WO2020040109A1 - Resin molded product - Google Patents

Abstract

A resin molded product (1) according to one embodiment of the present invention has: a glossy surface (11) on the surface thereof; and a non-glossy surface (12) protruding from the glossy surface (11), wherein the non-glossy surface (12) is a continuous surface which divides the glossy surface (11) into a plurality of independent regions (11a) surrounded by the non-glossy surface (12), and the width of the non-glossy surface (12) by which adjacent regions (11a) are separated is 50-500 μm.

Description

Resin molding

The present invention relates to a resin molded product.
Priority is claimed on Japanese Patent Application No. 2018-154180 filed on August 20, 2018, the content of which is incorporated herein by reference.

BACKGROUND ART A resin molded product obtained by molding a resin material is used for an exterior material and an interior material of an automobile or the like. When secondary processing such as painting or plating is not performed, a resin molded product may be required to have excellent gloss from the viewpoint of design and the like. However, the surface of the resin molded product is easily scratched, and when the surface of the resin molded product is a glossy surface, the scratch is easily noticeable.
Therefore, it has been proposed to provide a glossy surface and a plurality of protrusions projecting from the glossy surface and arranged along a predetermined direction on the surface of the resin molded product (Patent Document 1).

On the other hand, when washing a car, a car washer having a rotating brush may be used.
In general, when an automobile is washed by a car washer, the outer surface of the automobile body is rubbed with a rotating brush to remove dirt while discharging a cleaning liquid toward the vicinity of the outer surface of the automobile body. At this time, abrasion of the brush (car wash) may occur on the outer surface of the vehicle body.

JP 2018-34428 A

According to the study of the present inventors, the resin molded product of Patent Document 1 has insufficient scratch resistance, and when the surface is washed with the above-described car washing machine, the surface has car wash scratches. Car wash scratches are noticeable. When the resin molded product is a darkly colored resin molded product obtained by molding a resin material containing a colorant such as carbon black, a car wash scratch is particularly conspicuous.

An object of the present invention is to provide a resin molded product excellent in gloss and scratch resistance.

The present invention includes the following aspects.
[1] The surface has a glossy surface and a non-glossy surface provided to protrude from the glossy surface,
The non-glossy surface is a continuous surface that divides the glossy surface into a plurality of independent areas surrounded by the non-glossy surface,
A resin molded product, wherein a width of a non-glossy surface defining adjacent regions of the plurality of regions is 50 to 500 μm.
[2] The resin molded article according to [1], wherein the height of the non-glossy surface relative to the glossy surface is 10 to 100 μm.
[3] The resin molded article according to [1] or [2], wherein a maximum width of each of the plurality of regions is 1 to 6 mm.
[4] The resin molding according to any one of [1] to [3], wherein a ratio of an area of the glossy surface to a total area of the glossy surface and the non-glossy surface is 55 to 95% by area in a front view. Goods.
[5] The resin molded product according to any one of [1] to [4], wherein each of the plurality of regions has a polygonal shape.
[6] The resin molded product according to any one of [1] to [5], wherein the non-glossy surface is continuous in a lattice.
[7] The resin molded product according to any one of [1] to [6], containing a methacrylic resin.

樹脂 The resin molded product of the present invention is excellent in gloss and scratch resistance.

It is a partial perspective view of the resin molding concerning one embodiment. FIG. 2 is a front view illustrating a surface shape of the resin molded product shown in FIG. 1. FIG. 2 is a diagram illustrating a procedure for manufacturing a mold used for manufacturing the resin molded product illustrated in FIG. 1. It is a front view explaining the surface shape of the resin molded product concerning other embodiments. It is a front view explaining the surface shape of the resin molded product concerning other embodiments. FIG. 5 is a front view illustrating a surface shape of a resin molded product of Comparative Example 1.

The following definitions of terms apply throughout the present specification and claims.
The “resin molded article” is formed by molding a resin material.
The term “scratch resistance” indicates that the scratch is hardly formed and the scratch is hardly conspicuous.
The dimensional ratios in FIGS. 1 to 6 are different from actual ones for convenience of explanation.
"-" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit and the upper limit.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a partial perspective view of a resin molded product 1 according to one embodiment of the present invention, and FIG. 2 is a front view illustrating a surface shape of the resin molded product 1.
The resin molded article 1 has a glossy surface 11 and a non-glossy surface 12 on the surface.
The non-glossy surface 12 is provided so as to protrude from the glossy surface 11.
The non-glossy surface 12 is a continuous surface that partitions the glossy surface 11 into a plurality of regions 11a that are surrounded by the non-glossy surface 12 and are independent from each other.
The edge of the non-glossy surface 12 and the periphery of each of the plurality of regions 11a are connected by a peripheral surface surrounding the rising region 11a from the periphery of the region 11a.

The non-glossy surface 12 is a so-called matte surface. The non-glossy surface 12 includes, for example, a textured surface. The embossed surface is a surface having fine irregularities.
As an example of the non-glossy surface 12, when the resin molded product 1 is an injection molded product of the thermoplastic resin composition prepared in Example 1 described later, the degree of 60 ° gloss of the non-glossy surface 12 becomes 1 to 30. Uneven surface.
The 60 ° gloss value is measured using a gloss meter (IQ-S manufactured by Rhopoint) in accordance with JIS Z8741.

The width a of the non-glossy surface 12 that partitions adjacent areas 11a is 50 to 500 μm, preferably 100 to 400 μm, and more preferably 200 to 300 μm. If the width a is equal to or larger than the lower limit of the above range, it is possible to suppress the area 11a from being damaged. When the width a is equal to or less than the upper limit of the above range, the non-glossy surface 12 is less noticeable, and the surface of the resin molded product 1 has excellent gloss.
The width a of the non-glossy surface 12 that separates the adjacent areas 11a is, in other words, the distance between the areas 11a in the direction in which the adjacent areas 11a are arranged.
The width a of the non-glossy surface 12 that partitions the adjacent areas 11a may or may not be constant.

