JP2013173858A - Brightness coloring propylene-based resin composition and molding of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brightness coloring propylene-based resin composition in which optical transparency and surface gloss are high, and reflected light diffusivity is large, that has brightness coloring feeling abounding in viewing angle dependence polychroism that is a characteristic in which a different tone is seen by a seen angle, and that is excellent in a property balance such as a balance of a flexural modulus and an impact strength, and to provide a molding of the same.SOLUTION: A brightness coloring propylene-based resin composition or the like comprises the following (A) consisting of (A1) and/or (A2), and (B). (A): Propylene-based copolymer resin; 100 pts.wt. (A1): Propylene and propylene-ethylene block copolymer resin that satisfies four requirements of performing sequential polymerization by using a metallocene catalyst or the like. (A2): Propylene and α-olefin random copolymer resin that satisfies two requirements that an MFR (230°C, 2.16 kg load) is 0.5-200 g/10 minute or the like. (B): Brightness coloring component that has an interference effect of angle dependence; 0.1-10 pts.wt.

Description

  The present invention relates to a brightly colored propylene-based resin composition and a molded product thereof, and more specifically, the molded product has a high light transmittance and surface gloss, a large reflected light diffusivity, and a different color tone depending on the viewing angle. The present invention relates to a brightly colored propylene-based resin composition and a molded product thereof having a bright colored feeling rich in viewing angle dependent polychromaticity and excellent physical property balance such as a good balance between flexural modulus and impact strength.

  Propylene-based resin compositions are excellent in moldability, physical properties, and economics, so the field of use expands year by year. Among them, automotive parts such as instrument panels, trims, and bumpers, and electrical equipment parts such as televisions. , Propylene resin compositions such as propylene resins and composite propylene resins in which propylene resins are reinforced with fillers such as elastomers (rubbers) and talc are used for moldability, molded body appearance, flexural modulus and impact strength. It is widely used because of its excellent physical property balance, recyclability, and economic efficiency.

Propylene-based resin composition molded products require high levels of functionality, size, thickness, diversification / complexity, and physical properties at the same time. There is a need for further enhancement of the colored appearance of the resin composition, including the case of achieving the above.
As the sophistication of the colored appearance of the molded product, there is a demand for a particularly high level of brilliant coloring. There is a demand for bright coloring feeling that is rich in pleochroicity, that is, basically has a large reflected light diffusivity.
In the present specification, the “brilliant coloring sensation” refers to the original coloring property or degree of coloring of the coloring component itself and the texture or texture as if it is a metal, sometimes referred to as a metallic sensation. It is defined as a concept of a colored appearance having both a metallic feeling, which is a concept to be brought out, and a glittering feeling, which is also referred to as a brightness feeling, which is a concept representing the degree of brightness on the surface of the molded body.
In addition, “viewing angle dependent polychromaticity” is defined as a characteristic in which the color tone of the molded body looks different depending on the angle of viewing the molded body as described above. As the reflected light diffusivity increases, the viewing angle-dependent polychromaticity tends to increase.
Here, the “reflected light diffusivity” is the ratio of the reflected light intensity amount excluding the vicinity of the specularly reflected light to the total reflected light intensity amount under a specific incident light, measured by a variable angle photometer described later. It is defined as
The reflected light diffusivity will be described in detail in the Examples section below. The reflected light diffusivity is based on the premise that the coloring component has an angle-dependent interference effect described later, but basically, as the value increases, the viewing angle-dependent polychromaticity tends to increase.
The bright coloring feeling, combined with the high light transmittance and surface gloss of the molded body, significantly improves the appearance of the colored molded body of the propylene-based resin composition and thus the commercial value. It is necessary to improve as much as possible together with the balance of physical properties such as balance.
In recent years, for example, in the automotive interior parts field, there are many demands for a propylene-based resin composition having a high light transmittance and surface gloss of the molded body and having a bright coloring feeling rich in viewing angle-dependent polychromaticity and a molded body thereof. ing.

In many cases, the bright coloration of the propylene resin composition is obtained by adding a brightly colored component to the propylene resin composition.
The brightly colored component reflects the incident light from the outside on the surface of the colored propylene-based resin composition molded body and shines brilliantly. Gives the appearance of the molded body.
In the propylene-based resin composition and molded articles thereof, the improvement and improvement of the glittering coloring feeling of unpainted molded articles using a brightly colored component is combined with the improvement of the balance of physical properties such as the balance of flexural modulus and impact strength. Various methods have been proposed (see, for example, Patent Documents 1 to 3).

In Patent Document 1, a bright material such as metal flakes and interference mica, or a brightly colored component, etc., can be given without giving many coating layers by metallic coating treatment, etc. A glittering material-containing polypropylene-based resin molded product is disclosed in which a clear coating film layer is directly formed on the surface of a molded substrate made of a polypropylene-based resin composition.
The molded article has a high-grade metallic feeling and transparency or clearness and scratch resistance, and has an inconspicuous excellent appearance such as a weld line, a flow mark, etc., and should be suitable for automobile parts. Although it is described, the clear painting work is indispensable, the light transmittance and surface gloss level of the molded product, the level of viewing angle dependent polychromaticity in the bright coloring feeling, and the physical properties (flexural modulus and impact) It is not clear because there is no description on strength.

In Patent Document 2, a glittering material-containing resin composition having a silver metallic appearance and excellent in light resistance stability and a molded body comprising the same are used as a polypropylene resin (A) and 100 parts by weight of the resin (A). And 0.1 to 10 parts by weight of a glittering material (B) made of aluminum particles, 0.05 to 1 part by weight of a hindered amine light stabilizer (C), a benzoate compound represented by a specific formula and a specific formula A glittering material-containing resin composition containing 0.05 to 1 part by weight of at least one compound (D) selected from the group consisting of benzophenone compounds represented by the formula (1) and a molded body comprising the same are disclosed. .
Although the resin composition and the molded product are described to have a silver metallic appearance and excellent light resistance stability, the molded product has a large degree of light transmission, surface gloss level, and bright-colored appearance. It is not clear because there is no description of the color properties, physical properties of the molded body such as flexural modulus and impact strength.

The present applicant has previously proposed a solution to the problem of improving the balance of physical properties such as a brilliant coloring feeling such as metallic appearance and a balance between flexural modulus and impact strength (see Patent Document 3).
That is, Patent Document 3 discloses a propylene / α-olefin random copolymer (a1) 50 to 90 as a polypropylene-based resin material having good color developability, excellent weld-like metallic appearance, and excellent rigidity and impact resistance. Luminescent agent (B) such as aluminum flakes and interference mica with respect to 100 parts by weight of propylene resin component (A) consisting of 10% by weight and 10% to 50% by weight of propylene / α-olefin block copolymer (a2) A propylene-based copolymer composition containing 0.01 to 10 parts by weight, wherein the propylene-based resin component (A) has a light projection angle of 0 ° when a mirror-finished product having a plate thickness of 2 mm is received. A propylene-based copolymer composition is proposed, which has a light transmittance of 4% or more at an angle of 0 °.
The propylene-based copolymer composition has improved impact strength and rigidity, is excellent in transparency, can control the crystallization temperature, and is blended with a brightening agent to form a copolymer composition that is molded by injection molding or the like. Is effective for various automotive parts because it provides a good metallic appearance with a good color appearance and a good weld appearance, but further expands the application field of the copolymer composition, etc. For this purpose, there is a demand for further improvement in the sense of glittering coloring such as higher light transmittance and surface gloss of the molded product and development of high viewing angle dependent polychromaticity.

  As described above, in the propylene-based resin composition and the molded product thereof, although a certain bright coloring feeling and physical property balance are obtained, the molded product has high light transmittance and surface gloss, and has a large reflected light diffusivity, It has a bright coloring feeling rich in viewing angle-dependent polychromaticity that looks different depending on the viewing angle, and an excellent balance of physical properties such as a good balance between flexural modulus and impact strength has not been obtained.

JP 2000-313758 A JP 2006-137877 A JP 2009-138113 A

  In view of the above-mentioned problems of the prior art, an object of the present invention is a viewing angle dependent property which is a characteristic in which a molded article has high light transmittance and surface gloss, has a large reflected light diffusivity, and looks different colors depending on the viewing angle. An object of the present invention is to provide a brightly colored propylene-based resin composition and a molded product thereof having a brightly colored feeling rich in color and excellent in physical property balance such as a good balance between flexural modulus and impact strength.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have developed a brightly colored propylene-based resin composition containing specific components (A) and (B) and a molded product thereof. In addition to its high light transmission and surface gloss, it has a large reflected light diffusivity, has a bright coloring feeling rich in viewing angle-dependent polychromaticity, which is a characteristic that looks different colors depending on the viewing angle, and has a good flexural modulus The present inventors have found that the balance of physical properties such as the balance with impact strength is excellent and that the above problems can be solved, and the present invention has been completed based on these findings.

That is, according to the first aspect of the present invention, a brightly colored propylene-based resin comprising (A) and (B) comprising the following (A1) and / or (A2): A composition is provided.
(A): Propylene copolymer resin; 100 parts by weight (A1): Propylene / ethylene block copolymer resin satisfying the following requirements (A) to (D) (A): Using a metallocene catalyst, 30 to 95% by weight of propylene / ethylene random copolymer component (A1a) having propylene alone or ethylene content of 7% by weight or less in the first step, and 3 to 20% by weight more than the component (A1a) in the second step It is obtained by successively polymerizing 5-70 wt% of propylene / ethylene random copolymer component (A1b) containing ethylene.
(A): The melting peak temperature (Tm) measured by the DSC method is 110 to 150 ° C.
(C): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(D): Melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 min.
(A2): Propylene / α-olefin random copolymer resin satisfying the following requirements (f) and (g) (f): Melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 min.
(G): Consists of a structural unit obtained from propylene and a structural unit obtained from α-olefin.
(B): Bright colored component having an angle-dependent interference effect; 0.1 to 10 parts by weight.

