JP3204965B2 - Amino resin molding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an amino-based resin molding in which an infinite number of circular or elliptical marble-like patterns are revealed on the surface by heating and pressing in a conventional manner. With respect to the amino-based resin molding material from which the product can be manufactured, in detail, a re-crushed product of a pre-formed product obtained by heating and kneading a granule containing a crushed product of a pre-dried amino-based resin molding material, powder The present invention relates to an amino-based resin molding material characterized by being mixed with a state-of-art colorant or a coloring agent-containing amino-based resin molding material powder and a volatile organic solvent and dried.

[Conventional technology]

Conventionally, several methods have been disclosed for the purpose of revealing a marble-like pattern on the surface of an amino resin molded product.

For example, Japanese Patent Publication No. 43-18449 discloses that "cellulose-based filler is kneaded with a solution of an initial condensate of an amino-based thermosetting resin together with a curing catalyst and a lubricant, and a volatile material is obtained by drying a bulk material obtained by drying. A solvent is sprayed, and colored powder of the thermosetting resin molding material is applied to the bulk material for 5 minutes.
A material for forming a molded article having a marble pattern with various stripes or a fibrous pattern to which about 40% is adhered. ].

Molded articles obtained from this proposed material have a marble-like pattern on the surface, but the contours of the pattern are often slightly blurred and the surface lacks some smoothness. However, there still remains a problem to be improved that the gloss is not always sufficient.

Japanese Patent Application Laid-Open No. 54-105148 discloses a method for producing amino-based resin molding material capable of producing a molded product having a beautiful network pattern. By making a granular molding material with a compressive strength of 10 kg / cm ² or more and a particle size of 30 mesh or more, an amino-based resin molding material is obtained by mixing this granular molding material with a monochromatic agent using titanium as a carrier. A method for producing an amino-based resin molding material characterized by the following characteristics. "

However, even if the molding material of the second proposal is used,
There is a case that the intended mesh pattern is broken by flowing the pattern such as the rising part of the molded article, and because the `` colorant using titanium as a carrier '' is used, the color tone of the obtained pattern is naturally limited, for example, However, there is a problem that it is difficult to obtain a pattern having a clear translucent outline.

[Problems to be solved by the invention]

The present inventors have found that a beautiful marble-like pattern has emerged on the surface of a molded product, and is an amino-based resin molded product rich in decorativeness, and also excellent in practical strength such as crack resistance and impact resistance. As a result of repeated studies to obtain an amino-based resin molded product, the method of the first proposal was further improved, and a coarsely crushed amino-based resin molding material pre-dried product having an appropriate particle size was powdered as necessary. Heat-kneading together with a powdery colorant, a lubricant, a curing catalyst, etc., and re-crushing the obtained preformed product into granules having an appropriate particle size, and converting the granules into a powdery colorant and a volatile organic solvent such as methanol. It was found that a molding material capable of producing an excellent amino-based resin molded product which solved all of the above-mentioned problems and was obtained by mixing and drying with a mixer was obtained, and completed the present invention.

[Means for solving the problem]

The present invention relates to the following A to C, A. A preformed product obtained by heating, kneading and extruding a granule containing a crushed product of a pre-dried amino resin molding material according to JIS
B. JIS sieve 145 mesh repassable 70% by weight or more powdered colorant or colorant-containing amino-based resin molding material powder; It is an object of the present invention to provide an amino resin molding material, which is obtained by mixing and drying a volatile organic solvent.

 Hereinafter, the present invention will be described in detail.

The component (A), which is a main component used in the present invention, is a re-crushed preformed product obtained by heating and kneading a powder containing a crushed product of a pre-dried amino resin molding material.

The amino resin molding material pre-dried material (hereinafter, may be simply referred to as a pre-dried material) may be obtained by drying a wet kneaded material containing an amino resin and pulp as main components. A popcorn-like thing.

Examples of the amino resin include an amino resin alone obtained by reacting an amino resin-forming amino component (hereinafter, may be abbreviated as an amino component) with formaldehyde; the amino component, formaldehyde, and co-condensation thereof. An amino-based co-condensation resin obtained by reacting a possible amino-co-condensation component; and a thermosetting or thermoplastic resin other than these, for the amino-only resin and / or the amino-based co-condensation resin , Abbreviated as a blended resin component).