The height of the non-glossy surface 12 based on the glossy surface 11 is, for example, 3 to 170 μm, preferably 10 to 100 μm, more preferably 15 to 70 μm, and still more preferably 20 to 50 μm. If the height of the non-glossy surface 12 is equal to or more than the lower limit of the above range, it is possible to further suppress the area 11a from being damaged. When the height of the non-glossy surface 12 is equal to or less than the upper limit of the above range, the gloss of the surface of the resin molded product 1 is more excellent.
The height of the non-glossy surface 12 is the height from the position of the glossy surface 11 to the highest position of the non-glossy surface 12.

The glossy surface 11 is a so-called mirror surface.
As an example of the glossy surface 11, when the resin molded product 1 is an injection-molded product of the thermoplastic resin composition prepared in Example 1 described later, a mirror surface with a 60 ° gloss value of the glossy surface 11 of 70 to 100. Is mentioned.

Each of the plurality of regions 11a of the glossy surface 11 has a square shape.
The maximum width d of each of the plurality of regions 11a is, for example, 0.4 to 10 mm, preferably 1 to 6 mm, more preferably 1.5 to 5 mm, and still more preferably 2 to 4 mm. When the maximum width d is equal to or larger than the lower limit of the above range, the gloss of the surface of the resin molded product 1 is excellent. If the maximum width d is equal to or less than the upper limit of the above range, it is possible to further suppress the area 11a from being damaged. In addition, even when the area 11a is damaged, the length of the damage is short and less noticeable.
In the present embodiment, since the region 11a is square, the length of the diagonal corresponds to the maximum width d of the region 11a.

The plurality of regions 11a are regularly arranged in two directions of a first direction and a second direction in plan view. Here, the first direction is a direction (the left-right direction in FIG. 2) along one of the sides constituting the periphery of the region 11a. The second direction is a direction (vertical direction in FIG. 2) orthogonal to the first direction. Therefore, the non-glossy surface 12 has a lattice shape in which a plurality of parallel straight lines extending in the first direction and a plurality of parallel straight lines extending in the second direction intersect.

The pitch b of the plurality of regions 11a arranged in the first direction and the pitch c of the plurality of regions 11a arranged in the second direction are, for example, 0.3 to 9 mm, respectively, preferably 1 to 5 mm, more preferably 2 to 4 mm. preferable. When the pitches b and c are equal to or larger than the lower limit of the above range, the gloss of the surface of the resin molded product 1 is more excellent. If the pitches b and c are equal to or less than the upper limit of the above range, it is possible to further suppress the area 11a from being damaged. In addition, even when the area 11a is damaged, the length of the damage is short and less noticeable.
The pitch b is the distance between the centers of the adjacent regions 11a in the first direction, the distance between the centers of the non-glossy surfaces 12 adjacent through the region 11a in the first direction, or the adjacent regions in the first direction. It is equal to the sum of the width a of the non-glossy surface 12 that partitions the areas 11a and the width of one area 11a. The pitch c is the distance between the centers of the regions 11a adjacent in the second direction, the distance between the centers of the non-glossy surfaces 12 adjacent via the region 11a in the second direction, or the adjacent regions in the second direction. It is equal to the sum of the width a of the non-glossy surface 12 that partitions the areas 11a and the width of one area 11a.
The pitch b and the pitch c may be the same or different.

In a front view, the ratio of the area of the glossy surface 11 (total area of the plurality of regions 11a) to the total area of the glossy surface 11 and the non-glossy surface 12 is, for example, 50 to 99 area%, and 55 to 95 area%. Preferably, 60 to 90 area% is more preferable, and 70 to 85 area% is more preferable. When the ratio of the area of the glossy surface 11 is equal to or more than the lower limit of the above range, the gloss of the surface of the resin molded product 1 is more excellent. If the ratio of the area of the glossy surface 11 is equal to or less than the upper limit of the above range, the scratch is hardly noticeable.
The 20 ° gloss value of the entire surface of the resin molded product 1 having the glossy surface 11 and the non-glossy surface 12 is preferably more than 40, more preferably more than 55. The upper limit of the 20 ° gloss value is not particularly limited, but is, for example, 85.
The 20 ° gloss value is measured using a gloss meter (IQ-S manufactured by Rhopoint) in accordance with JIS Z8741.

(Resin material)
Examples of the resin material forming the resin molded product 1 include a resin material containing a thermoplastic resin. When the resin material contains a thermoplastic resin, the resin molded product 1 contains a thermoplastic resin.
Examples of the thermoplastic resin include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene- (meth) acrylate (ASA) resin, acrylonitrile-ethylene-α-olefin-styrene (AES) resin, methacryl resin, and polycarbonate resin. , Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester, polyethylene, polypropylene, fluorine resin , Polyamide (nylon), acrylonitrile-styrene (AS) resin and the like. One of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.
In that the glossy surface 11 can be made more glossy, the resin molded article 1 may contain, as the thermoplastic resin, at least one selected from the group consisting of ABS resin, ASA resin, AES resin, methacrylic resin and polycarbonate resin. preferable.
In terms of more excellent scratch resistance, the resin molded product 1 preferably contains at least one selected from the group consisting of a methacrylic resin and a polycarbonate resin as the thermoplastic resin.
It is particularly preferable that the resin molded article 1 contains a methacrylic resin from the viewpoints of higher gloss and better scratch resistance. Examples of the methacrylic resin include a methacrylic resin (C) described below. You may use together a methacryl resin and another thermoplastic resin.

The resin material can contain additives such as a coloring agent, an antioxidant, a lubricant, a processing aid, a pigment, a dye, a filler, silicone oil, and paraffin oil, in addition to the thermoplastic resin.
Examples of the coloring agent include pigments and dyes such as carbon black.

As an example of a preferred resin material, the following thermoplastic resin composition can be mentioned.
A graft copolymer (B) obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an alkyl (meth) acrylate polymer (A) When,
A methacrylic resin (C) which is a polymer of a vinyl monomer mixture (m2) containing a methacrylic acid ester,
A thermoplastic resin composition comprising:
“(Meth) acrylate” means acrylate or methacrylate.
According to such a thermoplastic resin composition, it is possible to obtain a resin molded product having excellent impact resistance, scratch resistance, weather resistance, and coloring properties, and particularly excellent jet-blackness when colored with black.

