KR101243755B1 - Fast curable phenol moulding compound for compressive or injection moulding with low ammonia volatile content after thermal hardness and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a resin comprising: (i) a novolak-type phenolic resin (a) and a high ortho novolak-type phenolic resin (b) having an ortho-bonding / para-bonding ratio of at least 1.0. bookbinder; And ii) a phenolic resin molding material comprising an inorganic filler, i) a high ortho novolac having a novolak type phenolic resin (a) and an ortho-bonding / para-bonding ratio of at least 1.0. Mixing a type phenol resin (b) to form a resin binder; Ii) mixing an inorganic filler with the resin binder to form a mixture; Iii) kneading the mixture by heat treatment; And iii) cooling to room temperature and then coarsely pulverizing. According to the present invention, it is possible to shorten the curing time without increasing the amount of the curing agent, thereby facilitating the manufacturing process and mass production, and to obtain a final finished product having a fast curing speed and minimizing ammonia volatilization after curing.

Description

FAST CURABLE PHENOL MOULDING COMPOUND FOR COMPRESSIVE OR INJECTION MOULDING WITH LOW AMMONIA VOLATILE CONTENT AFTER THERMAL HARDNESS AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a molding material for extrusion or injection molding, and in particular, the curing time is short, the molding time is shortened, the mass productivity is improved, and the minimization of the curing agent minimizes ammonia volatilization, thereby preventing corrosion of adjacent materials or parts. The present invention relates to a minimized fast curing phenolic resin molding material and a method for producing the same.

The extrusion and injection thermoforming process is performed by heating a molding material consisting of a resin serving as a binder, an inorganic filler serving as a filler, and a small amount of a plasticizer, a curing agent and a release agent to a temperature range of approximately 100 to 200 ° C. near the softening point of the binder resin. After making the fluidity, it is pushed into the mold of a certain shape so as to fill every corner with a strong pressure by extrusion or injection method, and the final temperature is made by curing the molding material by heating the mold temperature in the range of 150 ~ 250 ℃. You lose. By using the extrusion and injection thermoforming process, if the molded material containing the resin binder is thermoformed to complete curing, the product can be easily mass-produced in a complicated shape, and thus the application range is very wide. . Particularly, with the development of the IT industry in recent years, the use of injection molding materials in various parts for mobile communication has been widely used.

The curing process in extrusion and injection molding using a molding material containing a conventional resin binder proceeds by promoting the polycondensation reaction between the aromatic compounds of the resin binder as the amine-based curing agent contained in the molding material is decomposed by heat. The rate of cure is then proportional to the amount of hardener added. Therefore, in order to accelerate the production of products or parts by extrusion or injection, a method of shortening the curing rate by increasing the amount of the curing agent used has been used. However, in the case of using a curing agent whose main amine is mainstream, a small amount of ammonia (NH ₄ ) is continuously volatilized at room temperature even after curing is completed by thermoforming. Volatilized ammonia reacts with water vapor or -OH in the air to form nitric acid (HNO ₃ ), which causes corrosion of adjacent parts or materials, leading to product defects and shortened life. In particular, thermosetting molded parts used in mobile communication, which are composed of complex electronic circuits, are easily corroded even with a small amount of ammonia volatilization.

In order to shorten the curing time while reducing the amount of the curing agent, curing is performed using a high ortho phenol resin binder which has a nonuniform molecular structure instead of the conventional general phenol resin binder and has a high curing speed. The manufacturing technique to be described is described in Japanese Patent Laid-Open No. 194-345940. In addition, a method of promoting the curing reaction and enhancing the strength by adding an organopolysiloxane to an existing general phenol resin binder is disclosed in Japanese Patent Laid-Open No. 1994-459.

However, in the case of a method of shortening the curing time by simply replacing the existing general phenolic resin binder with a high ortho phenolic resin binder as described above, the curing is completed in a high temperature kneading process near 150 ° C after mixing and blending in the manufacturing process. As it is not demoulded or discharged to the equipment, it is difficult to control the process due to difficulties in the manufacturing process. In addition, when organopolysiloxane is added to an existing general phenol resin binder and used, there is a problem in that the viscosity is maintained and the molding material in powder state cannot be produced.

The present invention is to solve the problems of the prior art as described above, it is possible to shorten the curing time without increasing the amount of the addition of the curing agent, the manufacturing process is easy and mass production is possible, the curing speed is fast and the final ammonia volatilization is minimized after curing An object of the present invention is to provide a molding material for extrusion molding or injection molding, and a method for producing the same, from which a finished product can be obtained.

One embodiment of the present invention for achieving the above object is iii) a high ortho furnace having a novolak-type phenol resin (a), and an ortho-bond / para-bond ratio of 1.0 or more. A resin binder composed of a ballac phenol resin (b); And ii) an phenol resin molding material containing an inorganic filler.