Examples of the amino component include melamine; urea,
Ureas such as thiourea and ethylene urea; guanamines such as benzoguanamine, acetoguanamine, formguanamine, phenylacetoguanamine, and CTU guanamine; and other amino compounds such as guanidine, dicyandiamide, and paratoluenesulfonamide; These amino components may be used in combination.

The above-mentioned "formaldehyde" is a name including a compound that substantially acts as formaldehyde when reacting with the amino component, such as paraformaldehyde. Further, the formaldehyde can be partially replaced by an aldehyde component other than formaldehyde, for example, an aliphatic aldehyde such as acetaldehyde; an aromatic aldehyde such as benzaldehyde; furfural; and other aldehyde compounds capable of reacting with the amino component. . The amount of such an aldehyde component other than formaldehyde is preferably about 0.5 mol or less based on 1 mol of formaldehyde from the viewpoint of reactivity with the amino component and the curing rate of the obtained amino resin.

The molar ratio of formaldehyde to 1 mol of the amino component in the amino-only resin or 1 mol of the total of the amino component and the amino co-condensation component in the amino co-condensation resin is determined by the curing rate of the obtained molding material and the physical properties of the obtained molded article. From the viewpoint of, about 1 to 4 mol is preferable.

Examples of the amino co-condensation component include phenols such as phenol, cresol, xylenol, ethylphenol, butylphenol and bisphenol A; xylene and saccharose.

Further, as the blend resin component, for example,
Phenol resin, xylene resin, alkyd resin, polyester resin, acrylic resin and the like can be mentioned.

Among these thermosetting resins, the resin used in the present invention is more preferably an amino resin, and more preferably a melamine resin.

Examples of the melamine-based resin include a melamine resin obtained by reacting melamine and formaldehyde; melamine and one or more components selected from ureas, guanamines, other amino compounds, phenols, and the like (hereinafter, melamine). A melamine co-condensation resin obtained by reacting formaldehyde with a co-condensation component);
A melamine-based blend resin obtained by blending a melamine resin and / or a melamine co-condensation resin with at least one resin of the blend resin component can be used.

In the melamine-based co-condensation resin, the ratio of the melamine co-condensation component to melamine is about a molar ratio from the viewpoints of surface hardness, light (weather) resistance, heat resistance, and stain resistance of the obtained molded article. It is preferably not more than 0.7 and not more than about 1 by weight, more preferably not more than about 0.5 by mole, and particularly preferably not more than about 0.2 by mole. Further, the weight ratio of the blending resin component to the melamine resin and / or the melamine-based co-condensation resin in the melamine-based blended resin is preferably about 1 or less from the same viewpoint, more preferably about 0.5 or less, About 0.2
It is particularly preferred that:

The melamine resin or the melamine-based co-condensation resin is preferably reacted with formaldehyde in an amount of about 1 to 3 mol, based on 1 mol of melamine alone or the total amount of the melamine and the melamine co-condensation component, and is preferably about 1.4 to 2.5 mol. It is particularly preferred to react.

If the molar ratio is less than or equal to the upper limit of the above range, the molded article will not be brittle, and properties such as crack resistance will not be reduced.On the other hand, if the molar ratio is greater than or equal to the lower limit of the above range, Since the curing rate of the obtained melamine-based resin molding material does not decrease and the state of "soldering" of the melamine-based molded product also keeps a good level, the molar ratio is appropriately selected within the above range. Is preferred.

Among such melamine-based resins, resins used in the present invention include melamine resins, melamine-phenol co-condensation resins, melamine-urea co-condensation resins, and melamine-phenol blend resins obtained by blending melamine resins with novolak phenol resins. Preferably, a melamine-urea blend resin obtained by blending a urea resin with a melamine resin,
Melamine resins are most preferred.

As a method for producing the melamine-based resin used in the present invention, for example, a so-called melamine crystal powder that can be produced by a method known per se such as a carbide method and a urea method, and used as necessary, for example, ureas, guanamines, phenols, and the like Melamine co-condensation component and formaldehyde such as a formalin aqueous solution having a concentration of about 36% by weight are reacted in an aqueous solvent at a pH of about 7 to 9, and then, if necessary, further, for example, a urea resin. For example, an embodiment in which a blending resin component such as a phenol resin is blended in the form of an aqueous solution or an aqueous dispersion to obtain an aqueous solution or an aqueous dispersion, for example, can be given.

The pre-dried product in (A), which is a main component of the present invention, is obtained by drying a wet kneaded product containing the above-mentioned melamine resin and pulp as main components.

