JPH0689221B2 - Amino resin molding material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an amino resin molding material which is excellent in flexibility, weather resistance and stain resistance and is useful for parts such as tableware, household articles, and electric appliances. It is a thing.

(Prior Art) Conventionally, as an amino resin molding material of this kind, an amino obtained by adding a reinforcing material, a filler, a curing agent, a release agent, a coloring agent, etc. to a melamine resin, a benzoguanamine resin, a urea resin and a co-condensation resin thereof -Based resin molding materials are known and have been applied in various fields by taking advantage of their excellent heat resistance, colorability, surface hardness, electrical properties, solvent resistance, etc., but molding materials using melamine resin Then, there are drawbacks in flexibility and stain resistance, weather resistance in molding materials using benzoguanamine resin, and water resistance in molding materials using urea resin.
For the purpose of improving these drawbacks, a method of adding another resin or the like and a method of co-condensing another resin raw material have been proposed, and some improvements have been made.

(Problems to be Solved by the Invention) However, in these conventional methods, water resistance, chemical resistance, heat resistance, etc. are significantly lowered, and the characteristics inherent to the amino resin are impaired. hard.

The present invention has been made in view of the above-mentioned present circumstances, and therefore the object thereof is no problem with respect to flexibility, stain resistance, weather resistance, which is a drawback of benzoguanamine resin molding material, which is a drawback of melamine resin molding material. Another object of the present invention is to provide a novel amino-based molding material capable of obtaining a molded article having excellent flexibility, weather resistance, stain resistance and the like.

As a result of diligent research, the present inventors have completed the present study by finding that an amino resin molding material having excellent flexibility and weather resistance can be obtained by using a specific amino compound and an amino resin obtained from formaldehyde. I was able to do it.

(Means and Actions for Solving Problems) The present invention relates to an amino compound having at least one selected from the group consisting of cyclohexanecarboguanamine, cyclohexenecarboguanamine, norbornanecarboguanamine and norbornenecarboguanamine as an essential component. Amino Resin (I) Obtained from Formaldehyde and Formaldehyde
And an amino resin molding material characterized by comprising a base material (II) for amino resin molding material.

The amino compounds used in the present invention include cyclohexanecarboguanamine (structural formula I), cyclohexenecarboguanamine (structural formula II), norbornanecarboguanamine (structural formula III), norbornenecarboguanamine (structural formula IV), (hereinafter, these Are collectively referred to as carboguanamine (a)), and one or more selected from the group as an essential component.

(Structural formula) The amount and ratio of use can be arbitrarily set according to the desired performance, but in order to obtain an amino resin molding material having excellent flexibility, weather resistance, and stain resistance, 40% by weight or more of the amino compound is used. Is preferably used in an amount of 60% by weight or more. The amino compound may appropriately contain an amino compound other than the carboguanamine (a), for example, melamine, benzoguanamine, etc., depending on the purpose. Preferably less than 60% by weight. The method for obtaining the amino resin (I) in the present invention is not particularly limited, and for example, 1 mol of the amino compound is mixed with 1.2 to 3.5 mol of formaldehyde at a reaction temperature.
The amino compound formaldehyde condensate obtained by reacting under the conditions of 40 to 100 ° C. and pH 5 to 10 can be effectively used as the amino resin (I).

In addition, 1 mol of the amino compound and formaldehyde 1.2
~ 3.5 mol of mixture and react at 40 ~ 100 ℃ for 0.5 ~ 4 hours, then heat to 90 ~ 150 ℃ under normal pressure or reduced pressure water and condensation reaction derived from formalin, which is the raw material of formaldehyde The dehydration of the amino compound formaldehyde condensate obtained by removing the water generated in (1) can be effectively used as the amino resin (I). However, the present invention is not limited to these exemplified methods, and any conventionally known method can be applied.