Further, according to the second invention of the present invention, the brightly colored propylene resin composition according to the first invention, further comprising (A) 100 parts by weight of the following (C): Is provided.
(C): Elastomer; 1 to 100 parts by weight

Further, according to the third invention of the present invention, in the first or second invention, the degree of sag when measured in accordance with JIS K7136 in a molded body having a thickness of 2 mm is 80% or less, and the thickness The gloss when measured in accordance with JIS Z8741 in a molded product having a thickness of 2 mm is 80% or more, and the diffused light diffusivity when measured at an incident light angle of 45 degrees in a molded product having a thickness of 2 mm is 8 It is possible to provide a brightly colored propylene-based resin composition characterized by being at least%.
According to the fourth invention of the present invention, in any one of the first to third inventions, the bending elastic modulus when measured according to JIS K7171 in a molded body having a thickness of 4 mm is 400 MPa or less. A brightly colored propylene-based resin composition is provided.

According to a fifth aspect of the present invention, there is provided a molded article obtained by molding the brightly colored propylene-based resin composition of any one of the first to fourth aspects.
According to a sixth aspect of the present invention, in the fifth aspect, there is provided a molded body that is an automobile part.

The brightly colored propylene-based resin composition of the present invention and its molded product have a high light transmittance and surface gloss of the molded product, a large reflected light diffusivity, and a visual angle-dependent property that looks different tones depending on the viewing angle. It has a brilliant coloring feeling rich in color and is excellent in physical property balance such as a good balance between flexural modulus and impact strength.
Furthermore, in addition to the above effects, the physical properties can be easily controlled according to the desired performance level, such as expressing a soft and soft tactile sensation or a relatively high rigidity feeling such as a firm feeling. There is an effect.
Therefore, various decorative parts such as armrest decorative parts, instrument panel decorative parts, glove box decorative parts, console box decorative parts, switch panels, switch panel covers, moldings, cover moldings, side moldings, armrests, Armrest cover, instrument panel, glove box, console box, pillar, door trim, shift knob, shift knob cover, column shift knob, column shift knob cover, door grip cover, various trims, bumper, fender, wheel cap, back door, Automobile interior / exterior parts such as door protectors, mud guards, engine covers, washing machine drum top cover, rice cooker top cover, mobile phone case, portable information equipment case, It can be suitably used for applications such as home appliance parts such as sound equipment casings, TV casings, and vacuum cleaner casings, toilet equipment parts such as toilet seats and shock absorbers for fittings, various industrial parts, and various building material parts. .
In particular, the molded product has high light transmission and surface gloss, a large reflected light diffusivity, a bright coloring feeling rich in viewing angle-dependent polychromaticity, and a balance of physical properties such as a good balance between flexural modulus and impact strength. Various decorative parts such as armrest decorative parts, instrument panel decorative parts, glove box decorative parts, console box decorative parts, switch panels, etc. , Switch panel cover, molding, cover molding, side molding, armrest, armrest cover, shift knob, shift knob cover, column shift knob, column shift knob cover, door clip cover, assist grip, bumper, fender, rice cooker top cover, mobile phone casing, Such as portable information equipment housings, toilet seats, shock absorbers for joinery In Applications, it can be used particularly suitably.

It is explanatory drawing regarding the measuring method of a reflected light diffusivity. It is explanatory drawing regarding the calculation method of reflected light diffusivity, Comprising: It is a measurement data graph figure showing the detection angle dependence (reflected light intensity distribution) of reflected light intensity. It is a figure which shows the elution amount and elution amount integration by temperature rising elution fractionation (TREF).

The present invention relates to a brightly colored propylene-based resin composition comprising the following (A1) and / or (A2) and (B), and a molded product thereof.
(A): Propylene copolymer resin; 100 parts by weight (A1): Propylene / ethylene block copolymer resin satisfying the following requirements (A) to (D) (A): Using a metallocene catalyst, 30 to 95% by weight of propylene / ethylene random copolymer component (A1a) having propylene alone or ethylene content of 7% by weight or less in the first step, and 3 to 20% by weight more than the component (A1a) in the second step It is obtained by successively polymerizing 5-70 wt% of propylene / ethylene random copolymer component (A1b) containing ethylene.
(A): The melting peak temperature (Tm) measured by the DSC method is 110 to 150 ° C.
(C): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(D): Melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 min.
(A2): Propylene / α-olefin random copolymer resin satisfying the following requirements (f) and (g) (f): Melt flow rate (230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 minutes.
(G): Consists of a structural unit obtained from propylene and a structural unit obtained from α-olefin.
(B): Brightly colored component having angle-dependent interference effect; 0.1 to 10 parts by weight Hereinafter, the brightly colored propylene-based resin composition of the present invention and a molded product thereof will be described in detail for each item.

As described above, the present applicant is concerned with the solution to the problem of improving the balance of physical properties such as the brilliant coloring feeling such as the metallic appearance and the balance between the flexural modulus and the impact strength. Propylene-based copolymer compositions that are obtained and excellent in rigidity and impact resistance have been proposed (see Patent Document 3), but earnestly researched in order to solve the above problems and to make them more sophisticated. As a result, it has been found that when the propylene-based copolymer resin and the brightly colored component are specified, the above problems can be solved at a higher level including light transmittance, surface gloss and viewing angle dependent polychromaticity.
That is, in the brightly colored propylene-based resin composition containing the brightly colored component and the molded product thereof, the specific (A1): propylene / ethylene block copolymer resin and / or (A2): propylene / α-olefin random copolymer When (A): a propylene-based copolymer resin comprising a polymer resin and (B): a bright coloring component having an angle-dependent interference effect, the molded article has high light transmittance and surface gloss, It has a high reflected light diffusivity, a bright color feeling rich in viewing angle-dependent polychromaticity that looks different colors depending on the viewing angle, and excellent physical property balance such as a good balance between flexural modulus and impact strength The present inventors have found that a brightly colored propylene-based resin composition and a molded product thereof can be obtained, and have completed the present invention based on these findings.

I. Constituent components of brightly colored propylene resin composition (A): Propylene-based copolymer resin (A): Propylene-based copolymer resin (hereinafter also simply referred to as “(A)”) used in the present invention is the following (A1) and / or ( In the brightly colored propylene-based resin composition of the present invention and a molded body thereof (hereinafter, also simply referred to as “brilliantly colored composition and molded body thereof”), Increases surface gloss, increases reflected light diffusivity, gives bright colors with abundant viewing angle-dependent polychromaticity, and provides functions such as physical property balance and tactile sensation such as a good balance between flexural modulus and impact strength. It has a feature that contributes to this.
In addition, in the compounding quantity ratio of each component such as (B) and (C) in the present invention, the (A): 100 parts by weight of the propylene-based copolymer resin is used as a reference. Moreover, this (A) can also use 2 or more types together.
Hereinafter, (A1) propylene / ethylene block copolymer resin and (A2) propylene / α-olefin random copolymer resin will be described in detail.

1-1. (A1): Propylene / ethylene block copolymer resin (A1): Propylene / ethylene block copolymer resin (hereinafter also simply referred to as “(A1)”) used in the present invention includes the following (A) to (A1): A propylene / ethylene block copolymer resin that satisfies the requirements specified in (d), and in the brightly colored composition and molded product of the present invention, the light transmittance and surface gloss of the molded product are increased, and the diffused reflected light is diffused. It contributes particularly to providing functions such as a balance of physical properties such as a good balance of physical properties such as a good balance between flexural modulus and impact strength, and soft and soft tactile sensation. Has characteristics.
Here, (A1): propylene / ethylene block copolymer resin means propylene alone or a propylene / ethylene random copolymer component (A1a) (hereinafter referred to simply as “(component A1a)) having an ethylene content of 7% by weight or less. And a propylene / ethylene random copolymer component (A1b) containing 3 to 20% by weight of ethylene more than (Component A1a) (hereinafter also simply referred to as “(Component A1b)”). Is a block copolymer resin as a common name obtained by sequential polymerization, and (Component A1a) and (Component A1b) do not necessarily have to be combined in a block form.
(A): Using a metallocene-based catalyst, 30 to 95% by weight of propylene / ethylene random copolymer component (A1a) having propylene alone or ethylene content of 7% by weight or less in the first step, and the component ( A propylene / ethylene block copolymer resin obtained by sequential polymerization of 5 to 70% by weight of a propylene / ethylene random copolymer component (A1b) containing 3 to 20% by weight of ethylene more than A1a) .
(A): The melting peak temperature (Tm) measured by the DSC method is 110 to 150 ° C.
(C): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(D) Melt flow rate (hereinafter also referred to as “MFR”) (230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 minutes.

(1) Requirements (i) (A)
(A1): Propylene / ethylene block copolymer resin used in the present invention is, as described above, using a metallocene catalyst, in the first step, propylene alone or ethylene content of 7 wt% or less, preferably 5 wt% The propylene / ethylene random copolymer component (A1a) of 3% by weight or less, more preferably 30 to 95% by weight, and in the second step, 3 to 20% by weight of ethylene more than (Component A1a), Preferably, the propylene / ethylene random copolymer component (A1b) containing 6 to 18% by weight of ethylene, more preferably 8 to 16% by weight of ethylene needs to be sequentially polymerized in an amount of 5 to 70% by weight. . Here, if the difference in ethylene content between the second step component (component A1b) and the first step component (component A1a) is less than 3% by weight, the brightly colored composition of the present invention and the light transmittance of the molded product thereof In addition, surface gloss, reflected light diffusivity, lustrous coloring with abundant viewing angle dependence, physical properties such as impact strength, flexibility, and soft touch may be reduced. On the other hand, if it exceeds 20% by weight, the compatibility between (Component A1a) and (Component A1b) may be reduced.
That is, in (A1), by sequentially polymerizing components having different ethylene contents within a predetermined range in the first step and the second step, in the brightly colored composition of the present invention and the molded product thereof, the light transmittance of the molded product. In addition, the surface gloss is increased, the reflected light diffusivity is increased, the lustrous coloring feeling is rich in viewing angle-dependent polychromaticity, and the balance of physical properties such as a good balance between flexural modulus and impact strength, and the soft and soft feel. A method of polymerizing (component A1b) after polymerizing (component A1a) in order to prevent problems such as adhesion of reaction products to the reactor. It is necessary to use it.
In the present specification, the ethylene content is determined by the method described in Examples below.

