JPH02214747A - Rubber or resin composition having golden color - Google Patents

Abstract

PURPOSE:To obtain the subject composition exhibiting golden color, having excellent stability and useful for food-packaging film, etc., by compounding specific plate particles of hematite into a constituent base material of a rubber or resin composition. CONSTITUTION:The objective composition can be produced by compounding a constituent base material of a rubber or resin composition with plate hematite particles having an average particle diameter of 0.5-5.0mum, a thickness of 50-500Angstrom , a plate ratio of (50-500):1, a brightness L* of >=30, a hue theta=tan<-1>b*/a* of >=50 deg. and a chroma C*ab=(a*<2>+b*<2>)<1/2> of >=17 [in the formula L*, a* and b* are values expressed by CIE 1976 (L*, a*, b*) uniform perception color space].

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a golden color with metallic luster by blending plate-shaped hematite particles exhibiting a golden color into a base material constituting a rubber or resin composition. The object of the present invention is to provide a rubber or resin composition that exhibits the following properties. Its main uses include materials for electrical appliances, materials for daily miscellaneous goods such as tableware, materials for building materials, materials for containers,
Decorative materials such as buttons.

[Conventional technology]

Rubber or resin compositions include various rubbers or synthetic resins and various stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers, which are blended as necessary, into the base material of the rubber or resin composition. , are obtained by blending colored pigments with various glosses and colors from an aesthetic point of view.

Conventionally, hematite particles, which are the most typical iron oxide pigment, have a red color and are therefore widely used as rubber or resin compositions that are blended into rubber or resin composition base materials to give a red color. .

Furthermore, since the plate-like hematite particles exhibit a blackish-purple color, they are used as a rubber or resin composition that exhibits a blackish-purple color by being blended into a rubber or resin constituent base material.

In general, rubber or resin compositions containing iron oxide pigments have a high resistance to acids in the base material of the rubber or resin composition when the rubber or resin composition is created because the pigment is an oxide. Moreover, it is characterized by excellent weather resistance against environmental pollution and the like.

On the other hand, in recent years, due to the improvement of culture and lifestyle, in addition to improving the functional quality of products, quality characteristics from a sensual and hobby perspective are required. Color is strongly requested.

Conventionally, rubber or resin compositions exhibiting a golden color with metallic luster have been produced by blending brass powder, alloy powder of brass and zinc, or mixed powder of brass powder and zinc powder into the rubber or resin composition constituent base material. It is economically advantageous.

[Problem to be solved by the invention]

A rubber or resin composition that exhibits a golden color with metallic luster is
However, in the case of using the known method as described above, since the pigment is a metal powder, the resistance to acids in the base material of the rubber or resin composition is low, and it also causes environmental pollution. It also has poor weather resistance against
There was a problem of lack of stability.

On the other hand, as mentioned above, rubber or resin compositions containing iron oxide pigment powder have excellent stability;
I have not yet obtained anything that exhibits a golden color.

Therefore, the technical object of the present invention is to provide a rubber or resin composition that exhibits a golden color by incorporating iron oxide pigment powder.

[Means to solve problems]

The inventor of the present invention arrived at the present invention as a result of various studies aimed at obtaining a rubber or resin composition exhibiting a golden yellow color by incorporating iron oxide pigment powder.

That is, the present invention has an average diameter of 0.5 to 5.0 μm, a thickness of 50 to 500 μm, and a plate ratio of 50:1 to soo:t.
, and the brightness value is 30 or more, and the hue θ-tan-
'b/a is 501 or more, chroma C" ab-, /"-τ"
"End is 17 or more (where 111, .11, bll is a bond displayed in CT[!1976 (L"a'", bl) uniform perceptual color space.

This is a rubber or resin composition that exhibits a golden color and is made by blending plate-shaped hematite particles ( ) into a rubber or resin composition constituent base material.

[For production]

First, the most important point in the present invention is that the iron oxide pigment, which is a coloring pigment, has an average diameter of 0.5 to 5.0 μm, a thickness of 50 to 500 μm, and a plate ratio of 50:1 to 500:1.
, and the brightness value is 30 or more, and the hue θ-tan-
'b*/a* is 50' or more, chroma C" ab-, /-1
1+ b” is 17 or more (in the formula, Lm , all , il
l is a value expressed in the ClO41976 (pi a *, bll ) uniform perceptual color space. ) is used as a plate-shaped hematite particle powder.

