JP2017061625A - Colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition excellent in processability, which shows little warpage, deformation or shrinkage and can suppress development of aggregates without damaging characteristics of a colorant, and a molded body using the composition.SOLUTION: The colored resin composition comprises a colorant, a polyolefin wax (A) having a carboxyl group and/or an acid anhydride group, a polyolefin wax (B) having neither a carboxyl group nor an acid anhydride group, and a polyester resin. A molded body using the above composition is also disclosed.SELECTED DRAWING: None

Description

  The present invention relates to a colored resin composition and a molded body using the same. More specifically, the present invention relates to a colored resin composition in which warpage, deformation, and shrinkage are small and generation of aggregates is suppressed, and a molded body using the same.

  In order to suppress warping and deformation of a colored plastic molded body, technical studies have been made from various aspects such as a resin composition used in the molded body and processing conditions during molding. Among these, phthalocyanine pigments used as plastic colorants have characteristics such as weather resistance, heat resistance, migration resistance, clear hue, high coloring power, etc., but partially such as polyolefin and polyethylene terephthalate. It is known that when used for coloring a thermoplastic resin having crystallinity, it is a colorant that easily warps or deforms a plastic molded body. The cause of this warpage and deformation is considered to be because the phthalocyanine pigment acts as a crystallization agent for the resin used as plastic (hereinafter, this phenomenon may be referred to as “nucleation effect”). ).

  As a method for suppressing such a nucleation effect, a method for preventing the pigment from acting as a crystal nucleus has been studied, a method for changing the physical properties of the pigment itself, such as the crystal shape, particle diameter, and shape, and additives. A method for controlling the crystallinity of the resin is known.

  Patent Documents 1 to 3 are known as methods for changing the physical properties of the pigment itself. However, when the physical properties such as the crystal shape, particle diameter, and shape of the pigment itself are changed, the desired hue cannot be obtained when the molded body is created, the dispersibility for the resin is lowered, the coloring power of the molded body, There existed a problem that characteristics, such as heat resistance and a weather resistance, fell, and the curvature and distortion of a molded object could not be fully suppressed.

  On the other hand, as a method of controlling the crystallinity of the resin with an additive, for example, a method of adding an inorganic filler or a metal salt to a propylene copolymer and ethylene copolymer mixture (Patent Document 4), a talc is added to crystalline polypropylene. There is known a method (Patent Document 5) for kneading a high concentration. However, these methods have problems that the molecular weight and melt viscosity of the resin used are limited, and that the warping and distortion of the molded product cannot be suppressed depending on the type of the colorant used. Therefore, development of the colored resin composition which can suppress the curvature and distortion of a molded object was calculated | required.

JP-A-4-376232 JP 57-155242 A JP 58-125752 A JP 2011-225663 A JP 2002-69204 A

  The problem to be solved by the present invention is to use a colored resin composition excellent in workability capable of suppressing the generation of aggregates without causing deterioration of the properties of the colorant, little warpage, deformation, and shrinkage. It aims at providing a molded object.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, an embodiment of the present invention includes a colorant, a polyolefin wax (A) having a carboxyl group and / or an acid anhydride group, a polyolefin wax (B) having no carboxyl group and an acid anhydride group, and a polyester. The present invention relates to a colored resin composition comprising a resin.

  An embodiment of the present invention relates to the colored resin composition, wherein the colorant is a phthalocyanine pigment.

  In addition, an embodiment of the present invention relates to the colored resin composition, wherein the polyolefin wax (A) has a melting point in the range of 50 to 180 ° C.

  Moreover, the embodiment of the present invention relates to the colored resin composition, wherein the polyolefin wax (B) has a melting point in the range of 50 to 180 ° C.

  Moreover, the embodiment of this invention is related with the said colored resin composition whose softening point of the said polyester resin exists in the range of 50-200 degreeC.

  The embodiment of the present invention further relates to the colored resin composition comprising a polyolefin (excluding the polyolefin wax (A) and the polyolefin wax (B)).

  Moreover, the embodiment of this invention is related with the molded object created using the said colored resin composition.