As the base material (II) for amino resin molding material used in the present invention, those conventionally used for amino resin molding materials such as cellulose, wood powder and sulfate pulp can be used as they are. The amount used is not particularly limited, but is usually 5 to 200% by weight, and preferably 10% to the amino resin (I) obtained from the amino compound and formaldehyde.
Used in the range of up to 100% by weight.

Various methods can be adopted to obtain an amino resin molding material from the amino resin (I) obtained from an amino compound and formaldehyde and the amino resin molding material base material (II). As a concrete manufacturing method thereof, a known manufacturing method of a thermosetting resin molding material containing a curing agent, a release agent, a filler, a coloring agent and the like can be adopted.

For example, when the amino resin (I) is obtained, the base material (II) for an amino resin molding material such as pulp or wood flour is treated with the amino compound (formula aldedo condensate) in the process of obtaining the amino resin (I). The present invention is well kneaded with a formaldehyde condensate using a kneader, a heat roll, and an extruder at room temperature or under heating, and then is mixed with a curing agent, a release agent, a coloring agent, and pulverized using a ball mill. However, the present invention is not limited only by these methods.

If desired, the amino resin molding material of the present invention may contain a conventional additive to the amino resin molding material as a component other than the above components. Conventionally used additives include, for example, organic fillers such as paper, lint and cloth cutting; inorganic fillers such as asbestos, mica, glass fiber, calcium carbonate, aluminum hydroxide and barium sulfate; dimethyl oxalate. Examples thereof include release agents such as carboxylic acid esters, fatty acids such as maleic anhydride and phthalic anhydride, and metal salts thereof, waxes, grease-like substances, and coloring agents such as red iron oxide.

(Effects of the Invention) Moldings produced using the amino resin molding material of the present invention thus obtained are conventional melamine-formaldehyde resin, urea-formaldehyde resin, benzoguanamine-formaldehyde resin or benzoguanamine and melamine. And / or various properties such as flexibility, weather resistance and stain resistance are extremely excellent as compared with a molded article using a conventional amino resin such as urea-formaldehyde resin as a molding material. Therefore, the molding material of the present invention can be suitably used as a molded article for parts such as tableware, household appliances and electric appliances.

(Examples) The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. All parts in the examples mean parts by weight unless otherwise specified.

Example 1. A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was added to a mixture of 400 parts of cyclohexanecarboguanamine and 504 parts of 37% formalin.
After adding 30 parts of the resin to the resin for 30 minutes at 90 ° C. and cooling to 50 ° C., 100 parts of methanol was added to obtain a transparent resin solution (hereinafter referred to as amino resin (1) solution). Amino resin (1) solution 1004
Part, pulp sheet 215 parts kneader 3 at 45-55 ℃
After mixing for 0 minutes, it was dried in a hot air dryer at 75 ° C. for 4 hours.
100 parts of the obtained dried product, 1 part of phthalic anhydride, 0.5 part of zinc stearate and 1 part of titanium oxide as a pigment were pulverized and mixed in a ball mill for 16 hours to obtain an amino resin molding material (I). The performance and results of the amino resin molding material (I) thus obtained are shown in Table 1.

Example 2 Charge the same reaction vessel used in Example 1 with 400 parts of norbornenecarboguanamine, 504 parts of 37% formalin and 1.4 parts of 10% sodium carbonate aqueous solution with stirring 90
The reaction was carried out at 0 ° C for 2 hours. After that, the reflux condenser was switched to the Liebig condenser and heated at normal pressure, and the internal temperature of the flask was 120 ° C.
To remove water from the reaction system. Then, the contents of the flask were taken out to room temperature, cooled, solidified and pulverized to obtain an amino resin (2). 150 parts of pulp powder was added to 350 parts of amino resin (2), premixed at room temperature using a kneader, and then kneaded and pulverized with a hot roll heated to 100 ° C. until the water content generated by dehydration was 3.5%. 100 parts of the pulverized material thus obtained was mixed with 1 part of phthalic anhydride as a curing catalyst.
Parts, 0.5 parts of zinc stearate as a release agent, and 1 part of titanium oxide as a pigment were added and pulverized and mixed in a ball mill for 16 hours to obtain an amino resin molding material (II). The performance and results of the amino resin molding material (II) thus obtained are
Shown in the table.

