusion and injection thermoforming processes.

In the extrusion and injection thermoforming processes, a molding material composed of a resin serving as a binder, an inorganic filler serving as a filler, and a small amount of a plasticizer, a hardener and a release agent is heated to a temperature range near the softening point of the binder resin The molded product is cured by heating the mold temperature at a high temperature so as to fill the mold with a certain shape by a strong pressure by an extrusion or injection method. BACKGROUND ART [0002] With the recent development of the IT industry, such inorganic-organic composite materials have been widely used for various electric and electronic parts such as mobile communication and display.

However, in the conventional method for producing a phenolic resin molding material, since a composite material is produced by simple blending of a phenolic resin and a curing agent, there arises a compatibility problem with an inorganic filler, and since it is difficult to control the dispersibility and the functionality, There is a problem such that severe shrinkage occurs during molding and deformation occurs. Accordingly, it is required to develop a manufacturing technology of a phenol resin molding material capable of manifesting high functionality in accordance with the characteristics of each applicable product for electric and electronic parts, mechanical structure, and household appliances.

In the case of the phenolic resin molding material, an amine-based curing agent is used for the purpose of improving the curing rate. Such amine-based curing agent remains in the molded article after curing, and product corrosion due to ammonia volatilized from the amine- .

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a phenolic resin molding material which does not use an amine curing agent or can reduce the amount thereof.

The phenolic resin molding material according to one embodiment of the present invention comprises 10 to 30% by weight of a novolac phenolic resin, 25 to 50% by weight of a resol-type phenolic resin, 5 to 35% by weight of a phenol- And 5 to 20% by weight of an additive.

According to one embodiment, the novolac phenolic resin has a weight average molecular weight of 3,000 to 10,000.

According to one embodiment, the resolved phenolic resin has a weight average molecular weight of 5,000 to 10,000.

According to one embodiment, the resol type phenol resin is obtained by reacting a phenol compound and an aldehyde compound with at least one selected from the group consisting of manganese acetate, magnesium acetate and zinc acetate in the presence of a catalyst.

According to one embodiment, the phenol-cellulose composite powder is obtained by pulverizing a composite sheet obtained by impregnating a paper with a phenolic resin, followed by curing.

According to one embodiment, the phenol-cellulose composite powder comprises 20 to 30% by weight of a phenolic resin; And 70 to 80% by weight of cellulose.

According to one embodiment, the additive comprises 0.5 to 12% by weight of cotton powder, 0.5 to 3% by weight of calcium hydroxide, 2.5 to 6% by weight of calcium carbonate, 0.1 to 1.5% by weight of zinc stearate and 1 to 2% .

Since the phenolic resin molding material according to the present invention does not use an amine-based curing agent, it is possible to prevent corrosion caused by ammonia or damage of the molded product after molding.

Further, the durability and the heat resistance of the molded product can be improved by using the cotton powder and the phenol-cellulose composite powder.

Hereinafter, the phenolic resin molding material according to the embodiment of the present invention will be described in detail.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Phenolic resin molding material

The phenolic resin molding material according to one embodiment of the present invention includes a novolac phenolic resin, a resol-type phenol resin, a cellulose-phenol composite powder, and an inorganic filler.

The novolac phenolic resin is obtained by reacting a phenol compound and an aldehyde compound in the presence of an acidic catalyst. The novolak type phenol resin has different curing characteristics depending on the ratio of the bonding position of the methylene group or the substituted methylene group derived from the aldehyde compound to the phenolic hydroxyl group of the phenol compound.

The novolak type phenolic resin may be a conventional novolak type phenolic resin which has been conventionally used as a molding material. For example, the novolac phenolic resins have more para-bonds than ortho-bonds. The novolac phenolic resin is advantageous in that it is easy to produce and has high mechanical strength. In one embodiment, the novolac phenolic resin may have an ortho-bond / para-bond ratio of less than 0.2, more preferably less than 0.1.

In another embodiment, the novolac phenolic resin may comprise two or more novolac phenolic resins having different ortho-bond / para-bond ratios. For example, it is possible to use a mixture of a high para-novolak phenolic resin in which para-bonds are more present than an ortho-bond and a hy- oso novolac-type phenol resin in which a para- The hyorthophenol type phenolic resin has an ortho-bonding / para-bonding ratio of 1.0 or more, more preferably 1.0 to 2.5. The hyorthonovolak type phenolic resin has a high curing rate and minimizes the addition of a curing agent, which can shorten the production time of a product during extrusion or injection molding.