The above-mentioned "pulp" is usually a raw material of paper, chemical fiber, cellulosic plastic and the like, and is an aggregate of chain-like polymer fibers mainly composed of α-cellulose derived from a cellulose raw material. In general, industrially, an aggregate of cellulose fibers produced from a cellulose material obtained by mechanically and / or chemically treating a plant material such as wood or linter is used. The content of the pulp in 100% by weight of the pre-dried product is preferably about 20 to 40 from the viewpoint of the molding suitability of the obtained molding material and the excellent appearance, crack resistance and impact resistance of the obtained molded article. It is preferable that the amount is about% by weight.

In addition, the above-mentioned “comprising melamine resin and pulp as main components” means that the total of melamine resin and pulp in 100% by weight of the pre-dried product is generally 60 to 100% by weight, preferably 80% by weight. 100100% by weight.

In the pre-dried product, in addition to the melamine resin and the pulp, a melamine resin thermal fluidity improver (hereinafter, may be simply referred to as a fluidity improver), a filler other than pulp, a curing catalyst , A coloring pigment, a lubricant, and the like.

Examples of the fluidity improver include polyoxyalkylenes such as polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol block copolymer; and polyoxyalkylenes such as polyethylene glycol monooleate and polyethylene glycol distearate, and C _8. mono- and saturated or unsaturated higher fatty -C ₂₀ - or di - esters; for example, polyoxyethylene monolauryl ether, C ₈ polyoxyalkylene such as polyoxyethylene dioleyl ether -C ₂₀ saturated or unsaturated mono and higher aliphatic monoalcohol - or di - ethers; for example, polyoxyalkylene and C ₁₂ -C ₂₀ mono-ethers of alkyl phenols such as polyoxyethylene nonylphenol ether And the like; for example, methyl oleate,
Ethyl oleate, n- propyl oleate, i- propyl oleate, n- butyl stearate, n- hexyl laurate, n- octyl oleate, 2-ethylhexyl oleate C ₁ -C ₁₀ saturated aliphatic monoalcohols and C ₈ ~ such as C ₂₀
Esters with saturated or unsaturated higher fatty acids (preferably oleic acid); for example, trimethylolpropane triolate, pentaerythritol triolate and the like represented by the following general formula C (CH ₂ OH) _{2 + n} (CH ₂ R) _{2- n} [where, n is 0, 1 or 2; R is hydrogen or an alkyl group of C ₁ ~C _3] (hereinafter, sometimes abbreviated as neopentyl polyol)
A C ₆ -C ₂₅ (preferably oleic acid) (preferably C ₁₀ -C ₂₀₎ saturated or unsaturated higher fatty acid esters of; for instance stearic acid amide, oleic acid amide, C ₈ ~ such as linoleic acid amide amides, saturated or unsaturated higher fatty acids of C _20; for example, dioctyl phthalate, phthalic acid diesters of saturated aliphatic monoalcohols C ₄ -C _12, such as dibutyl phthalate; for example, .epsilon.-caprolactam, other glycerol And a fluidity improver.

Among these, polyoxyalkylenes and polyoxyalkylenes are considered from the viewpoint of excellent appearance of the obtained molded article.
Mono- and saturated or unsaturated higher fatty acids C ₈ -C ₂₀ - or di - esters, esters of saturated or unsaturated higher fatty acids, saturated aliphatic monoalcohols with C ₈ -C ₂₀ in C ₁ -C ₁₀ and use of esters of saturated or unsaturated higher fatty acid neopentyl polyol and C ₆ -C ₂₅ are preferred, the use of esters of saturated or unsaturated higher fatty acid neopentyl polyol and C ₆ -C ₂₅ particularly preferable.

The content of these fluidity improvers is preferably 0 to 2.5% by weight, particularly preferably 0.1 to 2% by weight, based on 100% by weight of the pre-dried product.

Examples of the filler include rock wool, glass fiber, glass powder, calcium carbonate, gypsum, barium sulfate, talc, clay, silica and other inorganic fillers, and the preliminary drying of the filler. The amount occupying in 100% by weight of the substance is preferably 0 to 40% by weight, particularly preferably 0 to 20% by weight.