Particularly preferred iron oxide pigment powder in the present invention has an average diameter of 1.0 to 4.0 μm and a thickness of 100 to 400 μm,
The plate ratio is 100:1 to 300:1, and
Brightness pi value is 35 to 65, hue θ-tan-'b/a' is 50° or more, saturation C"abm a + b"i<
20 or more.

Although the reason why the rubber or resin composition according to the present invention exhibits a golden color is not yet clear, the present inventor believes that the particle morphology and surface condition of the plate-shaped hematite particles used as the coloring pigment are involved. I believe.

In addition, conventionally, plate-shaped hematite particle powder was published by Color Materials Association.
"Coloring Materials Association Journal" Volume 60, No. 5 (1987) No. 265~
As described in 272, it is generally obtained by hydrothermally treating an alkaline suspension containing ferric iron and having a pH of 9 or more, and for controlling the particle morphology of the plate-like hematite particles that are produced, for example, There are methods described in JP-A-61-174120 and JP-A-55-104923.

When using the method described in JP-A-61-174120, the plate-shaped hematite particles obtained have an average diameter of 0.5 to 2.
0 μm, a plate ratio of 20:l to 100:l, and the hue θ-tac1b"/a' is 50° or less, or the saturation C"abm,/-1"71π is 17 or less, Furthermore, when using the method described in JP-A-55-104923, the obtained plate-like hematite particles have a hue of θ
-jan-'b*/a* is 50@ or less or the saturation C1l ab,=r+b'' is 17 or less,
In either case, these particles are completely different from the plate-shaped hematite particles used in the present invention.

Next, various conditions for implementing the present invention will be described.

The plate-shaped hematite particles in the present invention are ferric salts, hydrous ferric oxide particles, or EJJIX f'ezOs (0≦
X≦1) In a method of producing magite particle powder into a plate shape by hydrothermally treating an alkaline suspension containing p) 19 or more particles, Fe 1 s + ol is added in advance to the alkaline suspension. ,0°1=
15. The Os+ol ratio of water-soluble salt and Fe is 1.5 to 20 in terms of Si. It is obtained by adding OmolX and a compound containing si, and then hydrothermal treatment.

As the ferric salt, ferric chloride, ferric sulfate, etc. can be used.

Hydrous ferric oxide may be in any particle form, such as needle-shaped or spindle-shaped, obtained by various well-known reactions.
A wet cake obtained by washing a reaction mother liquor containing hydrated ferric oxide with water and heating in a furnace, and a dried product of the wet cake can be used.

Pressure x-Fe snow 0. (0 ≦ Acicular or spindle-shaped PiQ obtained by reducing the dried wet cake and the above-mentioned needle-shaped or spindle-shaped hydrous ferric oxide particles, or further oxidizing if necessary
x-Fe1o, (0≦X≦1) particles, etc. can be used.

The pi of the alkaline suspension is 9 or more. 9 or less, the plate-like heftite particles contain acicular hydrated ferric oxide particles or F130X/Fe12. Particles become mixed.

Hydrothermal treatment is carried out using an autoclave device, usually at a temperature of 150~
Generally, the higher the alkali concentration, the lower the reaction temperature at which plate-shaped hematite particles are produced. When the temperature is 150° C. or lower, hydrated ferric oxide or PeOx·Fe1O1 remains, and plate-like hematite particles are not generated. Although it is possible to produce plate-shaped hematite particles at a temperature of 330°C or higher, the upper limit of the temperature is 330°C in consideration of equipment safety.

Water-soluble salts include alkali metal sulfates, nitrates,
There are chlorides, acetates, etc.

The amount of water-soluble salt added is 0.1 to Pel sol.
~15, Omol ratio. If the amount is less than 0.1mol, the color of the plate-shaped hematite particles, especially the hue and saturation, will be small, and the desired plate-shaped hematite particles will not be obtained. Although plate-shaped hematite particles can be obtained, there is no point in adding more than necessary.

Examples of compounds containing St that can be used include potassium and sodium silicates, colloidal silica, and the like.

The amount of the compound containing Si added is 1 in Si equivalent to Fe.
．． 5 to 20.0 mol
Only particles with a diameter of 00 Å or more are obtained, resulting in a small plate-like ratio and a black-purple color. In the case of 20 atomic % or more, the thickness of the plate-like hematite particles becomes thinner than 50,
Compounds containing water-soluble salts and St that are likely to cause the particle-shaped fragmentation phenomenon affect the particle morphology and surface properties of the plate-shaped hematite particles that are produced. It is necessary to add them before the production reaction starts, and the order of addition may be either first or simultaneously.

