JPS5814462B2 - Manufacturing method of phenolic resin molding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a phenolic resin molding material.

Phenol resin molding materials can produce molded products with superior mechanical strength and physical performance when heated compared to thermoplastic resin molding materials.

In recent years, phenolic resin molding materials have been reviewed in order to reduce weight, rationalize manufacturing processes, and reduce costs by replacing metal materials with plastic materials.

In general, phenolic resin molding materials use organic materials such as wood flour and pulses as reinforcing materials and fillers, and inorganic materials such as asbestos, glass fiber, calcium carbonate curcum, and mica.

Among these materials, organic materials such as wood flour and pulp are not used as molding materials for manufacturing substitutes for metal parts that require heat resistance; in such cases, inorganic materials are used.

Although molding materials using inorganic materials can produce molded products with higher heat resistance than molding materials using organic materials such as wood flour and pulp, they are still not satisfactory.

In particular, molded products manufactured from molding materials that use mica alone or in combination with other inorganic substances as a reinforcing material or filler have the disadvantage that they blister when heated, resulting in poor appearance after heating. was there.

As a result of research to eliminate these drawbacks, the inventors discovered that when Myroku is subjected to pressurization and shear processing together with a resin liquid, blistering caused by heating of the molded product can be suppressed.

However, in this case, when the raw material for molding material is passed through heating rolls etc. to make molding material, instead of toluene and styrene, which have problems in terms of hygiene and pollution costs,
The use of low molecular weight plasticizers such as water or methanol has caused problems with adhesion to the rolls.

In addition, although the resulting molding material had considerably improved heat resistance, it was not fully satisfactory.

As a result of further research, the inventors found that using one or both of a boric acid compound and a zinc compound causes adhesion problems even when using the above-mentioned force and using methanol or water as a plasticizer. The present invention was completed by discovering that the heat resistance can be further improved without causing any damage.

That is, the present invention is a method for producing a phenolic resin molding material using a phenolic resin, a reinforcing material/filler, and a plasticizer, in which at least one of a boric acid compound and a zinc compound is pressurized together with a resin liquid. The gist of this method is to use mica that has been subjected to shear processing and a low molecular weight plasticizer.

Next, this invention will be explained in detail.

This invention uses mica that has been subjected to pressure and shear processing along with a resin liquid.

Such mica is produced by pressurizing and shearing it together with a resin liquid of resol resin, polyester resin, or novolak resin that is compatible with the phenol resin in the molding material.

Here, as the resin liquid, such as liquid resol resin,
Although it is preferable to use a resin that is itself liquid, it is also possible to use a solid resin dissolved in an organic solvent such as methanol, styrene, or toluene, or a liquid resin diluted with an organic solvent. You can also use things.

The amount of such resin liquid to be used is such that the resin content in the resin liquid is 0.1 parts by weight (hereinafter abbreviated as "parts") of mica.
From the viewpoint of effectiveness, it is preferable to select the amount to be 20.0 parts, more preferably 0.3 to 10.0 parts.

The pressurization and shearing treatments are usually performed by passing the resin liquid together with the resin liquid between two rotating rolls.

By doing this, the mica is peeled off and the resin liquid permeates into the peeled surface.

However, the treatment method is not limited to this, and any method may be used as long as the resin liquid can be infiltrated or applied to the peeled surface of the mica.

The boric acid compounds used with mica that has been subjected to pressure and shear pressure treatment as described above are boric acid (orthoboric acid,
Metaboric acid, tetraboric acid), boric acid condensate (intermediate process from boric acid to boron oxide (B203)), and boron oxide alone or as a mixture.

Furthermore, the term "zinc compound" refers to zinc hydroxide, zinc oxide, basic zinc carbonate, etc. alone or as a mixture, and stearin, which has traditionally been used as a lubricant, does not have the effect of improving the heat resistance of molded products. It does not include zinc oxide.

When using a boric acid compound, the weight ratio of the boric acid compound to the phenol resin is 0.5 to 15.0 (
(hereinafter abbreviated as "%").

That is, the greatest effect can be obtained by selecting the amount of the boric acid compound to be used within the above range.

Moreover, when using a zinc compound, it is preferable to choose so that a zinc compound may be 0.5-20.0% with respect to phenol resin.

That is, the effect is maximized by selecting the content of the zinc compound within the above range.

In addition, when using both together, the usage amount is determined suitably with reference to the said value.

Examples of low molecular weight plasticizers include water, methanol, etc., which may be used alone or in combination.

However, it is not limited to this, it is cheap, sanitary,
Any material can be used as long as it does not cause pollution problems.

When producing a phenol resin using the above raw materials, it is carried out, for example, as follows.

That is, one or both of a boric acid compound and a zinc compound and mica that has been pressurized and sheared together with a resin liquid (hereinafter referred to as "pressurized and sheared mica") are combined with a phenolic resin, a hardening agent, and other It is manufactured by mixing with additives, adding a low molecular weight plasticizer to the mixture, and applying it to heated rolls.

In this case, due to the action of one or both of the boric acid compound and the zinc compound, no adhesion to the heating roll occurs and the production is extremely smooth.

The phenolic ridge molding material thus obtained has extremely high heat resistance.

That is, the phenolic resin molding material obtained in this way can be used to produce a molded article whose heat resistance temperature according to JIS appearance after heating is 70 to 100° C. higher than that of molded articles made of conventional mica-containing molding materials.

Next, examples will be described together with comparative examples.

Example 1 15 parts of a methanol solution in which 3 parts of resol resin synthesized using ordinary phenol and formaldehyde were dissolved,
It was added uniformly to 100 parts of mica (manufactured by Kurera Corporation, sudurite mica, 20 mesh) and mixed.