The thermoplastic resin composition may contain carbon black, other thermoplastic resins, and various additives as necessary.
When the thermoplastic resin composition contains carbon black, the weather resistance and jet-blackness of the resin molded product are more excellent than when other colorants are used.

<Alkyl (meth) acrylate polymer (A)>
The alkyl (meth) acrylate polymer (A) is a polymer having an alkyl (meth) acrylate unit.
The alkyl (meth) acrylate-based polymer (A) may further have a monomer (other monomer) unit other than the alkyl (meth) acrylate unit, and is compounded with polybutadiene or polyorganosiloxane. It may be.

The alkyl group of the alkyl (meth) acrylate may have, for example, 1 to 20 carbon atoms.
Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate; hexyl methacrylate, 2-ethylhexyl methacrylate And alkyl methacrylates such as n-lauryl methacrylate. One of these alkyl (meth) acrylates may be used alone, or two or more thereof may be used in combination. Above all, n-butyl acrylate is preferable in that the impact resistance of the resin molded product is further improved.

The other monomer is not particularly limited as long as it can be copolymerized with the alkyl (meth) acrylate, but may be an aromatic vinyl compound (eg, styrene, α-methylstyrene, p-methylstyrene, etc.), a vinyl cyanide compound (For example, acrylonitrile, methacrylonitrile, etc.). One of these other monomers may be used alone, or two or more thereof may be used in combination.

In the alkyl (meth) acrylate polymer (A), the content of the alkyl (meth) acrylate unit is preferably from 80 to 100% by mass, more preferably from 90 to 100% by mass, based on the total mass of all the monomer units. preferable.

The alkyl (meth) acrylate-based polymer (A) is typically granular, and is present in the thermoplastic resin composition in granular form.
The volume average particle diameter of the alkyl (meth) acrylate polymer (A) is preferably from 10 to 1,000 nm, more preferably from 100 to 500 nm. If the volume average particle diameter of the alkyl (meth) acrylate polymer (A) is at least the lower limit of the above range, the impact resistance of the resin molded product is excellent, and if it is at most the upper limit of the above range, the resin molded product is Is excellent in color development, especially jet-blackness when colored black.
Here, the volume average particle size of the alkyl (meth) acrylate polymer (A) is obtained by measuring the volume-based particle size distribution using a dynamic light scattering type particle size distribution analyzer, and obtaining the obtained particle size distribution. It is a value calculated from:

The alkyl (meth) acrylate polymer (A) can be produced by polymerizing a monomer component containing one or more alkyl (meth) acrylates. This monomer component may contain other monomers.

The method for producing the alkyl (meth) acrylate polymer (A) is not particularly limited, but is preferably a method in which a monomer component containing one or more alkyl (meth) acrylates is subjected to radical polymerization.
When radically polymerizing a monomer component containing one or more alkyl (meth) acrylates, a graft crosslinking agent or a crosslinking agent may be used as necessary.
Examples of the graft crosslinking agent or the crosslinking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol diester dimethacrylate, propylene glycol diester dimethacrylate, 1,3-butylene glycol diester dimethacrylate, 1,4-butylene glycol diester dimethacrylate and the like. These may be used alone or in combination of two or more.
The polymerization conditions may be, for example, at 30 to 95 ° C. for 1 to 10 hours.

Usually, a radical polymerization agent and an emulsifier are used for the radical polymerization.
Examples of the radical polymerization initiator include peroxides, azo initiators, and redox initiators obtained by combining an oxidizing agent and a reducing agent. Among these, a redox initiator is preferred, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and hydroperoxide is particularly preferred.

The emulsifier is not particularly limited, but since it has excellent latex stability during radical polymerization and can increase the polymerization rate, carboxylic acids such as sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap are used. Salts are preferred. Among these, dipotassium alkenyl succinate is preferred because it can suppress gas generation when the obtained graft copolymer (B) and a thermoplastic resin composition containing the same are molded at a high temperature. Specific examples of dipotassium alkenylsuccinate include dipotassium octadecenylsuccinate, dipotassium heptadecenylsuccinate, and dipotassium hexadecenylsuccinate. One of these emulsifiers may be used alone, or two or more thereof may be used in combination.

<Vinyl monomer mixture (m1)>
The vinyl monomer mixture (m1) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.
The vinyl-based monomer mixture (m1) may contain, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith, as long as the effects of the present invention are not impaired.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, and ethylstyrene. Styrene and α-methylstyrene are preferred from the viewpoint of the fluidity of the thermoplastic resin composition, the color development of the resin molded product, and the impact resistance. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.

ビ ニ ル Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the vinyl cyanide compound, one type may be used alone, or two or more types may be used in combination.

Other monomers include, for example, acrylates (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylates (methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid) Butyl, etc.) and maleimide monomers (N-cyclohexylmaleimide, N-phenylmaleimide, etc.). As the other monomers, one kind may be used alone, or two or more kinds may be used in combination.

In the vinyl monomer mixture (m1), the content of the aromatic vinyl compound is preferably from 65 to 82% by mass, more preferably from 73 to 82% by mass, based on the total mass (100% by mass) of the vinyl monomer mixture (m1). 80 mass% is more preferable, and 75 to 80 mass% is still more preferable. When the content of the aromatic vinyl compound is within the above range, the impact resistance and the coloring properties of the resin molded product, particularly the jet-blackness when blackened, are further improved.

The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and more preferably 20 to 25% by mass based on the total mass (100% by mass) of the vinyl monomer mixture (m1). % Is more preferred. When the content of the vinyl cyanide compound is within the above range, the impact resistance and the coloring properties of the resin molded product, particularly the jet-blackness when colored black, are further excellent.

<Graft copolymer (B)>
The graft copolymer (B) is a copolymer obtained by polymerizing a vinyl monomer mixture (m1) in the presence of an alkyl (meth) acrylate polymer (A).
In the case of the graft copolymer (B), it is difficult to specify how the vinyl monomer mixture (m1) is polymerized in the presence of the alkyl (meth) acrylate polymer (A). is there. That is, there are circumstances (impossible / impractical circumstances) in which it is impossible or not practical to directly specify the graft copolymer (B) by its structure or properties. Therefore, it is more appropriate to define that the graft copolymer (B) is obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the alkyl (meth) acrylate polymer (A). It is said.