(Ii) (I)
(A1) used in the present invention: The melting peak temperature (Tm) measured by the DSC (Differential Scanning Calorimetry) method of the propylene / ethylene block copolymer resin is 110 to 150 ° C, preferably 115 to 148 ° C, More preferably, it is necessary to be in the range of 120 to 145 ° C. If the Tm is less than 110 ° C., the brightness of the brightly colored composition of the present invention and the molded body thereof may be excessively reduced. On the other hand, when the temperature exceeds 150 ° C., light transmittance, surface gloss, reflected light diffusivity, bright coloring feeling rich in viewing angle-dependent polychromaticity, impact strength, soft touch feeling and the like may be deteriorated.
In this specification, the melting peak temperature (Tm) is determined by the method described in the Examples section described later.

(Iii) (c)
The (A1): propylene / ethylene block copolymer resin used in the present invention has a single peak at 0 ° C. or lower in the tan δ curve in the temperature-loss tangent curve obtained by solid viscoelasticity measurement (DMA). is necessary.
That is, in the present invention, the brightly colored composition and its molded product have high light transmittance and surface gloss, a large reflected light diffusivity, a bright colored feeling rich in viewing angle-dependent polychromaticity, and a good (Component A1a) and (Component A1b) may not be phase-separated in (A1) in order to develop a physical property balance such as a balance between flexural modulus and impact strength and a relatively soft and soft tactile sensation. In that case, the tan δ curve shows a single peak below 0 ° C.
Incidentally, when (component A1a) and (component A1b) are in a phase separation structure, the glass transition temperature of the amorphous part contained in (component A1a) and the glass transition of the amorphous part contained in (component A1b). Since each temperature is different, there are a plurality of peaks.
In this specification, the solid viscoelasticity measurement is specifically performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. Here, the frequency is 1 Hz, and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured.
Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by this ratio is plotted against the temperature. It shows a sharp peak in the temperature range of 0 ° C. or lower, and generally the peak of the tan δ curve at 0 ° C. or lower is for observing the glass transition of the amorphous part, and here this peak temperature is the glass transition temperature Tg (° C.). Define as

(Iv) (d)
MFR (230 ° C., 2.16 kg load) of (A1): propylene / ethylene block copolymer resin used in the present invention is 0.5 to 200 g / 10 minutes, preferably 3 to 150 g / 10 minutes, more preferably Needs to be in the range of 5-50 g / 10 min. If the MFR is less than 0.5 g / 10 min, the brightly colored composition of the present invention and the molded article thereof may have a decreased colorability, surface gloss and fluidity, which are rich in viewing angle-dependent polychromaticity. There is.
On the other hand, if it exceeds 200 g / 10 minutes, physical properties such as impact strength may be lowered. The MFR can be adjusted by using a molecular weight lowering agent.
In addition, (A1) can also use 2 or more types together.
Moreover, in this specification, MFR is the value measured by test temperature = 230 degreeC and load = 2.16kg based on JISK7210.

(2) Production (i) Metallocene Catalyst (A1): Propylene / ethylene block copolymer resin used in the present invention requires the use of a metallocene catalyst.
The type of metallocene-based catalyst is not particularly limited as long as (A1) having the performance of the present invention can be produced. It is preferable to use a metallocene catalyst consisting of a), component (b), and component (c) used as necessary.
Component (a): at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1).
Component (b): at least one solid component selected from the following (b-1) to (b-4).
(B-1): A particulate carrier on which an organic aluminum oxy compound is supported.
(B-2): A particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (a) to convert component (a) into a cation.
(B-3): Solid acid fine particles.
(B-4): Ion exchange layered silicate.
Component (c): an organoaluminum compound.

As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) can be used.
^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b) MeXY (1)
[Wherein Q represents a divalent binding group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, X and Y represent a hydrogen atom, A halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group is shown, and X and Y may be the same or different from each other. R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Indicates. a and b are the number of substituents. ]

  Among them, preferred for the production of (A1) are a substituted cyclopentadienyl group, a substituted indenyl group, a substituted fluorenyl group crosslinked with a silylene group having a hydrocarbon substituent as Q, a germylene group or an alkylene group, Examples thereof include transition metal compounds composed of a ligand having a substituted azulenyl group, and particularly preferably a silylene group having a hydrocarbon substituent, or a 2,4-position substituted indenyl group bridged by a germylene group, 2,4- Examples thereof include transition metal compounds composed of a ligand having a position-substituted azulenyl group.

As the component (b), at least one solid component selected from the aforementioned components (b-1) to (b-4) is used. Each of these components is a well-known thing, and can be used selecting it suitably from well-known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, JP-A No. 2003-105015, and the like.
Among the components (b), particularly preferable are the ion-exchange layered silicates of the component (b-4), and more preferable are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. Is an ion-exchange layered silicate.

Examples of the organoaluminum compound used as the component (c) as necessary include the following general formula (2)
AlR _a P _3-a (2)
(In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, halogen or alkoxy group, and a represents a number of 0 <a ≦ 3.)
Or a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum or triisobutylaluminum, or a halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

  As a method for forming the catalyst, the component (a), the component (b) and, if necessary, the component (c) are brought into contact with each other to form a catalyst. In addition, the contact method will not be specifically limited if it is a method which can form a catalyst, A well-known method can be used.

Moreover, the usage-amount of component (a), (b), and (c) is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably such that the amount of transition metal is 0.001 μmol to 100 μmol, particularly preferably 0.005 μmol to 50 μmol, relative to 1 g of component (b).
Furthermore, it is preferable that the catalyst used in the present invention is subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance.

(Ii) Sequential Polymerization (A1): In the production of the propylene / ethylene block copolymer resin used in the present invention, it is necessary to sequentially polymerize (Component A1a) and (Component A1b).
That is, in the present invention, (A1) is a block copolymer obtained by sequentially polymerizing components having different ethylene contents in the first step and the second step. Increases the light transmittance and surface gloss of the body, increases the diffused light diffusivity, bright color with rich viewing angle dependence, and balance of physical properties such as a good balance between flexural modulus and impact strength and flexibility It is necessary to express soft touch.
In the present invention, it is necessary to use a method of polymerizing (component A1b) after polymerizing (component A1a) in order to prevent problems such as adhesion of reaction products to the reactor. is there.
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.

In the case of a batch method, it is possible to polymerize (component A1a) and (component A1b) even by using a single reactor by changing the polymerization conditions with time. A plurality of reactors may be connected in parallel as long as the effects of the present invention are not impaired.
In the case of a continuous process, it is necessary to use a production facility in which two or more reactors are connected in series because it is necessary to individually polymerize (component A1a) and (component A1b), but this does not impair the effects of the present invention. As long as each of (component A1a) and (component A1b) is used, a plurality of reactors may be connected in series and / or in parallel.

(Iii) Polymerization process (A1): The polymerization process of the propylene / ethylene block copolymer resin used in the present invention may be any polymerization method such as a slurry method, a bulk method, or a gas phase method. Although it is possible to use supercritical conditions as intermediate conditions between the bulk method and the gas phase method, they are substantially equivalent to the gas phase method, and are therefore included in the gas phase method without particular distinction.
Since (Component A1b) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method in the production of (Component A1b).
For the production of (Component A1a), there is no particular problem even if any process is used. It is desirable to use a vapor phase method to avoid problems.
Therefore, it is most desirable to first polymerize (Component A1a) by a bulk method or a gas phase method and then polymerize (Component A1b) by a gas phase method using a continuous method.

(Iv) Other polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range.
Specifically, a range of 0 to 200 ° C, more preferably 40 to 100 ° C can be used.
The polymerization pressure varies depending on the process to be selected, but the optimum pressure can be used without any problem as long as it is in a pressure range usually used. Specifically, a relative pressure with respect to atmospheric pressure can be used in the range of greater than 0 MPa to 200 MPa, more preferably 0.1 to 50 MPa. At this time, an inert gas such as nitrogen may coexist.
When performing sequential polymerization of (component A1a) in the first step and (component A1b) in the second step, it is desirable to add a polymerization inhibitor into the system in the second step. When producing a propylene / ethylene block copolymer resin, adding a polymerization inhibitor to the reactor for carrying out the random propylene / ethylene copolymerization in the second step results in particle properties (fluidity, etc.) and gel of the resulting powder. Product quality can be improved. Various techniques have been studied for this method, and examples thereof include the methods described in Japanese Patent Publication Nos. 63-54296, 7-25960, and 2003-2939. It is desirable to apply the method to the present invention.
In addition, as for the propylene / ethylene block copolymer resin satisfying these specified values, various products are commercially available under trade names such as “Wellnex” manufactured by Nippon Polypro, for example. A1): It may be used as a propylene / ethylene block copolymer resin.

(3) Blending ratio As described above, the blending ratio of each component used in the present invention is based on (A): 100 parts by weight of the propylene-based polymer resin. The blending amount of A1) is 100% by weight in total with (A2) described later.
Among these, the ratio between the (A1) and the postscript (A2) can be appropriately set depending on the design of the performance level of the brightly colored composition of the present invention and the molded product thereof.
That is, the brightly colored composition of the present invention and the molded product thereof have high light transmittance and surface gloss of the molded product, a large reflected light diffusivity, and a brightly colored feeling rich in viewing angle-dependent pleochroicity. The balance of physical properties such as the balance between flexural modulus and impact strength is good. However, in the case where importance is placed on the expression of soft and soft tactile sense, the blending ratio of (A1) is set to 100% by weight. It is preferably 51 to 100% by weight, more preferably 70 to 100% by weight, and even more preferably 100% by weight.

1-2. (A2): Propylene / α-olefin random copolymer resin (A2): Propylene / α-olefin random copolymer resin (hereinafter also simply referred to as “(A2)”) used in the present invention has the following requirements. (F) and (ki), and preferably satisfies (ku). In the brightly colored composition of the present invention and its molded product, the light transmittance and surface gloss of the molded product are increased, and the reflected light. It has a feature that contributes particularly to imparting functions such as an increased diffusivity, a bright coloring feeling rich in viewing angle-dependent polychromaticity, and a balance of physical properties such as a good balance between flexural modulus and impact strength.