As the amount of the water-soluble salt added increases, the average diameter of the plate-like hematite particles that are formed becomes thicker (tends to become larger), and as the amount of the compound containing St increases, the average diameter of the plate-like hematite particles that are formed increases. There is a tendency for the thickness to become thinner and the plate-like ratio to become larger.

The blending ratio of plate-shaped hematite particles in the present invention is 0.1 to 9 parts by weight based on 100 parts by weight of the rubber or resin composition base material.
It can be used in an amount of 0 parts by weight, and in consideration of color and gloss, it is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight.

The rubber or resin composition constituent base material in the present invention includes:
Resin and various stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers are blended as necessary.

As the resin, thermoplastic resins such as polystyrene resin, polyethylene resin, AS resin, ABS resin, vinyl chloride resin, EVA resin, PMMA resin, polyamide resin, and polypropylene resin, which are commonly used for resin compositions,
Thermosetting resins such as phenol resins, urea resins, melamine resins, alkyd resins, epoxy resins, and polyurethane resins can be used.

In addition, as rubber, nitrile rubber, isoprene rubber,
Styrene-butadiene rubber, silicone rubber, chloroprene rubber, etc. can be used.

〔Example〕

Next, the present invention will be explained with reference to Examples and Comparative Examples.

In addition, the average diameter of particles in the following Examples and Comparative Examples is shown as the average value of numerical values measured from electron micrographs, and the thickness and plate ratio are the specific surface area value measured by the BET method and the above average diameter. It is shown as a numerical value obtained from.

In addition, L of plate-shaped hematite particles and rubber or resin compositions
” value (brightness), a0 value and b0 value, respectively, are the sample piece for coloring and the sheet-like film molded body of Color 7970M.
-1500-A type (manufactured by Color Machine ■)
The PI value, a0 value, and b" value were measured using the Lab space of ter.
n Internationale de 1'
[Iclairage.

C1ε) 1976 (Pi, *, b*) Values expressed according to the uniform perceptual color space.

The sample piece for measurement was made of 0.5 g of hematite particle powder and 1.5 g of castor oil. Occ was kneaded with a two-bar muller to form a paste, and 4.5 g of clear lacquer was added to the paste to form a paint, which was applied onto cast coated paper using a 6 ml applicator.

<Production of plate-shaped hematite particles> Examples 1 to IO Comparative Examples 1 to 3; Example 1 α-PeOOII (long axis 1.Ottws, BflT
Specific surface area 50.2rrf/g) 0.2s+ol, Na
NOs 0.6 mol (3 mol for Felsol
Applies to. ) and No. 3 water glass (Sing 28.5
5wtχ)4.211 (10 in terms of Si for Fe)
An alkaline suspension with a pH of 13°8 obtained by mixing NaOH1, Ogeol (mo1%) and NaOH1, Ogeol was heated to 280°C in an autoclave and maintained at this temperature for 2 hours with mechanical stirring, resulting in a yellowish brown color. A precipitate formed.

After cooling to room temperature, the yellowish brown precipitate was filtered out, thoroughly washed with water, and then dried.

The obtained yellowish-brown particles are hematite particles as shown in the X-ray diffraction shown in FIG. 1, and have an average diameter of 2.5 mm as shown in the electron micrograph (x 10+ 000) shown in FIG.
4 #Il, BLIT specific surface area 22.6rrt/g,
The thickness was 180 mm and the plate ratio was 133:1. In Figure 1, peak A is hematite.

In addition, the lightness value of this particle powder is 44.9, and the hue is 64.
5°, and the saturation was 27.5.

Examples 2-10. Comparative Examples 1 to 3 The type and concentration of the iron raw material, the type and amount of NaOH3i, the type and amount of water-soluble salt added, the type and amount of St-containing compound, the pH of the suspension, and the temperature and time of hydrothermal treatment were varied. Plate-shaped hematite particles were obtained in the same manner as in Example 1 except for the above.

Table 1 shows the main manufacturing conditions and characteristics at this time.

An electron micrograph (X10.0OO) of the plate-shaped hematite particles obtained in Example 8 is shown in FIG.

<Manufacture of rubber or resin composition> Examples 11 to 16: Example 11 2 parts by weight of the plate-shaped heftite particles obtained in Example 1 were used as a coloring pigment and added to a base material constituting a resin composition having the following formulation. The mixture was blended and kneaded for 5 minutes at 130°C using two rolls to obtain a kneaded product.