  According to the present invention, there are provided a colored resin composition excellent in processability capable of suppressing the generation of aggregates and having little warpage, deformation, and shrinkage without impairing the properties of the colorant, and a molded body using the same. Became possible.

Hereinafter, the present invention will be described in detail.
<Colorant>
Examples of the colorant used in the present invention include pigments and dyes. Examples of the pigment include organic pigments and inorganic pigments. Organic pigments include azo pigments, isoindolinone pigments, quinophthalone pigments, benzimidazolone pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, and phthalocyanine pigments. Can be mentioned.

<Phthalocyanine pigment>
A preferred embodiment of the colorant used in the present invention is a phthalocyanine pigment. Examples of the phthalocyanine pigments include copper phthalocyanine pigments such as CI Pigment Blue 15: 1 and 15: 3, and halogenated copper phthalocyanine pigments such as CI Pigment Green 7, 36 and 58. The presence or absence and type of metal are not particularly limited. “CI” means a color index.

  The crystal form of the phthalocyanine pigment is not limited, but the crystal form is preferably amorphous (amorphous state) in order to weaken the function as a nucleating agent. The phthalocyanine pigment can be used in the form of powder or water paste.

  Content of the phthalocyanine-type pigment in a colored resin composition is 40-60 mass parts with respect to 100 mass parts of colored resin compositions, More preferably, it is 45-55 mass parts.

<Polyolefin wax (A) having carboxyl group and / or acid anhydride group>
Next, a polyolefin wax (A) having a carboxyl group and / or an acid anhydride group (hereinafter sometimes simply referred to as “wax (A)”) will be described. The wax (A) in the present specification refers to a polyolefin wax that has a carboxyl group and / or an acid anhydride group, is solid at less than 40 ° C., and melts within a range of 40 ° C. to 160 ° C. The “acid anhydride group” in the present specification means “—CO—O—CO—” and means, for example, a residue of acid anhydride such as maleic anhydride or phthalic anhydride.

  The wax (A) is a polymer of an olefin monomer such as ethylene, propylene and butylene, and may be a block, a random copolymer or a terpolymer. Specifically, carboxyl groups and acid anhydride groups are introduced into α-olefin polymers such as low-density polyethylene (HDPE), high-density polyethylene (LDPE), and polypropylene (PP), and graft modified products thereof. And polyolefin wax. The wax (A) is preferably in a powder form at a temperature below 40 ° C.

  The melting point of the wax (A) is preferably a melting point measured using a differential scanning calorimeter “DSC6200” (manufactured by Seiko Instruments Inc.) under conditions of a temperature range of 40 to 200 ° C. and a heating rate of 10 ° C./min. 50-180 degreeC, More preferably, it exists in the range of 80-140 degreeC. The acid value of the wax (A) is preferably 5 to 60 mgKOH / g, more preferably 10 to 40 mgKOH / g.

  The content of the wax (A) in the colored resin composition is preferably 3 to 15 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the colored resin composition.

  Specific examples of the wax (A) include AC polyethylene 316A (manufactured by Honeywell, carboxyl group-containing wax (A), acid value 16, melting point 134 ° C.), high wax NP-50605A (manufactured by Mitsui Chemicals, acid anhydride). Examples include a substance group-containing wax (A), an acid value of 11, a melting point of 132 ° C., and a sun wax E-250P (manufactured by Sanyo Chemical Industries, Ltd., a carboxyl group-containing wax (A), an acid value of 17, a melting point of 96 ° C.).

<Polyolefin wax (B) having no carboxyl group or acid anhydride group>
Next, the polyolefin wax (B) having no carboxyl group and acid anhydride group (hereinafter sometimes simply referred to as wax (B)) will be described. The wax (B) refers to a polyolefin wax that does not have a carboxyl group and an acid anhydride group, is solid at less than 40 ° C, and melts within a range of 40 ° C to 160 ° C. The wax (B) is preferably in a powder form at a temperature below 40 ° C.

  The number average molecular weight of the wax (B) is preferably in the range of 500 to 20,000, more preferably in the range of 900 to 18,000 in JIS (Japanese Industrial Standard) K2207: 1996.