(1) Requirements (i) (F)
The total MFR (230 ° C., 2.16 kg load) of the (A2): propylene / α-olefin random copolymer resin used in the present invention is 0.5 to 200 g / 10 minutes, preferably 1 to 120 g / It is necessary to be 10 minutes, more preferably 5 to 50 g / 10 minutes.
If the MFR is less than 0.5 g / 10 min, the brightly colored composition of the present invention and the molded product thereof may deteriorate the moldability such as bright colored feeling, surface gloss and fluidity rich in viewing angle dependent polychromaticity. There is. On the other hand, if it exceeds 200 g / 10 minutes, physical properties such as impact strength may be lowered. The MFR can be adjusted by using a molecular weight lowering agent.

(Ii) (ki)
The (A2): propylene / α-olefin random copolymer resin used in the present invention needs to be composed of a structural unit obtained from propylene and a structural unit obtained from α-olefin. Specifically, the structural unit obtained from propylene is 100 to 90% by weight (excluding 100% by weight), preferably 99 to 92% by weight, and the structural unit obtained from α-olefin is 0 to 10% by weight (provided that 0% by weight is excluded.), Preferably 1 to 8% by weight.
When the content of the structural unit obtained from the α-olefin exceeds 10% by weight, physical properties such as rigidity of the brightly colored composition of the present invention and the molded product thereof may be deteriorated.

Examples of the α-olefin of the comonomer copolymerized with propylene include ethylene and / or an α-olefin having 4 to 20 carbon atoms. Specifically, ethylene, butene-1, pentene-1, hexene- 1, octene-1, 4-methylpentene-1, and the like. Among these, ethylene is preferable as the α-olefin of the comonomer from the viewpoint that the effect of the present invention is great. Further, the α-olefin is ethylene, and the content thereof is 1.5 to 4% by weight, which increases the light transmittance and surface gloss of the brightly colored composition of the present invention and the molded product thereof, and reflects the reflected light. It is preferable from the standpoint of increasing the diffusion rate, providing a bright color feeling rich in viewing angle-dependent polychromaticity, and attaining a higher level of physical properties such as a good balance between flexural modulus and impact strength. When (A2) has such a structure, it may have a structure similar to (component A1a) in (A1). That is, it is presumed that such a structure of the random copolymer resin is effective for manifesting the effects of the present invention. In addition, alpha-olefin can also use 2 or more types together.
Here, the structural unit obtained from the propylene in the propylene-based copolymer and the structural unit obtained from the α-olefin are values measured using ¹³ C-NMR (nuclear magnetic resonance method). Specifically, it is a value measured by a 270 MHz apparatus of FT-NMR manufactured by JEOL.

(Iii) (ku)
(A2): The crystallization temperature (Tc) is mentioned as other preferable requirements for the propylene / α-olefin random copolymer resin used in the present invention. The crystallization temperature is preferably 80 to 115 ° C, and more preferably 85 to 105 ° C. If the crystallization temperature is less than 80 ° C., the properties such as the rigidity of the brightly colored composition of the present invention and the molded article thereof may be lowered.
On the other hand, when the temperature exceeds 115 ° C., there is a balance of physical properties such as light transmittance of the molded product, surface gloss, reflected light diffusivity, bright coloring feeling rich in viewing angle dependent polychromaticity, and a good balance between flexural modulus and impact strength. May decrease.
In this specification, the crystallization temperature is measured by using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.), and a sample piece made into a sheet is packed in a 5 mg aluminum pan and once raised from 50 ° C. to 200 ° C. It is measured as the maximum crystallization peak temperature when the temperature is raised at a temperature rate of 100 ° C./min, held for 5 minutes, and then cooled down to 40 ° C. at 10 ° C./min for crystallization. Note that the crystallization temperature was measured for (A2) alone.
In addition, (A2) can also use 2 or more types together.

(2) Production (A2) used in the present invention: As a production method of the propylene / α-olefin random copolymer resin, various known catalysts, for example, a method using a Ziegler-Natta catalyst or a metallocene catalyst are used. Can be mentioned. That is, it can be obtained by copolymerizing propylene and an appropriate α-olefin in the presence of the catalyst. The polymerization reaction may be bulk polymerization, gas phase polymerization, or melt polymerization in addition to solution polymerization using a solvent.
The polymerization method may be either continuous polymerization or batch polymerization. In general, with Ziegler-Natta catalysts, the α-olefin composition distribution in propylene / α-olefin random copolymer resins produced from the heterogeneity of active sites tends to be wide, and there is a concern about rigidity reduction, etc. It is preferable to use (A2) obtained by using a metallocene-based catalyst.

  The metallocene-based catalyst here means (i) a transition metal compound of Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton, (ii) an aluminum oxy compound, and the above transition metal At least one cocatalyst selected from the group consisting of an ionic compound or Lewis acid capable of reacting with a compound to be converted into a cation, a solid acid fine particle, and an ion-exchange layered silicate, and if necessary, (Iii) A catalyst composed of an organoaluminum compound, and any known catalyst capable of producing the propylene / α-olefin random copolymer resin (A2) according to the present invention can be used.

  The metallocene compound is a cross-linked metallocene compound capable of stereoregular polymerization of propylene, and preferably a metallocene compound capable of isoregular polymerization of propylene. For example, JP-A-2-131488 and JP-A-2 JP-A-776887, JP-A-4-21694, JP-A-4-300787, JP-A-5-43616, JP-A-6-1000057, JP-A-5-209913, JP-A-6-239914. No. 11-240909, JP-A 6-184179, JP 2003-533550 A, and the like.

More specifically, dimethylsilylene bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, dimethyl Silylenebis [1- (2-methyl-4- (1-naphthyl) -indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylene [ 1- (2-methyl-4- (4-t-butylphenyl) indenyl)] [1- (2-i-propyl-4- (4-t-butylphenyl) indenyl)] zirconium dichloride, dimethylsilylenebis [ 1- (2-methyl-4-phenyl-4H-azurenyl)] zirconium dichloride, di Tylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (2-fluorobiphenylyl) -4H-azurenyl) ] Zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4-phenylindenyl)] Zirconium compounds such as zirconium dichloride can be exemplified.
In the above, compounds in which zirconium is replaced with hafnium can also be used. Two or more types of complexes can also be used. Further, the chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, hydride groups and the like.
Of these, metallocene compounds having substituents at the 2-position and 4-position and having a bisindenyl group or azulenyl group crosslinked with silicon or a germyl group as a ligand are preferred.

As for the cocatalyst, methylaluminoxane, isobutylaluminoxane and the like are used as the aluminum oxy compound, and as the ionic compound which can be converted into a cation by reacting with the transition metal compound, N, N-dimethylanilinium tetrakispenta is used. Fluorophenylborate, triphenylcarbyltetrakispentafluorophenylborate, etc., Lewis acid is trispentaphenylborate, solid acid fine particles are alumina, silica-alumina, etc. Examples of layered silicates include silicates having a 2: 1 type structure, such as montmorillonite, bentonite, and mica that may be chemically treated.
When these compounds are soluble in a solvent or the like, they can be used by being supported on a porous fine-particle inorganic or organic carrier. Among the above promoters, an ion-exchange layered silicate is preferable.

  Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, and organoaluminum alkoxide.

Examples of the polymerization method include a slurry method using an inert solvent in the presence of the catalyst, a solution method, a gas phase method substantially using no solvent, or a bulk polymerization method using a polymerization monomer as a solvent. . In order to control to a desired MFR and ethylene content, for example, the polymerization temperature, the amount of comonomer, and the amount of hydrogenation can be adjusted.
In addition, propylene / α-olefin random copolymer resins that satisfy these specified values are commercially available under various trade names such as “Wintech” manufactured by Nippon Polypro Co., Ltd. The desired product can be purchased from (A2): a propylene / α-olefin random copolymer resin in the present invention.

(3) Blending ratio As described above, the blending ratio of each component used in the present invention is based on (A): 100 parts by weight of the propylene-based polymer resin. The blending amount of A2) is 100% by weight in total with (A1).
Among these, the ratio between the (A2) and the (A1) can be appropriately set depending on the performance level of the brightly colored composition of the present invention and the molded product thereof.
That is, the brightly colored composition of the present invention and the molded product thereof have high light transmittance and surface gloss of the molded product, a large reflected light diffusivity, and a brightly colored feeling rich in viewing angle-dependent pleochroicity. The balance of physical properties such as the balance between flexural modulus and impact strength is good, but in the case where importance is attached to the appearance of a relatively high rigidity feeling such as a firm feeling, the blending ratio of the (A2) is set to 100 wt. % Is preferably 51 to 100% by weight, more preferably 70 to 100% by weight, and even more preferably 100% by weight.
On the other hand, when it is necessary to set the performance level of the brightly colored composition of the present invention and the molded body thereof more comprehensively and at a high level, for example, when it is necessary to express a high impact strength including a low temperature region, As (A), the (A1) is preferably 51 to 100% by weight, and more preferably 100% by weight.

2. (B): Bright colored component having angle-dependent interference effect (B): Bright colored component having angle-dependent interference effect (hereinafter also simply referred to as “(B)”) used in the present invention. In the case where the resin material is colored by containing it, the molded article has a large reflected light diffusivity, and allows the expression of viewing angle-dependent polychromaticity, which is a characteristic that looks different tones depending on the viewing angle. In other words, it is possible to give a bright colored feeling rich in viewing angle-dependent polychromaticity that makes it possible to look different in hue such as hue at the light receiving angle near each regular reflection angle for a plurality of incident angles. It is a bright coloring component. This is sometimes referred to as a luster pigment.
The brightly colored composition of the present invention and the molded product thereof have a feature that contributes to imparting an excellent brightly colored feeling, in particular, a brightly colored feeling having a large reflected light diffusivity and rich in viewing angle-dependent polychromaticity.
Moreover, this (B) can also contain coloring components, such as various pigments other than this (B). In addition, this (B) can also use 2 or more types together.