Examples of the curing catalyst include phthalic anhydride, p
-Toluenesulfone, dimethyl oxalate, dibenzyl oxalate,
Dimethyl phthalate, benzoyl peroxide, epichlorohydrin, p-toluenesulfonic acid triethanolamine salt, p-toluenesulfonic acid triethylamine salt, 2-aminoethylsulfonic acid, dimethylanilinesulfonic acid hydrochloride, melamine oxalate, ammonium chloride, phosphoric acid Ammon, trimethyl phosphate, acetamide, oxamide and the like can be exemplified, and the pre-dried product of the curing catalyst
The content in 100% by weight is 0 to 2% by weight, particularly 0 to 2% by weight.
Preferably it is 1% by weight.

Examples of the coloring pigments include, for example, titanium oxide, zinc oxide, zinc sulfide, red iron oxide, dark blue, iron black, ultramarine, carbon black, lithopone, titanium yellow, cobalt blue, Hansa yellow, benzidine yellow, lake red, aniline black, Examples thereof include inorganic or organic pigments such as dioxazine violet, quinacridone red, quinacridone violet, naphthol yellow, phthalocyanine blue, and phthalocyanine green. The amount of the coloring pigments in 100% by weight of the pre-dried product is preferably 0 to 8% by weight, particularly preferably 0 to 5% by weight.

Examples of the lubricant include, for example, zinc stearate, zinc myristate, aluminum stearate, calcium stearate, and the like.
The amount in 100% by weight is 0 to 3% by weight, particularly 0 to 3% by weight.
Preferably it is 2% by weight.

The pre-dried product used in the present invention can be suitably adjusted, for example, by a so-called wet method as described below.

That is, for example, the proportion of pulp in an aqueous solution of the above-mentioned miramine-based resin having a resin solid content concentration of about 40 to 60% by weight, for example, is 20 to 30% by weight in 100% by weight of the pre-dried product. In addition, if necessary, for example, the above-mentioned fluidity modifier such as trimethylolpropane triolate is added so as to be 0.1 to 2% by weight in 100% by weight of the pre-dried product, and kneaded. For example, about 70-100
It is dried at a temperature of about ℃ to obtain, for example, a popcorn-like pre-dried product having a diameter of about 0.5 to 3 cm.

As a kneading means at the time of forming the popcorn-like pre-dried material, a kneader, a co-kneader, or the like can be used.
As drying means, hot air drying, band dryer drying,
Fluid drying and the like can be exemplified.

The pre-dried product thus obtained is crushed by an appropriate means such as an impact hammer mill and a rotary cutter mill.

The particle size of the obtained crushed material is, from the viewpoint of good surface appearance pattern of the obtained molded product, a particle size range of 2 to 42 mesh with a JIS sieve, and 40% by weight with respect to 100% by weight of the crushed material. It is preferably at least 60% by weight.

In addition, the dry small pieces which are generated in a drying process such as band dryer drying and are usually discarded, so-called “under the cutter” are also appropriately crushed as necessary,
It can be used as the above crushed material.

Next, the obtained crushed material is, if necessary, a powdery colorant and / or a colorant-containing amino resin molding material powder [hereinafter may be abbreviated as a powdery colorant component (a)]. Mixing with a filler, a curing catalyst and a lubricant, etc., and kneading the obtained powder and granules by heating and kneading to obtain a preformed product, which is re-crushed to obtain a re-crushed product which is the component (A) in the present invention. Can be. The amount of the crushed material occupying in the whole amount of the granules is determined from the viewpoints of good physical properties such as good appearance and crack resistance and impact strength of the obtained molded article.
It is preferably from 70 to 100% by weight, particularly preferably from 80 to 100% by weight.

Examples of the “powder colorant” include a powdery color pigment, a so-called masterbatch obtained by adding the filler such as calcium carbonate or melamine crystal to the color pigment and uniformly dispersing the same. Examples of the “colorant-containing amino-based resin molding material powder” include those obtained by pulverizing the pre-dried product together with color pigments and, if necessary, the curing catalyst, a lubricant, and the like by appropriate means as described above. Can be exemplified.

The particle size of the powdery coloring component (a) is preferably 50% by weight or more, particularly 145 meshes passing through a JIS sieve, from a viewpoint of good appearance of the obtained molded article, more preferably 7%.
It is preferably at least 0% by weight. Further, the amount of the powdery coloring component (a) used is preferably 0 to 30% by weight, particularly preferably 0 to 20% by weight, based on the total amount of the powdery granules subjected to the heat kneading.