For example, the weight average molecular weight of the novolak type phenolic resin may be 3,000 to 10,000.

The content of the novolak type phenolic resin may be about 10 to 30% by weight based on the total weight of the phenolic resin molding material.

The resol-type phenol resin is obtained by reacting a phenol compound and an aldehyde compound in the presence of a metal catalyst. The resol type phenol resin has a hydroxy reactive group and can act as a curing agent to form a crosslinked structure by reacting with the novolak type phenolic resin.

The phenolic compound may include phenol, m-cresol, p-cresol, xylose, and the like. The aldehyde compound may include formaldehyde, paraformaldehyde, and the like. These may be used alone or in combination.

The metal catalyst may include manganese, magnesium, zinc, and the like. Specifically, the metal catalyst may be a metal acetate. For example, the metal catalyst may include manganese acetate, magnesium acetate, zinc acetate, and the like. These may be used alone or in combination.

In the presence of the metal catalyst, the phenol compound reacts with the aldehyde compound. For example, phenol and formalin react with each other to form methylol phenol according to the following reaction formula.

<Reaction Scheme 1>

In the above reaction formula, methylol phenol is obtained. However, this is for the purpose of explanation, and dimethylol phenol, trimethylol phenol and the like can be obtained depending on the reaction conditions and the like. Dimethylolphenol reacts to form 4,4-dihydroxydiphenylmethane (Formula 1), 2,4-dihydroxydiphenylmethane (Formula 2), or 2,2-dihydroxydiphenylmethane (Formula 3) .

&Lt; Formula 1 >

(2)

(3)

The dihydroxyphenyl dimethane is obtained by mixing the compounds of formulas (1) to (3). When a general catalyst (basic catalyst) is used, 2,2-dihydroxydiphenylmethane formed by ortho- To 30% by weight. When the metal catalyst is used, 2,2-dihydroxydiphenylmethane is obtained in a proportion of 60 to 80% by weight, whereby the molecular weight and the curing rate of the final product are .

In order to prepare the resol-type phenol resin, firstly, the aldehyde compound and the phenol compound are mixed in a molar ratio of 1.2 to 1.7. Next, the reaction of the aldehyde compound and the phenol compound is performed by adding the metal catalyst. Through the above reaction, methylolphenol can be formed, and polymerization is carried out therebetween to obtain the resol-type phenol resin. The resol-type phenol resin may have a weight average molecular weight of 5,000 to 10,000.

The content of the resol-type phenol resin may be about 25 to 50% by weight based on the total weight of the phenolic resin molding material.

The cellulose-phenol composite powder may be obtained by impregnating a paper with a phenol resin, and then curing the resultant to crush the composite sheet obtained. The composite sheet may be one that has been recycled from being used as a support in a punching operation of a PCB substrate. The content of the phenol resin in the cellulose-phenol composite powder may be 20 to 30% by weight, and the content of cellulose (paper) may be 70 to 80% by weight.

For example, the particle size of the composite powder may be about 100 탆 or less. Preferably, the particle size of the composite powder may be between about 5 탆 and 100 탆.

The cellulose-phenol composite powder can reinforce the heat resistance of a phenol molded article. The content of the cellulose-phenol composite powder may be about 5 to 35% by weight based on the total weight of the phenolic resin molding material.

The phenolic resin molding material may further include about 5 to 20% by weight of an additive including filler. For example, the phenol resin molding material may be a phenol resin molding material, a phenol resin molding material, a phenol resin molding material, a phenol resin molding material, a phenol resin molding material, a vulcanization accelerator, a vulcanization accelerator, A solvent, and the like.

For example, the phenolic resin molding material may further comprise cotton powder. The above-mentioned cotton powder not only can serve as a filler, but also can improve the strength of a phenol resin molded article. The content of the cotton powder may be about 0.5 to 12% by weight based on the total weight of the phenolic resin molding material. The particle size of the cotton powder may be about 150 탆 or less. Preferably, the particle size of the composite powder may be about 50 탆 to 150 탆. The phenolic resin molding material may include a filler such as talc, glass fiber, wood powder or the like instead of the cotton powder.

