JPH01247438A - Molding material for potterylike coating and pottery-like coated molding prepared therefrom - Google Patents

Abstract

PURPOSE:To obtain the title molding giving an impression of weightiness and good quality, having a strong adhesion to a paint film and being applicable to tableware, by subjecting the surface to the coated of a molding formed from a molding material comprising a resin composition formed by mixing a polyolefin resin with a specified filler to plasma irradiation and coating this surface. CONSTITUTION:The title molding is obtained by molding a molding material comprising a resin composition formed by mixing 100 pts.wt. mixture of 40-80wt.% polyolefin resin with 60-20 pts.wt. talc with 0.1-10 pts.wt. at least one filler selected from among mica, an aluminum powder and an inorganic fiber (e.g., silica-alumina fiber) into any desired shape, subjecting the surface to be coated of this molding to plasma irradiation and coating this surface. Accordingly to the above process, the obtained molding is one which gives a suitable impression of weightiness and good quality and very strong adhesion to a paint film, can be easily given the desired pottery-like appearance and can be applied to a microwave oven when applied to tableware.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a molding material for pottery-like coating and a pottery-like coated molded article using the same. In more detail,
The ceramic of the present invention has excellent characteristics such as having a moderate weight feeling, good texture, extremely strong coating film adhesion strength, and can be used in a microwave oven when applied to tableware. This invention relates to a molding material that can give a painted molded product and that can easily produce a desired pottery-like appearance, and a ceramic-like painted molded product that has the above-mentioned excellent characteristics and is produced using this molding material. be.

[Prior Art] Plastics have been widely used in many fields because they are lightweight, highly corrosion resistant, and inexpensive. However, when these plastics are used, for example, in general containers, tableware, decorations, and household appliances, these products lack a sense of weight and have insufficient texture, giving the impression that they are cheap products. An unavoidable problem arises.

For this reason, various attempts have been made to make the weight, texture, appearance, etc. of the plastic products more ceramic-like in order to give them an image as high-class products. For example, attempts have been made to apply multiple coats of paint or texture to the surface of plastic molded products. However, with painting alone, a sufficient pottery texture cannot be obtained, and the adhesion strength of the coating film is insufficient, leading to problems such as poor durability.

On the other hand, inorganic fillers, organic fillers,
Attempts have been made to incorporate a large amount of metal powder.

However, in this method, the filler is uniformly dispersed, making it impossible to create a natural ceramic feel.Also, even with complementary color coating as described above, the adhesion of the coating film may be insufficient, and it is difficult to produce a natural ceramic feel. When applied to a microwave oven, there are some drawbacks such as difficulty in using it in a microwave oven.

[Problems to be Solved by the Invention] Under these circumstances, the present invention has a suitable weight feeling, a good texture, an extremely strong coating film adhesion strength, and a desired ceramic material. The purpose was to provide a pottery-like coated molded product that has the excellent characteristics of being able to easily create the desired tone and also being able to be used in a microwave oven when applied to tableware. .

[Means for Solving the Problem] As a result of intensive research to achieve the above object, the present inventors have developed a molding material consisting of a resin composition in which a predetermined amount of a specific filler is blended with a polyolefin resin. After molding the molded product into a desired shape and subjecting the surface of the molded product to plasma irradiation treatment, the inventors discovered that the coated product has scales that are suitable for the purpose.Based on this knowledge, the present invention was completed.

That is, the present invention provides (A) polyolefin resin 10
to 100 parts by weight of a mixture of ~80% by weight and (B) 60 to 20% by weight of talc, (C) at least one selected from thermosetting resin powder, mica, aluminum powder, and inorganic fibers. A molding material for pottery-like painting consisting of a resin composition containing 1 to 10 parts by weight, and this molding material was molded into a desired shape, and then the surface of the molded object to be painted was subjected to plasma irradiation treatment. Later, a pottery-like coated molded product was provided by applying a coating.

The present invention will be explained in detail below.

The resin composition used as the molding material of the present invention includes (
A) A polyolefin resin is used as the component. Examples of the polyolefin resin include ethylene, propylene, butene-1゜3-methylbutene-113-methyl-pentene-1,4-methylpentene-1, etc.
- Examples include homopolymers of olefins, copolymers thereof, and copolymers of these and other copolymerizable unsaturated monomers. Typical examples include high density, medium density,
Polyethylenes such as low-density polyethylene, linear polyethylene, ultra-high molecular weight polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, atactic, syndiotactic, isotactic polypropylene, and propylene. Polypropylenes such as ethylene block copolymers or random copolymers,
Examples include poly-4-methylpentene-1.