When these powdery coloring components (a) are not used,
The inside of a circular or elliptical pattern that appears on the surface of the obtained molded product has a light color close to white, while the use of the coloring component allows the inside of the pattern to be colored to the color of the coloring component. Becomes Accordingly, the coloring component (a) is contained in the powder and the color tone of the component (B) powder colorant or the colorant-containing amino resin molding material powder described later is changed to the color tone of the coloring component (a). With this, it is possible to change the color tone between the inside and the outline of the pattern to be revealed, thereby giving a unique taste.

Here, "different in color tone" means that at least one of the lightness, saturation, hue, and density of the color of the appearing pattern is different.

Further, the powdery granules generally contain 0 to 20% by weight of the filler, 0 to 2% by weight, preferably 0 to 1% by weight, and 0 to 3% by weight of a lubricant in 100% by weight of the powdery particles, Preferably
0.1 to 2% by weight can be contained.

The re-crushed product as the component (A) in the present invention is obtained by mixing the powdered coloring component (a), a filler, a curing catalyst, a lubricant, and the like, if necessary, with a pre-dried product by an appropriate mixing means. It is formed by mixing and heating and kneading the obtained granules to obtain a preformed product, which is then crushed again by an appropriate means.

As the above mixing means, for example, a V-type mixer, a super mixer, a Nauter mixer, a tumbler mixer, an omni mixer, a Hensiel mixer, a Ladyge mixer, a ribbon blender, a planetary mixer, and the like can be used. Further, as a means for heating and kneading, an extruder, a heating roll machine or the like can be used.

The extruder can be appropriately selected and used without any particular limitation, and examples thereof include a single-screw extruder and a twin-screw extruder. Compression ratio and temperature can be selected appropriately,
For example, temperature conditions such as a compression ratio of 1.1 to 3 and about 50 to 130 ° C. can be exemplified. The extrusion end of the extruder may be of any type such as an open type or a screen die type, and the twin-screw extruder may be either a co-directional bi-axial type or a bi-directional bi-axial type. Further, the type of the heating roll machine can be appropriately selected. In addition, from the viewpoint of the beauty of the marble-like appearance of the obtained molding material and the good practical strength such as crack resistance and impact strength, the conditions of heating and kneading are set to 80 to 120 ° C.
For 10 to 30 seconds.

Re-grinding of the preformed product obtained by the heat kneading can be performed by using any re-grinding means capable of forming a re-grinded product. If desired, sieving means may be used in combination. Examples of crushers used for such re-crushing include:
Examples thereof include a rotary cutter mill, a roll mill, and a pulperizer.

The particle size of the granular re-crushed product (A) in the present invention thus obtained can be changed by changing the diameter of the screen hole of the pulverizer or by sieving according to the desired pattern size of the molded product. It can be appropriately prepared by changing the roughness of, for example, the JIS sieve 42 mesh non-passing portion is 80 wt% or more, preferably, the JIS sieve 2 to 42 mesh particle size is 90 wt% or more. Is good. In order to obtain a molded product having a preferable pattern, the width of the particle size distribution of the component (A) used is preferably not too large. For example, when a fine pattern is desired, a JIS sieve of 24 to 42 mesh is used. Grade of medium size; JIS sieve 16 for slightly coarser patterns
Particle size of ~ 32 mesh; JIS for coarser patterns
5-16 mesh sieve; JIS sieve 2-1 for coarse pattern
It is preferable to select and use particles having a particle size of about 0 mesh so as to be 80% by weight or more.

The amino-based resin molding material of the present invention is prepared by adding a powdery colorant or a colorant-containing amino-based resin molding material powder (hereinafter, referred to as a coloring powder component) to the re-crushed product [component (A)] as described above. In some cases) [Component (B)] and a volatile organic solvent [Component (C)], and dried.

Examples of the powdery colorant include, as in the powdery color component (a), for example, titanium oxide, zinc oxide, zinc sulfide, red iron blue, iron black, ultramarine, carbon black, lithopone, titanium yellow, and cobalt. Powders of inorganic or organic pigments such as blue, Hansa yellow, benzidine yellow, lake red, aniline black, dioxazine violet, quinacridone red, quinacridone violet, naphthol yellow, phthalocyanine blue, phthalocyanine green, or the coloring A so-called master batch in which the filler such as calcium carbonate, melamine crystal, or the like is added to pigments and uniformly dispersed can be exemplified.

As the colorant-containing amino-based resin molding material powder, a pre-dried amino-based resin molding material is finely pulverized together with the coloring pigments and, if necessary, the curing catalyst, a lubricant and the like by the appropriate means as described above. Can be exemplified.