2-1. Types, Structures, etc. Used in the Present Invention (B): The type of brightly colored component having an angle-dependent interference effect is not particularly limited as long as it has an angle-dependent interference effect as described above. Specifically, Examples thereof include interference aluminum, metal oxide-coated silica flakes, various metal oxide-coated flaky metal substances, and various metal oxide-coated flaky inorganic substances.
Among them, when used together with (A) of the present invention, interference aluminum and metal oxides have a large reflected light diffusivity and are rich in viewing angle-dependent polychromaticity, and the beautiful color tone of the colored molded article. Coated silica flakes are preferred and interference aluminum is more preferred.
Here, examples of the interference aluminum include aluminum flake as a base material, a surface treated with a silica (silicon dioxide) layer (light interference medium), a metal particle layer, a protective layer, and the like. For example, the product name “Chromashine” manufactured by Toyo Aluminum Co., Ltd. may be mentioned.
In addition, as a product number of the “chroma shine”, for example, BL20-R (blue interference color), BL10-R (blue interference color), GR20-R (green interference color), GR10-R (green interference color), Examples thereof include GD20-R (golden interference color), GD10-R (golden interference color), OR20-R (orange interference color), and PK20-R (pink interference color).
The structure and effect manifestation mechanism of the interference aluminum are not particularly limited. For example, as described above, the surface of the aluminum flake, which is a flaky fine substrate, is coated with silica, which is an angle-dependent interference effect. Among the light incident from the outside, there is a phase difference due to the optical path difference between the reflected light reflected on the silica surface and the reflected light reflected on the aluminum surface after passing through the silica coating of the medium. As a result, viewing angle-dependent polychromaticity, which is an angle-dependent interference effect, is manifested. Furthermore, the interference aluminum can exhibit high reflectivity with respect to incident light without causing light transmission to the back side of the substrate because aluminum is used as the substrate and has a strong light shielding power.

Examples of the metal oxide-coated silica flakes include silicon dioxide flakes coated with iron oxide (iron monoxide or ferric trioxide) or titanium dioxide.
As commercial products of iron oxide-coated silica flakes and titanium dioxide-coated silica flakes,
For example, the product name “Color Stream” manufactured by Merck & Co., Inc. may be mentioned.
In addition, the manufacturing method of these (B) will not be specifically limited if the said function is expressed and stable manufacture is possible.
Furthermore, in (B), if necessary, coloring components such as various pigments other than (B), processing stability imparting components, antioxidant components, dispersion improving components, strength improving components, durability improving components, Addition, mixing, kneading, addition, adhesion, reaction adhesion, adhesion, lamination, and the like of various components such as a weather resistance improving component and a resin component can be performed.

2-2. Shape and dimensions (B) used in the present invention: The shape of the brightly colored component having an angle-dependent interference effect is not particularly limited, but is excellent in viewing angle-dependent polychromaticity, which is an angle-dependent interference effect Therefore, a shape having a base layer basically having a flake shape is preferable. In general, the base layer is preferably obtained by flaking a powder or flakes of a metal or inorganic substance such as aluminum.
Moreover, the dimension of (B) is not specifically limited as long as the said function is expressed, but the average particle diameter is preferably 3 to 50 μm, more preferably 5 to 40 μm, and even more preferably 10 to 30 μm. When the average particle size is less than 3 μm, the viewing angle dependent polychromaticity may be lowered in the brightly colored propylene-based resin composition of the present invention and its molded product. On the other hand, if it exceeds 50 μm, the glittering feeling may be reduced because the glittering feeling becomes excessive, or the surface of the molded body is likely to have a rough appearance. May also decrease.
The average particle size is measured by a particle size distribution meter, specifically, a laser diffraction particle size distribution meter, for example. Examples of the laser diffraction particle size distribution analyzer include Honeywell's Microtrac HRA and Horiba Ltd. LA-920.

2-3. Form of use (B) used in the present invention: The form of use of the brightly colored component having an angle-dependent interference effect is not particularly limited. For example, a powder such as an interference aluminum powder or an interference aluminum-containing paste Paste, resin such as interference aluminum-containing resin, for example, resin masterbatch such as interference aluminum-containing resin masterbatch, which is a resin masterbatch containing 5% to 80% by weight of interference aluminum, interference aluminum-containing low-molecular-weight polyolefin masterbatch Examples of use products such as a low molecular weight polyolefin wax masterbatch can be given.
Among them, the brightly colored composition of the present invention and the molded product thereof, the level of the effect of the present invention, the ease of manufacturing, the ease of handling, the stability of quality, the cost, etc. A resin masterbatch and a low molecular weight polyolefin masterbatch are preferred, and a resin masterbatch is more preferred.

In the resin master batch, a polyolefin resin master batch such as an interference aluminum-containing polyolefin resin master batch is preferable, and a low density polyethylene resin master batch such as an interference aluminum-containing low density polyethylene resin master batch is more preferable.
Here, for example, the content of (B) in a resin masterbatch such as the interference aluminum-containing low-density polyethylene resin masterbatch is not particularly limited, but the effect of the present invention in the colored composition of the present invention and its molded body, From the viewpoint of a good balance with cost, the amount is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, and still more preferably 20 to 70% by weight with respect to 100% by weight of the entire master batch.
If necessary, various additive components such as processing stabilizers, antioxidants, dispersants, weathering agents, and coloring components such as various pigments other than the above (B) may be added to these various master batches. Good.
Moreover, the manufacturing method of said various masterbatch is not specifically limited as long as this masterbatch is manufactured stably.
In addition, when using the interference aluminum containing resin masterbatch, for example, the compounding quantity of (B) in this invention is calculated based on the actual quantity of (B) contained in this masterbatch.

2-4. Blending ratio (B): The blending ratio of the bright coloring component having an angle-dependent interference effect used in the present invention is an actual amount with respect to 100 parts by weight of the above-mentioned (A): propylene-based polymer resin. 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, and still more preferably 0.4 to 2 parts by weight. If the blending amount of (B) is less than 0.1 parts by weight, the brightly colored composition of the present invention and the brightly colored feeling of the molded product thereof, in particular, viewing angle dependent polychromaticity, appearance, texture and texture may be reduced. There is. On the other hand, when the amount exceeds 10 parts by weight, the brilliant coloring feeling may decrease due to excessive brilliant feeling or the occurrence of a rough sensation, and the balance of physical properties such as the balance between flexural modulus and impact strength may decrease. Economic efficiency is also reduced.

3. (C): Elastomer (C): Elastomer (hereinafter also referred to simply as “(C)”), which is optionally used in the present invention, is a thermoplastic elastomer, and examples thereof include olefin elastomers and styrene elastomers. it can. The (C): elastomer contributes to improvement in light transmission, bright coloring feeling, flexibility, touch, physical properties (impact strength, etc.) and dimensional stability in the brightly colored composition of the present invention and molded articles thereof. Has characteristics.

3-1. Type (C): The type of elastomer used in the present invention is, for example, an ethylene / butene copolymer elastomer (EBR), an ethylene / hexene copolymer elastomer (EHR), or an ethylene / octene copolymer. Ethylene / α-olefin copolymer elastomers such as united elastomer (EOR) and ethylene / propylene copolymer elastomer (EPR); ethylene / propylene / ethylidene norbornene copolymer, ethylene / propylene / butadiene copolymer, ethylene / propylene -Ethylene / α-olefin / diene terpolymer elastomer such as isoprene copolymer.
Examples of the styrene elastomer include styrene / butadiene / styrene triblock copolymer elastomer (SBS), styrene / isoprene / styrene triblock copolymer elastomer (SIS), styrene-ethylene / butylene copolymer elastomer ( SEB), styrene-ethylene / propylene copolymer elastomer (SEP), styrene-ethylene / butylene-styrene copolymer elastomer (SEBS), styrene-ethylene / butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene / Butadiene elastomer (HSBR), Styrene-ethylene / propylene-styrene copolymer elastomer (SEPS), Styrene-ethylene / ethylene / propylene-styrene copolymer elastomer (SEEPS) , Styrene - butadiene butylene - styrene copolymer elastomer (SBBS), partially hydrogenated styrene - isoprene - styrene copolymer elastomer can be exemplified. Further, hydrogenated polymer elastomers such as ethylene-ethylene / butylene-ethylene copolymer elastomer (CEBC) can also be mentioned.
Among them, the ethylene / butene copolymer elastomer (EBR), the ethylene / octene copolymer elastomer (EOR) and the styrenic elastomer are used in the present invention as light transmittance, reflected light diffusivity, bright coloring feeling, flexibility, touch feeling and It is preferable for the reason that the physical property balance is highly expressed. In addition, (C) may be used in combination of two or more.

3-2. Production (C) used in the present invention: Examples of elastomer production methods include various known methods, such as ethylene / α-olefin copolymer elastomers of olefin elastomers and ethylene / α-olefin / dienes. Ternary copolymer elastomers and the like are produced by polymerizing each monomer in the presence of a catalyst.
Examples of the catalyst include titanium compounds such as titanium halides, organoaluminum-magnesium complexes such as alkylaluminum-magnesium complexes, so-called Ziegler-type catalysts such as alkylaluminum or alkylaluminum chloride, and WO 91/04257 pamphlet. The metallocene compound catalysts described can be used.
As the polymerization method, polymerization can be performed by applying a production process such as a gas phase fluidized bed method, a solution method, or a slurry method. Styrenic elastomers can be produced by ordinary anionic polymerization methods and polymer hydrogenation techniques.
Various products are commercially available as these elastomers, and those satisfying desired physical properties may be purchased and used as (C): elastomer of the present invention.

3-3. Physical properties (C) used in the present invention: MFR (230 ° C., 2.16 kg load) of the elastomer is not particularly limited, but is usually 0.5 to 100 g / 10 minutes, and 1 to 90 g / 10. Minute is preferable, 2 to 80 g / 10 min is more preferable, and 4 to 60 g / 10 min is further preferable.
In consideration of the automobile member which is the main application of the present invention, the MFR is in the above-mentioned range, and the physical properties and dimensional stability such as light transmittance, reflected light diffusivity, bright coloring feeling, flexibility, touch feeling, and impact strength are included. In many cases, a brightly colored composition having good properties and a molded product thereof can be obtained.

