JP2023024386A - Thermoplastic resin composition - Google Patents

Abstract

To provide a thermoplastic resin composition capable of obtaining a molded body which has high jet-blackness and is excellent in color migration resistance, fluidity, strength at a low temperature, toughness, light shielding property and heat deformation resistance.SOLUTION: There is provided a thermoplastic resin composition which contains a methacrylic resin (A), a thermoplastic elastomer (B) and 0.05 to 1 pt.mass of a dye or pigment based on the total 100 pts.mass of the methacrylic resin (A) and the thermoplastic elastomer (B), wherein when a molded body having a thickness of 2 mm is molded at a molding temperature of 240°C and a mold temperature of 55°C using a mold of a mold polishing count of 8000, a brightness L* of the molded body measured by a D65 light source, an SCE system and a 10-degree field of view reflection mode is 3 or less.SELECTED DRAWING: None

Description

The present invention relates to thermoplastic resin compositions.

As a transparent resin, methacrylic resin is characterized by having higher light transmittance, weather resistance, and rigidity than other plastic transparent resins. , windows of display devices, etc. In addition, methacrylic resins, due to their high light transmittance, become glossy and highly designed materials when dyes or pigments are added to make colored compositions. Due to its excellent appearance, it is often used as design parts for home appliances and OA products and as design parts for interior and exterior of automobiles.
However, methacrylic resin compositions have low toughness, and their use is often limited in applications where materials are fixed in molded articles or jigs having mechanical parts. Further, for example, when a hard material such as canvas used for tote bags is repeatedly brought into contact with the material, there is a problem that the colorant component is transferred.
On the other hand, thermoplastic elastomers are resins with excellent toughness, but have low thermal deformation resistance and rigidity, and their use as molded articles, particularly injection molded articles, has been limited.

Patent Document 1 discloses methacrylic resin compositions suitable for members having mechanical parts, but these compositions do not have sufficient strength at low temperatures. Moreover, when a colored material is used, for example, when a hard material such as a canvas used for a tote bag contacts repeatedly, there is a problem that the colorant component is transferred.
Generally, in methacrylic resins, if the weight average molecular weight (Mw) is decreased, molding fluidity represented by melt mass flow rate (MFR) is improved, but mechanical properties such as tensile strain at break are decreased. A methacrylic resin composition to which an acrylic rubber polymer is added is expected to have improved mechanical properties, but loses fluidity.

In Patent Document 2, by combining silica and methacrylic resin, and in Patent Document 3, by combining silicone resin, surface-treated carbon black, and methacrylic resin, excellent scratch resistance is achieved. Jet-black colored injection molded articles have been disclosed, but these injection molded articles do not have sufficient strength, and there remains the problem of color transfer of the aforementioned coloring agent component. There is also room for improvement in terms of jet-blackness.

As an approach to improve toughness, Patent Document 4 discusses the combination of a thermoplastic polyurethane and a strength-modified methacrylic resin composition, and describes a low-temperature impact resistant resin composition with acceptable transparency. It is shown here that a mixture of thermoplastic polyurethanes with aliphatic bonds achieves a transmittance of 83%, and this is used as a thermoplastic resin composition with good color transfer resistance and jet-blackness. A method for achieving this is not disclosed, and the obtained resin composition has room for improvement in heat deformation resistance. If the resistance to heat deformation is poor, the dimensions of the joint may change in applications where heat is applied, and the joint may not function satisfactorily.

In Patent Document 5, as an improvement in transparency, which was insufficient in Patent Document 4, by combining a thermoplastic polyurethane using an aliphatic isocyanate and a diol with a specific structure with a methacrylic resin composition, high transmittance and Compositions are indicated which at the same time exhibit low haze, in particular low haze and high transparency. However, a method for making this into a thermoplastic resin composition having good color transfer resistance and jet-blackness is not disclosed, and the obtained resin composition does not change when placed in a moist and heat environment. Bleeding out of the components in the product occurred, and there was still room for improvement in maintaining the appearance. If the appearance retention is poor, there is a possibility that the jet-blackness cannot be fully exhibited in the long-term use in an environment exposed to moist heat such as outdoors.

JP 2016-006164 A WO2017/200048 JP 2017-137474 A Japanese Patent Publication No. 2009-516766 Japanese Patent Publication No. 2015-532345

An object of the present invention is to provide a thermoplastic resin composition capable of obtaining a molded article having excellent light-shielding properties, jet-blackness, color transfer resistance, heat deformation resistance, fluidity, strength at low temperatures, and toughness. That is.

That is, the present invention is as follows.
[1]
0.05 to 1 part by mass of a dye or pigment per 100 parts by mass of the methacrylic resin (A), the thermoplastic elastomer (B), and the methacrylic resin (A) and the thermoplastic elastomer (B) and
Molding temperature: 240 ° C. Mold temperature: 55 ° C. using a mold with a mold polishing number of 8000 When molding a molded product with a thickness of 2 mm, D65 light source, SCE method, 10 degree field of view reflection mode Measurement was performed. The thermoplastic resin composition, wherein the molded article has a lightness L* of 3 or less.
[2]
The total light transmittance is 0.3% or less when a molded article having a thickness of 2 mm is molded at a molding temperature of 240°C and a mold temperature of 55°C using a mold with a mold polishing count of No. 8000 [ 1], the thermoplastic resin composition.
[3]
The thermoplastic resin composition according to [1] or [2], wherein the thermoplastic elastomer (B) is a thermoplastic polyurethane.
[4]
The thermoplastic resin composition according to any one of [1] to [3], wherein the thermoplastic elastomer (B) is a thermoplastic polyurethane having 70% by mass or more of isocyanate-derived structural units having an alicyclic ring.
[5]
The thermoplastic resin composition [6] according to any one of [1] to [4], which has a VICAT softening temperature of 95° C. or higher as measured according to ISO 306 B50.
Melt mass flow rate (MFR) measured at 230 ° C. under a 3.8 kgf load is 2.8 g / 10 minutes or more, and a Charpy impact test value at -30 ° C. measured in accordance with JIS K7111-1 is 23 kJ/m ² or more, the thermoplastic resin composition according to any one of [1] to [5] [7]
Any one of [1] to [6], wherein 10 to 35 parts by mass of the thermoplastic elastomer (B) is contained with respect to a total of 100 parts by mass of the methacrylic resin (A) and the thermoplastic elastomer (B). to a thermoplastic resin composition [8]
The thermoplastic elastomer (B) is a thermoplastic polyurethane having an isocyanate-derived structural unit, and an isocyanate having one alicyclic ring relative to 100% by mass of the total weight of the isocyanate-derived structural units contained in the thermoplastic polyurethane. The thermoplastic resin composition according to any one of [1] to [7], wherein the mass ratio of the derived structural unit is 70% by mass or more.
[9]
The heat according to any one of [1] to [8], wherein the weight average molecular weight of the methacrylic resin (A) measured using gel permeation chromatography (GPC) is 50,000 to 250,000. A plastic resin composition.
[10]
The thermoplastic according to any one of [1] to [9], characterized in that the methacrylic resin (A) and the thermoplastic elastomer (B) are blended at a temperature in the range of 200 to 260°C. A method for producing a resin composition.
[11]
[1] A molded article comprising the thermoplastic resin composition according to any one of [9].
[12]
The molded article according to [11], which is an injection molded article.
[13]
The molded article according to [11] or [12], which has a joint with another member.
[14]
[11] A vehicle member comprising the molded article according to any one of [11] to [13].
[15]
The vehicle member according to [14], which is selected from automotive pillar garnishes, rear spoilers, front garnishes, rear garnishes, slide rail covers, and front grilles.

According to the thermoplastic resin composition of the present invention, it is possible to obtain a molded article having excellent light shielding properties, jet blackness, color transfer resistance, thermal deformation resistance, fluidity, toughness, and strength at low temperatures.

FIG. 1 is a perspective view showing a molded body having joints produced in Examples.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is a methacrylic resin (A), a thermoplastic elastomer (B), and a total of 100 parts by mass of the methacrylic resin (A) and the thermoplastic elastomer (B). 0.05 to 1 part by mass of dye and pigment, and a mold with a mold polishing count of 8000 is used at a molding temperature of 240 ° C. and a mold temperature of 55 ° C. to form a molded body with a thickness of 2 mm. Secondly, the lightness L* of the molded body measured in the D65 light source, SCE 10-degree visual field reflection mode is 3 or less.
In this specification, the total mass of the methacrylic resin (A) and the thermoplastic elastomer (B) is 100 parts by mass unless otherwise specified.

<Methacrylic resin (A)>
The methacrylic resin (A) may contain at least one kind of methacrylic resin, and a single kind of methacrylic resin may be used, or two or more kinds of methacrylic resins may be used in combination.
The methacrylic resin (A) contains 80.0 to 99.9% by mass of methacrylic acid ester monomer units and methacrylic acid ester monomers other than maleic acid and maleic anhydride based on 100% by mass of the methacrylic resin. Consists of 0.1 to 20.0% by mass of vinyl monomer units composed of vinyl monomers copolymerizable with and 0 to 4.0% by mass of maleic acid and/or maleic anhydride monomer units It is preferable that
When the content of the methacrylic acid ester monomer unit is 99.9% by mass or less, it is possible to prevent the decomposition of the resin during molding, and the occurrence of methacrylic acid ester monomers, which are volatile components, and molding defects called silver. can be effectively prevented. In addition, deterioration due to decomposition and yellowing of the thermoplastic elastomer (B) caused by radicals generated by decomposition of the methacrylic resin (A) can be prevented, and molding defects due to yellowing of the thermoplastic resin composition and generation of volatile components can be prevented. can effectively prevent the occurrence of Further, when the methacrylic acid ester monomer unit is 80.0% by mass or more, the heat resistance generally required for the molded article can be ensured. By having sufficient heat resistance, rigidity can be ensured, and strength generally required for a molded article can be ensured.

The methacrylic acid ester monomer constituting the methacrylic acid ester monomer unit contained in the methacrylic resin (A) is not limited to the following, but examples include butyl methacrylate, ethyl methacrylate, and methacrylic acid. methyl, propyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylate (2-ethylhexyl), methacrylate (t-butylcyclohexyl), benzyl methacrylate, methacrylate (2,2,2-trifluoro ethyl) and the like. Among them, methyl methacrylate and ethyl methacrylate are preferable from the viewpoint of availability and price.
The above methacrylic acid ester monomers may be used alone or in combination of two or more.

The content of the methacrylic acid ester monomer unit is preferably 85.0 to 99.9% by mass, more preferably 85.0 to 99.8% by mass, with respect to 100% by mass of the methacrylic resin (A). more preferably 85.0 to 99.5% by mass, even more preferably 90.0 to 99.5% by mass, and 93.0 to 99.5% by mass is even more preferable, and from the viewpoint of obtaining a thermoplastic resin composition having higher jet-blackness and heat deformation resistance when made into a thermoplastic resin composition, 94.0 to 99.0% by mass is particularly preferable.

The vinyl monomer copolymerizable with the methacrylic acid ester monomer constituting the vinyl monomer unit contained in the methacrylic resin (A) is a vinyl monomer other than maleic acid and maleic anhydride, One acrylate group such as, but not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, 2-ethylhexyl acrylate, etc. acrylic acid ester monomers having
In addition, ethylene glycol having two or more (meth)acrylate groups, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. Or esterification of both terminal hydroxyl groups of the oligomer with acrylic acid or methacrylic acid; esterification of hydroxyl groups of two alcohols such as neopentyl glycol di(meth)acrylate and di(meth)acrylate with acrylic acid or methacrylic acid polyhydric alcohol derivatives such as trimethylolpropane and pentaerythritol esterified with acrylic acid or methacrylic acid; and acrylic acid ester monomers.
In particular, methyl acrylate, ethyl acrylate and n-butyl acrylate are preferred, and methyl acrylate and ethyl acrylate are more preferred due to their easy availability.
Vinyl monomers (preferably acrylic acid ester monomers) copolymerizable with methacrylic acid ester monomers may be used singly or in combination of two or more.