The mass ratio of the alkyl (meth) acrylate polymer (A) to the vinyl monomer mixture (m1) is not particularly limited, but the alkyl (meth) acrylate polymer (A) is 10 to 80% by mass, The content of the monomer mixture (m1) is preferably 20 to 90% by mass, the content of the alkyl (meth) acrylate polymer (A) is 30 to 70% by mass, and the content of the vinyl monomer mixture (m1) is 30 to 90% by mass. It is particularly preferred to be 70% by mass (provided that the total of the alkyl (meth) acrylate polymer (A) and the vinyl monomer mixture (m1) is 100% by mass). With such a mass ratio, the flowability of the thermoplastic resin composition, and the balance between the impact resistance and the color developing properties of the resin molded product, particularly the jet-blackness when blackened, are more excellent.
As the graft copolymer (B), one type may be used alone, or two or more types may be used in combination.

The graft copolymer (B) is obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the alkyl (meth) acrylate polymer (A).
The method for carrying out the polymerization is not particularly limited, but emulsion polymerization is preferred because it can be controlled so that the reaction proceeds stably. Specifically, a method in which the latex of the alkyl (meth) acrylate-based polymer (A) is charged with the vinyl-based monomer mixture (m1) at a time and then polymerized; the alkyl (meth) acrylate-based polymer (A) A method in which a part of the vinyl monomer mixture (m1) is firstly charged into the latex of the above, and the remainder is added dropwise to the polymerization system while polymerizing as needed; a vinyl monomer is added to the latex of the alkyl (meth) acrylate polymer (A). Polymerization may be carried out as needed while dropping the entire amount of the monomer mixture (m1). These may be carried out in one stage or in two or more stages. In the case of dividing into two or more stages, it is also possible to carry out by changing the type and composition ratio of the monomers constituting the vinyl-based monomer mixture (m1) in each stage.

In the emulsion polymerization, a radical polymerization initiator and an emulsifier are usually used. Examples of the radical polymerization initiator and the emulsifier include the radical polymerization initiator and the emulsifier exemplified above in the description of the method for producing the alkyl (meth) acrylate polymer (A).
At the time of polymerization, various known chain transfer agents may be added in order to control the molecular weight and graft ratio of the obtained graft copolymer (B).
The polymerization conditions may be, for example, at 30 to 95 ° C. for 1 to 10 hours.

The graft copolymer (B) obtained by emulsion polymerization is usually in a latex state.
As a method for recovering the graft copolymer (B) from the latex of the graft copolymer (B), for example, the latex of the graft copolymer (B) is poured into hot water in which a coagulant is dissolved. A wet method of coagulating into a slurry; a spray drying method of semi-directly recovering the graft copolymer (B) by spraying a latex of the graft copolymer (B) in a heated atmosphere.

Examples of the coagulant used in the wet method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate, and are selected according to the emulsifier used in the polymerization. . For example, when only a carboxylic acid soap such as a fatty acid soap or a rosin acid soap is used as an emulsifier, one or more of the above-described coagulants can be used. When an emulsifier having a stable emulsifying power even in an acidic region such as sodium alkylbenzene sulfonate is used as the emulsifier, a metal salt is preferable as the coagulant.

When the wet method is used, a slurry-like graft copolymer (B) is obtained.
As a method for obtaining the graft copolymer (B) in a dry state from the graft copolymer (B) in a slurry state, first, the remaining emulsifier residue is eluted in water and washed, and then the slurry is centrifuged or press dewatered. A method of drying with a flash dryer or the like after dehydrating with a machine or the like; a method of simultaneously performing dehydration and drying with a compression dehydrator or an extruder, and the like. By such a method, a powdery or particulate dry graft copolymer (B) is obtained.

The washing conditions are not particularly limited, but it is preferable to wash under the condition that the amount of the emulsifier residue contained in 100% by mass of the dried graft copolymer (B) is in the range of 0.3 to 2% by mass. When the amount of the emulsifier residue in the graft copolymer (B) is 0.3% by mass or more, the flowability of the obtained graft copolymer (B) and the thermoplastic resin composition containing the same tend to be further improved. . On the other hand, when the amount of the emulsifier residue in the graft copolymer (B) is 2% by mass or less, generation of gas when the thermoplastic resin composition is molded at a high temperature can be suppressed. The amount of the emulsifier residue can be adjusted by, for example, the washing time.
The drying temperature may be, for example, 50-90 ° C.
The volume average particle size and the volume-based particle size distribution of the alkyl (meth) acrylate-based polymer (A) in the obtained graft copolymer (B) are the same as those of the alkyl used in the production of the graft copolymer (B). It is the same as the volume average particle size and the volume-based particle size distribution of the alkyl (meth) acrylate polymer (A) in the latex of the (meth) acrylate polymer (A).
In addition, it is also possible to send directly to an extruder or a molding machine for producing a resin composition without collecting the graft copolymer (B) discharged from the compression dehydrator or the extruder to obtain a resin molded product. .

<Vinyl monomer mixture (m2)>
The vinyl monomer mixture (m2) contains at least a methacrylic acid ester.
The vinyl monomer mixture (m2) comprises at least one of a maleimide monomer, an aromatic vinyl monomer, an acrylate, and another vinyl monomer copolymerizable with a methacrylate. It may further include.
When heat resistance is required for the resin molded product, the vinyl monomer mixture (m2) preferably contains a maleimide monomer. When the vinyl monomer mixture (m2) contains a maleimide monomer, the resin molded article is also excellent in heat resistance. Even if heat resistance is imparted to the resin molded product, impact resistance is not impaired.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, Examples include isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl methacrylate. As the methacrylate, a methacrylate having a hydrocarbon group having 1 to 8 carbon atoms is preferable. At least one of methyl methacrylate and ethyl methacrylate is preferred from the viewpoint that the heat resistance and impact resistance of the resin molded product are further excellent. The methacrylic acid esters may be used alone or in combination of two or more.