In addition, another embodiment of the present invention is a high ortho novolak-type phenolic resin having a novolak-type phenolic resin (a) and an ortho-bonding / para-bonding ratio of 1.0 or more (b) mixing to form a resin binder; Ii) mixing an inorganic filler with the resin binder to form a mixture; Iii) kneading the mixture by heat treatment; And iii) cooling to room temperature and then coarsely pulverizing.

Since the molding material according to the present invention has a fast curing speed during extrusion or injection molding without additional addition of a curing agent, it is possible to mass-produce a thermosetting molded article having a precise shape by reducing the working speed once.

In addition, by minimizing the addition of the amine-based curing agent, it is possible to minimize the ammonia volatilization of the thermosetting molded product produced, it can be applied to a wide range of applications, particularly improved applicability to IT products composed of precise circuits.

In addition, in the present invention, by using a binder in which a heteroatom resin of a high ortho novolak-type phenolic resin is blended with a conventional novolak-type phenolic resin having a high ratio of para bonds, a process for producing a molding material It is easy to combine the advantages of each resin is economical and excellent functionality can be utilized in various applications in various fields.

Furthermore, the molding material of the present invention can implement various functions depending on the characteristics of the resin or inorganic filler used.

1 is a graph showing the curing time according to the content of the high ortho phenolic resin according to Example 1.
Figure 2 is a graph showing the bending strength (bending stregth) according to the methanol content according to Example 1.
FIG. 3 is a graph showing changes in fluidity and curing time according to kneader holding time in the final molded article according to Example 2. FIG.
Figure 4 is a graph showing the thermogravimetric analysis of the conventional phenolic resin molding material according to Example 2 and the phenolic resin molding material according to the present invention.

Hereinafter, the most preferred embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art may easily implement the technical idea of the present invention. do.

The phenolic resin molding material according to an embodiment of the present invention is a high ortho furnace having a novolak-type phenolic resin (a) and an ortho-bonding / para-bonding ratio of 1.0 or more. A resin binder composed of a ballac phenol resin (b); And ii) inorganic fillers.

As used herein, "molding" includes extrusion molding and injection molding. In addition, in this specification, "molding material" means a molding material that is molded by a method such as extrusion molding or injection molding to be manufactured into a molded article.

In one embodiment of the present invention, as a binder of the molding material, a hetero resin, that is, a novolak-type phenol resin (a), and a high ortho having a ortho-bond / para-bond ratio of 1.0 or more ortho) a novolac type phenol resin (b).

The high ortho novolak-type phenol resin (b) has an ortho-bond / para-bond ratio of 1.0 or more, more preferably 1.0 to 2.5. This high ortho novolak-type phenolic resin has a fast curing speed, minimizes the addition of a curing agent, shortens the product production time during extrusion or injection molding, and minimizes ammonia volatilization after thermosetting, thus improving productivity and not causing corrosion. There is this.

The novolak-type phenol resin (a) is a general novolak-type phenol resin that has been used as a molding material, and more para-bonds exist than ortho-bonds. Such a novolak-type phenolic resin (a) has the advantages of easy production and high mechanical strength.

In one embodiment, it is preferred to have an ortho-bond / para-bond ratio of less than 0.2, more preferably less than 0.1 of the novolak type phenolic resin (a).

In the present invention, by using the combination of the novolak-type phenol resin (a) and the high ortho novolak-type phenol resin (b) as a binder of the molding material in this way, the disadvantages of the respective resins as described above are eliminated. You can complement each other and combine the advantages of each.

In one embodiment, the resin binder is preferably composed of 50 to 90% by weight of the novolak-type phenolic resin (a) and 10 to 50% by weight of the high ortho novolic phenolic resin (b) based on the total weight of the resin binder. .

The high ortho novolic phenolic resin (b) may exhibit compatibility problems due to non-uniform mixing and fluidity difference caused by the curing rate difference with the novolak-type phenolic resin (a), which is a base material, and is mixed in the above range. It is preferable.

In particular, when the content of the high ortho novolak-type phenolic resin (b) is less than 10% by weight, the effect of shortening the curing rate or the minimization of ammonia volatilization after curing is exhibited by adding the high ortho novolak-type phenolic resin (b). There is a problem. In addition, when the content of the high ortho novolak-type phenolic resin (b) exceeds 50% by weight, the kneader may be mixed due to the rapid curing rate during the process of mixing the heterogeneous resin with the novolak-type phenolic resin (a), followed by heat treatment and kneading. kneader), there is a problem that the molding material mixture hardens and does not demold.

The novolac phenolic resin (a) and the high ortho novolic phenolic resin (b) may be in powder form.