The content of the vinyl monomer unit composed of the vinyl monomer copolymerizable with the methacrylic acid ester monomer (preferably the content of the acrylic acid ester monomer) is 100 mass of the methacrylic resin (A) %, preferably 0.1 to 20.0% by mass, more preferably 0.1 to 15.0% by mass, and further preferably 0.2 to 15.0% by mass. It is preferably 0.5 to 7.0% by mass, and from the viewpoint of obtaining a thermoplastic resin composition having higher jet-blackness when made into a thermoplastic resin composition, the amount is 1.0 to 6.0% by mass. 0% by mass is particularly preferred. When it is 0.1% by mass or more, decomposition of the methacrylic resin (A) during molding, decomposition and yellowing of the thermoplastic elastomer (B) caused by radicals generated by decomposition of the methacrylic resin (A) It is possible to effectively prevent the deterioration of the thermoplastic resin composition due to yellowing and the occurrence of molding defects due to the generation of volatile components. In addition, when the vinyl monomer unit is 20.0% by mass or less, the heat resistance generally required for molded articles can be ensured.
In addition, the content of the vinyl monomer unit is 0.4 relative to the methacrylic resin (A) (100% by mass), particularly when a monomer having two (meth)acrylate groups is used. When using a monomer having 3 (meth) acrylate groups, the use of 0.25% by mass or less is a monomer having 4 or more (meth) acrylate groups. is preferably used in an amount of 0.15% by mass or less from the viewpoint of securing fluidity during injection molding and maintaining transparency.

Vinyl monomers other than acrylic acid ester monomers that can be copolymerized with the methacrylic acid ester monomers other than maleic acid and maleic anhydride are not limited to the following, For example, α, β-unsaturated acids such as acrylic acid and methacrylic acid; fumaric acid, itaconic acid, unsaturated group-containing divalent carboxylic acids such as cinnamic acid and their alkyl esters; styrene, o-methylstyrene, m- Methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene , p-tert-butylstyrene, styrenic monomers such as isopropenylbenzene (α-methylstyrene); 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, Aromatic vinyl compounds such as isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; unsaturated compounds such as itaconic anhydride Carboxylic anhydrides; maleimide, N-substituted maleimide such as N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; amides such as acrylamide and methacrylamide; functional monomer; and the like.

The methacrylic resin (A) may optionally contain maleic acid and/or maleic anhydride monomer units.
Maleic acid and maleic anhydride can be copolymerized into methacrylic acid ester monomers, but they prevent yellowing when formed into a thermoplastic resin composition with the thermoplastic elastomer (B) and prevent yellowing during molding. From the viewpoint of preventing the occurrence of silver and silver and maintaining good weather resistance, it cannot be used excessively, so the content of maleic acid monomer units and / or maleic anhydride monomer units should be ) with respect to 100% by mass, preferably 0 to 4.0% by mass, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, and may not be included .

In addition, in the methacrylic resin (A), for the purpose of improving properties such as heat resistance and molding processability, vinyl monomers other than the vinyl monomers exemplified above may be appropriately added and copolymerized. good. The acrylate monomer copolymerizable with the methacrylate monomer and the vinyl-based monomers other than the acrylate monomers exemplified above may be used singly or in combination. More than one species may be used in combination.

The total mass ratio of the methacrylic acid ester monomer unit and the acrylic acid ester monomer unit in 100% by mass of the methacrylic resin (A) is such that a molded article having even better transparency and haze is obtained. From the viewpoint of obtaining, it is preferably 88% by mass or more, more preferably 94% by mass or more, and still more preferably 100% by mass.

The content of the methacrylic resin (A) in the thermoplastic resin composition of the present embodiment is 100% of the total mass of the methacrylic resin (A) and the thermoplastic elastomer (B) in order to prevent whitening in a hot and humid environment. It is preferably from 50 to 99 parts by mass. From the viewpoint of preventing the color transfer of the colorant component and obtaining a molded article having excellent toughness and low-temperature strength, the content is more preferably 95 parts by mass or less, further preferably 90 parts by mass or less, and particularly preferably 85 parts by mass or less. . 55 parts by mass or more is more preferable, 60 parts by mass or more is even more preferable, 65 parts by mass or more is even more preferable, and 70 parts by mass or more is particularly preferable in order to improve the heat deformation resistance and rigidity of the molded article. .

(Weight average molecular weight)
The weight average molecular weight (Mw) of the methacrylic resin (A) contained in the thermoplastic resin composition of this embodiment will be described.
The methacrylic resin (A) preferably has a weight average molecular weight (Mw) of 50,000 to 250,000 as measured by GPC (gel permeation chromatography).
In order to obtain good mechanical strength and solvent resistance when made into a thermoplastic resin composition, the lower limit of the weight average molecular weight (Mw) of the methacrylic resin (A) is preferably 50,000 or more. 000 or more is more preferable, and 85,000 or more is even more preferable.
In order for the thermoplastic resin composition to exhibit good fluidity, the upper limit of the weight average molecular weight (Mw) of the methacrylic resin (A) is preferably 250,000 or less, more preferably 230,000 or less. 190,000 or less is more preferable, and 150,000 or less is particularly preferable.
The weight average molecular weight (Mw) of the methacrylic resin (A) is in the range of 50,000 to 250,000, so that the thermoplastic resin composition has fluidity, mechanical strength, and solvent resistance. A balance can be achieved, and good moldability is maintained.

(Molecular weight distribution)
The molecular weight distribution (Mw/Mn) of the methacrylic resin (A) contained in the thermoplastic resin composition of the present embodiment is preferably 1.0 to 6.0, more preferably 1.0 to 5.5. more preferably 1.0 to 5.0, and particularly preferably 1.01 to 2.1 from the viewpoint of obtaining stable mechanical properties and solvent resistance. When the molecular weight distribution (Mw/Mn) of the methacrylic resin (A) is 1.0 to 6.0, the physical properties exhibited by the methacrylic resin (A) are stabilized.
Here, Mw represents the weight average molecular weight and Mn represents the number average molecular weight.
The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the methacrylic resin (A) can be measured by GPC, and specifically, can be measured by the method described in Examples below.
Specifically, a standard methacrylic resin that is available as a reagent with a known monodisperse weight-average molecular weight and an analytical gel column that first elutes high-molecular-weight components are used to create a calibration curve from the elution time and weight-average molecular weight. Keep Subsequently, based on the obtained calibration curve, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the methacrylic resin (A) to be measured can be determined, and the molecular weight distribution (Mw/Mn ) can be calculated. The number average molecular weight (Mn) is the average molecular weight per simple molecule and is defined as the total weight of the system/number of molecules in the system. Weight average molecular weight (Mw) is defined as the average molecular weight by weight fraction.

(Unsaturated double bond terminal amount)
The amount of unsaturated double bonds in the methacrylic resin (A) is such that radicals generated by decomposition of the methacrylic resin (A) decompose or deteriorate the thermoplastic elastomer (B) in the thermoplastic resin composition of the present embodiment. 0.02 mol % or less is preferable in order to effectively prevent yellowing of the thermoplastic resin composition caused by causing the above and molding defects derived from the monomer caused by decomposition of the thermoplastic resin composition. It is more preferably 0.015 mol % or less, still more preferably 0.010 mol % or less, and particularly preferably 0.008 mol % or less.
The amount of unsaturated double bond ends can be controlled by controlling the polymerization temperature or using a chain transfer agent. In order to reduce the amount of unsaturated double bond ends, specifically, when the methacrylic resin (A) is produced by a suspension polymerization method, the polymerization temperature is preferably 80° C. or lower. ° C. or lower, and more preferably 70 °C or lower. Although the polymerization temperature may be kept constant, setting the polymerization temperature to 70° C. or less at the initial stage of polymerization is also effective in reducing the amount of terminal unsaturated double bonds. In the polymerization initiator, it is preferable to produce the polymerization initiator at 0.5% by mass or less, more preferably 0.3% by mass or less, and 0.25% by mass with respect to 100% by mass of the methacrylic resin (A). The following are more preferable, and 0.23% by mass or less is particularly preferable. When it is produced by a solution polymerization method, the polymerization temperature is preferably 185° C. or lower, more preferably 180° C. or lower, still more preferably 170° C. or lower, and particularly preferably 160° C. or lower. In the polymerization initiator, it is preferable to produce the polymerization initiator at 0.4% by mass or less, more preferably 0.2% by mass or less, and 0.15% by mass with respect to 100% by mass of the methacrylic resin (A). The following are more preferable, and 0.1% by mass or less is particularly preferable.
The amount of unsaturated double bond ends can be measured by the method described in Examples below.

(Method for producing methacrylic resin (A))
The methacrylic resin (A) contained in the thermoplastic resin composition of the present embodiment can be produced by a solution polymerization method, a bulk polymerization method, a cast polymerization method, or a suspension polymerization method, but is not limited to these methods. do not have. Bulk polymerization, solution polymerization and suspension polymerization are preferred.

As for the polymerization temperature, an optimum polymerization temperature may be appropriately selected according to the polymerization method. It is below. By setting the polymerization temperature to 185 ° C. or less, the amount of unsaturated double bond ends can be reduced, and the decomposition of the methacrylic resin (A) during molding and the decomposition of the methacrylic resin (A) induce thermoplasticity. It is possible to effectively prevent yellowing and molding defects of the thermoplastic resin composition due to deterioration of the elastomer (B). Further, by setting the temperature to 50° C. or higher, the methacrylic resin can be produced with good productivity.

A polymerization initiator may be used when producing the methacrylic resin (A). The polymerization initiator is not limited to the following, but when performing radical polymerization, for example, di-t-butyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, t-butylperoxy neodecanate, t-butyl peroxypivalate, dilauroyl peroxide, dicumyl peroxide, t-butyl peroxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3, Organic peroxides such as 3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, azobisisobutyronitrile, azobisisovaleronitrile, 1,1-azobis(1-cyclohexane carbonitrile), 2,2′-azobis-4-methoxy-2,4-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-2- Common azo-based radical polymerization initiators such as methylbutyronitrile can be used. These may be used singly or in combination of two or more. A combination of these radical polymerization initiators and a suitable reducing agent may be used as a redox initiator.
These radical polymerization initiators and/or redox initiators are used in the range of 0 to 1 part by mass with respect to 100 parts by mass of the total amount of all monomers used in the polymerization of the methacrylic resin (A). is generally used, and can be appropriately selected in consideration of the polymerization temperature and the half-life of the polymerization initiator.

When bulk polymerization, cast polymerization, or suspension polymerization is selected as the polymerization method for the methacrylic resin (A), from the viewpoint of preventing coloration of the methacrylic resin (A), peroxide-based polymerization is initiated. It is preferable to polymerize using an agent.
Examples of the peroxide polymerization initiator include, but are not limited to, lauroyl peroxide, decanoyl peroxide, and t-butylperoxy-2-ethylhexanoate. Peroxides are more preferred.

Further, when the methacrylic resin (A) is polymerized by a solution polymerization method at a high temperature of 90 ° C. or higher, a peroxide having a 10-hour half-life temperature of 80 ° C. or higher and soluble in the organic solvent used , an azobis initiator or the like is preferably used as the polymerization initiator.
Examples of the peroxides and azobis initiators include, but are not limited to, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2 ,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyronitrile and the like.