Examples of the maleimide monomer include N-alkylmaleimides (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butyl Maleimide, Nt-butylmaleimide, etc.), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.) and the like. Can be N-arylmaleimide is preferred, and N-phenylmaleimide is particularly preferred, in that the heat resistance and impact resistance of the resin molded product are further excellent. As the maleimide-based compound, one type may be used alone, or two or more types may be used in combination.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Styrene and α-methylstyrene are preferred from the viewpoint of further improving the heat resistance and impact resistance of the resin molded product. One kind of the aromatic vinyl compound may be used alone, or two or more kinds may be used in combination.

Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and the like. Methyl acrylate is preferred from the viewpoint that the heat resistance and impact resistance of the resin molded product are further excellent. Acrylic esters may be used alone or in combination of two or more.

Other vinyl monomers include, for example, vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.). As the other vinyl monomers, one type may be used alone, or two or more types may be used in combination.

In the vinyl-based monomer mixture (m2), the content of the methacrylic acid ester is determined from the viewpoint of the scratch resistance of the resin molded product, the coloring property, and particularly the jet-blackness during black coloring. m2) is preferably from 50 to 100% by mass relative to the total mass (100% by mass).

When the vinyl monomer mixture (m2) contains a maleimide monomer, the content of the maleimide monomer is determined based on the heat resistance and scratch resistance of the resin molded product. Is preferably from 5 to 49% by mass based on the total mass (100% by mass) of

As the vinyl monomer mixture (m2), the content of the methacrylic acid ester is 50 to 94% by mass relative to the total mass (100% by mass) of the vinyl monomer mixture (m2), Preferably, the content is 5 to 49% by mass and the content of the aromatic vinyl monomer is 1 to 45% by mass. When the content of each monomer is within the above range, the resin molded product is further excellent in scratch resistance and color development, particularly jet-blackness when impacted with black, impact resistance and heat resistance.

<Methacrylic resin (C)>
The methacrylic resin (C) is a polymer of a vinyl-based monomer mixture (m2) and contains at least a methacrylic ester unit.
The content of the methacrylate unit based on the total mass of all the units constituting the methacrylic resin (C) can be considered to be the same as the content of the methacrylate based on the total mass of the vinyl monomer mixture (m2). The same applies to units other than the methacrylate unit.

The mass average molecular weight (Mw) of the methacrylic resin (C) is preferably from 6 × 10 ⁴ to 30 × 10 ^4, more preferably from 8 × 10 ⁴ to 20 × 10 ⁴ . When the mass average molecular weight of the methacrylic resin (C) is at least the lower limit of the above range, the thermal stability during molding will be more excellent. When the weight average molecular weight of the methacrylic resin (C) is at most the upper limit of the above range, the fluidity during injection molding will be more excellent.
The mass average molecular weight of the methacrylic resin (C) is a value in terms of standard polystyrene measured using gel permeation chromatography (GPC).
As the methacrylic resin (C), one type may be used alone, or two or more types may be used in combination.

The methacrylic resin (C) is obtained by polymerizing a vinyl monomer mixture (m2). The polymerization method of the vinyl monomer mixture (m2) is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, and the like).
When the vinyl-based monomer mixture (m2) contains two or more types of monomers, the resulting methacrylic resin (C) typically has random units derived from these two or more types of monomers. Are random copolymers.

As a method for producing the methacrylic resin (C) by the emulsion polymerization method, for example, a vinyl monomer mixture (m2), an emulsifier, a polymerization initiator, and a chain transfer agent are charged into a reactor, and the mixture is heated and polymerized. A method of obtaining an aqueous dispersion containing the methacrylic resin (C) and recovering the methacrylic resin (C) from the aqueous dispersion by a precipitation method may be used.
The polymerization conditions for the emulsion polymerization may be, for example, 30 to 95 ° C. for 1 to 10 hours.
Examples of the emulsifier include ordinary emulsifiers for emulsion polymerization (eg, potassium rosinate, sodium alkylbenzenesulfonate).
Examples of the polymerization initiator include organic and inorganic oxide-based initiators.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.
As the precipitation method, the same method as that used when recovering the graft copolymer (B) from the latex of the graft copolymer (B) can be employed.

As a method for producing the methacrylic resin (C) by the suspension polymerization method, for example, a vinyl monomer mixture (m2), a suspending agent, a suspending aid, a polymerization initiator, and a chain transfer agent are placed in a reactor. A method of charging, polymerizing by heating, dehydrating and drying the slurry, and recovering the methacrylic resin (C) can be mentioned.
The polymerization conditions for the suspension polymerization may be, for example, at 60 to 150 ° C. for 1 to 20 hours.
Examples of the suspending agent include tricalcium phosphite, polyvinyl alcohol and the like.
Examples of the suspending aid include sodium alkylbenzenesulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of the chain transfer agent include mercaptans, α-methylstyrene dimer, terpenes and the like.

<Carbon black>
Carbon black is used for black coloration of the thermoplastic resin composition.
Generally, an organic dye is used for black coloring of a thermoplastic resin composition because of the ease with which jet blackness can be achieved.However, when colored with an organic dye, there is a problem that deterioration in weather resistance and color transfer are likely to occur. is there. As a coloring agent for coloring the thermoplastic resin composition, carbon black is preferable to an organic dye from the viewpoint of weather resistance.

The carbon black is not particularly limited, but is preferably a carbon black having an average primary particle diameter of 10 to 20 nm. When the average primary particle size is 10 nm or more, aggregation of carbon black in the thermoplastic resin is suppressed, and sufficient jet-blackness is easily developed. Further, those having an average primary particle diameter of less than 10 nm are difficult to produce, and are inferior in industrial practicality. When the average primary particle size is 20 nm or less, the jet-blackness of the black-colored resin molded product is excellent.
Here, the average primary particle size of the carbon black is measured according to JIS K6221.

As carbon black, commercially available products can be used. For example, Mitsubishi Carbon Black (registered trademark) # 2600, # 2300, # 1000, # 980, # 970, # 960, # 950, # 44 (manufactured by Mitsubishi Chemical Corporation) ), Toka Black (registered trademark) # 8500, # 8300 (manufactured by Tokai Carbon Co., Ltd.) and the like. However, it is not limited to these.