These polyolefin resins are suitable as materials for tableware and the like that can be used in microwave ovens.

In the present invention, these polyolefin resins are
A species may be used, or two or more species may be used in combination.

Talc is used as the (B) component in the resin composition of the present invention. This talc is also called soapstone, talcum, French chalk, and steatite, and its component is hydrous magnesium silicate, which is less toxic to the human body and is therefore suitable for use as a filler for tableware. The talc used in the present invention has an average particle size of 0.
The thickness is preferably in the range of 1 to 20 μm, more preferably 1 to 10 μm.

The talc has the effect of imparting weight, rigidity, heat resistance, and hiding properties to the molded product, and its blending amount is as follows:
20 to 20% based on the total weight of the polyolefin resin
It is selected in the range of 60% by weight, preferably 30 to 50% by weight. If the amount is less than 20% by weight, the above effects will not be fully exhibited, and if it exceeds 60% by weight, the surface appearance of the molded product may be impaired.

The resin composition in the present invention contains thermosetting resin powder, mica, aluminum powder, and inorganic molar powder as component (C).
At least one type selected from fibers is used. .

Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, diallyl phthalate resin, and guanamine resin, among which phenol resin is preferred. These thermosetting resins are used in powder form, and the particle size thereof is usually selected in the range of 1 to 100 μm, preferably 10 to 700 μm. Further, mica or aluminum powder having a particle size in the range of 1 to 500 μm, preferably 3 to 300 μm is used.

Examples of the inorganic fibers include fibers such as silica-alumina fibers, glass fibers, poron fibers, silicon carbide fibers, brass fibers, stainless steel fibers, alumina fibers, single crystal potassium titanate fibers, and whiskers thereof.

These component (C) fillers have the effect of imparting a good surface appearance by appropriately protruding onto the surface of the molded product. In the present invention, the filler of the component (C) may be used alone or in combination of two or more, and the blending amount is determined by the amount of the component (A) and the component (B). The amount is selected in the range of 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight, based on 100 parts by weight of the total amount. If the amount is less than 0.1 parts by weight, it is difficult to obtain a molded product with a good surface appearance, and if it exceeds 10 parts by weight, there is a risk that the adhesion of the coating film may deteriorate.

The resin composition of the present invention may contain other inorganic fillers, metallic fillers, and organic fillers as desired within a range that does not impair the purpose of the present invention.

Examples of the inorganic filler include porphyry, diatomaceous earth, pumice, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, dolomite, dawsonite, barium sulfate, ammonium sulfate, and KR. Examples include clay, asbestos, glass balloons, glass peas, calcium silicate, montmorillonite, bentonite, carbon dioxide, molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate, etc. . Examples of metal fillers include:
Zinc, copper, iron, lead, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium 9,
Powders and granules of metal elements such as cobalt and strontium, oxides of these metals, alloys such as stainless copper, solder, and brass, and metal ceramics such as silicon carbide, silicon nitride, zirconia, aluminum nitride, and titanium carbide. One example is the body. In addition, the organic filler C is
For example, husk fibers such as rice husks, wood flour, cotton, jute, paper strips, cellonite strips, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, polypropylene m1! I can list things like &. Depending on the desired stiffness, one type of filler may be used, or two types of fillers may be used.
You may use combinations of more than one species.

In the resin composition of the present invention, the inorganic filler or metal filler used as an essential component or an optional component can be surface-treated with a known surface treatment agent as desired. Examples of the surface treatment agent include silane coupling agents, titanate coupling agents, silica powder, silicone oil, higher fatty acids, higher alcohols, and waxes. Among these, silane coupling agents, titanate coupling agents and silicone oils are preferred. These surface treating agents may be used alone or in combination of two or more.