When producing the methacrylic resin (A), the molecular weight of the methacrylic resin (A) may be controlled as long as the object of the present invention is not impaired. Methods for controlling the molecular weight of the methacrylic resin (A) include, but are not limited to, alkylmercaptans, dimethylacetamide, dimethylformamide, chain transfer agents such as triethylamine, dithiocarbamates, triphenyl A method of controlling the molecular weight by using an iniferter such as methylazobenzene and tetraphenylethane derivatives can be mentioned. Moreover, it is also possible to adjust the molecular weight by adjusting the addition amount of these.
As the chain transfer agent, alkyl mercaptans are preferable from the viewpoint of handleability and stability. Examples of the alkyl mercaptans include, but are not limited to, n-butyl mercaptan and n-octyl mercaptan. , n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate) ), etc.
These can be added as appropriate according to the molecular weight of the desired methacrylic resin, but generally, 0 per 100 parts by mass of the total amount of all monomers used in the polymerization of the methacrylic resin. It is used in the range of 0.001 part by mass to 5 parts by mass.
Further, other molecular weight control methods include a method of changing the polymerization method, a method of adjusting the amount of the polymerization initiator, the above-described chain transfer agent, iniferter, etc., and a method of changing various polymerization conditions such as the polymerization temperature. .
As for these molecular weight control methods, only one method may be used, or two or more methods may be used in combination.

<Thermoplastic elastomer (B)>
The thermoplastic resin composition of this embodiment contains a thermoplastic elastomer (B). By including the thermoplastic elastomer (B), it is possible to improve the fluidity while improving the toughness, which is a problem of the methacrylic resin (A).
Examples of the thermoplastic elastomer (B) include, but are not limited to, (meth)acrylic elastomers, thermoplastic polyurethanes, vinyl chloride thermoplastic elastomers, polystyrene thermoplastic elastomers, polyamide elastomers, and the like. . (Meth)acrylic elastomers and thermoplastic polyurethanes are preferable from the viewpoint of excellent compatibility with the methacrylic resin (A) and the ability to easily achieve a high appearance, and thermoplastic from the viewpoint of color transfer resistance, abrasion resistance, and low temperature properties. Polyurethane is more preferred. Rubber having a core-shell structure is not included in the thermoplastic elastomer (B).

<<Thermoplastic Polyurethane>>
In this embodiment, the thermoplastic polyurethane is preferably contained in the thermoplastic resin composition. Thermoplastic polyurethane is particularly excellent in the function of incorporating the dye into the resin structure when the dye is mixed, and is particularly excellent in color transfer resistance.
The thermoplastic polyurethane preferably contains a structural unit derived from a polyester polyol and a structural unit derived from an isocyanate having an alicyclic ring. In order to improve the appearance retention, heat distortion temperature, and moldability of the thermoplastic resin composition, 70 isocyanate-derived structural units having an alicyclic ring are used when the total isocyanate-derived structural units are 100% by mass. % or more is preferable. More preferably, the isocyanate-derived structural unit having one alicyclic ring is 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass when the total isocyanate-derived structural units are 100% by mass. % or more, particularly preferably 100% by mass. By improving the appearance retention, heat distortion temperature, and moldability of the thermoplastic resin composition, it can be suitably used for applications such as automotive parts that are exposed to wet heat environments such as exposure to direct sunlight after rain. .
The thermoplastic polyurethane may be at least one type of thermoplastic polyurethane. A single type of thermoplastic polyurethane may be used, or two or more types of thermoplastic polyurethane may be used in combination.

Thermoplastic polyurethanes typically contain the following components: (a) isocyanates, (b) compounds reactive with isocyanates, and optionally at least one (c) catalyst and/or (d) conventional aids. by reacting in the presence of agents and/or additives. The following components: (a) isocyanates and (b) isocyanate-reactive compounds are referred to as structural components. Methods for identifying these structural components include conventionally known methods, such as, but not limited to, those described in Journal of the Adhesion Society of Japan, Vol. 40 No. 6 (2004).

(a) As the isocyanate, it is preferable to use an isocyanate having an alicyclic ring in the structure from the viewpoint of obtaining good appearance retention when it is made into a thermoplastic resin composition, and an isocyanate having an unsaturated carbon bond and an aromatic ring. It is more preferable to use an isocyanate having an alicyclic ring. Although not limited to the following, specifically, 4,4-diisocyanatodicyclohexylmethane (H12MDI), 1,3-bisisocyanatomethylcyclohexane (XDI), isophorone diisocyanate (IPDI) are preferable, and 1 , 3-bisisocyanatomethylcyclohexane (XDI) and isophorone diisocyanate (IPDI) are more preferred. The isocyanate may be an isocyanate containing 5% by mass or less of inclusions or additives as long as the effects of the present invention are not impaired.

(a) The number of alicyclic rings contained in the isocyanate is preferably 1 to 4, and heat deformation resistance, appearance retention of the thermoplastic resin composition, heat deformation resistance, and productivity during heat processing are improved. One is more preferred for good results.
When the (a) isocyanate contains a plurality of isocyanates having an alicyclic ring, the number of the alicyclic rings is the number of the alicyclic rings of the compound with the largest molar fraction among the compounds contained in the (a) isocyanate. You can

(b) The compound reactive with isocyanate includes at least one polyether polyol and polyester polyol. In the present embodiment, the inclusion of a structural unit derived from a polyether polyol, a polyester polyol, or a mixture of two or more thereof in the structure of the thermoplastic polyurethane improves the molding fluidity of the thermoplastic resin composition. preferred to make It is more preferable to contain a structural unit derived from a polyester polyol or a mixture of two or more thereof, since compatibility with the methacrylic resin (A) is excellent and mechanical properties are improved. The above polyester polyols include polycarbonate diols.

The total mass ratio of structural units derived from polyether polyol and structural units derived from polyester polyol in 100 mass % of structural units derived from polyol contained in the thermoplastic polyurethane is 80 to 100 mass %. is preferred, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.

Polyether polyols include, for example, polyethers derived from polypropylene glycol, polytetramethylene glycol, polyoxypropylene triol, and tetrahydrofuran.

Examples of polyester polyols include organic dicarboxylic acids having 2 to 12 carbon atoms (preferably aromatic dicarboxylic acids having 8 to 12 carbon atoms), and polyhydric alcohols (preferably 2 to 12 diols having 1 carbon atom, more preferably diols having 2 to 6 carbon atoms), polyester polyols, and the like.
Examples of the organic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and isomers of naphthalene dicarboxylic acid. is. Dicarboxylic acids are used either alone or in mixtures with other dicarboxylic acids. Instead of the free dicarboxylic acids, it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms, or dicarboxylic acid anhydrides.
A diol is preferable as the polyhydric alcohol. Examples of the diol include ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 - decanediol, glycerol, trimethylol propane, preferably ethylene glycol, 1,3-propanediol, methyl-1,3-propanediol, 1,4-butanediol, 3-methyl-1,5- Pentanediol or 1,6-hexanediol. As the polyhydric alcohol, a polyester diol produced from a lactone (eg, ε-caprolactone) and a hydroxycarboxylic acid (eg, ω-hydroxycarboxylic acid, hydroxybenzoic acid) may be used.

In the production of polyester polyols, the reaction conditions of organic dicarboxylic acids and polyalcohols may be selected in such a way that the polyesterols produced have no free acid groups. The actual functionality of the polyesterols produced is preferably between 1.9 and 2.1, more preferably 2.0.

In the preparation of polyester polyols, mixtures of organic dicarboxylic acids and polyalcohols may be polycondensed in the presence or absence of a catalyst. Among these, the reaction in the presence of a catalyst is preferred, and the reaction in the presence of an esterification catalyst is more preferred.
Also, in the production of polyester polyols, mixtures of organic dicarboxylic acids and polyalcohols may be polycondensed under an atmosphere of inert gas (eg, nitrogen, carbon monoxide, helium, argon, etc.).
The temperature during polycondensation of the organic dicarboxylic acid and the polyalcohol is preferably 150 to 250°C, more preferably 180 to 220°C. The polycondensation can optionally be carried out under reduced pressure.
The polycondensation is usually continued until the desired acid number (eg, acid number less than 10, preferably less than 2) is reached.
The molar ratio of the organic dicarboxylic acid to the polyalcohol used in the polycondensation is preferably 1:1 to 1.8, more preferably 1:1.05 to 1.2.

In particular structural units derived from polyester polyols prepared from ε-caprolactone and/or adipic acid or sebacic acid with ethylene glycol, 1,3-propanediol, methyl-1,3-propanediol, 1,4- The thermoplastic polyurethane contains a structural unit derived from a condensate with at least one polyhydric alcohol selected from the group consisting of butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. preferably.

The polyester polyol used preferably has a number average molecular weight Mn of 500 to 4,000, more preferably 650 to 3,500, still more preferably 800 to 3,000.
In addition, the number average molecular weight Mn can be measured by the GPC method.

(b) Compounds reactive with isocyanate include polyhydric alcohols in addition to polyether polyols and polyester polyols. Among polyhydric alcohols, ethylene-1,2-diol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1 At least one polyhydric alcohol selected from the group consisting of ,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, and neopentyl glycol is preferred. More preferred are polyhydric alcohols selected from the group consisting of ethylene-1,2-diol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. Polyhydric alcohols function as chain extenders.

In the thermoplastic resin composition of the present embodiment, the polyol is selected from the group consisting of ethylene-1,2-diol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. At least one polyhydric alcohol-derived structural unit is preferably contained in the thermoplastic polyurethane.

The catalyst (c) is preferably a catalyst (c) that speeds up the reaction between (a) the NCO group of the isocyanate and (b) the hydroxy group of the compound reactive with the isocyanate. Examples of the catalyst (c) include tertiary amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol or diazabicyclo[2.2. 2] Octane is preferred. In addition, the catalyst (c) is an organometallic compound (e.g., titanate ester, iron compound (preferably iron (III) acetylacetonate), tin compound (preferably tin diacetate, tin dioctoate, tin dilaurate ) or dialkyltin salts of aliphatic carboxylic acids (preferably dibutyltin diacetate, dibutyltin dilaurate, bismuth salts in which bismuth is preferably present in the 2 or 3, especially 3 oxidation state).

The (c) catalyst is preferably a carboxylic acid salt. The carboxylic acids are preferably carboxylic acids with 6 to 14 hydrocarbons, particularly preferably 8 to 12 hydrocarbons. Bismuth salts are preferred as salts of carboxylic acids, examples of suitable bismuth salts being bismuth(III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate.

As the (c) catalyst used in the production of the thermoplastic polyurethane, it is preferable to use a tin catalyst, particularly tin dioctoate, and the mass ratio is 100 masses of the (b) compound reactive with isocyanate. It is preferably 0.0001 to 0.1 part by mass per part. (c) When a tertiary amine is used as a catalyst, from the viewpoint of preventing the tertiary amine from being incorporated into the structural skeleton of the thermoplastic polyurethane and yellowing during molding of the thermoplastic resin composition, The tertiary amine content in 100% by mass of the thermoplastic resin composition of the present embodiment is preferably 0.9% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass. The following are more preferable, and 0% by mass is particularly preferable. In addition, the content of the tertiary amine contained in 100% by mass of the thermoplastic polyurethane is preferably 0.9% by mass or less from the viewpoint of preventing yellowing during molding. 0.5% by mass or less is more preferable, 0.1% by mass or less is even more preferable, and 0% by mass is particularly preferable.