<Other thermoplastic resins>
Other thermoplastic resins include, for example, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, Allylate, liquid crystal polyester, polyethylene, polypropylene, fluororesin, polyamide (nylon) and the like.

<Additives>
Examples of the additive include an antioxidant, a lubricant, a processing aid, a pigment (excluding carbon black), a dye, a filler, a silicone oil, a paraffin oil, and the like.

<Content of each component>
The ratio (rubber content) of the alkyl (meth) acrylate polymer (A) to the total mass (100 mass%) of the thermoplastic resin composition is preferably 5 to 30 mass%, more preferably 10 to 25 mass%. . When the rubber content is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the resin molded product, the scratch resistance, the coloring property, and particularly the jet-blackness when blackened are further improved.

The proportion of the graft copolymer (B) to the total mass (100% by mass) of the graft copolymer (B) and the methacrylic resin (C) is preferably from 20 to 55% by mass, more preferably from 30 to 45% by mass. . When the content of the graft copolymer (B) is within the above range, the thermoplastic resin composition has good fluidity, scratch resistance, impact resistance, color development, especially jet-blackness when colored black, and heat resistance. Excellent physical property balance.

When the thermoplastic resin composition contains carbon black, the content of carbon black is 0.1 to 5 mass% with respect to the total mass (100 mass%) of the graft copolymer (B) and the methacrylic resin (C). % Is preferred. When the content of carbon black is 0.1% by mass or more, the jet-blackness of the resin molded product is more excellent, and when it is 5% by mass or less, the impact resistance of the resin molded product tends to be more excellent.

The method for producing the thermoplastic resin composition is not particularly limited. For example, the graft copolymer (B), the methacrylic resin (C) and, if necessary, other components (carbon black, other thermoplastic resins, additives) are mixed with a V-type blender or a Henschel mixer. The thermoplastic resin composition is manufactured by dispersing the mixture and melt-kneading the resulting mixture using a melt-kneader such as a screw type extruder, a Banbury mixer, a pressure kneader, or a mixing roll. After the melt-kneading, the melt-kneaded product may be pelletized using a pelletizer or the like as necessary.
The carbon black may be melt-kneaded in advance with a part of the methacrylic resin (C) to provide a masterbatch for mixing with the graft copolymer (B) or the like.

(Production method of resin molded product)
The resin molded product 1 can be manufactured, for example, by molding a resin material using a mold whose surface shape of the cavity surface is the inverted shape of the surface shape of the resin molded product 1.
Such a mold can be produced, for example, by the procedure shown in FIG.
First, a mold 20 having a glossy cavity surface is prepared, and a plurality of masks 32 are formed at positions corresponding to the plurality of regions 11a on the cavity surface, as shown in FIG.
The plurality of masks 32 can be formed by a known method such as a photolithography method.
Next, as shown in FIG. 3B, the cavity surface of the mold 20 is etched through a plurality of masks 32. As a result, portions of the cavity surface that are not covered with the plurality of masks 32 are etched, and a continuous non-glossy surface 22 and a plurality of mutually independent convex portions 24 surrounded by the non-glossy surface 22 are formed. The positions of the plurality of projections 24 correspond to the positions of the plurality of masks 32, respectively. Further, since the upper surface of each of the plurality of convex portions 24 is covered with the mask 32, the upper surface remains glossy. Examples of the etching method include chemical etching and electrolytic etching.
Next, as shown in FIG. 3C, the plurality of masks 32 are removed, and the upper surfaces of the plurality of projections 24 are exposed. As a result, a mold is obtained in which the surface shape of the cavity surface is the inverted shape of the surface shape of the resin molded product 1.

方法 The method of molding the resin material using the above mold may be a known molding method, such as an injection molding method or a press molding method.

(Effects)
The resin molded article 1 described above has a glossy surface 11 on the surface and a non-glossy surface 12 provided so as to protrude from the glossy surface 11. It is a continuous surface surrounded by the surface 12 and divided into a plurality of independent regions 11a, and the width of the non-glossy surface 12 that partitions the adjacent regions 11a is 50 to 500 μm, so that it has excellent gloss and scratch resistance.
That is, the surface of the resin molded article 1 has gloss as a whole by having the glossy surface 11 and the width of the non-glossy surface 12 being as narrow as 500 μm or less.
Also, the glossy surface 11 is divided into a plurality of regions 11a by the non-glossy surface 12 protruding from the glossy surface 11, and the width of the non-glossy surface 12 is 50 μm or more, whereby the surface of the resin molded product 1 rotates. When the brush or the like comes into contact, the brush or the like is prevented from contacting the area 11a by the non-glossy surface 12, and the area 11a is hardly damaged. Further, the scratches on the non-glossy surface 12 are less noticeable than the scratches on the glossy surface 11 (region 11a). Even when the glossy surface 11 is damaged, the length of the damage is short and inconspicuous because the glossy surface 11 is divided into a plurality of regions 11a by the non-glossy surface 12. As described above, the area 11a is hardly damaged, and even if it is damaged, the scratch is hardly conspicuous, so that the scratch resistance is excellent.
On the other hand, for example, as shown in FIG. 6, when the glossy surface 11 is a continuous surface and a plurality of independent non-glossy surfaces 12 are provided so as to protrude from the glossy surface 11, the glossy surface 11 is easily damaged by a long scratch. . For example, when a rotating brush or the like comes into contact with the surface of the resin molded product and moves along the direction in which the plurality of non-glossy surfaces 12 are arranged, the glossy surface 11 is long scratched. Such scratches are prominent.

(Other embodiments)
Although the present invention has been described with reference to the embodiment, the present invention is not limited to the above embodiment. Each configuration in the above-described embodiment and a combination thereof are merely examples, and addition, omission, substitution, and other changes of the configuration are possible without departing from the spirit of the present invention.
For example, the shape of the plurality of regions 11a of the glossy surface 11 is not limited to a square, but may be a polygon, a circle, or the like. A polygonal shape is preferable from the viewpoint of making the scar less noticeable.
The polygonal shape may be, for example, a triangular shape to an octagonal shape, and is preferably a quadrilateral shape, a hexagonal shape, or an octagonal shape in terms of the balance between the inconspicuous scratches and the gloss value of the molded product surface.
The shape of each of the plurality of regions 11a may be the same or different.