There are no particular limitations on the silane coupling agent, and any one can be selected from conventionally known ones. Specific examples of the silane coupling agent include triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4 -epoxycyclohexyl)
Ethyltrimethoxysilane, N-β-(aminoethyl)γ-amino/propyltrimethoxysilane, N-β-(
aminoethyl) γ-aminopropylmethyldimethoxy,
Ran, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxy, Vran, γ-
Examples include mercaptoglobiltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like. Among these, γ-aminopropyltriethoxysilane, N-β
-(Aminoethyl)γ-aminopropyltrimethoxysilane is preferred.

There are no particular limitations on the titanate coupling agent, and any titanate coupling agent can be selected and used from among conventionally known ones. Specific examples of the titanate coupling agent include isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyltitanate, isopropyltris(dioctylpyrophosphate)titanate, tetraisoglopyrubis(dioctylphosphite)titanate, and tetraoctylbis( ditridecyl phosphite) titanate, tetra(
2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isoprobyltriotatanoyl titanate , isopropyl dimethacrylic isostearoyl titanate,
Isopropyl isostearoyl diacrylic titanate,
Examples include isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N-amidoethyl aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, and the like. Among these, isopropyl triisostearoyl titanate, isopropyl tri(N-amidoethyl
Aminoethyl) titanate is preferred.

Furthermore, examples of the silicone oil include dimethyl silicone, methylphenyl silicone, polyether-modified silicone, alkyl-modified silicone, and methylhydrodiene polysiloxane, with dimethyl silicone and methylhydrodiene polysiloxane being particularly preferred.

There are no particular restrictions on the method of surface treating the filler using these surface treatments, and the surface treatment can be carried out using commonly used methods, or the temperature, treatment speed, etc. can be arbitrarily changed. From the viewpoint of possibility, it is preferable to spray the surface treatment agent onto the filler and mix and stir the mixture in a Henschel mixer.

There is no particular restriction on the amount of treatment agent used in such surface treatment, but usually per 100 parts by weight of the filler,
0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight,
More preferably, it is selected within the range of 0.1 to 2 parts by weight. If this amount is less than 0.01 part by weight, the effect of wetting the polyolefin resin and filler will not be sufficiently exerted, resulting in poor molding workability, which is not preferable. On the other hand, if it exceeds 5 parts by weight, the lubricating effect is too great, causing slipping, resulting in poor pellet productivity and molding workability, and excessive bleed-out of the treatment agent, which impairs the appearance, which is not preferable.

Furthermore, in the resin composition, the compatibility between the polyolefin resin and the inorganic filler or metal filler used as an essential component or an optional component is improved, and mechanical properties and dimensional stability are improved. For the purpose of providing molded articles with excellent properties, chemical modifiers such as modified polyolefins, low molecular weight polypropylene, oxidized low molecular weight polypropylene, etc. may be blended as desired.

Examples of the modified polyolefin include unsaturated organic acids or derivatives thereof, such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; acid anhydrides, esters of unsaturated organic acids such as methyl acrylate, monomethyl maleate, acrylamide,
An amide of an unsaturated organic acid such as fumaric acid monoamide or an imide of an unsaturated organic acid such as itaconic acid imide is added to 100 parts by weight of an ethylene or propylene polymer.
Examples include those modified by the grafting method with the addition of o, os to 20 stone parts. In this modification, organic peroxides such as penzoyl peroxide, lauroyl peroxide, dicumyl peroxide, (-butylhydroperoxide/1-) are used to promote the modified polymerization.

Also, in addition to the above, are there other materials such as ethylene and propylene polymers? Glycidyl acrylate, glycidyl methane lylate, vinyl glycidyl ether, acrylic glycidyl ether, etc. are graft-modified with unsaturated epoxy compounds, etc. Those to which rubber is added can also be used.

In addition, as a low molecular weight polypropylene, the molecule ff11
．． 500-20. Those within the OQO range are preferably used. On the other hand, oxidized low-molecular-weight polypropylene is obtained, for example, by oxidatively decomposing isotactic polypropylene with an oxidizing agent such as peroxide in the internal phase, melt phase, or solution phase. It exists in the form of The oxidized low molecular weight polypropylene preferably has an average molecular weight in the range of i,soo to 20,000. Among these chemical modifiers, modified polyolefins are preferred. Moreover, in the composition, one type of the chemical modifier may be used, or two or more types may be used in combination.

Second, the amount of the chemical modifier is usually 0.5 parts by weight per 100 parts by weight of the total amount of polyolefin resin and filler.
~10 parts by weight, preferably 1 to 7 parts by weight.