3-4. Compounding Ratio The compounding ratio of (C): elastomer optionally used in the present invention is preferably 1 to 100 parts by weight, more preferably 5 with respect to 100 parts by weight of (A): propylene polymer resin. It is -97 weight part, More preferably, it is 10-95 weight part, Especially preferably, it is 25-90 weight part, Most preferably, it is 40-87 weight part. When the blending amount of the (C) is less than 1 part by weight, the light-colored composition of the present invention and the molded product thereof, such as light transmittance, reflected light diffusivity, bright-colored feeling, flexibility, touch and impact strength, etc. There is a risk that physical properties and the like will deteriorate. On the other hand, when the amount exceeds 100 parts by weight, there is a risk that excessive flexibility or insufficient rigidity may be caused, and economical efficiency is also lowered.

4). Optional addition component In the present invention, in addition to the above (A) to (C), if necessary, for example, the effect of the present invention can be further improved or other effects can be imparted within a range that does not significantly impair the effects of the present invention. For this reason, an optional additive component can be contained.
Specifically, bright coloring components that do not fall under (B), aluminum flake coloring components, flaky coloring components such as various metal / glass flakes, inorganic coloring components such as carbon black and titanium oxide, azo pigments and phthalocyanines Organic pigments such as pigments, inorganic and organic fillers such as talc, glass fibers, whiskers and carbon fibers, antioxidants such as phenols, phosphorus and sulfur, hindered amines and other light stabilizers, benzotriazoles UV absorbers, nucleating agents, foaming agents, antistatic agents, lubricants, dispersants, metal deactivators, antibacterial / antifungal agents, plasticizers, neutralizing agents, propylene-based products that do not fall under (A) above Polyolefin resins such as resins, modified polyolefin resins such as maleic anhydride-modified polyolefin resins, polyamide resins and polyester resins And the like thermoplastic resins such as elastomers does not correspond to the (C) (rubber component).
These optional addition components may be used in combination of two or more, and may be added, mixed, or added to the brightly colored composition, or added, mixed, or mixed with the components (A) to (C). -It may be kneaded and added, and each component can be used in combination of two or more.

II. Method for producing brightly colored propylene-based resin composition, method for producing molded article, and use Production Method The brightly colored composition of the present invention comprises (A): a propylene-based copolymer resin, (B): a brightly colored component having an angle-dependent interference effect, and, if necessary, (C): an elastomer. Or an optional additive component, blended by a conventionally known method at the blending ratio, and mixed or melt-kneaded.
When manufacturing by mixing, it is usually performed using a mixing device such as a tumbler, V blender, ribbon blender, etc. When manufacturing by melt kneading, it is usually a single screw extruder, twin screw extruder, Banbury mixer, roll. The mixture is melt-kneaded and granulated using a kneader such as a mixer, Brabender plastograph, kneader, or stirring granulator.
Here, as an example of producing by mixing, for example, the (A) pellets and the (B) containing resin master batch pellets are produced by mixing with a tumbler, or the mixing step is injected. The method of manufacturing using the mixing apparatus attached to the molding machine is mentioned.
When producing by melt-kneading and granulating, the blend of the above components may be kneaded simultaneously, that is, batch-mixed, or the components may be divided and kneaded to improve performance. As the method of dividing and kneading, for example, a method in which part or all of (A) and part of (B) are first kneaded and then the remaining components are kneaded and granulated can be employed. .
In addition, for example, (A) and, if necessary, (C) are also collectively melt-kneaded pellets and (B) simple substance or pellets of the (B) -containing resin master batch are mixed, melt-kneaded. A brightly colored composition can also be produced. Among them, (A) pellets, or (C) batch melt-kneaded pellets if necessary, and (B) pellets of the resin masterbatch are melt-kneaded using a twin-screw extruder or the like, and brightly colored. The method for producing the composition increases the light transmittance and surface gloss of the brightly colored composition of the present invention and its molded product, increases the reflected light diffusivity, and enriches the brightly colored viewing angle. It is preferable because it can express a feeling and a balance of physical properties such as a better balance between flexural modulus and impact strength.

2. Molded product and use The molded product of the present invention is a brightly colored composition produced by the above-described method, for example, a batch mixture, a batch kneaded product, a mixture of each kneaded product of divided kneading, or a batch blend of some components ( B) Mixing with the contained resin masterbatch, for example, gas injection molding, two-color injection molding, core back injection molding, injection molding including sandwich injection molding, injection compression molding such as press injection, extrusion molding, sheet molding and It can be obtained by molding by a known molding method such as hollow molding. Among these, it is preferable to form by molding by injection molding or injection compression molding.

The molded article of the present invention has a high light transmission and surface gloss, a large reflected light diffusivity, a bright coloring feeling rich in viewing angle dependent polychromaticity, and a good balance between flexural modulus and impact strength. A balance of physical properties can be expressed.
Specifically, the degree of sag when measured in accordance with JIS K7136 in a molded body having a thickness of 2 mm is 80% or less, 1% or more, more preferably 70% or less, 1% or more, and particularly 60% or less, 1% or more. And the brightly colored composition of the present invention and the molded product thereof are particularly preferable because the light transmittance is better and a bright colored feeling rich in viewing angle dependent polychromaticity is obtained.
Further, when the gloss when measured according to JIS Z8741 in a molded product having a thickness of 2 mm is 80% or more and 99% or less, the brightly colored composition of the present invention and the molded product thereof have a better surface gloss and a viewing angle. This is particularly preferred because a rich lustrous feeling can be obtained due to the dependency polychromaticity.
In addition, the larger the reflected light diffusivity, the higher the viewing angle-dependent polychromaticity, and the larger the preferable in the present invention. Specifically, when the value measured on a molded product having a thickness of 2 mm is 8% or more, particularly 9% or more, the brightly colored composition of the present invention and the viewing angle dependent polychromaticity of the molded product are enriched. A brightly colored feeling is obtained, which is particularly preferable. The upper limit of the value is usually 80%, and the preferable upper limit is 50%.
Also, when the main use of the molded body is desired, for example, when relatively soft and soft tactile sensation is desired, for example, in automobile interior parts such as a shift knob cover, the molded body having a thickness of 4 mm conforms to JIS K7171. It is desirable to use a material having a flexural modulus of 400 MPa or less, preferably 300 MPa or less, more preferably 200 to 50 MPa when measured.
In addition, when the main use of the molded body of the present invention is desired to have a relatively high rigidity or firmness, for example, in automobile interior parts such as a console box, the molded body having a thickness of 4 mm is compliant with JIS K7171. It is desirable to use a material having a flexural modulus of 700 MPa or more, preferably 800 MPa or more, more preferably 1000 to 3000 MPa when measured in accordance with the standard.

Therefore, various decorative parts such as armrest decorative parts, instrument panel decorative parts, glove box decorative parts, console box decorative parts, switch panels, switch panel covers, moldings, cover moldings, side moldings, armrests, Armrest cover, instrument panel, glove box, console box, pillar, door trim, shift knob, shift knob cover, column shift knob, column shift knob cover, door grip cover, various trims, bumper, fender, wheel cap, back door, Automobile interior / exterior parts such as door protectors, mud guards, engine covers, washing machine drum top cover, rice cooker top cover, mobile phone case, portable information equipment case, It can be suitably used for applications such as home appliance parts such as sound equipment casings, TV casings, and vacuum cleaner casings, toilet equipment parts such as toilet seats and shock absorbers for fittings, various industrial parts, and various building material parts. .
Above all, in addition to the balance of physical properties such as excellent light transmission, surface gloss, reflected light diffusivity, brilliant coloring with rich viewing angle dependence and good balance between flexural modulus and impact strength, the molded product is flexible and soft. Various decorative parts such as armrest decorative parts, instrument panel decorative parts, glove box decorative parts, console box decorative parts, switch panels, switch panel covers, moldings, covers Molding, side molding, armrest, armrest cover, shift knob, shift knob cover, column shift knob, column shift knob cover, door clip cover, assist grip, bumper, fender, rice cooker top cover, mobile phone casing, portable information equipment casing, toilet seat, It is particularly suitable for applications such as shock absorbers for joinery. Can.

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The evaluation methods, analysis methods and materials used in the examples are as follows.

1. Evaluation method and analysis method 1-1. Itching degree (haze, haze)
The following test piece, which was injection-molded under the following molding conditions, was measured according to JIS K7136, with the brightly colored propylene-based resin composition having the composition shown in Table 3 to be described later. However, the test piece dimensions were as follows.
This value represents light transmittance, and the smaller the value, the better the light transmittance. In the present invention, the smaller the value, the better.
<Specimen>
Flat plate: 40mm x 80mm x 2mmt
Mold: Mirror finish (After hard chrome plating, buffing (Abrasive # 800))
<Molding conditions>
Molding machine: Toshiba Machine Co., Ltd., injection molding machine EC20P
Clamping force: 20 tons Cylinder temperature: 220 ° C
Mold temperature: 40 ℃
Injection pressure: 55MPa
Filling time: 8 seconds Cooling time: 12 seconds

1-2. Gloss Using the same test piece as used in 1-1 above, the gloss of the surface was measured according to JIS Z8741. The incident angle and the light receiving angle were both 60 degrees.
The larger the value, the higher the surface gloss. In the present invention, the larger the value, the more preferable.

1-3. Reflected light diffusivity Using the same test piece as used in 1-1 above, the measurement was performed with the following measuring apparatus and measurement conditions (see FIGS. 1 and 2).
Measuring device: Nippon Denshoku Industries Co., Ltd. variable angle photometer "GC5000L"
Incident light angle: 45 degrees (see FIG. 1)
Detection angle (detection range): 5 to 85 degrees (see FIG. 1)
Detection (measurement) interval: 1 degree (see Fig. 1)
Reflected light diffusivity: In the measurement data graph (FIG. 2) showing the detection angle dependence (reflected light intensity distribution) of the reflected light intensity measured under the above conditions, the reflected light intensity amount in the vicinity of the regular reflected light is α, The amounts of reflected light intensity other than the vicinity of the reflected light were β1 and β2. Here, the reflected light diffusivity was defined as the ratio of the reflected light intensity amount (β1 + β2) excluding α to the total reflected light intensity amount (α + β1 + β2).
Specifically, the reflected light intensity amount (α) in the vicinity of the total reflected light intensity amount (regularly reflected light (45 degrees in the present invention)) (42 to 48 degrees in the present invention) and the others (in the present invention, 5 to 42 degrees). And 48 to 85 degrees) is calculated by the ratio of the reflected light intensity (total) amount (β1 + β2) excluding α to the total integrated amount (α + β1 + β2) of the reflected light intensity amount (β1 + β2).
That is, the calculation formula was (β1 + β2) / (α + β1 + β2).
The amount of reflected light intensity was measured and recorded at intervals of 1 degree within a detection angle range of 5 to 85 degrees. The numerical value of the reflected light intensity was the numerical value displayed by the measuring device.
The larger the reflected light diffusivity, the higher the viewing angle dependent polychromaticity is. Basically, the larger the value, the better in the present invention.