FIG. 4 shows an example in which the glossy surface 11 is partitioned into a plurality of hexagonal regions 11a. In this example, the plurality of glossy surfaces are regularly arranged in three directions.
FIG. 5 shows an example in which the glossy surface 11 is divided into a plurality of octagonal regions 11b having a maximum width d1 and a plurality of square regions 11c having a maximum width d2. In this example, octagonal regions 11b and quadrangular regions 11c are alternately arranged in two directions. It can also be said that the octagonal regions 11b are arranged in two directions, and the rectangular regions 11c are arranged between them.

As in the example shown in FIG. 5, when the glossy surface 11 is divided into a plurality of areas having different shapes, the maximum width of the area having the largest width among the areas of each shape is the above-mentioned preferred maximum. It is preferable to be within the range of a large d.
The maximum width of the glossy surface other than the glossy surface having the largest maximum width may be within the range of the preferred maximum width d, and may be outside the range of the preferred maximum width d. , Within the above-mentioned preferred maximum width d.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.
Unless otherwise specified, “%” described below means “% by mass”, and “parts” means “parts by mass”.

<Graft copolymer (B)>
(Preparation of graft copolymer (B))
In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, 0.6 part of dipotassium alkenylsuccinate, 175 parts of ion-exchanged water, 50 parts of n-butyl acrylate, 0.16 of allyl methacrylate were used. A mixture of parts, 0.08 parts of 1,3-butylene glycol dimethacrylate and 0.1 part of t-butyl hydroperoxide was charged to the reactor. The inside of the reactor was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal temperature reached 50 ° C., an aqueous solution consisting of 0.00015 part of ferrous sulfate, 0.00045 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalite, and 5 parts of ion-exchanged water was added. The polymerization was started, and the internal temperature was raised to 75 ° C. This state was further maintained for 1 hour to obtain an aqueous dispersion of the alkyl (meth) acrylate polymer (A). The volume average particle diameter of the alkyl (meth) acrylate polymer (A) dispersed in the aqueous dispersion was 182 nm.

While maintaining the internal temperature of the reactor at 75 ° C., 0.15 part of Rongalite and 0 parts of dipotassium alkenyl succinate were added to the aqueous dispersion of the alkyl (meth) acrylate polymer (A) (50 parts as solids). An aqueous solution consisting of 0.65 parts and 10 parts of ion-exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene and 0.11 part of t-butyl hydroperoxide was dropped over 1 hour. Then, graft polymerization was performed. Five minutes after the completion of the dropwise addition, an aqueous solution consisting of 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.15 part of Rongalite, and 5 parts of ion-exchanged water was added, followed by acrylonitrile 6 A mixture of 0.3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 parts of n-octyl mercaptan was added dropwise over 1 hour to carry out graft polymerization. After dropping, the internal temperature was maintained at 75 ° C. for 10 minutes, and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of an antioxidant (Antage W500, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) and alkenyl succinate were added. An aqueous solution in which 0.2 part of dipotassium acid was dissolved in 5 parts of ion-exchanged water was added. By the above operations, graft polymerization of acrylonitrile and styrene onto the alkyl (meth) acrylate polymer (A) was performed. Subsequently, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a dry powder of the graft copolymer (B).

<Methacrylic resin (C)>
(Preparation of methacrylic resin (C))
In a stainless steel polymerization tank equipped with a stirrer, 150 parts of ion-exchanged water, 77 parts of methyl methacrylate, 17 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl 0.25 parts of mercaptan and 0.7 parts of polyvinyl alcohol were charged. The internal temperature of the polymerization tank was set to 75 ° C., and the reaction was performed for 3 hours. The temperature was raised to 90 ° C., and the reaction was performed for 1 hour. The content was extracted, washed with a centrifugal dehydrator, and dried to obtain a powdery methacrylic resin (C) (mass average molecular weight (Mw) 11.1 × 10 ⁴ ).

<Example 1>
(Preparation of thermoplastic resin composition)
40 parts of the graft copolymer (B), 60 parts of the methacrylic resin (C), and 0.8 part of carbon black (Mitsubishi Carbon Black (registered trademark) # 1000B) are mixed, and a 28 mmφ twin-screw extruder with a vacuum vent ( The mixture was melt-kneaded at a cylinder temperature of 240 ° C. and a vacuum of 93.325 kPa using a “TEX-28V” manufactured by Japan Steel Works, Ltd. to prepare a thermoplastic resin composition. After melt-kneading, the thermoplastic resin composition was pelletized using a pelletizer (“SH-type pelletizer” manufactured by Soken Co., Ltd.).

(Molding of thermoplastic resin composition)
The surface shape of the cavity surface is a shape (continuous non-glossy surface) in which the surface shape (front view) shown in FIG. 2 is inverted, and a plurality of square-shaped convex portions which are surrounded by the non-glossy surface and are independent from each other. A mold insert (having a length of 100 mm and a width of 100 mm) having a shape having a plurality of convex portions regularly arranged in two orthogonal directions was prepared. The top surface of the convex portion of the cavity surface has been subjected to mirror finishing (polishing ♯ 8000) such that the 60 ° gloss value of the glossy surface of the resin molded product obtained by injection molding the thermoplastic resin composition becomes 89. . The non-glossy surface surrounding the convex portion has been subjected to texture processing so that the 60 ° gloss value of the non-glossy surface of the resin molded product obtained by injection-molding the thermoplastic resin composition becomes 4. The width a of the non-glossy surface separating adjacent convex portions is 200 μm, the pitch b is 2.4 mm, the pitch c is 2.4 mm, and the height of the convex portion (corresponding to the height of the non-glossy surface of the resin molded product) Was 25 μm. The maximum width of the projection (corresponding to the maximum width d of each of the plurality of regions on the glossy surface of the resin molded product) was 3.4 mm.
Using this mold insert, pellets of the above-mentioned thermoplastic resin composition were subjected to a cylinder setting temperature of 220 to 260 ° C. using a 75-ton injection molding machine (“J-75EII-P” manufactured by Nippon Steel Works, Ltd.). Molding was performed at a mold temperature of 60 ° C. to obtain a flat test piece (resin molded product) having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm and having the surface shape shown in FIG.