Furthermore, the resin composition may optionally contain various additives commonly used in polyolefin resin compositions, such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, and flame retardants. , a plasticizer, etc. can be added.

The molding material of the present invention comprises a required amount of the above component (A), (B)
It can be prepared by melt-kneading and compounding the components, component (C), and various fillers and additives used as desired according to a conventional method. Melt kneading can be carried out, for example, by a method using a Henschel mixer, a single-screw or twin-screw extruder, a Banbury mixer, a roll, etc., or by other seat methods, but in particular, by using a Henschel mixer, an extruder, or a Banbury mixer. It is preferable to do so.

In order to create the ceramic-like molded article of the present invention using a molding material made of the polyolefin resin composition thus prepared, first, the molding material is shaped into a desired shape using a molding method or the like. After molding, the surface of the molded product to be painted is subjected to plasma irradiation treatment, and then paint is applied. If the plasma irradiation treatment is not performed, there is a risk that sufficient coating film adhesion may not be obtained.

Examples of such materials include solvent evaporation paints, self-curing paints, heat-curing paints, photo-curing paints, and natural lacquer paints. Among the paints described in 111 (1), self-curing paints, heat-curing paints, photo-curing paints, and natural lacquer paints are preferred.

Examples of the solvent evaporation paint include cellulose-based, vinyl-based, acrylic-based, etc. Examples include ri-sei varnish,
Examples of self-curing paints include oxidative polymerization paints such as alkyd-based, epoxy resin ester-based, fatty acid-modified urethane-based, oil-modified phenol-based, lacquer-based, and oil-based varnish, as well as polyurethane-based, epoxy-based, and unsaturated polyester. Examples include multi-component reactive paints such as In addition, examples of heat-curing paints include alkyd-based, aminoalkyd-based, epoxy ester-based, epoxy-based, polyurethane-based, acrylic-based, acrylic urethane-based, vinyl-based, and boronoxane-based paints, and photocurable paints. Examples include unsaturated polyesters, acrylics, acrylated alkyds, polyester acrylates, polyether acrylates, acrylated epoxys, acrylics, acrylated spiranes, acrylated silicones, polythiols, and cationically polymerized epoxies. Examples include those that harden by irradiation with ultraviolet rays, such as irradiation with ultraviolet rays.

In order to obtain a ceramic-like product, as mentioned above, it is preferable to use a paint that forms a hard coating, and when making products such as tableware, the parts that come into contact with food should be coated with a paint that complies with the Quality Sanitation Law. It is preferable that

There are no particular limitations on the method of coating the surface of the molded article, and methods such as spraying, brushing, dipping, etc. can be employed as appropriate. Also, painting is not limited to one time,
You may apply multiple coats such as undercoat, intermediate coat, and topcoat,
In order to emphasize the ceramic appearance, paint sag may be formed on the surface of the molded product, or texture coating may be applied.

The ceramic-like coated molded product of the present invention thus obtained is
It has a moderate weight, has a good texture, has an extremely high adhesion strength to the coating, and when applied to tableware, it can be used in a microwave oven.
Suitable for use in Japanese tableware, vases, flowerpots, containers such as flower arranging basins, decorative items, and housings for home appliances.

[Example 1] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

In addition, the evaluation of the painted product was performed as follows.

(1) Flexural modulus Measured in accordance with ASTM D790.

(2) Heat distortion temperature Compliant with ASTM D 648, The measurements were carried out under the conditions of loads of 4 and 6 kg/cm2.

(3) FiJ flexibility A plate of length 100 mm, width 100 mm, and thickness 3.2 mm was molded, and its condition was checked according to the following criteria.

O: The filler inside the molded product is not visible at all.

Δ: The filler inside the molded product is slightly visible.

×: The filler inside the molded product is visible.

(4) Surface appearance The state of dispersion of the filler in the plate in (3) was checked according to the following criteria.

○: Distributed unevenly on the batter surface, giving a feeling of relief.

67 It is unevenly distributed on the surface, and the feeling of relief is slightly lacking.

×: Uniformly dispersed on the surface, lacking a sense of relief.

(5) Performance of a 1ft Microwave Microwave A sample bowl was placed in a 500W microwave oven, and the time it took for an abnormality to occur in the bowl was measured while the bowl was in an empty state.