The ratio of the structural components (a) and (b) when producing the thermoplastic polyurethane is such that the equivalent ratio of the NCO groups of the isocyanate (a) to the total number of hydroxy groups of the structural component (b) is 0.9-1. It is preferably 1:1, more preferably 0.95 to 1.05:1, still more preferably 0.96 to 1.0:1. The production of thermoplastic polyurethanes is preferably carried out in the presence of (c) catalysts and optionally (d) auxiliaries and/or additives.

The content of the thermoplastic elastomer (B) in the thermoplastic resin composition of the present embodiment is 1 to 50 parts by mass with respect to a total of 100 parts by mass of the methacrylic resin (A) and the thermoplastic elastomer (B). is preferred. From the viewpoint of good toughness and fluidity and effective prevention of color transfer of the colorant component, the amount is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. Further, from the viewpoint of obtaining a molded article having good heat deformation resistance, jet-blackness, and rigidity, it is more preferably 45 parts by mass or less, further preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and 30 parts by mass. The following are particularly preferred.

The total content of the methacrylic resin (A) and the thermoplastic elastomer (B) in the thermoplastic resin composition of the present embodiment is 80% by mass or more with respect to 100% by mass of the thermoplastic resin composition. is preferably 90% by mass or more, more preferably 94% by mass or more, and particularly preferably 97% by mass or more.

<Dye and Pigment>
The thermoplastic resin composition of the present embodiment contains 0.05 to 1 part by mass of the dye/pigment per 100 parts by mass of the total mass of the methacrylic resin (A) and the thermoplastic elastomer (B). When the total mass of the methacrylic resin (A) and the thermoplastic elastomer (B) is 100 parts by mass, the dye content (total content of pigment and dye) is From the viewpoint of cost reduction, it is necessary to be 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less, further preferably 0.4 parts by mass or less, and 0.3 parts by mass. The following are particularly preferred. In addition, in order to exhibit jet-blackness, improve light-shielding properties, and prevent transparency in the molded product, it is necessary to be 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and 0.12. It is more preferably at least 0.15 parts by mass, even more preferably at least 0.15 parts by mass.

<<Pigments>>
Pigments include those conventionally known for coloring such as iron oxide, zinc ferrite, cobalt aluminate, iron and/or manganese doped forms of copper oxide, carbon black, etc.; Carbon black is preferable from the viewpoint. You may use these individually by 1 type or in combination of 2 or more types.

When carbon black is used as the pigment, its surface is preferably coated with a surface coating agent, so that a deeper jet-blackness can be expressed. Examples of suitable surface coating agents include zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitic acid amide, methylenebisstearylamide and ethylenebisstearylamide. (EBS) are preferred. Among these, zinc stearate and EBS are more preferable from the viewpoint of achieving a deeper jet-blackness. A surface coating agent may be used individually by 1 type or in combination of 2 or more types.
The compounds mentioned above as surface coating agents are also commonly used as dispersants for dyes and pigments such as carbon black. However, when these compounds are used as dispersants, carbon black and powders are simply mixed together, so they do not function as surface coating agents for coating the surface of carbon black. Carbon black in this state tends to be less jet-black when compounded with the methacrylic resin (A) than when the above compound is used as a surface coating agent. The present inventors have found that by heating the above compound to a temperature above its melting point and then mixing it with carbon black, applying shear, and sufficiently stirring, the compounding ratio of the above compound with carbon black is exactly the same as when using it as a dispersant. It was found that even with the same composition, the above compound functions as a surface coating agent and can remarkably improve jet-blackness. The present inventors presume the following as this mechanism. That is, the present inventors have found that there is a gap between the surface of the carbon black and the surface of the resin that is the matrix, and the incident light is scattered here, which is a state in which the jet-blackness cannot be sufficiently expressed. I believe this is the cause of the "white blur". By mixing and stirring the above compound with carbon black after heating to the melting point or higher, fine irregularities existing on the surface of the carbon black or voids existing between a plurality of carbon black particles can be more easily filled. It is estimated that In addition, before compounding with the molten resin, filling the unevenness of the carbon black surface or the gaps between the carbon black particles with a surface coating agent allows the molten resin, which is the matrix at the time of compounding, to fill those unevennesses and gaps. Regardless of whether or not it is possible, it is considered to be an extremely effective means from the viewpoint of sufficiently suppressing "white blur".
In addition, based on the presumed mechanism described above, the surface coating agent is not particularly limited to the compounds exemplified above, and any substance that is compatible with the methacrylic resin (A) and does not easily affect its physical properties is suitable. It can be easily inferred that it can be used for
When the surface of the carbon black is coated with a surface coating agent, the ratio (Wc/Ws) between the mass Wc of the carbon black and the mass Ws of the surface coating agent is preferably 20/80 to 60/40, It is more preferably 30/70 to 50/50. When Wc/Ws is within this range, jet-blackness with greater depth can be achieved.

When carbon black is used, the content of carbon black is preferably 0.001 to 0.6% by mass, more preferably 0.01 to 0.5% by mass, based on the total mass of the thermoplastic resin composition. , 0.05 to 0.4% by mass is more preferable. When the carbon black content is 0.001% by mass or more, a high shielding property can be maintained even for a particularly thin molded body. In addition, when the content is 0.6% by mass or less, sufficiently deep jet-blackness can be exhibited.
The content of carbon black represents the content of carbon black containing the surface coating agent.

Further, as the type of carbon black contained in the thermoplastic resin composition of the present embodiment, more specifically, the arithmetic average particle size by microscopic observation is 10 to 40 nm, and the nitrogen adsorption specific surface area defined by JIS K6217: 2001. Carbon black that satisfies one or more conditions of 50 to 300 m ² /g and 0.5 to 3% by mass of volatile matter when heated at 950° C. for 7 minutes can be preferably used.
The thermoplastic resin composition of the present embodiment preferably does not contain carbon black.

<<Dye>>
The thermoplastic resin composition of the present embodiment preferably contains a dye in order to increase the depth of the jet-blackness. From the viewpoint of expressing a deeper jet-blackness, the thermoplastic resin composition preferably contains three or more dyes, more preferably three or more dyes with different hues, Three or more dyes selected from the group consisting of red, yellow, green, blue and purple dyes are more preferred. Rather than simply combining only blue dyes and yellow dyes, or combining green dyes and red dyes in a narrow range, a combination that evenly includes the so-called three primary colors of light expresses jet-blackness. This is because it is preferable from the viewpoint of expressing jet-blackness with greater depth. Such combinations include, for example, purple dyes, green dyes, combinations of yellow dyes and blue dyes, combinations of purple dyes, yellow dyes, green dyes and red dyes, red dyes, green Combinations of appropriate amounts of multiple types of dyes, such as combinations of dyes and blue dyes, are mentioned. Among these, there are already many commercial products, and there are many types of light-resistant dyes described later, so it is more desirable. A combination of a red dye, a green dye, a yellow dye and a blue dye is preferred from the viewpoint of easily realizing the jet-blackness.
Examples of red dyes represented by a color index include Solvent red 52, 111, 135, 145, 146, 149, 150, 151, 155, 179, 180, and 181. , 196, 197, 207, Disperse Red 22, 60, and 191. Examples of blue dyes include Solvent Blue 35, 45, 78, 83, 94, 97, 104, and 105 in terms of color index. Examples of yellow dyes include Disperse Yellow 160, Disperse Yellow 54, 160, and Solvent Yellow 33 in terms of color index. Examples of green dyes include Solvent Green 3, 20, and 28 in terms of color index. Examples of purple dyes include Solvent Violet 28, 13, 31, 35, and 36 in terms of color index. These dyes may be used singly or in combination of two or more for each color.
Although the type of dye is not particularly limited, it is preferably selected from the group consisting of anthraquinone dyes, heterocyclic compound dyes and perinone dyes from the viewpoint of weather resistance.
Examples of anthraquinone dyes include Solvent Violet 36, Solvent Green 3, 28, Solvent Blue 94, 97, Disperse Red 22, etc., in terms of color index. Examples of heterocyclic compound dyes include Disperse Yellow 160 and the like when represented by a color index. Examples of perinone-based dyes include Solvent red 179 and the like when represented by a color index. Each of these may be used alone or in combination of two or more.
In order to further improve the color transfer resistance, a dye having a maximum absorption wavelength between 600 nm and 760 nm in the wavelength range of 380 nm to 780 nm, which has a large molecular weight and is difficult to bleed out, is used as a total of dyes and pigments. It is preferably contained in an amount of 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. Also, in order to express a jet black color even in a molded body with a thin plate thickness, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less relative to the total mass of the dye and pigment. The maximum absorption wavelength is measured with a spectrophotometer. At this time, the content of dye and pigment is the content of pure pigment excluding the surface treatment agent.
When a thermoplastic polyurethane is used as the thermoplastic elastomer (B), it is preferable not to use an azo dye that may decompose to form an amine.

<Other ingredients>
The thermoplastic resin composition of the present embodiment contains components other than the methacrylic resin (A), the thermoplastic elastomer (B), and the dye and pigment within a range that does not impair the effects of the present invention. good too. Other conventionally known resins can be mixed as the other components.
The other resin is not particularly limited, and known curable resins and thermoplastic resins are preferably used.
Examples of thermoplastic resins include, but are not limited to, polypropylene-based resins, polyethylene-based resins, polystyrene-based resins, syndiotactic polystyrene-based resins, AS-based resins, AAS resins, biodegradable resins, and polycarbonates. , polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate, polyalkylene arylate resins such as polyethylene naphthalate, polyamide resins, polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, and the like.
In particular, AS resin is preferred for improving fluidity, and polyester resin is preferred for improving chemical resistance.
In addition, polyphenylene ether-based resins, polyphenylene sulfide-based resins, phenol-based resins, and the like have the effect of improving flame retardancy.
Examples of curable resins include, but are not limited to, unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, cyanate resins, xylene resins, triazine resins, urea resins, and melamine resins. , benzoguanamine resin, thermosetting urethane resin, oxetane resin, ketone resin, alkyd resin, furan resin, styrylpyridine resin, silicone resin, thermosetting synthetic rubber, and the like.
These resins may be used singly or in combination of two or more.

To the thermoplastic resin composition of the present embodiment, in order to impart various predetermined properties such as rigidity and dimensional stability, the methacrylic resin (A), the thermoplastic elastomer (B ), and various additives other than dyes and pigments may be mixed.
Examples of additives include, but are not limited to, phthalate-based, fatty acid ester-based, trimellitate-based, phosphate-based, polyester-based plasticizers; higher fatty acids, higher fatty acid esters; Higher fatty acid mono-, di-, or triglyceride release agents; polyether, polyether ester, polyether ester amide, alkyl sulfonate, alkyl benzene sulfonate antistatic agents; phosphine stabilizers Stabilizers such as agents, light stabilizers; Flame retardants; Flame retardant aids; Curing agents; Curing accelerators; anti-oxidant; impact-imparting agent; slidability improver; compatibilizer; nucleating agent; anti-foaming agent; coupling agent; antirust agent; antibacterial/antifungal agent; antifouling agent;
In particular, an impact resistance imparting agent such as an acrylic rubber multi-layer polymer having a core-shell structure is preferred.