  The melting point of the wax (B) is preferably a melting point measured by using a differential scanning calorimeter “DSC6200” (manufactured by Seiko Instruments Inc.) under conditions of a temperature range of 40 to 200 ° C. and a heating rate of 10 ° C./min. -180 degreeC, More preferably, it exists in the range of 80-140 degreeC.

  Specific examples of the wax (B) include sun wax 131-P (manufactured by Sanyo Chemical Industries, number average molecular weight 3500, melting point 105 ° C.), high wax NL500 (manufactured by Mitsui Chemicals, number average molecular weight 4200, melting point 104 ° C.). Etc.

  Content of the wax (B) in a colored resin composition is 10-40 mass parts with respect to 100 mass parts of colored resin compositions, More preferably, it is 15-35 mass parts.

<Polyester resin>
The polyester resin is obtained by subjecting a polyol component such as a diol and a polycarboxylic acid component such as a dicarboxylic acid as constituent components and, if necessary, polycondensation in the presence of a catalyst.

  As a diol component which comprises a polyester resin, the C2-C3 alkylene oxide adduct of bisphenol A and a C2-C6 lower alkyl diol are mentioned. Examples of the lower alkyl diol having 2 to 6 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, , 5-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, neopentyl glycol and the like. Two or more of these diol components may be used in combination.

  Examples of the dicarboxylic acid constituting the polyester resin include terephthalic acid, lower alkyl dicarboxylic acid, and alkenyl dicarboxylic acid. Examples of lower alkyl dicarboxylic acids include malonic acid, succinic acid, adipic acid and sebacic acid. Examples of the alkenyl dicarboxylic acid include alkenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid and the like. Two or more of these dicarboxylic acid components may be used in combination.

  The softening point of the polyester resin is preferably in the range of 50 to 200 ° C, more preferably 80 to 140 ° C.

  The polyester resin preferably has an amorphous crystal form in which a black angle 2θ in an X-ray diffraction pattern by CuKα rays does not show a peak within a range of 10 ° to 45 °. In addition, the X-ray diffraction pattern by CuKα ray in this specification uses a desktop X-ray diffractometer manufactured by Rigaku Corporation, and a black angle range of 2θ = 5 ° to 90 ° with an X-ray sampling interval of 0.05 °. Measurements were made.

  The content of the polyester resin in the colored resin composition is preferably 7 to 30 parts by mass, more preferably 10 to 25 parts by mass with respect to 100 parts by mass of the colored resin composition.

  Specific examples of the polyester resin include M-302 (manufactured by Sanyo Chemical Industries, softening point 100 ° C., no diffraction peak in the range of 10 ° ≦ 2θ ≦ 45 °) M-325 (manufactured by Sanyo Chemical Industries, softening point) 130 ° C., 10 ° ≦ 2θ ≦ 45 °, no diffraction peak), M-412 (manufactured by Sanyo Chemical Industries, softening point 140 ° C., 10 ° ≦ 2θ ≦ 45 °, no diffraction peak), etc. Is mentioned.

<Polyolefin>
Next, polyolefins other than the polyolefin wax (A) and the polyolefin wax (B) will be described.

  The polyolefin preferably has a MFR (melt flow rate, also referred to as melt viscosity) in the range of 0.001 to 30 in JIS (Japanese Industrial Standard) K7210: 1999 (ISO 1133: 1997). Polyolefin can be used in the form of powder or pellets, preferably in the form of pellets.

  Specific examples of the polyolefin include Hi-Zex 2208J (manufactured by Prime Polymer, MFR 5.0, HDPE), Prime Polypro J105G (manufactured by Prime Polymer, MFR 9.0, PP), and the like.

  The colored resin composition of the present invention includes a heavy metal deactivator, an alkali metal, alkaline earth metal or zinc metal soap, hydrotalcite, nonion within a range that does not impair the effects of the present invention or cause sanitary problems. Surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, antistatic agents such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylene bisalkylamides, Antioxidants, ultraviolet absorbers, processing aids, fillers, various additives for known polymers, and the like can be included.

<Molded body>
The molding method for obtaining a molded product by molding the colored resin composition is not particularly limited. Regardless of the molding method such as injection molding, blow molding, inflation molding, extrusion molding, engel molding, vacuum molding, etc., a molded body in which warpage and deformation are suppressed can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.