In one embodiment, the resin binder further comprises an alcohol. By containing alcohol, the uniformity and compatibility between resin (a) and (b) contained in the said resin binder can be improved.

The alcohol is preferably contained 1 to 10% by weight based on the total weight of the resin binder. If the added amount of alcohol is less than 1% by weight, the viscosity is expressed due to dissolution of the resin by alcohol, and thus, it is difficult to achieve uniform mixing.If the added amount is more than 10% by weight, the resin is excessively dissolved by alcohol, It exists in the liquid phase has a problem that it is difficult to achieve uniform mixing.

The alcohol that can be used in the present invention is not particularly limited, and for example, methanol, ethanol and the like can be appropriately selected and used.

The inorganic filler included in the phenolic resin molding material of the present invention is not particularly limited, and may be appropriately selected from conventional inorganic fillers used in extrusion or injection thermoforming materials. For example, in one embodiment of the present invention, the inorganic filler may be one or more selected from the group consisting of glass fibers, CaCO ₃ , talc, wood powder, feldspar and clay.

The amount of the inorganic filler to be added is not particularly limited and may be depending on the amount of the inorganic filler to be used for the resin in conventional compression or injection molding materials. For example, in one embodiment of the present invention, the inorganic filler may be included in the range of 50 to 150 parts by weight based on 100 parts by weight of the resin binder.

In one embodiment, the phenolic resin molding material according to the present invention may further include one or more selected from the group consisting of a plasticizer, a curing agent and a releasing agent for the improvement of moldability, acceleration of curing, improvement of mold release.

In addition, in addition to the known additives used in conventional thermoforming materials may be further included.

On the other hand, the manufacturing method of the phenol resin molding material according to another embodiment of the present invention is iii) a high ortho having a novolak-type phenol resin (a) and an ortho-bond / para-bond ratio of 1.0 or more (high ortho) mixing a novolak-type phenol resin (b) to form a resin binder; Ii) mixing an inorganic filler with the resin binder to form a mixture; Iii) kneading the mixture by heat treatment; And iii) co-milling after cooling to room temperature.

In one embodiment, the step iii), by mixing 50 to 90% by weight of the novolak-type phenolic resin (a) and 10 to 50% by weight of the high ortho novolic phenolic resin (b) based on the total weight of the resin binder Can be done.

In one embodiment, in order to improve the uniformity of the heterogeneous resin mixture and the heterogeneous resin compatibility, the step iii) is performed for 5 to 50 minutes, preferably about 30 minutes, in a high speed mixer at a rotational speed of 980 to 1100 rpm. It is preferable to achieve by doing this.

In addition, in one embodiment, the step iii) may further comprise mixing alcohol, in order to induce uniform mixing. The alcohol is preferably mixed 1 to 10% by weight based on the total weight of the resin binder.

In one embodiment, alcohol can be mixed by spraying on the resin binder.

In one embodiment, the step ii) may be performed by mixing 50 to 150 parts by weight of the inorganic filler with respect to 100 parts by weight of the resin binder.

In addition, in one embodiment, the step ii) may include further mixing one or more selected from the group consisting of a plasticizer, a curing agent and a release agent.

This mixing process can be done using a high speed mixer to ensure uniform mixing.

In one embodiment, the step iii) is preferably a high temperature kneading by heat-treating the mixture for 90 to 200 seconds at a temperature in the range of 150 ~ 200 ℃. In the high temperature kneading process, the holding time is in the range of 90 to 200 seconds, but the curing time is not completely cured, and the curing time can be shortened in the curing process by thermoforming during final extrusion or injection molding.

The high ortho novolak-type phenol resin (b) has an ortho-bond / para-bond ratio of 1.0 or more, more preferably 1.0 to 2.5.

The novolak-type phenol resin (a) is a general novolak-type phenol resin that has been used as a molding material, and more para-bonds exist than ortho-bonds. In one embodiment, it is preferred to have an ortho-bond / para-bond ratio of less than 0.2, more preferably less than 0.1 of the novolak type phenolic resin (a).

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited by these examples.

Example  1: resin binder manufacturer

(1) 50 to 90% by weight of the powdered novolac-type phenolic resin and 10 to 50% by weight of the powdered novolac-type high ortho phenolic resin were mixed, and placed in a high-speed mixer at 980 to 1,100 rpm and maintained for 30 minutes to be uniformly mixed. . Figure 1 shows the curing time according to the content of the high ortho phenolic resin.

(2) In order to improve the uniformity and compatibility in the heterogeneous resin mixing process of (1), methanol was sprayed in a range of 1 to 10% by weight based on the total weight of the resin binder. The injected methanol dissolves the polymer resin and makes it viscous to promote uniform mixing between different resins during mixing in a high speed mixer. 2 is a change in the bending strength value of the molding material according to the content of methanol.