(6) Paint film adhesion Make 100 base marks on the paint film surface with a sharp knife, strongly press cellophane tape (16 mm width) manufactured by Nichiban Co., Ltd.
When the cellophane tape was then rapidly peeled off, the number of base lines remaining was defined as χ, and the film adhesion was expressed as χ/100.

Moreover, the following matrix resin and filler were used.

(I) 7 Toss Z resin 1) P: Polypropylene (3 = 0.90g7cm
” (Idemitsu Petrochemical, J-2000G) PE: Polyethylene d = 0.96 g/cm3 (
Idemitsu Petrochemical, ll0J) 1) ET: Polyethylene terephthalate d = 1.2
1 g7cm3 (Unitika, MA, -2101) 6-PA: 6-nylon d = 1.14 g/cm
'(Kanebuchi Chemical, LM-102) 1) C: Polycarbonate d = 1.20 g/c
m3 (Idemitsu Petrochemical Co., Ltd., N-2500) ABS: Acrylonitrile-butadiene-styrene copolymer d = 1.05 g/cm3 (Japan Synthetic Rubber Co., Ltd., JSR-35) Phenol: Phenol resin (II) Filler Talc: Morning Made by Izu Flour, average particle size 5 pm, d = 2.7 g/cm3 Mica: Made by Kuraray, average particle size 10 pm, d -2.7 g/cm1'4;
IL/P-converted tL resin: Phenolic resin particles, manufactured by Unitika, Rt ¥50-500μm 7' Lumiyaku/Showa Aluminum, ・1j-average particle size 101'nl, d = 2.7 g7
cm3 Inorganic fibers, alumina fibers, Asano cement return ring: Cal carbonate 7. Lamb, manufactured by Dowa Calfa Inn, average particle size 2
μm, d = 2.7 g/cm” Berium sulfate: Manufactured by Barai I-Ko1, average particle size 3 μm, d = 4.59/C1I+3Example X'
lll ~ 22 Extruded at a temperature of 200 to 230 ° C. with a single screw extruder (manufactured by Tokata Ni Kikai, 50 ■) with the composition shown in Table 1,
A pellet was prepared. 2) Form this pellet into a bowl of the shape shown in Figure 1, and use a microwave treatment system (manufactured by Toshiba Corporation, TI (W-7407)) for treatment gas: air, treatment time. : The bowl was subjected to Fu!Suma irradiation treatment under the conditions of 1 minute, 500 W of power, and 1 Torr of pressure.Next, this was coated with %J of Power/Nee Co., Ltd., and urethane paint (S) Ron 800. The product was spray-painted and then baked at 100'C for 30Ij' to finish.Evaluations were made on this product, and the results are shown in Table 1.

(The following is a blank space) Comparative Examples 1 to 16 Coated products were prepared and evaluated in the same manner as in the examples, except that the formulations shown in Table 2 were used. The results are shown in Table 2.

Comparative Examples 17 to 19 Painted products were prepared and evaluated in the same manner as in the Examples, except that the formulations shown in Table 2 were used and the plasma irradiation treatment was not performed.

The results are shown in Table 2.

(F margin) [Invention gold,! I! l] The molding material for pottery and painting of the present invention is polyolefin-based! jl iij'Il: The ceramic-like coated molded article of the present invention, which is made of a resin composition containing a predetermined amount of a specific filler, and which is made using the molding material, has a moderate It has a good texture, and the coating film is extremely strong, and when applied to tableware, it is excellent in that it can be used in a microwave oven. It has the following characteristics and is suitably used for tableware, general containers, ornaments, home appliances, etc.

[Brief explanation of the drawing]

Figure 1 shows the ceramic-like (
FIG. 2 is a perspective view of a p-packaged molded product.

Claims (1)

[Scope of Claims] 1 (A) 40 to 80% by weight of polyolefin resin and (
B) 100 parts by weight of the mixture with 60 to 20% by weight of talc, (C) at least one selected from thermosetting resin powder, mica, aluminum powder, and inorganic fibers.
．． A molding material for pottery-like coating comprising a resin composition containing 1 to 10 parts by weight. 2. A pottery-like coated molded product formed by molding into a desired shape using the molding material according to claim 1, then subjecting the surface of the molded product to plasma irradiation treatment, and then painting.