In the thermoplastic resin composition for obtaining a molded article containing the thermoplastic resin composition of the present embodiment, the content of the other components described above maintains the transparency of the thermoplastic resin composition and prevents bleed out and the like. In order to prevent molding defects, it is preferably 0 to 40% by mass, more preferably 0.01 to 30% by mass, and even more preferably 0.02 to 25% by mass, based on 100% by mass of the thermoplastic resin composition. By containing in the said range, the function of each material can be exhibited.
The impact resistance imparting agent is preferably 3 to 50% by mass, preferably 5 to 20% by mass, based on 100% by mass of the thermoplastic resin composition, in order to effectively impart impact resistance and ensure transparency. % is more preferred, and 5 to 9% by mass is even more preferred.
In order to improve weather resistance, the ultraviolet absorber is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, more preferably 0.01% by mass or more, based on 100% by mass of the thermoplastic resin composition. 02 parts by mass or more is more preferable. In order to suppress contamination of the mold and bleeding out of the ultraviolet absorber, the content is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.08% by mass or less.
The release agent is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, relative to 100% by mass of the thermoplastic resin composition in order to effectively improve the releasability from the mold. Preferably, 0.2% by mass or more is more preferable. In order to prevent contamination of the mold and not to adversely affect the heat distortion resistance of the thermoplastic resin composition, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.

<L* of the thermoplastic resin composition>
When the thermoplastic resin composition of the present embodiment is molded into a molded body having a thickness of 2 mm at a mold temperature of 240° C. and a mold temperature of 55° C. using a mold with a mold polishing count of No. 8000, D65 light source, The lightness L* of the molded article measured in the SCE 10-degree visual field reflection mode is 3 or less.
L* is an index representing the blackness of the molded body, and the closer to 0, the better the jet-blackness. When L* is 3 or less, it has an excellent jet-blackness and an appearance that does not look whitish even under outdoor light. L* is preferably 2 or less, more preferably 1.5 or less, and even more preferably 0.8 or less.
L* can be adjusted by adjusting the amount and amount ratio when using a combination of black dyes and pigments and/or a plurality of types of dyes and pigments. The pigment is preferably surface-coated carbon black, and the dye is an anthraquinone dye, anthraquinone dye, quinoline dye, quinophthalone dye, or the like in order to improve the weather resistance of the thermoplastic resin composition. Perinone dyes are preferred.
In addition, L* can be measured by the method described in Examples below.

<Total light transmittance of thermoplastic resin composition>
The thermoplastic resin composition of the present embodiment is molded into a molded product having a thickness of 2 mm at a mold temperature of 240 ° C. and a mold temperature of 55 ° C. using a mold with a mold polishing count of 8000. It is preferred that the percentage be 0.5% or less. When the content is 0.5% or less, the inside of the molded product can be prevented from being seen through even when used outdoors, and it can be said that the light shielding property is good. The total light transmittance is more preferably 0.3% or less, more preferably 0.1% or less, and particularly preferably 0.05% or less.
The total light transmittance can be adjusted by adjusting the amount and amount ratio when using a black dye and/or a combination of a plurality of dyes and pigments.
The total light transmittance can be measured by the method described in Examples below.

<Vicat softening temperature of thermoplastic resin composition>
The thermoplastic resin composition of the present embodiment preferably has a VICAT softening temperature of 91° C. or higher according to ISO 306 B50. When the temperature is 91° C. or higher, it can be said that the thermoplastic resin composition of the present embodiment has sufficient heat deformation resistance even when used outdoors. The Vicat softening temperature is more preferably 95°C or higher, more preferably 98°C or higher, in order to ensure compatibility with applications that are exposed to direct sunlight for a long time, such as vehicle components, and applications that have joints with other members. It is more preferably 100° C. or higher, particularly preferably 102° C. or higher, and particularly preferably 104° C. or higher.
The Vicat softening temperature can be adjusted by adjusting the molecular weight and composition of the methacrylic resin (A) and the type, content and composition of the thermoplastic elastomer (B).
More specifically, the Vicat softening temperature can be measured by the method described in Examples below.

<Melt mass flow rate (MFR) of thermoplastic resin composition>
The thermoplastic resin composition of the present embodiment has an MFR of 2.4 g/10 minutes or more measured under the conditions of 230° C., 3.8 kgf load, preheating time of 4 minutes, sampling every 30 seconds, and n = 5 average values. is preferably When it is 2.4 g/10 minutes or more, it can be said to have excellent molding fluidity capable of molding even a long member. The MFR is 2.8 g/10 minutes or more, because it is suitable for applications such as automotive pillar garnishes, rear garnishes, front garnishes, rear spoilers, slide rail covers, and front grills that require particularly excellent fluidity. is more preferable, 3.4 g/10 minutes or more is more preferable, and 3.8 g/10 minutes or more is particularly preferable.
The MFR can be adjusted by adjusting the molecular weight of the methacrylic resin (A) and the composition and quantity ratio of the thermoplastic elastomer (B).
More specifically, the MFR can be measured by the method described in Examples below.

<Tensile fracture strain or tensile fracture nominal strain of thermoplastic resin composition>
The thermoplastic resin composition of the present embodiment preferably has a tensile breaking strain or a tensile breaking nominal strain measured according to JISK7161 of 9% or more. If it is 9% or more, even if the mechanical part or the joint with other members is required for installation of a long member, the joint with the mechanical part or other members will not crack or break easily. It can be said that it has excellent toughness that can be suitably used. The tensile breaking strain or tensile breaking nominal strain is more preferably 12% or more, still more preferably 20% or more, and particularly preferably 25% or more.
The tensile breaking strain or tensile breaking nominal strain can be adjusted by adjusting the molecular weight of the methacrylic resin (A) and the composition and amount ratio of the thermoplastic elastomer (B).
More specifically, the tensile breaking strain or nominal tensile breaking strain can be measured by the method described in Examples below.

<Strength of Thermoplastic Resin Composition at Low Temperature>
The thermoplastic resin composition of the present embodiment preferably has an unnotched Charpy impact test value of 22 kJ/m ² or more at −30° C. according to JIS K7111-1. If it is 22 kJ/m ² or more, it can be said that it has a strength suitable for use even in cold regions. In addition, as a member having joints with other members in cold districts, the strength of the joints is improved, so that it can be suitably used. The unnotched Charpy impact test value is more preferably 23 kJ/m ² or more, and even more preferably 24 kJ/m ² or more.
The Charpy impact test value can be adjusted by adjusting the molecular weight of the methacrylic resin (A) and the composition and amount ratio of the thermoplastic elastomer (B).
More specifically, the Charpy impact test value can be measured by the method described in Examples below.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition is prepared by mixing and kneading the methacrylic resin (A), the thermoplastic elastomer (B), the dye and pigment, and, if necessary, the various additives and other resins described above. can get.
For example, it can be produced by kneading using a kneader such as an extruder, a heating roll, a kneader, a roller mixer, or a Banbury mixer.
Kneading by an extruder is particularly preferable from the viewpoint of productivity.
From the viewpoint of productivity, the kneading temperature (that is, the temperature at which the methacrylic resin (A), the thermoplastic elastomer (B), and the dye/pigment are blended) is preferably 200°C or higher, and preferably 210°C or higher. It is more preferably 220° C. or higher. From the viewpoint of preventing deterioration of the methacrylic resin (A) and thermoplastic elastomer (B) and volatilization of various additives, the temperature is preferably 280°C or lower, more preferably 260°C or lower, and still more preferably 250°C or lower. The kneading temperature in the present embodiment refers to the set temperature at the center of the cylinder when an extruder is used.

<Molded body>
The molded article of the present embodiment is characterized by containing the thermoplastic resin composition of the present embodiment. From the viewpoint of productivity, the molded article is preferably an injection molded article.

(Thickness t of molded body)
The thickness t of the molded article in the present embodiment means that the molded article containing the thermoplastic resin composition of the present embodiment (hereinafter also referred to as "thermoplastic resin composition molded article") is arranged in the flow direction of the resin. It refers to the maximum thickness (the thickness of the thickest part) of the flow cross section that appears when cut vertically, excluding the original molded body end portion.
In some cases, the molded body is partially provided with a vein-like channel structure to support the flow. It does not refer to the thickness of the portion having the structure, but the thickness of the thickest portion adjacent to the portion having the channel structure, other than the portion having the channel structure.
The molded article of the present embodiment can be suitably used as a molded article having a thickness t of 1 to 5 mm, and particularly suitably as an injection molded article. If the thickness is more than 5 mm, the productivity tends to decrease due to the longer molding cycle time required to prevent appearance changes (so-called sink marks) due to heat shrinkage. The thickness t is more preferably 4 mm or less, and even more preferably 3 mm or less. On the other hand, if the thickness is less than 1 mm, it becomes difficult for the holding pressure to be transmitted during injection molding, and there is a tendency for the mold transferability to deteriorate at the end of the flow. The thickness t is more preferably 1.5 mm or more, and even more preferably 2 mm or more.

(Length L of compact)
The length L of the compact in this embodiment means the maximum length (the length to the furthest point) from the gate corresponding position (the position corresponding to the gate of the mold) in the compact. If two gates (gate 1 and gate 2) are used, the midpoint between gate 1 and gate 2 is midpoint 1, and the distance from the farthest location U from midpoint 1 to the nearest gate to location U is and the length from gate 1 or gate 2 to midpoint 1 is the longest length. If three gates (gate 1, gate 2, and gate 3) are used, the midpoint between gates 1 and 2 is midpoint 1, the midpoint between gates 1 and 3 is midpoint 2, and gate 2 is the midpoint between gates 1 and 3. and gate 3 is the middle point 3, the length from the farthest place W from the middle point 1 to the gate closest to the place W, the distance from the farthest place X from the middle point 2 to the nearest gate to the place X from midpoint 3 to the farthest location Y to the gate closest to location Y, from gate 1 or gate 2 to midpoint 1, from gate 1 or 3 to midpoint 2 Let length L be the longest length among the lengths and the length from gate 2 or gate 3 to midpoint 3 . A similar definition applies when four or more gates are used.
The intermediate point between the gates and the length L can be measured along the surface of the compact with a radius gauge, a pin gauge, a digital caliper, a micrometer, or the like. If the compact is spherical and has a plurality of midpoints, any one of them may be adopted as the midpoint and the farthest point and length L may be obtained.
L is preferably 130 mm or more, more preferably 150 mm or more, more preferably 180 mm or more, from the viewpoint of reducing the occurrence of weld lines generated by the confluence of resin and resin flows and obtaining a molded product with a high appearance that takes advantage of the jet-blackness. is more preferable, 190 mm or more is even more preferable, and 200 mm or more is even more preferable. If L is 130 mm or more, it can be said that the molded body is long.
In addition, in order to measure the length L, it is necessary to use a mold having a final filling portion inside the mold.

(Ratio L/t between length L and thickness t of compact)
In order to prevent cracks in the molded body due to the external force applied to the molded body during molding and the stress generated during installation, and in injection molding, appropriate holding pressure is applied to prevent silver streaks, sink marks, weld lines, etc. The ratio L / t between the length L and the thickness t is preferably 700 or less, more preferably 500 or less, and still more preferably 300 or less so that the appearance defects of the product can be effectively prevented. In order to effectively prevent defects and obtain a molded product with good productivity, it is preferably 65 or more, more preferably 70 or more, even more preferably 75 or more, even more preferably 90 or more, and even more preferably 110 or more.
Among others, the molded body of the present embodiment preferably has a thickness t of 1 to 5 mm, a length L of 130 mm or more, and a L/t of 65 or more.

(joint part for joining with other member)
It is preferable that the molded article containing the thermoplastic resin composition of the present embodiment has a joining portion for joining with another member.
The joint portion is a portion constituting the thermoplastic resin composition molded article of the present embodiment, which has a function of physically bonding with other members other than the thermoplastic resin composition molded article of the present embodiment. To tell.
Examples of the joint portion include a projection structure, a through-hole structure, and a non-through-hole structure for coupling with another member.