The particle size of the coloring powder component (B) is preferably 70% by weight or more when passed through a 145 mesh using a JIS sieve from the viewpoint of good appearance of the obtained molded article.

The amount of the coloring powder component (B) used is such that when a powdery coloring pigment is used as the component (B),
0.001 to 5 parts by weight per 100 parts by weight of the component (A); when the masterbatch is used as the component (B), 0.001 to 15 parts by weight relative to 100 parts by weight of the component (A);
When a colorant-containing amino resin molding material powder is used as the component (B), the amount is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the component (A).

When the amount of the coloring powder component (B) used is not less than the above lower limit value, the contour of a circular or elliptical pattern on the surface of the obtained molded product is preferably manifested with appropriate sharpness. If the amount of the powdered color pigments is less than the above upper limit, poor dispersion of the pigment is unlikely to occur. "Can prevent roughening;
Further, if the amount of the colorant-containing amino resin molding material powder used is not more than the above upper limit, the number of appearances of the pattern is not reduced or the shape is not incomplete, each beautiful It is preferable because a marble-like pattern appears.

Examples of the volatile organic solvent as the component (C) include organic solvents having a boiling point of about 100 ° C. or less, such as methyl alcohol, ethyl alcohol, i-propyl alcohol, and acetone. One or more of these organic solvents may be mixed, or one or more of these organic solvents may be mixed with water. The amount of the volatile organic solvent used is 2 to 20 parts by weight based on 100 parts by weight of the component (A).
It is preferably from 5 parts by weight, especially from 5 to 15 parts by weight.

In the present invention, the above-mentioned component (A), component (B) and component (C) can be mixed in the same mixing means as used in the process of forming component (A), for example, a V-type mixer, a supermixer, a NOW. Mixer using a ter mixer, tumbler mixer, omni mixer, Henschel mixer, Loedige mixer, ribbon blender, planetary mixer, etc., for example, drying with a hot air circulation dryer, fluidized bed dryer, paddle dryer, etc. By means, for example 50-100
The desired amino resin molding material can be obtained only by drying at a temperature of about ° C.

A molded product obtained by molding such an amino resin molding material of the present invention by a known method such as compression molding or the like has countless circular or elliptical clear patterns on the surface thereof. Outstanding, has a beautiful marble-like appearance, has a remarkably higher gloss than conventional molded products of this type, and has excellent practical strength such as impact resistance. It will be.

〔Example〕

Hereinafter, several embodiments of the present invention will be described in more detail with reference to Examples along with Comparative Examples and Reference Examples.

In the following, the test methods of the disk flow characteristics of the molding material and the surface gloss, appearance and impact resistance of the molded product are as follows.

(1) Disk flow characteristics A 5 g sample was kept at a die temperature of 150 ± 3 ° C using a disk-type test die described in Section 5.3.2 of JIS K-6911. Place the sample in a conical shape using a metal cylinder of 50 mm and a height of about 10 mm, and apply a load of 2000 kgf within 15 seconds.
Then, compression molding is performed for 2 minutes under a pressure.

Measure the major axis and minor axis of the glossy part of the molded disc to 1 mm with a dimension measuring instrument, calculate the average value, and calculate the elongation (m
m).

(2) Surface gloss of molded product Compression molding of test pieces 70 mm long, 60 mm wide and 8 mm high (molding temperature 160 ° C, molding pressure 210 kg / cm ² , curing time
120 seconds). The surface gloss of the molded product is measured using a digital gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. Measured at an incident angle of 60, the specular gloss of the glass surface with a refractive index of 1.567 was 100
The gloss is measured as%.

(3) Appearance of molded product A bowl of 6 inches in diameter and 120 g in weight is compression molded under the following conditions.

Mold temperature 165 ° C (upper mold) 160 ° C (lower mold) Pressure 180kg / cm ² Degassing time 1 second Molding time 120 seconds Observing the bowl molded in this way, the shape of the exposed pattern , The sharpness of the contour, the degree of flow, etc. are visually determined.

(4) Impact strength of molded article An impact strength test is conducted using a flat plate having a diameter of 9 inches and a weight of 150 g, which is compression-molded under the same conditions as in the above (3).

First, a 95 g steel ball is dropped 50 times from a height of 30 cm to a substantially central portion of the flat plate in a prone state. If a crack occurs during that time, the number of steel ball drops until the crack occurs is recorded (for example, if the 35th crack occurs, it is recorded as 30 cm-35 times). If the crack does not occur even after falling 50 times, increase the height by 10 cm (that is, from the height of 40 cm), repeat the above experiment, and record the height and the number of times when the crack occurs. (For example, if a steel ball is dropped from a height of 40 cm and a crack occurs on the 25th time,
Record 40cm-25 times).