First, materials used for the colored resin composition are listed below.
<Colorant>
VYNAMON BLUE 515100 (manufactured by Heubach, CI Pigment Blue 15: 1, hereinafter referred to as V.B.15: 1)
Lionol Blue FG7330 (Toyocolor Co., Ltd., CI Pigment Blue 15: 3, hereinafter referred to as FG7330)
Lionol Blue POG-TONNER (Toyocolor Co., Ltd., CI Pigment Green 7, hereinafter referred to as POG-T)

<Polyolefin wax (A) having carboxyl group and / or acid anhydride group>
AC polyethylene 316A (manufactured by Honeywell, carboxyl group-containing wax (A), acid value 16, melting point 134 ° C., hereinafter referred to as AC)
High wax NP50605A (Mitsui Chemicals, maleic anhydride group-containing wax (A), acid value 11, melting point 132 ° C., hereinafter referred to as NP)
Sun wax E-250P (manufactured by Sanyo Chemical Industries, Ltd., carboxyl group-containing wax (A), acid value 17, melting point 96 ° C., hereinafter referred to as E-250P)

<Polyolefin wax (B) having no carboxyl group and acid anhydride group>
Sunwax 131-P (manufactured by Sanyo Chemical Industries, number average molecular weight 3500, melting point 105 ° C., hereinafter referred to as 131P)
High wax NL500 (manufactured by Mitsui Chemicals, number average molecular weight 4200, melting point 104 ° C., hereinafter referred to as NL500)

<Polyester resin>
M-302 (manufactured by Sanyo Chemical Industries, softening point 100 ° C., no diffraction peak in the range of 10 ° ≦ 2θ ≦ 45 °)
M-325 (manufactured by Sanyo Chemical Industries, softening point 130 ° C., no diffraction peak in the range of 10 ° ≦ 2θ ≦ 45 °)
M-412 (manufactured by Sanyo Chemical Industries, softening point 140 ° C., no diffraction peak within the range of 10 ° ≦ 2θ ≦ 45 °)

<Polyolefin>
Hi-Zex 2208J (Prime Polymer, MFR5.0, HDPE)
Prime Polypro J105G (Prime Polymer, MFR9.0, PP)

(Production and evaluation of colored resin composition)
<Example 1>
(Colored resin composition)
V. As a colorant B. 15: 1 45 parts, 5 parts of AC as wax (A), 30 parts of 131P as wax (B), 20 parts of M-302 as polyester resin were melt-kneaded at 150 ° C. and then pulverized to obtain a colored resin composition It was.

<Examples 2-39 and Comparative Examples 1-27>
A colored resin composition was obtained in the same manner as in Example 1 except that the materials and parts by mass shown in Table 1 were changed. In addition, the item in which a numerical value is not described in Table 1 represents that it does not contain.

(Processability evaluation of colored resin composition)
The workability of the colored resin composition was evaluated from the visual evaluation of the material remaining (metal adhesion of the colored resin composition) to the kneader after the material was melt-kneaded and the yield of the obtained colored resin composition. “A” (particularly good) when there is almost no material remaining in the kneader and the yield is 95% or more, and “B” when the material remaining in the kneader is confirmed and the yield is 90% or more and less than 95%. (Good), the material remaining in the kneading machine was remarkably low, and the yield was less than 90%.

(Manufacture and evaluation of compacts (molded plates))
2 parts of each colored resin composition produced and HDPE or PP998 parts were mixed according to Table 1, melt-mixed at 200 ° C. with a single screw extruder (manufactured by Thermoplastics Co., Ltd.), and colored pellets ( An embodiment of a colored resin composition) was obtained. The obtained colored pellets were molded into a plate shape by an injection molding machine (manufactured by Toshiba Machine Co., Ltd.) to obtain a molded plate (one mode of a molded body). About each obtained shaping | molding plate, shrinkage | contraction difference rate, curvature, dispersion | distribution, and the nucleation effect were evaluated. In addition, the metal mold | die at the time of producing a shaping | molding plate used the metal mold | die which produces the plate of length 150mm, width 120mm, and thickness 2mm in which the marking line of 10.00cm was provided in the injection direction and the perpendicular direction. In addition, 15 sheets were continuously injection-molded at a molding temperature of 220 ° C. and a mold temperature of 40 ° C. For evaluation, 6 of the 9th to 14th sheets were controlled at 23 ° C. and 50 RH. And after 24 hours storage. In addition, as an evaluation standard, a molded plate (sometimes referred to as “natural”) formed by molding only polyolefin (HDPE or PP) under the same conditions was used.