1-4. Viewing angle-dependent polychromaticity (visual feeling)
While holding the same test piece as used in 1-1 above and changing the viewing angle and direction, the degree of change in color and saturation of the test piece surface, beauty, transparency, gloss, etc. Visual observation was performed, and the quality of viewing angle-dependent polychromaticity was evaluated according to the following criteria. In this case, it was judged that ◎ and ○ were practical.
<Judgment criteria>
◎: A multi-color property that looks different colors, including saturation, over a wide range of viewing angles is clearly recognized, and a viewing angle-dependent multi-color property that combines excellent transparency, beauty, and high gloss. Very good.
○: The polychromaticity is clearly recognized over a wide range of viewing angles, the transparency is also good, the glossiness is high, and the viewing angle dependent polychromaticity is good.
Δ: Although some polychromaticity is recognized, the saturation and transparency are low, and the viewing angle dependent polychromaticity is insufficient.
X: Due to the low transparency, the polychromaticity is hardly recognized, and the viewing angle dependent polychromaticity is poor.

1-5. Flexural modulus Measured at 23 ° C. according to JIS K7171. The test piece was injection molded under the following conditions.
<Molding conditions>
Molding machine: EC20P type injection molding machine manufactured by Toshiba Machine Co., Ltd. Mold: Two flat plate test pieces (10 x 80 x 4 (mm)) for physical property evaluation Molding conditions: Molding temperature 220 ° C, mold temperature 40 ° C, injection Pressure 50 MPa, injection time 5 seconds, cooling time 20 seconds

1-6. Charpy impact strength Measured at 23 ° C. according to JIS K7111 (notched). The test piece was prepared in the same manner as in 1-5 above.

1-7. Melt flow rate (MFR)
According to JIS K7210, the measurement was performed at a test temperature of 230 ° C. and a load of 2.16 kg.

1-8. Identification of (Component A1a) and (Component A1b) in (A1), etc. Method for evaluating the crystallinity distribution of a propylene / ethylene random copolymer by temperature-temperature elution fractionation (TREF, hereinafter, also simply referred to as TREF). Is well known to those skilled in the art. For example, detailed measurement methods are shown in the following documents.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)
The identification of (component A1a) and (component A1b) in (A1) used in the present invention was based on TREF.
A specific method will be described with reference to the figure showing the elution amount and the elution amount integration by TREF in FIG. In the TREF elution curve (plot of elution amount against temperature), (component A1a) and (component A1b) show their elution peaks at T (A) and T (B), respectively, due to the difference in crystallinity, and the difference is sufficiently large Therefore, separation is possible at an intermediate temperature T (C) (= {T (A) + T (B)} / 2).

In addition, the lower limit of the TREF measurement temperature is −15 ° C. in the apparatus used for this measurement, but in the case where the crystallinity of (Component A1b) is very low or an amorphous component, There may be no peak within the range (in this case, the concentration of (component A1b) dissolved in the solvent at the lower limit of the measurement temperature (ie, −15 ° C.) is detected).
At this time, T (B) is considered to exist below the measurement temperature lower limit, but the value cannot be measured. In such a case, T (B) is the measurement temperature lower limit − It is defined as 15 ° C.
Here, if the integrated amount of the components eluted up to T (C) is defined as W (B) wt%, and the integrated amount of the component eluted at T (C) or higher is defined as W (A) wt%, W (B) Almost corresponds to the amount of the low crystalline or amorphous (component A1b), and the integrated amount W (A) of the component eluted at T (C) or higher is relatively high (component A1a). Almost corresponds to the amount of. The elution amount curve obtained by TREF and the above-described methods for calculating the various temperatures and amounts obtained therefrom are performed as illustrated in FIG.

(A) TREF measuring method In the present invention, the TREF was specifically measured as follows. A sample is dissolved in orthodichlorobenzene (ODCB (containing 0.5 mg / mL BHT)) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, ODCB (containing 0.5 mg / mL BHT) as a solvent is flowed through the column at a flow rate of 1 mL / min, and the components dissolved in ODCB at −15 ° C. are eluted in the TREF column for 10 minutes, and then the temperature is raised. The column is linearly heated to 140 ° C. at a rate of 100 ° C./hour to obtain an elution curve.
The outline of the apparatus is as follows.
TREF column: 4.3 mmφ × 150 mm stainless steel column Column filler: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve Injection method: Loop injection method Detector: Fixed wavelength infrared detector MIRAN 1A manufactured by FOXBORO
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5 mm Window shape 2φ × 4 mm long round Synthetic sapphire window Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL

(B) Identification of ethylene content in (component A1a) and (component A1b) (i) Separation of (component A1a) and (component A1b) Based on T (C) determined by the previous TREF measurement, preparative type Using a fractionation apparatus, the solution is separated into soluble (component A1b) in T (C) and insoluble (component A1a) in T (C) by a temperature rising column separation method, and the ethylene content of each component is determined by NMR.
As the temperature rising column fractionation method, a detailed measurement method is shown in the following document, for example.
Macromolecules; 21, 314-319 (1988).
Specifically, the following method was used in the present invention.

(Ii) Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C.
Next, 200 mL of a sample ODCB solution (10 mg / mL) dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (C) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (C), 800 mL of ODCB of T (C) is flowed at a flow rate of 20 mL / min to elute and recover components soluble in T (C) existing in the column. To do.
Next, the column temperature is increased to 140 ° C. at a rate of temperature increase of 10 ° C./min, held at 140 ° C. for 1 hour, and then 800 mL of a 140 ° C. solvent (ODCB) is flowed at a flow rate of 20 mL / min to obtain T (C). Insoluble components are eluted and recovered.
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer.

^(Iii) 13 C-NMR obtained by measuring the separation of the ethylene content by (component A1a) (component A1b) ethylene content for each is complete proton was measured according to the following conditions by decoupling method ¹³ C- It is determined by analyzing the NMR spectrum.
Model: GSX-400 (carbon nuclear resonance frequency 400 MHz) manufactured by JEOL Ltd.
Solvent: ODCB / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more The attribution of the spectrum may be performed with reference to the following documents, for example.
Macromolecules; 17, 1950 (1984).
The attribution of spectra measured under the above conditions is as shown in the table below. In the table, symbols such as S _αα follow the notation in the following literature, P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.
Carman, Macromolecules; 10,536 (1977)

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules, 15 1150 (1982), the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions <1> to <6>.
[PPP] = k × I (T _ββ ) <1>
[PPE] = k × I (T _βδ ) <2>
[EPE] = k × I (T _δδ ) <3>
[PEP] = k × I (S _ββ ) <4>
[PEE] = k × I (S _βδ ) <5>
[EEE] = k × [I (S _δδ ) / 2 + I (S _γδ ) / 4} <6>
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads.
Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 <7>.
Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .

By using the relational expressions <1> to <7> above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
Note that the propylene random copolymer according to the present invention contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), thereby producing the following minute peaks.

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds. Since the amount is small, the ethylene content in the present invention uses the relational expressions <1> to <7>, as in the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. To ask.
Conversion from mol% to wt% of ethylene content is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
Here, X is the ethylene content in mol%. The ethylene content [E] W of the entire propylene / ethylene block copolymer was calculated from the ethylene contents [E] A, [E] B and TREF of (component A1a) and (component A1b), respectively, measured from the above. From the weight ratios W (A) and W (B)% by weight of the respective components to be calculated, the following formula is used.
[E] W = {[E] A × W (A) + [E] B × W (B)} / 100 (% by weight)

1-9. Melting peak temperature (Tm) of (A1)
Using a Seiko Instruments DSC6200 model, take 5.0 mg of sample, hold at 200 ° C for 5 minutes, crystallize to 40 ° C at a cooling rate of 10 ° C / min, and further melt at a heating rate of 10 ° C / min. And measured.

1-10. Peak of tan δ curve of (A1) A sheet piece of 10 mm width × 18 mm length × 2 mm thickness cut out from a 2 mm thick sheet injection molded under the following conditions is used as a sample piece, and the sample piece has a frequency of 1 Hz. Strain was applied and the generated stress was detected. From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained, the loss tangent (= loss elastic modulus / storage elastic modulus) defined by the ratio is plotted against the temperature, and the peak is observed. Specific measurement conditions are shown below.
Equipment: ARES manufactured by Rheometric Scientific
Standard number: JIS 7152 (ISO294-1)
Frequency: 1Hz
Measurement temperature: from -60 ° C until the sample is melted until the sample melts Strain: 0.1 to 0.5% Range Molding machine: TU-15 injection molding machine manufactured by Toyo Kikai Co., Ltd. Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds
Mold shape: Flat plate (2mm thickness, 30mm width, 90mm length)

1-11. Crystallization temperature (Tc) of (A2)
Using a differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.), a sample piece made into a sheet is packed in a 5 mg aluminum pan, heated from 50 ° C. to 200 ° C. at a heating rate of 100 ° C./min, and held for 5 minutes. Then, the temperature was lowered to 40 ° C. at 10 ° C./min for crystallization.
The maximum crystallization peak temperature at this time was defined as the crystallization temperature (Tc).