Reference Example 1 Melamine (manufactured by Yuka Melamine Co., Ltd .; Yuka Melamine) 1260
g (10 mol), 1380 g (17 mol) of a 37% strength formalin aqueous solution and 900 g of water were placed in a flask equipped with a reflux condenser, and the F / M
The reaction was carried out at 90 ° C. with stirring under the condition of 1.7. When the cloudiness point of the reaction mixture solution reached 60 ° C., 0.8 g of sodium hydroxide was added and cooled to obtain an aqueous solution of a melamine resin precondensate (melamine resin solution). The cloudiness point used as a standard at the end of the reaction refers to the temperature at which cloudiness occurs when 5 ml of a reaction mixture solution is collected, 45 ml of hot water of about 80 ° C. is added, stirred, and cooled.

To 3000 g of the melamine resin liquid (solid content: about 50% by weight) thus obtained, 500 g of pulp (about 25% by weight in 100% by weight of the obtained pre-dried melamine resin molding material) was added. After adding 16 g of methylol propane triolate (0.8% by weight with respect to 100% by weight of the preliminarily dried melamine resin molding material) and kneading with a kneader, the kneaded material was dried at 90 ° C. for 90 minutes with a hot-air drier to form a popcorn-like product. A pre-dried melamine resin molding material was obtained.

Then, 1500 g of the above preliminarily dried product was crushed using a rotary cutter mill having a screen hole diameter of 3 mmφ to obtain a roughly crushed melamine resin molding material preliminarily dried product. This crushed material is JIS
It contained 70% by weight of a sieve having a particle size of 10.5 to 42 mesh.

Reference Example 2 In the same manner as in Reference Example 1, except that the obtained popcorn-like pre-dried melamine resin molding material was pulverized for about 6 hours using a ball mill to obtain 100% by weight of a JIS sieve 42 mesh passing powder. A melamine resin molding material powder was obtained.

Reference Example A 1000 g of the crushed pre-dried product obtained in Reference Example 1, 0.02 g of phthalic anhydride as a curing catalyst, and 0.5 g of zinc stearate as a lubricant were mixed for about 1 minute using a super mixer to obtain a homogeneous powder. I got a body. Next, the powder was heated and kneaded with a twin-screw extruder. The kneading extruder has a shaft diameter of 55 mmφ, L / D = 2
0, using a screw with a compression ratio of 2.0, the powder and granular material supply speed is 2k
The preform was extruded by heating under the conditions of g / min, a cylinder temperature of 100 ° C., and a screw rotation speed of 100 rpm.

After crushing this preform, the screen hole diameter is 6mm
Pulverize using a rotary cutter mill of φ and sieving
A re-crushed product having a JIS sieve of 5 to 16 mesh particle size was obtained.

Reference Example B In Reference Example A, 950 g of the crushed product of the pre-dried product obtained in Reference Example 1 was replaced with 950 g of the crushed product and a red melamine resin molding material as a powder coloring component [trade name: Nicalet
MC, color No. R3833; manufactured by Nippon Carbide Industry Co., Ltd.] (particle size: J
A re-crushed product having a particle size of 5 to 16 mesh of JIS sieve was obtained in the same manner as in Reference Example A except that 50 g of IS sieve passing through 200 mesh (80% by weight or more) was used.

Reference Example C In Reference Example A, 900 g of the crushed product of the pre-dried product obtained in Reference Example 1 was replaced by 900 g of the crushed product and 100 g of a red melamine resin molding material similar to that of Reference Example B as a powder coloring component.
A re-crushed product having a JIS sieve having a particle size of 5 to 16 mesh was obtained in the same manner as in Reference Example A except that it was used.

Reference Example D In Reference Example A, instead of 1000 g of the pre-dried material obtained in Reference Example 1, 1000 g of the crushed material and a barium sulfate-based masterbatch containing 2% by weight of bengara (particle size: JIS
A re-crushed product having a particle size of 5 to 16 mesh of JIS sieve was obtained in the same manner as in Reference Example A except that 40 g of a 145 mesh sieve was used (90% by weight or more).