Examples of the projecting structure include, but are not limited to, a snap-fit male type as shown in FIG. 1 of Patent Document 1, a positioning post, a cylindrical boss, a rib, a fitting and a cylindrical boss for self-tapping.
Examples of the through-hole structure and the non-through-hole structure include, but are not limited to, snap-fit female molds, self-tapping through-holes, and press-fitting female molds.
Snap fit is a type of mechanical joining method used for joining metals, plastics, etc., and is a method of fixing by fitting using the elasticity of the material.

The joints in the molded article made of the thermoplastic resin composition of the present embodiment are used for the purpose of physically bonding with other members, that is, for the purpose of preventing them from falling off from other members, and also for the purpose of positioning the mounting position of the molded article. It also has functions.

<Method for manufacturing molded body>
The molded article of this embodiment can be manufactured by a known molding method. Examples of known molding methods include, but are not limited to, injection molding, extrusion molding, blow (hollow) molding, vacuum molding, compression molding, calendar molding, and inflation molding. Molding by injection molding is particularly preferable from the viewpoint of productivity.
From the viewpoint of productivity, the molding temperature is preferably 170° C. or higher, more preferably 190° C. or higher, and even more preferably 200° C. or higher. From the viewpoint of preventing deterioration of the methacrylic resin (A) and thermoplastic elastomer (B) and volatilization of various additives, the temperature is preferably 290°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower.
From the viewpoint of productivity, the cylinder temperature during molding is preferably 170° C. or higher, more preferably 190° C. or higher, and even more preferably 200° C. or higher. From the viewpoint of preventing deterioration of the methacrylic resin (A) and thermoplastic elastomer (B) and volatilization of various additives, the temperature is preferably 290°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower.

<Uses of compacts>
The molded article containing the thermoplastic resin composition of the present embodiment is excellent in toughness, fluidity, strength at low temperatures, color transfer resistance, jet blackness, light shielding properties, and heat deformation resistance. , members for vehicles, members for household appliances, miscellaneous goods, and the like. Specific uses of the molded product of the present embodiment include, for example, pillar garnishes, rear spoilers, front garnishes, rear garnishes, slide rail covers, front grilles, and window panels and instrument panels that are exterior members of automobiles. Panels, motorcycle members, refrigerator partitions, rice cooker covers, washing machine panels, mixer members, decorative members for chairs, and the like. Since the molded article containing the thermoplastic resin composition of the present embodiment can be adapted to low temperature environment and high temperature environment, it is preferably used as a vehicle member exposed to various environments. It is particularly preferable to use it as molded articles such as pillar garnish, rear spoiler, front grill, front garnish, rear garnish and slide rail cover.

Other embodiments of the invention can be found in the claims and the examples. The features mentioned above and the features to be described below of the article, process and method of use according to the invention can of course be used not only in the respectively mentioned combination, but also in other combinations without going beyond the scope of the invention. can be done. Thus, for example, the invention also implicitly includes combinations of preferred features with particularly preferred features or combinations of features not specifically characterized with particularly preferred features, even if the combination is not explicitly recited. including things.

Examples of the invention are given below, which are not intended to limit the invention. In particular, the invention also includes embodiments resulting from combinations thereof.

[Raw materials used in Examples and Comparative Examples]
<Raw material for methacrylic resin (A)>
The raw materials of the methacrylic resin (A) used in the production of the thermoplastic resin composition are as follows.
・ Methyl methacrylate (MMA): Asahi Kasei (2.5 ppm by mass of 2,4-dimethyl-6-t-butylphenol manufactured by Chugai Boeki as a polymerization inhibitor)
・Methyl acrylate (MA): Mitsubishi Chemical (with 14 ppm by mass of 4-methoxyphenol manufactured by Kawaguchi Chemical Industry Co., Ltd. as a polymerization inhibitor)
・Ethyl acrylate (EA): Mitsubishi Chemical ・n-octyl mercaptan: Arkema ・Lauroyl peroxide: NOF ・Tertiary calcium phosphate: Nippon Kagaku Kogyo, used as a suspending agent ・Calcium carbonate: Shiraishi Kogyo, Used as a suspending agent ・Sodium lauryl sulfate: manufactured by Wako Pure Chemical Industries, used as a suspending aid

<Thermoplastic elastomer (B)>
・Elastollan NY5685N00A: Polyurethane 1 made by FCI
・FPUXCT-A1095: Polyurethane 2 made by FCI
・Elastollan NY1385V3-10HB: Polyurethane 3 made by FCI
・ Elastollan HD595A10: Polyurethane 4 made by FCI

<Dye and Pigment>
・Sumiplast Yellow HLR (quinophthalone dye): maximum absorption wavelength 440 nm
・Plast Yellow 8040 (quinoline dye): Maximum absorption wavelength 440 nm
・Plastread 8315 (anthraquinone dye): Maximum absorption wavelength 510 nm
・Macrolex Violet 3R (anthraquinone dye): Maximum absorption wavelength 560 nm
・Macrolex Blue RR (anthraquinone dye): Maximum absorption wavelength 630 nm
・ Plast Blue 8520 (anthraquinone dye): Maximum absorption wavelength 580 nm
・Macrolex Green G (anthraquinone dye): maximum absorption wavelength 685 nm
・Sumiplast Green G (anthraquinone dye): Maximum absorption wavelength 640 nm
- Surface-treated carbon black: 40% by mass of carbon black surface-treated with 60% by mass of ethylenebisstearylamide

<Other ingredients>
・ Silica (additive): Admatechs SO-C5 average particle size 1.5 μm
・Tegomer H-Si6441P (additive): silicone additive manufactured by Evonik ・NOFALLOY KA200 (release agent): manufactured by NOF ・Stearic acid amide (release agent): manufactured by Tokyo Kasei ・Kane Ace M-210 (impact resistance) agent): manufactured by Kaneka, Tinuvin P (ultraviolet absorber): manufactured by BASF, melting point 128°C
・Stearyl alcohol (release agent): Calcoal 8098 manufactured by Kao
・ Sumoil PS-260 (spreading agent): manufactured by Matsumura Oil Research Institute

[Measurement and evaluation method]
<Molecular weight measurement of methacrylic resin (A)>
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) (Mn is the number average molecular weight) of the methacrylic resin (A) were measured using the following equipment and under the following conditions.
・ Measuring device: Gel permeation chromatography (HLC-8320GPC) manufactured by Tosoh Corporation
·Measurement condition:
Column: One TSKguard column SuperH-H, two TSKgel SuperHM-M, and one TSKgel SuperH2500 were connected in series and used. In this column, high-molecular-weight compounds are eluted early, and low-molecular-weight compounds are eluted slowly.
Detector: RI (differential refraction) detector Detection sensitivity: 3.0 mV/min
Column temperature: 40°C
Sample: 20 mL of tetrahydrofuran solution of 0.02 g of methacrylic resin Injection volume: 10 μL
Developing solvent: tetrahydrofuran, flow rate: 0.6 mL/min, 0.1 g/L of 2,6-di-t-butyl-4-methylphenol (BHT) was added as an internal standard.
As standard samples for the calibration curve, the following 10 types of polymethyl methacrylate (manufactured by Polymer Laboratories; PMMA Calibration Kit MM-10) with known monodisperse peak molecular weights and different molecular weights were used.
Since the standard samples of polymethyl methacrylate used as standard samples for the calibration curve each have a single peak, the peak corresponding to each is indicated as the weight peak molecular weight Mp. In this regard, it is distinguished from the peak top molecular weight calculated when there are multiple peaks for one sample.
Weight peak molecular weight (Mp)
Standard sample 1 1,916,000
Standard sample 2 625,500
Standard sample 3 298,900
Standard sample 4 138,600
Standard sample 5 60,150
Standard sample 6 27,600
Standard sample 7 10,290
Standard sample 8 5,000
Standard sample 9 2,810
Standard material 10 850
Under the above conditions, the RI detection intensity with respect to the elution time of the methacrylic resin (A) was measured.
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the methacrylic resin (A) were obtained based on the area area in the GPC elution curve and the calibration curve of the cubic approximation formula.

<Analysis of methacrylic resin (A) structural unit>
A structural unit was identified by ¹ H-NMR measurement, and its abundance (% by mass) was calculated.
The measurement conditions for ¹ H-NMR measurement are as follows.
Device: JEOL-ECA500
Solvent: CDCl ₃ -d ₁ (deuterated chloroform)
Sample: 1 g of methacrylic resin (A) was dissolved in 10 ml of acetone, 20 ml of methanol was added dropwise, and filtered. 15 mg of the insoluble matter was vacuum-dried at 40° C. for 15 hours, dissolved in 0.75 mL of CDCl ₃ -d ₁ , and used as a sample for measurement.

<Amount of unsaturated double bond ends of methacrylic resin (A)>
The structural unit was identified by ¹ H-NMR measurement, and the abundance (mol%) in the methacrylic resin (A) was calculated.
From the integral value of the unsaturated double bond end peak (5.4 to 5.6 ppm) and the peak integral value (3.6 ppm) of the methyl group bonded to the oxygen atom of the ester group of the methacrylic resin (A), The amount of saturated double bond ends was calculated.
The measurement conditions for ¹ H-NMR measurement are as follows.
Device: JEOL-ECA500
Number of scans: 5000 Measurement temperature: Room temperature Observation core: 1H (500MHz)
Solvent: CDCl ₃ -d ₁ (deuterated chloroform)
Sample: 1 g of methacrylic resin (A) was dissolved in 10 ml of chloroform, 20 ml of methanol was added dropwise, and the solution was filtered. The insoluble matter after filtration is again dissolved in 10 ml of chloroform, 20 ml of methanol is added dropwise, and filtration is repeated twice. Finally, the remaining insoluble matter was vacuum-dried at 40° C. for 15 hours, and 75 mg was dissolved in 0.75 mL of CDCl ₃ -d ₁ to prepare a sample for measurement. When the insoluble matter after the final filtration did not reach 75 mg, the above operation was repeated until it reached 75 mg.

<Evaluation of jet-blackness>
The lightness L* of a flat plate sample with a thickness of 2 mm obtained by the method described later is measured using a Konica Minolta spectrophotometer CM-700d with a D65 light source, SCE method, 10 degree field of view reflection mode, and a measurement diameter of φ11 mm. bottom.
If L * is 0.8 or less, "◎" (excellent), if over 0.8 and 1.5 or less, "○" (good), and if over 1.5 and 2 or less, "△" ( Sufficient for practical use), "△△" (practical) if more than 2 and 3 or less, and "x" (defective) if more than 3, and jet-blackness was evaluated.

<Evaluation of light shielding>
For the evaluation of the light-shielding properties, the total light transmittance of a 2 mm-thick flat plate sample obtained by the method described later was measured using NDH7000 manufactured by Nippon Denshoku according to JIS K7361.
If the total light transmittance is 0.1% or less, "◎"(excellent); % or less was evaluated as "Δ" (practically no problem), and if it exceeded 0.5%, it was evaluated as "X" (defective).