The phenolic resin molding material may further comprise calcium hydroxide. Calcium hydroxide can increase the curing reaction of the phenolic resin molding material. The content of the calcium hydroxide may be about 0.5 to 3% by weight based on the total weight of the phenolic resin molding material.

The phenolic resin molding material may further comprise calcium carbonate. The content of the calcium carbonate may be about 2.5 to 6% by weight based on the total weight of the phenolic resin molding material.

The phenolic resin molding material may further comprise zinc stearate. The content of zinc stearate may be about 0.1 to 1.5% by weight based on the total weight of the phenolic resin molding material.

The phenol resin molding material may further include a coloring pigment such as carbon black. The content of the colored pigment may be about 1 to 2% by weight based on the total weight of the phenolic resin molding material.

The phenolic resin molding material can be prepared by the following process. First, each component is mixed. For example, a novolac phenolic resin, a resorcinol phenol resin, a cellulose-phenol composite powder, a cotton powder, a calcium hydroxide, a calcium carbonate, a zinc stearate and a color pigment are put into a vertical mixer and mixed. Preferably, each component is pulverized together or separately before mixing the components.

Next, the mixture is heated and melted while being conveyed through a kneader. The heating temperature may be about 120 ° C to 150 ° C.

Next, the molten mixture is dried to form a fillet shape, and then pulverized to form a powdery phenol resin molding material having an appropriate particle size. The phenolic resin molding material in the form of powder may be mixed again by a vertical mixer or the like, and then manufactured (packaged).

Hereinafter, the phenolic resin molding material of the present invention and its manufacturing method will be described with reference to concrete examples.

Example

According to the following Table 1, each component was put into a vertical mixer and mixed for about 1 hour, and then the mixed materials were melted by heating at about 130 DEG C for about 1 minute while being conveyed through a kneader. The molten composition is dried in the form of a fillet, followed by pulverization in a pulverizer, and the pulverized particles are mixed again in a vertical mixer to obtain a powder-form phenolic resin molding material. The molding material (automobile commutator) And the properties thereof are shown in Table 2.

In the following Table 1, the content of each component is in parts by weight, KC-3750 is a novolac phenolic resin as a product of the applicant (Kangnam Hwaseong Co., Ltd.), KC-5565 is a product of the applicant, to be. Further, in the cellulose-phenol composite powder, the weight ratio of phenol resin to cellulose was 25:75 and the particle size of the powder was about 50 μm. The particle size of the cotton powder was about 100 mu m.

Table 1

Table 2

Referring to Table 2, it can be confirmed that a phenol resin molded article having excellent physical properties can be produced by using the phenol resin molding material of the present invention.

The phenolic resin molding material according to the present invention can be used for manufacturing various electric parts, electronic parts, automobile parts and the like.

Claims (7)

10 to 30% by weight of a novolak type phenolic resin;
25 to 50% by weight of resol type phenolic resin;
5 to 35% by weight of a phenol-cellulose composite powder; And
And 5 to 20% by weight of an additive comprising a filler. The phenolic resin molding material according to claim 1, wherein the novolak type phenol resin has a weight average molecular weight of 3,000 to 10,000. The phenolic resin molding material according to claim 1, wherein the resol-type phenol resin has a weight average molecular weight of 5,000 to 10,000. The phenol resin molding according to claim 3, wherein the resol-type phenol resin is obtained by reacting a phenol compound and an aldehyde compound with at least one selected from the group consisting of manganese acetate, magnesium acetate and zinc acetate in the presence of a catalyst. material. The phenolic resin molding material according to claim 1, wherein the phenol-cellulose composite powder is obtained by pulverizing a composite sheet obtained by impregnating a paper with a phenol resin, followed by curing. 6. The method of claim 5, wherein the phenol-
20 to 30% by weight of a phenolic resin; And
And 70 to 80% by weight of cellulose. The method according to claim 1,
0.5 to 12 wt% of a cotton powder;
0.5 to 3% by weight of calcium hydroxide;
2.5 to 6% by weight of calcium carbonate;
0.1 to 1.5% by weight of zinc stearate; And
And 1 to 2% by weight of carbon black.