Polystyrene resin 98 parts by weight Calcium stearate 0.1 parts by weight The obtained kneaded product was formed into a sheet-like film by hot pressing, and then cooled and hardened.

The tensile strength of this sheet-like film is 740 kg/d.

The elongation was 3.5%, and it was sufficiently durable for use as a resin molded product. Further, this sheet-like film had a brightness pi value of 46, a hue θ of 646, a chroma saturation 011ab of 28, and exhibited a golden color with metallic luster.

Examples 12 to 14 Type and amount of plate-shaped hematite particles, type and amount of resin,
Example 1 except that the types and amounts of additives were varied.
A sheet-like film was obtained in the same manner as in 1.

Table 2 shows the main manufacturing conditions and characteristics at this time.

The sheet-like films obtained in Examples 12 to 14 were all durable enough to be used as resin moldings, and had a golden color with metallic luster.

The sheet-like film obtained in Example 12 had a tensile strength of 310 kg/cj and an elongation of 700%.

Example 15 10 parts by weight of the plate-shaped hematite particles obtained in Example 6 were used as a coloring pigment, and 200 parts by weight of epoxy resin, 30 parts by weight of polyamide amine, and 7 parts by weight of lauroyl peroxide were kneaded for 24 hours using a ball mill. After that, it was formed into a sheet-like film.

This sheet-like film was sufficiently durable for use as a resin molded article. Further, this sheet-like film had a lightness value of 44.5, a hue θ of 61°, and a chroma C''ab of 24, and had a golden color with metallic luster.

Example 16 15 parts by weight of the plate-shaped hematite particles obtained in Example 9 were blended as a coloring pigment into a constituent base material of a rubber having the following formulation,
The mixture was kneaded using two rolls at 82°C for 15 minutes to obtain a kneaded product.

Nitrile butadiene rubber OP Zinc stearate sulfur vulcanization accelerator (N-cyclohexylbendithia 9 to
) The obtained kneaded product was formed into a sheet-like film, and further 1
After vulcanization at 50°C, it was cooled and hardened.

The tensile strength of this sheet-like film is 100 kg/c,
It had an elongation of 300% and was sufficiently durable for use as a rubber molded product. Further, this sheet-like film had a lightness value of 42, a hue θ of 541, a chroma C''ab of 23, and had a golden color with metallic luster.

80 parts by weight 7.5 parts by weight 1.5 parts by weight 4 parts by weight 1.5 parts by weight 1.5 parts by weight [Effects of the Invention] The rubber or resin composition according to the present invention can be prepared as shown in the above examples. , average diameter 0.5~5.0μ-5 thickness 50~500
The plate ratio is 50:l to 500:t,
In addition, the brightness value is 40 to 65, and the hue θ-tan-'b'
/aJ is 50@ or more and chroma C"ab-2 is 17 or more, plate-shaped hematite particles are blended as a coloring pigment into a rubber or resin constituent base material to give a golden yellow color, and
Since a rubber or resin composition with excellent stability resistance can be obtained, it is suitable as a material for rubber or resin molded bodies.

In addition, the rubber or resin composition according to the present invention is made of polypropylene, polystyrene, PvC, etc., which have high oxygen and hydrogen permeability, because the iron oxide pigment used as the coloring pigment has a thin plate shape. Since the resin permeability can be made as low as possible, it is expected to be used as a food packaging film.

[Brief explanation of the drawing]

FIG. 1 is an X-ray diffraction diagram of plate-shaped hematite particles obtained in Example 1.Beak A in FIG. 1 is hematite. Figures 2 and 3 are both electron micrographs (×10.0
00), which are the plate-shaped hematite particles obtained in Example 1 and Example 8, respectively.

Claims (1)

[Claims] (1) Average diameter is 0.5-5.0 μm, thickness 50-500
Å, the plate ratio is 50:1 to 500:1, the lightness L^* value is 30 or more, and the hue θ = tan^-^1b
^*/a^* is 50° or more, saturation C^*ab=√(a^
*^2+b^*^2) is 17 or more (in the formula, L^*, a^
*, b^* are CIE1976 (L^*, a^*, b^*
) Values expressed in uniform perceptual color space. 1. A rubber or resin composition exhibiting a golden color, characterized in that plate-shaped hematite particles having the following formula are blended into a base material constituting the rubber or resin composition.