<Evaluation of color transfer resistance>
A flat plate sample having a thickness of 2 mm obtained by the method described later was subjected to a reciprocating sliding test under the following conditions. The color tone of the No. 6 cotton canvas before and after the test is measured using a Konica Minolta spectrophotometer CM-700d, and the place where the color tone of the No. 6 cotton canvas changes the most is the measurement point. Evaluation was made by the SCE method, reflection mode, and a measurement diameter of φ11 mm, and the color difference ΔE was used as an index of color transfer resistance. Commercially available copy paper was placed under the canvas when measuring the color tone.
The test was conducted 3 times, and if the average value of the color difference ΔE was 2.5 or less, "⊚"(excellent); If it was 5 or less, it was rated as “Δ” (sufficient for practical use), and if it exceeded 7.5, it was rated as “×” (defective).
(Reciprocating sliding test conditions)
Indenter: A 20 mm x 20 mm center portion in the sliding direction protruding to the test surface side with R45 Load: 1 kgf
Counterpart material: No. 6 cotton canvas Test speed: 100 mm/sec Number of tests: 100 reciprocations Test direction: TD direction

<Evaluation of liquidity>
A dumbbell test piece produced by the method described later was finely crushed with a nipper or the like, dried at 80° C. under reduced pressure for 24 hours, and used as a measurement sample.
Using a measurement sample, a load of 3.8 kgf based on JIS K7210: 1999, a test temperature of 230 ° C., a preheating time of 4 minutes, sample sampling every 30 seconds, n = 5 average value melt mass flow rate (MFR) Values (g/10 min) were measured.
If the MFR is 3.8 g/10 min or more, "◎"(excellent); Minutes or more and less than 2.8 g/10 minutes were evaluated as "Δ" (practically sufficient), and less than 2.4 g/10 minutes as "X" (defective).

<Evaluation of toughness>
A tensile test was performed according to ISO527-1 (JIS K7161) using a dumbbell test piece obtained by the method described later. Autograph AGS-5kNX manufactured by Shimadzu Corporation was used for the test. Tensile fracture strain or tensile fracture nominal strain was measured five times with a gauge length of 80 mm, and the average value was used as an index of toughness.
If the tensile breaking strain or tensile breaking nominal strain was 20% or more, "◎" (excellent), if it was 12% or more and less than 20%, "○" (good), 9% or more and less than 12% If it was less than 9%, it was rated as "X" (defective).

<Evaluation of strength at low temperature>
The conditioned dumbbell test piece obtained by the method described later was stored at -30 ° C. for 24 hours, and the test was performed within 30 seconds after taking it out. carried out. The room temperature of the test space was set at 23°C.
If the result is 24 kJ/m ² or more, “◎” (excellent), if 23 kJ/m ² or more and less than 24 kJ/m 2 ^, “◯” (good), 22 kJ/m ² or more and less than 23 kJ/m ² If it is less than 22 kJ/m 2 , it is rated as “Δ” (sufficient for practical use), and if it is less than 22 kJ/m ² , it is rated as “×” (defective). If it is 22 kJ/m ² or more, it is possible to obtain a molded article having good strength at the portion where it is attached to other members even in a cold environment.

<Evaluation of heat deformation resistance>
Using dumbbell test pieces molded using resin pellets obtained in Examples and Comparative Examples to be described later, the VICAT softening temperature (° C.) is measured in accordance with ISO 306 B50, and is used as an index for heat deformation resistance evaluation. bottom. The test piece used was dried under reduced pressure at 75° C. for 16 hours.
If the VICAT softening temperature is 100 ° C or higher, "◎"(excellent); Sufficient), 91° C. or more and less than 95° C. was evaluated as “ΔΔ” (practical, but application is limited), and less than 91° C. was evaluated as “X” (defective).

<Evaluation of appearance retention>
A flat plate sample having a thickness of 2 mm obtained by the method described later was left to stand for 1000 hours in a thermo-hygrostat manufactured by Espec under conditions of a temperature of 60° C. and a humidity of 95% RH. Before and after the test, the lightness L* was measured in the same manner as in <Evaluation of jet-blackness> (measurement of lightness L*) described above, and the values were compared.
If there is no surface deposit due to bleeding out of the components in the resin composition, and the change in lightness L* (ΔL*) is 0.5 or less, “◯” (good), surface attachment due to bleeding out of the components in the resin composition When there was a kimono and/or ΔL* exceeded 0.5, it was rated as “Δ” (practical, but limited in usage).

<Mass ratio of methacrylic resin (A) and thermoplastic elastomer (B)>
The thermoplastic resin composition of the present embodiment can be analyzed for the mass ratio of the methacrylic resin (A) and the thermoplastic elastomer (B) in the thermoplastic resin composition by the following method.
400 mg of the thermoplastic resin composition is dissolved in 40 mL of tetrahydrofuran. The solution phase contains the methacrylic resin (A), and the swelling layer contains the thermoplastic elastomer (B). The solution phase is separated by filtration, reprecipitated with 350 mL of methanol, dissolved again in 40 mL of tetrahydrofuran, reprecipitated with 350 mL of methanol, dried at 60° C. under a nitrogen blow, and used as sample A, and the mass is measured. 2 mg of dimethylsulfone standard substance was added to 10 mg of sample A, and dissolved in 1 mL of CDCl ₃ -d ₁ to obtain sample 1 for measurement. The mass of methacrylic resin (A) in 10 mg of sample A is determined by ¹ H-NMR measurement (ECA-500 manufactured by JEOL Ltd.). The mass ratio of methacrylic resin (A) in 10 mg of sample A is applied to sample A to determine the mass ratio of methacrylic resin (A) in the thermoplastic resin composition. At this time, the structure of the methacrylic resin (A) can also be identified.
In addition, with respect to the swollen layer, the mass of sample B dried at 60° C. under a nitrogen blow is measured. 10 mg of sample B was added with 2 mg of bistrimethylsilylbenzene-d4 standard substance and dissolved in 1 mL of deuterated dimethylformamide to obtain measurement sample 2. 10 mg of sample B was analyzed by ¹ H-NMR measurement (ECA-500 manufactured by JEOL Ltd.). Determine the mass of the thermoplastic elastomer (B) inside. The mass ratio of thermoplastic elastomer (B) in 10 mg of sample B is applied to sample B to determine the mass ratio of thermoplastic elastomer (B) in the thermoplastic resin composition. At this time, the structure of the thermoplastic elastomer (B) can also be identified.
If the detailed composition of the thermoplastic elastomer (B) is unclear, the composition can be identified using both IR measurement and pyrolysis GC/MS measurement. In the IR measurement, the freeze-pulverized sample B is mixed with KBr and tableted, and IR measurement is performed to identify the composition of the thermoplastic elastomer (B). For pyrolytic GC/MS measurements, 25.0 mg of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is taken in a 100 mL volumetric flask. Add dimethylformamide to fill the marked line of this volumetric flask to prepare a 0.025% by mass octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate standard solution. A solution for pyrolysis GC/MS measurement is obtained by adding 1 mL of the standard solution to the sample B and dissolving it. Pyrolysis GC/MS measurement was performed using a double-shot pyrolyzer. The first step was heat extraction at 300°C, and the second step was pyrolysis at 500°C to perform pyrolysis GC/MS measurement. ).

<Mass ratio of tertiary amine>
For the thermoplastic resin composition of the present embodiment, the mass ratio of tertiary amine contained in the thermoplastic resin composition can be measured by the following method.
200 mg of the thermoplastic resin composition is freeze-pulverized and immersed in 10 mL of 0.01 mol % hydrochloric acid aqueous solution for 3 hours. 0.05 mL of phenolphthalein solution is added here, and neutralization titration is carried out with a 0.01 mol % sodium hydroxide aqueous solution. The substance amount of hydrochloric acid consumed was calculated from the titration amount, and the content of the tertiary amine in the thermoplastic resin composition was converted into the mass ratio of the tertiary amine in the thermoplastic resin composition.
Also, the mass ratio of the tertiary amine contained in the thermoplastic elastomer (B) can be measured.
The above sample B is freeze-pulverized and immersed in 10 mL of a 0.01 mol % hydrochloric acid aqueous solution for 3 hours. 0.05 mL of phenolphthalein solution is added here, and neutralization titration is carried out with a 0.01 mol % sodium hydroxide aqueous solution. Calculate the substance amount of hydrochloric acid consumed from the titration amount, set it as the content of tertiary amine in sample B, and calculate the ratio of the content of tertiary amine in sample B to the content of thermoplastic elastomer (B). It was defined as the mass ratio of the tertiary amine in the thermoplastic elastomer (B).

[Thermoplastic resin composition]
The methacrylic resin (A) used as a constituent component of the thermoplastic resin composition in Examples and Comparative Examples to be described later is described below.

<Methacrylic resin (A)>
As the methacrylic resin (A), methacrylic resins (A-1) to (A-3) produced according to Production Examples A1 to A3 below were used.

(Production Example A1 (Production of methacrylic resin (A-1)))
Ion-exchanged water: 2 kg, tribasic calcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container having a stirrer to obtain a mixture (a).
Next, ion-exchanged water: 26 kg was put into a 60 L reactor and the temperature was raised to 80 ° C., and the mixture (a), methyl methacrylate: 21.2 kg, methyl acrylate: 0.65 kg, lauroyl peroxide: 27 g and n-octyl mercaptan: 62 g were charged.
Thereafter, polymerization was carried out at an initial polymerization temperature of about 60°C for 1 hour, then the temperature was raised to about 80°C and suspension polymerization was carried out while maintaining the temperature at about 80°C. The temperature was raised at a speed of min and aged for 60 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50° C. and dissolve the suspending agent, 20% by mass sulfuric acid was added, and then the polymerization reaction solution was passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer was separated. After washing, dehydration and drying, polymer microparticles 1 were obtained. The fine polymer particles 1 were pelletized by a twin-screw extruder of φ26 mm set at 240° C. to obtain a “methacrylic resin (A-1)”. The resulting resin had a weight average molecular weight of 101,000, a molecular weight distribution (Mw/Mn) of 1.91, a structural unit of MMA/MA=98/3% by mass, and an unsaturated double bond terminal amount of 0. 0.003 mol %.

(Production Example A2 (Production of methacrylic resin (A-2)))
Ion-exchanged water: 2 kg, tribasic calcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container having a stirrer to obtain a mixture (c).
Next, ion-exchanged water: 26 kg was put into a 60 L reactor and the temperature was raised to 80 ° C., and the mixture (c), methyl methacrylate: 21.2 kg, methyl acrylate: 0.43 kg, lauroyl peroxide: 27 g and n-octyl mercaptan: 76 g were charged.
Thereafter, suspension polymerization was carried out while maintaining the temperature at about 75°C, and after observing an exothermic peak, the temperature was raised to 92°C at a rate of 1°C/min and aged for 60 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50° C. and dissolve the suspending agent, 20% by mass sulfuric acid was added, and then the polymerization reaction solution was passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer was separated. After washing, dehydration and drying, polymer fine particles 2 were obtained. The fine polymer particles 2 were pelletized by a twin-screw extruder of φ26 mm set at 230° C. to obtain a “methacrylic resin (A-2)”. The resulting resin had a weight average molecular weight of 83,000, a molecular weight distribution (Mw/Mn) of 1.89, a structural unit of MMA/MA=98/2% by mass, and an unsaturated double bond terminal amount of 0. 0.006 mol %.