(Evaluation of gloss and scratch resistance)
The 20 ° gloss value (G ₀ ) of the entire surface of the obtained test piece was measured using a gloss meter (IQ-S manufactured by Rhopoint) in accordance with JIS Z8741. As G ₀ is high, excellent luster.
When G ₀ is 40 or less, no gloss, low design.
When G ₀ is 40 super 45 or less, there is a shiny, there is a design property.
When G ₀ is 45 super 55 or less, high gloss, high design property.
When G ₀ is 55 greater than gloss is very high, even higher design.

Next, 1 cc of test dust water (20% aqueous solution of eight test powders specified in JIS Z 8901) was dropped on the surface of the test piece using a pipette, and the dust water was applied to the test piece using a brush. After spreading over the entire surface and drying at 80 ° C., it was allowed to stand until it returned to room temperature, and then this test piece was set on a laboratory car wash tester (manufactured by Techno UMG).
Next, while spraying water at 4 L / min, the polyethylene car wash brush was brought into contact with the surface of the test piece for 10 seconds while rotating at 150 rpm. The above cycle (application of dust water + test with a car washer) was defined as one cycle, and a test of five cycles was performed.
The 20 ° gloss value (G ₁ ) of the test piece surface after the test was measured such that the incident light was in a direction perpendicular to the car wash scratches.

"Judgment of scratch resistance"
The determination index ΔG of the degree of conspicuousness of scratches on the test piece was calculated from the following equation (1). The smaller the absolute value of ΔG, the less noticeable the scratch. Table 1 shows the absolute values of ΔG.
ΔG = G ₁ -G ₀ (1)

When the absolute value of ΔG is 8 or less, scratches on the car wash are not conspicuous, and the design of the resin molded product is not impaired.
When the absolute value of ΔG is more than 8 and equal to or less than 12, car wash scratches are hardly conspicuous, and the design of the resin molded product is hardly impaired.
When the absolute value of ΔG is more than 12, car wash damage is conspicuous and the design of the resin molded product is impaired.

<Comparative Example 1>
The surface shape of the cavity surface has a shape (continuous glossy surface) obtained by inverting the surface shape (front view) shown in FIG. 6, and a plurality of circular recesses surrounded by the glossy surface and independent from each other in a front view, A mold insert (length 100 mm, width 100 mm) having a shape in which a plurality of concave portions are regularly arranged in two orthogonal directions was prepared. The top surface of the concave portion of the cavity surface is subjected to a textured surface treatment so that the 60 ° gloss value of the non-glossy surface of the resin molded product obtained by injection molding the thermoplastic resin composition becomes 4. The glossy surface surrounding the recess is mirror-finished (polished 8000) such that the 60 ° gloss value of the glossy surface of the resin molded product obtained by injection molding the thermoplastic resin composition becomes 89.
The diameter e of the concave portion was 500 μm, the pitch b was 0.8 mm, the pitch c was 0.8 mm, and the depth of the concave portion (corresponding to the height of the non-glossy surface of the resin molded product) was 25 μm.
Except having molded the thermoplastic resin composition using this mold insert, it is 100 mm in length, 100 mm in width, and 3 mm in thickness in the same manner as in Example 1, and is a flat plate having the surface shape shown in FIG. A test piece (resin molded product) was obtained. About the obtained test piece, gloss and scratch resistance were evaluated similarly to Example 1. Table 2 shows the results.

<Comparative Example 2>
A mold insert (mirror-finished (polished: 8000)) in which the entire surface of the cavity is flat and has a 60 ° gloss value of 89, which is a resin molded product obtained by injection-molding the above thermoplastic resin composition. (Length 100 mm, width 100 mm).
A flat-plate test having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm and a flat mirror surface was performed in the same manner as in Example 1 except that the thermoplastic resin composition was molded using this mold insert. A piece (resin molded product) was obtained. About the obtained test piece, gloss and scratch resistance were evaluated similarly to Example 1. Table 2 shows the results.

<Examples 2 to 16, Comparative Examples 3 and 4>
A test piece (resin molded product) was obtained in the same manner as in Example 1 except that the surface shape (front view) of the resin molded product was changed as shown in Tables 1 and 2. About the obtained test piece, gloss and scratch resistance were evaluated similarly to Example 1. The results are shown in Tables 1 and 2.

The test pieces of Examples 1 to 16 had sufficient gloss and excellent scratch resistance.
The test piece of Comparative Example 1 in which the glossy surface was not partitioned by the non-glossy surface protruding from the glossy surface, and the test piece of Comparative Example 2 having no non-glossy surface protruding from the glossy surface were each inferior in scratch resistance. . Comparative Example 3, in which the width of the non-glossy surface was less than 50 μm, was poor in scratch resistance. Comparative Example 4, in which the width of the non-glossy surface exceeded 500 μm, was inferior in gloss.

The resin molded product of the present invention is useful as vehicle interior / exterior parts, office equipment, home appliances, building materials, and the like, and is particularly useful as vehicle exterior parts.

1 Resin molded product 11 Glossy surface 11a Area 12 Non-glossy surface

Claims (7)

On the surface, having a glossy surface, a non-glossy surface provided to protrude from the glossy surface,
The non-glossy surface is a continuous surface that divides the glossy surface into a plurality of independent areas surrounded by the non-glossy surface,
A resin molded product, wherein a width of a non-glossy surface defining adjacent regions of the plurality of regions is 50 to 500 μm. (4) The resin molded product according to (1), wherein the height of the non-glossy surface is 10 to 100 μm with respect to the glossy surface. 3. The resin molded product according to claim 1, wherein a maximum width of each of the plurality of regions is 1 to 6 mm. 4. The resin molded product according to any one of claims 1 to 3, wherein in front view, a ratio of an area of the glossy surface to a total area of the glossy surface and the non-glossy surface is 55 to 95 area%. The resin molded product according to any one of claims 1 to 4, wherein each of the plurality of regions has a polygonal shape. The resin molded article according to any one of claims 1 to 5, wherein the non-glossy surface is continuous in a lattice. The resin molded article according to any one of claims 1 to 6, further comprising a methacrylic resin.

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