Example  2: Manufacture of Phenolic Resin Molding Material with Minimized Curing Speed and Ammonia Volatilization

The total weight of the resin binder prepared in Example 1 was mixed with glass fibers as an inorganic filler in a ratio of 1: 1 (weight ratio), and then a plasticizer, a curing agent, and a releasing agent were respectively added in an amount of 0.7 wt%, 0.8 wt%, 0.7 wt% was added and uniformly mixed using a high speed mixer. Then, the mixture was uniformly mixed into a kneader, followed by heat treatment in the range of 150 to 200 ° C. to remove volatiles and to have an appropriate thermal fluidity. At this time, the degree of hardening was promoted by maintaining 90 to 200 seconds in the kneader. After such a high temperature kneading step, it was cooled to room temperature and coarsely pulverized to obtain a phenol resin molding material according to the present invention capable of extrusion and injection molding.

Extrusion or injection molding of the molding material of the present embodiment thus obtained can produce a desired final product or part. 3 is a result showing the change in fluidity and curing time according to the kneader holding time in the final part thus formed.

Figure 4 is a thermogravimetric analysis of the conventional phenolic resin molding material and the phenolic resin molding material according to the present invention.

The phenol resin molding material according to the present invention is applicable to various applications depending on the resin used, and in particular, it can be advantageously used for IT parts or electronic parts having a very small and complicated shape. As such, when the phenolic resin molding material according to the present invention is used for producing a variety of parts, the curing time is short during extrusion or injection molding, so that the production time is shortened and mass production of parts is possible. The volatilization is minimized to minimize corrosion of surrounding materials or parts, which does not cause defects or shorten the life.

Claims (23)

Iii) 50 to 90% by weight of novolac type phenolic resin (a) having an ortho-bond / para-bond ratio of less than 0.2 and ortho-bond / para of 1.0 to 2.5 A resin binder composed of 10 to 50% by weight of a high ortho novolak-type phenol resin (b) having a bonding ratio; And
Ii) at least one inorganic filler selected from the group consisting of fiberglass, CaCO ₃ , talc, wood flour, feldspar and clay,
The inorganic filler is included in the range of 50 to 150 parts by weight based on 100 parts by weight of the resin binder.
Phenolic Resin Molding Material.
The method of claim 1,
The resin binder further comprises an alcohol
Phenolic Resin Molding Material.
The method of claim 2,
The alcohol is contained in 1 to 10% by weight based on the total weight of the resin binder
Phenolic Resin Molding Material.
The method of claim 1,
The phenol resin molding material further comprises at least one member selected from the group consisting of plasticizers, curing agents and release agents.
Phenolic Resin Molding Material.
The method of claim 1,
The novolac type phenol resin (a) has an ortho-bond / para-bond ratio of less than 0.1.
Phenolic Resin Molding Material.
Iii) 50-90% by weight of novolac type phenolic resin (a) having an ortho-bond / para-bond ratio of less than 0.2, and ortho-bond / para of 1.0-2.5 Mixing 10 to 50% by weight of a high ortho novolak-type phenol resin (b) having a) -bond ratio to form a resin binder;
Ii) mixing the resin binder with at least one inorganic filler selected from the group consisting of glass fibers, CaCO ₃ , talc, wood flour, feldspar and clay, to form a mixture;
Iii) kneading the mixture by heat treatment; And
Iii) co-milling after cooling to room temperature,
The step ii) is made by mixing 50 to 150 parts by weight of the inorganic filler with respect to 100 parts by weight of the resin binder.
Method for producing phenolic resin molding material.
The method according to claim 6,
The step iii) is performed by mixing for 5 to 50 minutes in a high speed mixer at a rotational speed of 980 to 1100 rpm.
Method for producing phenolic resin molding material.
The method according to claim 6,
The step iii) further comprises mixing alcohol.
Method for producing phenolic resin molding material. 9. The method of claim 8,
The alcohol is mixed 1 to 10% by weight based on the total weight of the resin binder
Method for producing phenolic resin molding material.
9. The method of claim 8,
It is mixed by spraying the alcohol to the resin binder, characterized in that
Method for producing phenolic resin molding material.
The method according to claim 6,
Step ii) further comprises mixing at least one member selected from the group consisting of a plasticizer, a curing agent and a release agent.
Method for producing phenolic resin molding material.
The method according to claim 6,
Heat treatment in the step iii) is made for 90 to 200 seconds at a temperature in the range of 150 ~ 200 ℃
Method for producing phenolic resin molding material.
The method according to claim 6,
The novolac type phenol resin (a) has an ortho-bond / para-bond ratio of less than 0.1.
Method for producing phenolic resin molding material. delete delete delete delete delete delete delete delete delete delete

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