Comparative Example 1. 400 parts of benzoguanamine, 520 parts of 37% formalin and sodium carbonate in the same reaction vessel used in Example 1.
1.4 parts of 10% aqueous solution was charged and reacted at 90 ° C. for 2 hours while stirring. After that, the reflux condenser was switched to the Liebig condenser and heated at normal pressure until the inner temperature of the flask reached 120 ° C. to remove water from the reaction system. Then, the contents of the flask were taken out to room temperature, solidified by cooling, and then pulverized to obtain a comparative amino resin (1). Amino resin for comparison (1) 350
After adding 150 parts of pulp powder to the above parts and premixing at room temperature using a kneader, the mixture was kneaded and pulverized with a hot roll heated to 100 ° C until the water content produced by dehydration was 3.5%. To 100 parts of the pulverized product thus obtained, 1 part of phthalic anhydride as a curing catalyst, 0.5 part of zinc stearate as a release agent, and 1 part of titanium oxide as a pigment were added and pulverized and mixed in a ball mill for 16 hours for comparison. A molding material (I) was obtained. The performance results of the comparative molding material (I) thus obtained are shown in Table 1.

Comparative Example 2. Melamine 300 in the same reaction vessel used in Example 1.
3.0 parts of 28% ammonia solution was added to a mixture of 1 part and 580 parts of 37% formalin, and a resin reaction was carried out at 70 ° C. for 120 minutes to obtain a transparent resin solution (hereinafter referred to as a solution of comparative amino resin (2)). 514 parts of a solution of comparative amino resin (2) and 220 parts of pulp sheet were charged in a kneader and mixed at 45 to 55 ° C for 30 minutes, and then dried in a hot air dryer at 70 ° C for 4 hours. 100 parts of the obtained dried product, 0.05 part of phthalic anhydride, 0.5 part of zinc stearate, and 1 part of titanium oxide as a pigment were ball milled to 1 part
The mixture was pulverized and mixed for 6 hours to obtain a comparative molding material (II). The performance results of the comparative molding material (II) thus obtained are shown in Table 1.

Test method Disc flow: According to JIS-K6911-1970.

Cup moldability; according to JIS-K6911-1970.

Rockwell hardness; according to JIS-K6911-1970.

Bending strength; according to JIS-K6911-1970.

Flexural modulus; according to JIS-K6911-1970.

Soy sauce stain resistance; Using a test piece according to JIS-K6911-1970 for measuring water absorption, soaked in commercially available soy sauce (manufactured by Kikkoman Corp.) kept in a fluffy state for 2 hours and then washed thoroughly with cold water. To observe.

Resistance to coffee stains; Using a test piece according to JIS-K6911-1970 for measuring water absorption, add 57 g of commercially available instant coffee (Nescafe) to 500 ml of water and let it soak for 2 hours, then rinse well with cold water Observe the appearance after the exposure.

Weather resistance: A test piece according to JIS-K6911-1970 for measuring water absorption was used and the appearance of the test piece was observed after a 60-hour weather resistance test with a fade tester.

It can be seen from Table 1 that the amino resin molding material of the present invention does not impair the characteristics of the conventional amino resin molding material, and is excellent in flexibility, weather resistance and stain resistance.

Claims (1)

[Claims] 1. An amino resin obtained from formaldehyde and an amino compound containing at least one selected from the group consisting of cyclohexanecarboguanamine, cyclohexenecarboguanamine, norbornanecarboguanamine and norbornenecarboguanamine as essential components and formaldehyde ( Amino resin molding material comprising I) and a base material (II) for amino resin molding material.