(Production Example A3 (Production of methacrylic resin (A-3)))
Ion-exchanged water: 2 kg, tribasic calcium phosphate: 65 g, calcium carbonate: 39 g, and sodium lauryl sulfate: 0.39 g were put into a container having a stirrer to obtain a mixture (b).
Next, ion-exchanged water: 26 kg was put into a 60 L reactor and the temperature was raised to 80 ° C., and the mixture (b), methyl methacrylate: 20.2 kg, ethyl acrylate: 1.4 kg, lauroyl peroxide: 33 g. , and n-octyl mercaptan: 32.4 g.
Thereafter, suspension polymerization was carried out while maintaining about 80°C, and after observing an exothermic peak, the temperature was raised to 92°C at a rate of 1°C/min.
After that, the mixture was aged for 60 minutes to substantially complete the polymerization reaction.
Next, in order to cool to 50° C. and dissolve the suspending agent, 20% by mass sulfuric acid was added, and then the polymerization reaction solution was passed through a 1.68 mm mesh sieve to remove aggregates, and the obtained bead-like polymer was separated. After washing, dehydration and drying, polymer fine particles 3 were obtained. The fine polymer particles 2 were pelletized by a twin-screw extruder of φ26 mm set at 270° C. to obtain a “methacrylic resin (A-3)”. The resulting resin had a weight average molecular weight of 164,000, a molecular weight distribution (Mw/Mn) of 1.96, a structural unit of MMA/EA = 94/6.5% by mass, and an unsaturated double bond terminal amount. was 0.009 mol %.

[Examples 1 to 20] [Comparative Examples 1 to 6]
After weighing the methacrylic resin (A), the thermoplastic elastomer (B), dyes and pigments, and other additives so that the blending ratios shown in Table 2 are obtained, the dyes and pigments and other additives are added to the thermoplastic resin composition. In order to mix the additives uniformly, a tumbler with 0.03 parts by mass of Sumoyl PS260 added for the purpose of spreading dyes and pigments and other additives on the methacrylic resin (A) and thermoplastic elastomer (B) pellets was added and mixed. After thorough mixing, the mixed raw material is fed into a φ26 mm twin-screw extruder, melt-kneaded (compounded) to form a strand, cooled in a water bath, and then cut with a pelletizer to obtain pellets. rice field. During compounding, a vacuum line was connected to the vent portion of the extruder to remove volatile components such as moisture and monomer components under the condition of −0.06 MPa. Thus, a thermoplastic resin composition was obtained. The kneading temperature of the thermoplastic resin composition was 240°C. The numerical values in Table 2 represent the number of blended parts (parts by mass) when the total mass of the methacrylic resin (A) and the thermoplastic elastomer (B) is 100 parts by mass.
The mass ratio of the methacrylic resin (A) and the thermoplastic elastomer (B) in the thermoplastic resin compositions obtained in Examples 1 to 20 and Comparative Examples 1 to 6 were analyzed, and the results are shown in Table 2. was the same mass proportion as that of The mass ratio of the tertiary amine in the thermoplastic resin compositions obtained in Examples 1 to 20 and Comparative Examples 1 and 2 was 0% by mass, and the mass ratio of the tertiary amine in the thermoplastic elastomer (B) was It was 0% by mass.

<Flat plate sample>
(injection molding)
The obtained pellets of the thermoplastic resin composition were placed in a 100t class injection molding machine (Shibaura Kikai EC-100SX) and molded into a 100 mm square flat plate with a thickness of 2 mm to obtain a flat plate sample for evaluation. The mold used had its surface (inner surface of the mold cavity) polished with a polishing number of 8000.
The molding conditions for the evaluation flat plate samples were set as follows.
Molding temperature (cylinder temperature): 240°C
Mold temperature: 55°C
In addition, it is important to keep the mold temperature at the time of injection molding high in order to improve the transferability of the mold surface polished with a polishing number of 8000, but even if the mold temperature is too high, the cooling time is is too long and impractical. The temperature range of the mold to improve the quality is 40° C. or higher and 100° C. or lower, more preferably 50° C. or higher and 90° C. or lower.

<Dumbbell test piece>
(injection molding)
The obtained pellets of the thermoplastic resin composition were put into an injection molding machine (EC-100SX manufactured by Shibaura Kikai Co., Ltd.) to mold a type 1A dumbbell test piece, which was used as a sample for evaluation. Molding conditions conformed to ISO8257-2. The filling speed was 10 cm ³ /sec.

<Molded body having a joint>
The pellets of the thermoplastic resin compositions obtained in Examples 2 to 7, 9, 11, 13, 18, and 20 were put into an injection molding machine (Shibaura Kikai EC-100SX), and the cylinder temperature was 255 ° C. and the mold temperature 150 mm × 180 mm × t3 mm (L = 227 mm, L / t = 76) having a joint (snap-fit male part) with other members as ^shown in FIG. ) was produced. The male part of the snap-fit has a structure in which a claw part of 2 mm×2 mm×1 to 2 mm is provided at the tip of a column part of 2 mm×10 mm×10 mm, and is installed near the center part of the molded body. When this claw portion was bent, the claw portion showed good elasticity and resistance to breakage required for a snap-fit structure.

As shown in Table 2, in Examples 2 to 7, 9, 11, 13, 18, and 20, excellent jet blackness, color transfer resistance, toughness, strength at low temperatures, heat deformation resistance, light shielding properties, and fluidity are combined. Also, a thermoplastic resin composition exhibiting good appearance retention was able to be produced.
In Comparative Example 1, since the amount of dye and pigment added was too small, jet-blackness and light-shielding properties were not good.
In Comparative Example 2, since the amount of dye and pigment added was excessive, color transfer resistance was not good.
In Comparative Example 3, since the thermoplastic elastomer (B) was not included, color transfer resistance, strength at low temperatures, and toughness were not good. In addition, it was slightly inferior to Examples 2 to 7, 9, 11, 13, 18 and 20 in jet blackness and fluidity.
In Comparative Example 4, since the thermoplastic elastomer (B) was not included, color transfer resistance and fluidity were not good.
In Comparative Example 5, since the thermoplastic elastomer (B) was not included, the strength, toughness, color transfer resistance and fluidity at low temperature were not good.
In Comparative Example 6, since the thermoplastic elastomer (B) was not included, toughness and color transfer resistance were not good. In addition, it was slightly inferior to Examples 2 to 7, 9, 11, 13, 18 and 20 in strength at low temperature, jet blackness and fluidity.
Although Example 1 is at a practically sufficient level, it is slightly inferior to Examples 2 to 7, 9, 11, 13, 18, and 20 in fluidity, strength at low temperatures, toughness, and color transfer resistance. was This is probably because the amount of the thermoplastic elastomer (B) added was less than in Examples 2-7, 9, 11, 13, 18 and 20.
Although Example 8 had a sufficient level for practical use, it was slightly inferior to Examples 2 to 7, 9, 11, 13, 18 and 20 in heat deformation resistance. This is probably because the amount of thermoplastic elastomer (B) added is larger than in Examples 2-7, 9, 11, 13, 18 and 20.
Although Example 10 had a sufficient level for practical use, it was slightly inferior to Examples 2 to 7, 9, 11, 13, 18 and 20 in light shielding properties. This is probably because the amount of dye and pigment added is less than in Examples 2-7, 9, 11, 13, 18 and 20.
Although Example 12 was at a practically sufficient level, it was slightly inferior in color transfer resistance to Examples 2 to 7, 9, 11, 13, 18 and 20. This is probably because the amount of dye and pigment added is larger than in Examples 2-7, 9, 11, 13, 18 and 20.
Although Example 14 was at a practically sufficient level, it was slightly inferior in color transfer resistance to Examples 2 to 7, 9, 11, 13, 18 and 20. This is thought to be due to the combination of dyes and pigments.
Although Example 15 is at a practically sufficient level, it is slightly inferior in jet-blackness compared to Examples 2 to 7, 9, 11, 13, 18, and 20, and although it is at a practical level, it has heat resistance. The deformability and appearance retention were slightly inferior. This is probably because the amount of thermoplastic elastomer (B) added is larger than in Examples 2-7, 9, 11, 13, 18 and 20.
Although Example 16 had a sufficient level for practical use, it was slightly inferior to Examples 2 to 7, 9, 11, 13, 18 and 20 in heat deformation resistance. It is considered that this is due to the ratio and combination of the methacrylic resin (A) and the thermoplastic elastomer (B).
Although Example 17 was at a practical level, it was slightly inferior to Examples 2 to 7, 9, 11, 13, 18, and 20 in jet-blackness. Further, although the level was sufficient for practical use, the toughness was slightly inferior to those of Examples 2 to 7, 9, 11, 13, 18 and 20. It is believed that this is because the thermoplastic elastomer (B) is a thermoplastic polyurethane containing a structure derived from polyether polyol monomers.
Compared to Examples 2 to 7, 9, 11, 13, 18, and 20, Example 19 was practically usable but inferior in appearance retention. It is believed that this is due to the composition of the thermoplastic elastomer (B).

According to the thermoplastic resin composition of the present invention, it is possible to obtain a resin molded article having excellent toughness, fluidity, strength at low temperature, color transfer resistance, jet blackness, light shielding property, and heat deformation resistance when formed into a molded article. It can be used industrially as parts for vehicles, parts for home appliances, and miscellaneous goods.

Claims (15)

0.05 to 1 part by mass of a dye or pigment per 100 parts by mass of the methacrylic resin (A), the thermoplastic elastomer (B), and the methacrylic resin (A) and the thermoplastic elastomer (B) and
Molding temperature: 240 ° C. Mold temperature: 55 ° C. using a mold with a mold polishing number of 8000 When molding a molded product with a thickness of 2 mm, D65 light source, SCE method, 10 degree field of view reflection mode Measurement was performed. The thermoplastic resin composition, wherein the molded article has a lightness L* of 3 or less. The total light transmittance is 0.3% or less when a molded body having a thickness of 2 mm is molded at a molding temperature of 240°C and a mold temperature of 55°C using a mold with a mold polishing count of 8000. Item 1. The thermoplastic resin composition according to item 1. 2. The thermoplastic resin composition according to claim 1, wherein said thermoplastic elastomer (B) is a thermoplastic polyurethane. 4. The thermoplastic resin composition according to claim 3, wherein the thermoplastic elastomer (B) is a thermoplastic polyurethane having 70% by mass or more of isocyanate-derived structural units having an alicyclic ring. 5. The thermoplastic resin composition according to claim 1, wherein the VICAT softening temperature measured according to ISO 306 B50 is 95° C. or higher. Melt mass flow rate (MFR) measured under a load of 3.8 kgf at 230 ° C. is 2.8 g / 10 minutes or more, and a Charpy impact test value at -30 ° C. measured in accordance with JIS K7111-1 is 23 kJ/m ² or more, the thermoplastic resin composition according to claim 1 or 3 The thermoplastic resin composition according to claim 1 or 2, containing 10 to 35 parts by mass of the thermoplastic elastomer (B) with respect to a total of 100 parts by mass of the methacrylic resin (A) and the thermoplastic elastomer (B). thing The thermoplastic elastomer (B) is a thermoplastic polyurethane having an isocyanate-derived structural unit, and an isocyanate having one alicyclic ring relative to 100% by mass of the total weight of the isocyanate-derived structural units contained in the thermoplastic polyurethane. 4. The thermoplastic resin composition according to claim 1 or 3, wherein the weight ratio of the derived structural unit is 70% by weight or more. 4. The thermoplastic resin composition according to claim 1, wherein the methacrylic resin (A) has a weight average molecular weight of 50,000 to 250,000 as measured by gel permeation chromatography (GPC). Production of the thermoplastic resin composition according to claim 1 or 2, wherein the methacrylic resin (A) and the thermoplastic elastomer (B) are blended at a temperature in the range of 200 to 260°C. Method. A molded article comprising the thermoplastic resin composition according to claim 1 . 12. The molded article according to claim 11, which is an injection molded article. 13. The molded article according to claim 11 or 12, which has a joint with another member. A vehicle member comprising the molded article according to claim 11 or 12. 15. The vehicle member according to claim 14, which is selected from automotive pillar garnishes, rear spoilers, front garnishes, rear garnishes, slide rail covers, and front grilles.

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