(Evaluation of shrinkage difference and warpage)
The shrinkage difference rate calculated by the ratio between the injection direction and the shrinkage rate in the vertical direction, and the degree of warping visually were evaluated. The shrinkage difference rate was calculated according to the following formulas 1 and 2 by measuring the length in the injection direction and the vertical direction (direction perpendicular to the injection direction and the thickness direction) with precision calipers for each molded plate. The value was an average value for the 6 th to 14 th molded plates. The smaller the difference in shrinkage difference rate (ΔSDR), the better.

Shrinkage difference rate (SDR) = (shrinkage rate in injection direction−shrinkage rate in vertical direction) / shrinkage rate in injection direction (Equation 1)
ΔSDR = | natural shrinkage difference ratio−coloration resin shrinkage difference ratio | (Formula 2)
The standard of warpage is “A” (good) if the warpage is comparable to that of natural using the same type of polyolefin, and “C” (bad) is clearly warped. did.

(Evaluation of dispersibility)
The dispersibility was evaluated by the number of pigment aggregates observed in the molded plate. The molded plate was observed with an optical microscope “Digital Microscope VHX-100” (manufactured by Keyence Corporation) in a field of view with a magnification of 1000 times, and 10 or less pigment aggregates having a length of 15 μm or more were observed in the field of view. “A” (good), 11 or more observed were taken as “C” (bad).

(Evaluation of nucleation effect)
The nucleation effect was evaluated by the crystallization temperature of the molded plate. The crystallization temperature (Tc) of the molded plate was measured using a differential scanning calorimeter “DSC6200” (manufactured by Seiko Instruments Inc.) under conditions of a temperature range of 40 to 200 ° C. and a heating and cooling rate of 10 ° C./min. The difference in crystallization temperature from natural (ΔTc) was calculated according to Equation 3. The smaller the value of ΔTc, the weaker and better the nucleation effect.

ΔTc = | Tc of natural Tc-colored resin | (Formula 3)

  The evaluation results are shown in Table 1.

The colored resin composition of the present invention was found to have good results for all evaluation items of processability, shrinkage, and dispersibility. Among these examples, when the softening point of the polyester resin is M-302 closest to the melting point of the wax (B) (Examples 1 to 3, 5, 6, 9, 10, 13 to 16, 18, 19, 22, 23, 26 to 29, 31, 32, 35, 36, 39), and it was revealed that particularly good workability was exhibited.
On the other hand, when any of the wax (A), the wax (B), and the polyester resin is not included (Comparative Examples 1 to 27), one or more evaluation items of workability, shrinkage, and dispersibility are included. It was found to give bad results.

Table 1

Table 1 (continued)

Claims (7)

  Colored resin composition comprising a colorant, a polyolefin wax (A) having a carboxyl group and / or an acid anhydride group, a polyolefin wax (B) having no carboxyl group and an acid anhydride group, and a polyester resin object.   The colored resin composition according to claim 1, wherein the colorant is a phthalocyanine pigment.   The colored resin composition according to claim 1 or 2, wherein the polyolefin wax (A) has a melting point in the range of 50 to 180 ° C.   The colored resin composition according to any one of claims 1 to 3, wherein the polyolefin wax (B) has a melting point in the range of 50 to 180 ° C.   The colored resin composition according to any one of claims 1 to 4, wherein a softening point of the polyester resin is in a range of 50 to 200 ° C.   Furthermore, the colored resin composition in any one of Claims 1-5 which comprises polyolefin (however, except the said polyolefin wax (A) and polyolefin wax (B)).   The molded object created using the colored resin composition in any one of Claims 1-6.