Reference Example E In Reference Example A, a granular form was obtained in the same manner as in Reference Example A except that 1000 g of the melamine resin molding material powder obtained in Reference Example 2 was used instead of 1000 g of the crushed pre-dried product obtained in Reference Example 1. Obtain a re-crushed material, sieving this re-crushed material, JIS sieve 30
The non-meshed portion was collected. The compressive strength of this reground product was about 10 kg / cm ² or more.

Reference Example F In Reference Example 1, the obtained pre-dried popcorn-shaped melamine resin molding material was crushed using a rotary cutter mill having a screen hole diameter of 6 mmφ, and melamine having a particle size of JIS sieve 5 to 16 mesh was sieved. A crushed product of a pre-dried resin molding material was obtained.

Example 1 450 g of a re-crushed melamine resin preform obtained in Reference Example A, a barium sulfate-based masterbatch containing 0.2% by weight of carbon black as a powdery colorant (particle size: J
After mixing 50 g of an IS sieve 145 mesh passing 90 wt% or more) and 50 g of acetone as a volatile organic solvent using a tumbler mixer having a capacity of 5 for about 10 minutes, the internal temperature was adjusted to 70 ° C. It was dried for about 30 minutes by a hot air circulation type dryer to obtain a melamine resin molding material. Using this molding material, the disk flow characteristics of the molding material, the gloss of the molded product, the appearance of the molded product, and the impact strength of the molded product were tested in accordance with the above-described test methods. Table 1 shows the obtained results.

Examples 2-3 A melamine resin molding material was obtained in the same manner as in Example 1 except that the ratio of the re-crushed product obtained in Reference Example A to the master batch was changed. Table 1 shows the composition of the molding material and the test results of various tests.

Example 4 In Example 1, instead of the masterbatch based on barium sulfate containing 0.2% by weight of carbon black as a powdery colorant, a black melamine resin component material [trade name:
Nicaret MC, color No.S-6524; Nippon Carbide Industry Co., Ltd.
(Particle size: JIS sieve 200 mesh passing 80% by weight or more), and based on 480 g of the re-crushed melamine resin preform obtained in Reference Example A, the melamine resin molding material
A melamine resin molding material was obtained in the same manner except that 20 g was used. Table 1 shows the composition of the molding material and the test results of various tests.

Examples 5 to 7 In Example 1, the re-crushed products obtained in Reference Examples BD to D were used instead of the re-crushed products obtained in Reference Example A, and the same as those used in Example 1 and these re-crushed products A melamine resin molding material was obtained in the same manner as in Example 1 except for changing the use ratio with the master batch. Table 1 shows the composition of the molding material and the test results of various tests.

Comparative Example 1 Only 450 g of the re-crushed material obtained in Reference Example A and 50 g of the same master batch as in Example 1 (without using a volatile organic solvent) were placed in a tumbler mixer having a capacity of 5 and mixed for about 10 minutes. Thus, a melamine resin molding material was obtained. Table 1 shows the composition of the molding material and the test results of various tests.

Comparative Example 2 In Comparative Example 1, 450 g of the re-crushed product obtained in Reference Example A
Same as Comparative Example 1 except that instead of using 50 g of the same master batch as in Example 1, 499 g of the re-crushed product obtained in Reference Example E and 1 g of a mixture of 5 parts by weight of titanium and 2 parts by weight of cobalt blue were used. Thus, a melamine resin molding material was obtained. Table 1 shows the composition of the molding material and the test results of various tests.

Comparative Example 3 A melamine resin molding material was obtained in the same manner as in Example 1, except that the crushed product of Reference Example F was used instead of using the re-crushed product obtained in Reference Example A. Table 1 shows the composition of the molding material and the test results of various tests.

Continuation of the front page (56) References JP-A-59-8747 (JP, A) JP-A-63-7911 (JP, A) JP-A-2-227450 (JP, A) JP-A-62-36452 (JP, A) JP-A-3-139553 (JP, A) JP-A-60-262848 (JP, A) JP-A-60-262849 (JP, A) JP-A-57-117533 (JP, A) 62-243637 (JP, A) JP-B-43-18449 (JP, B1) JP-B-43-27494 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 61/20 -61/32 C08G 12/00-12/46 WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. A preformed product obtained by heating, kneading and extruding a powder containing a crushed product of the following A to C, A. amino resin molding material predried material,
B. JIS sieve 145 mesh repassable 70% by weight or more powdered colorant or colorant-containing amino resin molding material powder; 70% by weight or more; An amino-based resin molding material obtained by mixing and drying a volatile organic solvent.