2. Materials Propylene-based resins other than (A) to (C) and (A) used are shown below.
2-1. (A): Propylene copolymer resin Hereinafter, both are pellets to which an antioxidant and a neutralizing agent have been added.
(A1): Propylene / ethylene block copolymer resin (A1-1): The grade of the following composition and physical properties of “Wellnex” manufactured by Nippon Polypro Co., Ltd. was used.
Polymerized with a metallocene catalyst, 55.8% by weight of propylene / ethylene random copolymer component (component A1a) having an ethylene content of 1.9% by weight in the first step, and 9% by weight in the second step than (component A1a) % Obtained by sequential polymerization of 44.2% by weight of a propylene / ethylene random copolymer component (component A1b) containing a large amount of ethylene, and the melting peak temperature (Tm) measured by the DSC method is 133. In the temperature-loss tangent curve obtained by solid viscoelasticity measurement at 1 ° C., the tan δ curve has a single peak at −8 ° C., and the MFR (230 ° C., 2.16 kg load) of the entire copolymer is 5.8 g / 10 min.
(A2): Propylene / α-olefin random copolymer resin (A2-1): The grade of the following composition and physical properties of “Wintech” manufactured by Nippon Polypro Co., Ltd. was used.
Propylene / ethylene random polymerized with metallocene catalyst, MFR (230 ° C, load 2.16kg) of the whole component is 28g / 10min, ethylene content is 3.5wt%, crystallization temperature (Tc) is 95 ° C Copolymer resin.

2-2. (B): Colored component (bright colored component and other colored components)
(B-1): Interference aluminum-containing polyolefin resin masterbatch (blue interference color, coloring component content 20% by weight, coloring component average particle size 13 μm (Chromashine “BL10-R” manufactured by Toyo Aluminum Co., Ltd.)). ... bright colored component.
(B-2): Interference aluminum-containing polyolefin resin master batch (orange interference color, coloring component content 20 wt%, coloring component average particle size 20 μm (Chromashine “OR20-R” manufactured by Toyo Aluminum Co., Ltd.)). ... bright colored component.
(B-3): A black colored master batch obtained by melting and kneading Mitsubishi Carbon Black # 45 = 30% by weight and low density polyethylene = 70% by weight using a twin screw extruder manufactured by Mitsubishi Chemical Corporation. ... other coloring ingredients.
(B-4): Aluminum flake-containing low density polyethylene masterbatch (aluminum flake content 70 wt%, aluminum flake average particle size 20 μm (METAXNEO “NME020T2” manufactured by Toyo Aluminum Co., Ltd.)). ... other coloring ingredients.

2-3. (C): Elastomer (C-1): An ethylene-octene copolymer elastomer having an MFR (230, 2.16 kg load) of 6 g / 10 min (engage “8452” manufactured by Dow Chemical Japan Co., Ltd.).

2-4. Propylene resin (PP-1) not corresponding to (A): Propylene / ethylene block copolymer resin having an MFR (230, 2.16 kg load) polymerized using a Ziegler-Natta catalyst of 30 g / 10 min. (Novatech PP “NBC03HR” manufactured by Nippon Polypro Co., Ltd.).
(PP-2): A propylene homopolymer resin (Novatech PP “MA3” manufactured by Nippon Polypro Co., Ltd.) having an MFR (230, 2.16 kg load) polymerized using a Ziegler-Natta catalyst of 11 g / 10 min.

3. Examples and Comparative Examples [Examples 1 to 6] and [Comparative Examples 1 to 4]
3-1. Production of Colored Composition The above ingredients were blended in the proportions shown in Table 3 together with the following additives, dry blended with a super mixer, and then kneaded and granulated under the following conditions for production.
At this time, 0.1 part by weight of IRGANOX 1010 manufactured by BASF and 0.05 part by weight of IRGAFOS 168 manufactured by BASF were blended per 100 parts by weight of the total composition comprising the above components.
Kneading apparatus: “KZW-15-MG” type twin screw extruder manufactured by Technobel.
Kneading conditions: temperature = 200 ° C., screw rotation speed = 400 rpm.

3-2. Molding of colored composition After melt-kneading, the colored composition (pellet) is injection-molded under the above-mentioned conditions. And Charpy impact strength (notched) test pieces.

3-3. Evaluation Performance evaluation was performed on the above molded product. The results are shown in Table 4.

As is clear from Table 4, Examples 1 to 6 satisfying the requirements of the specific matters of the colored propylene-based resin composition of the present invention all have high light transmittance and surface gloss of the molded product. Further, it had a large reflected light diffusivity, had a bright color feeling rich in viewing angle-dependent polychromaticity, and had a good physical property balance such as a balance between flexural modulus and impact strength.
Therefore, various decorative parts such as armrest decorative parts, instrument panel decorative parts, glove box decorative parts, console box decorative parts, switch panels, switch panel covers, moldings, cover moldings, side moldings, armrests, Armrest cover, instrument panel, glove box, console box, pillar, door trim, shift knob, shift knob cover, column shift knob, column shift knob cover, door grip cover, various trims, bumper, fender, wheel cap, back door, Automobile interior / exterior parts such as door protectors, mud guards, engine covers, washing machine drum top cover, rice cooker top cover, mobile phone case, portable information equipment case, It can be suitably used for applications such as home appliance parts such as sound equipment casings, TV casings, and vacuum cleaner casings, toilet equipment parts such as toilet seats and shock absorbers for fittings, various industrial parts, and various building material parts. It has become clear.
Among them, Examples 1, 2, 5 and 6, especially Example 5, have a high light transmittance and surface gloss of the molded article, a large reflected light diffusivity, and a bright coloring feeling rich in viewing angle dependent polychromaticity. Armrest decoration parts and instrument panels that often require a soft and soft feel because they have a good balance of physical properties such as a balance between flexural modulus and impact strength. Various decorative parts such as decorative parts, glove box decorative parts, console box decorative parts, switch panels, switch panel covers, moldings, cover moldings, side moldings, armrests, armrest covers, shift knobs, shift knob covers, column shift knobs , Column shift knob cover, door clip cover, assist grip, bumper, fender, rice cooker Top cover, mobile phone housing, portable information apparatus housing, seat, for applications such as fittings buffer device, that can be used especially suitably have become apparent.

On the other hand, in Comparative Example 1, although the physical property balance such as the balance between the flexural modulus and the impact strength was good, the light transmittance, the surface gloss, and the bright coloring feeling were significantly inferior to Example 1.
This is considered to be because the component corresponding to (A): propylene-based copolymer resin, which is a requirement of the present invention, is not contained.
In Comparative Example 2, the surface gloss and rigidity (flexural modulus) were good, but the light transmission, bright coloring feeling and impact strength were significantly inferior to Example 1.
This is considered to be because the component corresponding to (A): propylene-based copolymer resin, which is a requirement of the present invention, is not contained.
Further, in Comparative Example 3, although the physical property balance such as the balance between the surface gloss and the flexural modulus and the impact strength was good, the light transmittance and the bright coloring feeling were remarkably inferior to Example 1.
This is considered because (B): the coloring component does not satisfy the requirements of the present invention.
Further, in Comparative Example 4, although the physical property balance such as surface gloss, reflected light diffusivity, and balance between flexural modulus and impact strength is good, light transmittance and viewing angle dependent polychromaticity (visual feeling) are examples. Remarkably inferior to 1.
This is considered because (B): the coloring component does not satisfy the requirements of the present invention.

The brightly colored propylene-based resin composition and molded product thereof according to the present invention contain the specific (A1) and / or (A2) (A) and (B). It has a high surface gloss, a large reflected light diffusivity, a bright colored feeling rich in viewing angle dependent polychromaticity, and a good balance of physical properties such as a balance between flexural modulus and impact strength.
Therefore, various decorative parts such as armrest decorative parts, instrument panel decorative parts, glove box decorative parts, console box decorative parts, switch panels, switch panel covers, moldings, cover moldings, side moldings, armrests, Armrest cover, instrument panel, glove box, console box, pillar, door trim, shift knob, shift knob cover, column shift knob, column shift knob cover, door grip cover, various trims, bumper, fender, wheel cap, back door, Automobile interior / exterior parts such as door protectors, mud guards, engine covers, washing machine drum top cover, rice cooker top cover, mobile phone case, portable information equipment case, It can be suitably used for applications such as home appliance parts such as sound equipment casings, TV casings, and vacuum cleaner casings, toilet equipment parts such as toilet seats and shock absorbers for fittings, various industrial parts, and various building material parts. .

Claims (6)

A brightly colored propylene-based resin composition comprising (A) and (B) comprising the following (A1) and / or (A2).
(A): Propylene copolymer resin; 100 parts by weight (A1): Propylene / ethylene block copolymer resin satisfying the following requirements (A) to (D) (A): Using a metallocene catalyst, 30 to 95% by weight of propylene / ethylene random copolymer component (A1a) having propylene alone or ethylene content of 7% by weight or less in the first step, and 3 to 20% by weight more than the component (A1a) in the second step It is obtained by successively polymerizing 5-70 wt% of propylene / ethylene random copolymer component (A1b) containing ethylene.
(A): The melting peak temperature (Tm) measured by the DSC method is 110 to 150 ° C.
(C): In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.
(D): Melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 min.
(A2): Propylene / α-olefin random copolymer resin satisfying the following requirements (f) and (g) (f): Melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.5 to 200 g / 10 min.
(G): Consists of a structural unit obtained from propylene and a structural unit obtained from α-olefin.
(B): Bright coloring component having angle-dependent interference effect; 0.1 to 10 parts by weight The brightly colored propylene-based resin composition according to claim 1, further comprising (C): 100 parts by weight of (A):
(C): Elastomer; 1 to 100 parts by weight   The degree of stagnation when measured according to JIS K7136 in a molded body having a thickness of 2 mm is 80% or less, and the gloss when measured according to JIS Z8741 in a molded body having a thickness of 2 mm is 80% or more. The brightly colored propylene-based resin composition according to claim 1 or 2, wherein a diffused light diffusivity when measured at an incident light angle of 45 degrees in a molded body having a thickness of 2 mm is 8% or more. Resin composition.   The brightly colored propylene-based resin composition according to any one of claims 1 to 3, wherein the molded article having a thickness of 4 mm has a flexural modulus of 400 MPa or less when measured according to JIS K7171. object.   A molded article obtained by molding the brightly colored propylene-based resin composition according to any one of claims 1 to 4. The molded article according to claim 5, which is an automobile part.

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