Next, the mixture was passed between two rotating rolls (roll spacing: 0.3 mm, rotation: constant speed (15 times/min)) at room temperature.

This operation was repeated 10 times to obtain a pressurized and sheared material.

Next, this mica and the following raw materials were blended in the following proportions.

Phenol resin: 100 parts Hexamine: 15 parts Pressure, shearing: 150 parts Treated mica stearic acid-gnesium 2 parts Orthoboric acid
Next, add 10 parts of methanol as a low molecular weight plasticizer to this.
A processed material was obtained by adding 50% of the mixture and processing in the usual manner using a heated roll.

Example 2 Water was used as a low molecular weight plasticizer.

A molding material was obtained in the same manner as in Example 1 except for the above.

Example 3 Instead of a methanol solution containing 3 parts of resol resin as a resin liquid, 15 parts of an acetone solution containing 2 parts of polyester resin was used.

A molding material was obtained in the same manner as in Example 1 except for the above.

Example 4 Pressurized and sheared mica treated in the same manner as in Example 1 and the following raw materials were blended in the following proportions.

A molding material was obtained in the same manner as in Example 1 except for the above.

Phenol resin: 100 parts Hexamine: 15 parts Pressure, shear processing: 100 parts treated mica Glass fiber: 50 parts stearic acid -Gnesium: 2 parts Orthoboric acid: 5 parts Example 5 Metaboric acid was used instead of orthoboric acid.

A molding material was obtained in the same manner as in Example 1 except for the above.

Example 6 Oxidized boric acid was used in place of orthoboric acid.

A molding material was obtained in the same manner as in Example 1 except for the above.

Example 7 Zinc hydroxide was used in place of orthoboric acid.

A molding material was obtained in the same manner as in Example 1 except for the above.

Example 8 Water was used as a low molecular weight plasticizer.

A molding material was obtained in the same manner as in Example 7 except for this.

Example 9 Instead of a methanol solution containing 3 parts of resol resin as the resin liquid, 15 parts of an acetone solution containing 2 parts of polyester resin was used.

Other than that, a molding material was obtained by straining in the same manner as in Example 7.

Example 10 The pressurized and sheared Myroku processed in the same manner as in Example 1 and the following raw materials were blended in the following proportions.

A molding material was obtained in the same manner as in Example 1 except for the above.

Phenol resin: 100 parts Hexamine: 15 parts Pressure, shearing: 100 parts Treated mica glass fiber: 50 parts Stearic acid-gnesium 2 parts Zinc hydroxide
Part 5 Example 11 Zinc oxide was used in place of zinc hydroxide.

A molding material was obtained in the same manner as in Example 7 except for this.

Example 12 Basic zinc carbonate was used in place of zinc hydroxide.

A molding material was obtained in the same manner as in Example 7 except for this.

Comparative Example 1 Using ordinary mica (untreated mica) that was not subjected to pressure or shear processing, this mica and the following raw materials were blended in the following proportions.

Phenol resin: 100 parts Hexamine: 15 parts Untreated mica: 150 parts Stearic acid: 2 parts For each magnesium, add 1 part methanol as a low molecular weight plasticizer.
A molding material was obtained by adding 0 parts and processing in the usual manner using a heating roll.

Comparative Example 2 Untreated mica was used in place of pressurized and sheared mica.

A molding material was obtained in the same manner as in Example 1 except for the above.

Comparative Example 3 A resol resin-dissolved methanol solution was not added to the mica, and only the mica was passed between two rotating rolls.

Then, a molding material was obtained in the same manner as in Example 1 using this force.

Comparative Example 4 In the same manner as in Example 1, a resol resin-dissolved methanol solution was uniformly added to mica and mixed.

Then, this product was used as it was without passing it between two rotating rolls.

A molding material was obtained in the same manner as in Example 1 except for the above.

Comparative example 5 We stopped using orthoboric acid.

A molding material was obtained in the same manner as in Example 1 except for the above.

Comparative example 6 Calcium hydroxide was used in place of orthoboric acid.

A molding material was obtained in the same manner as in Example 1 except for the above.

The molding materials obtained in the above Examples and Comparative Examples were directly pressure molded in the usual manner, and the molded products obtained were evaluated according to JI
The heat resistance temperature and the manufacturability of S in molding material were investigated based on the appearance after heating.

The results are shown in the table below.

Claims (1)

[Claims] 1. A method for producing a phenolic resin molding material using a phenolic resin, a reinforcing material/filler, and a plasticizer, the method comprising at least one of a boric acid compound and a zinc compound as the reinforcing material/filler. A resin solution of at least one of a resol resin, a polyester resin, and a novolak resin that is compatible with the phenol resin is used, as well as mica that has been subjected to pressurized and shear processing, and a low molecular weight plasticizer is used as a plasticizer. A method for producing a phenolic resin molding material. 2. The method for producing a phenolic resin molding material according to claim 1, wherein the boric acid compound is at least one compound selected from the group consisting of boric acid, boric acid condensates, and boric oxide. 3. The method for producing a phenolic resin molding material according to claim 1, wherein the zinc compound is at least one compound selected from the group consisting of zinc hydroxide, zinc oxide, and basic zinc carbonate. 4. The method for producing a phenolic resin molding material according to claim 1, wherein the low molecular plasticizer is at least one of water and methanol. 5 Mica that has been pressurized and sheared together with resin liquid,
5. The method for producing a phenolic resin molding material according to any one of claims 1 to 4, which is obtained by passing a resin liquid together with a force between two rotating rolls. 6. The method for producing a phenolic resin molding material according to any one of claims 1 to 5, wherein the resin liquid is a liquid resol resin.