JP2021095482A - Methacrylic resin composition, molding, and vehicle member - Google Patents

Abstract

To provide a resin molding excellent in scratch resistance and a methacrylic resin composition for molding the molding.SOLUTION: The methacrylic resin composition contains an acrylic resin (A) and a polyester-modified silicone (B) having a mass average molecular weight of 11,000 or more and 20,000 or less. The resin molding comprises the methacrylic resin composition containing the acrylic resin (A) and the polyester-modified silicone (B) and has a coefficient of dynamic friction measured according to JIS K7125 of 0.28 or less.SELECTED DRAWING: None

Description

The present invention relates to a methacrylic resin composition, a resin molded product, and a vehicle member.

(Meta) Acrylic resin is a material for housing equipment such as vanities, bathtubs, flush toilets, etc.; building materials; vehicle parts such as interior and exterior materials of vehicles, etc. due to its excellent appearance, scratch resistance, and chemical resistance. , Widely used in many applications.
When the (meth) acrylic resin is used for the above purposes, the product may be scratched by contact with a person or an object, and therefore, more excellent scratch resistance is required.

As a method for solving such a problem, for example, in Patent Document 1 and Patent Document 2, an organically modified polysiloxane having a specific structure or a polysiloxane having a polysiloxane block and a polyester block (block copolymer) is blended with an acrylic resin. A methacryl-based resin composition is disclosed.

Special Table 2013-537252 Special Table 2013-504680

However, the methacrylic resin compositions disclosed in Patent Document 1 and Patent Document 2 have insufficient scratch resistance. In addition, the transparency, which is a characteristic of acrylic resin, was also insufficient.

Therefore, an object of the present invention is to provide a methacrylic resin composition having excellent scratch resistance of a resin molded product.

The problem is solved by the following invention.
The first gist of the present invention is a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B) having a mass average molecular weight of 11,000 or more and 20,000 or less.
The second gist of the present invention is a resin molded product obtained by molding the methacrylic resin composition.
The third gist of the present invention is a resin molded product made of a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B), and has a dynamic friction coefficient of 0.28 measured according to JIS K7125. It is in the resin molded body, which is as follows.
A fourth gist of the present invention is a method for producing a resin molded product obtained by injection molding or extrusion molding of a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B). Alternatively, when extrusion molding is performed, the cylinder temperature of the extruder is within the range of 230 ° C. or higher and 285 ° C. or lower, and the mold temperature is within the range of 70 ° C. or higher and 95 ° C. or lower. It is in the manufacturing method of the body.
A fifth gist of the present invention lies in a vehicle member including the resin molded body.

The methacrylic resin composition of the present invention is excellent in scratch resistance of the obtained resin molded product.
Further, the resin molded product of the present invention has excellent scratch resistance.
Further, the vehicle member of the present invention is excellent in scratch resistance.

It is a figure exemplifying ^{the 29} Si-NMR spectrum of polyester modified silicone. It is a figure which illustrated ¹ H-NMR spectrum of polyester modified silicone.

In the present specification, "(meth) acrylate" means at least one selected from "acrylate" and "methacrylic acid", and "(meth) acrylic acid" is selected from "acrylic acid" and "methacrylic acid". Means at least one species.
In the present specification, "monomer" means an unpolymerized compound, and "repeating unit" means a unit derived from the monomer formed by polymerizing the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or a part of the unit may be converted into another structure by processing a polymer.
In the present specification, "mass%" indicates the content ratio of a predetermined component contained in 100% by mass of the total amount.

<Methacrylic resin composition>
The methacrylic resin composition of the present invention is a resin composition containing an acrylic resin (A) described later and a polyester-modified silicone (B) described later.
The methacrylic resin composition of the present invention is a molded product obtained by molding the methacrylic resin composition by containing an acrylic resin (A) and a polyester-modified silicone (B) (hereinafter, appropriately "obtained resin molded product". ”) Has excellent scratch resistance. Further, the transparency of the obtained resin molded product can be maintained satisfactorily.

<Acrylic resin (A)>
The acrylic resin (A) is one of the constituents of the methacrylic resin composition of the present invention.
The acrylic resin (A) in the present invention preferably contains a repeating unit derived from methyl methacrylate (hereinafter referred to as "methyl methacrylate unit") in an amount of 70% by mass or more based on the total mass of the acrylic resin (A).
One embodiment of the acrylic resin (A) in the present invention is a copolymer of methyl methacrylate, or the content ratio of the methyl methacrylate unit in the acrylic resin (A) is 70% by mass or more and less than 100% by mass. A certain methyl methacrylate copolymer (hereinafter, also referred to as “polymer (A1)”) can be mentioned.

<Polymer (A1)>
The polymer (A1) is a homopolymer of methyl methacrylate, or a methyl methacrylate unit of 70% by mass or more and less than 100% by mass, and other methyl methacrylate units of more than 0% by mass and 30% by mass or less, which can be copolymerized with methyl methacrylate. It is a methyl methacrylate copolymer containing a repeating unit derived from a monomer (hereinafter, referred to as “another monomer unit”).

Among these polymers (A1), since the original performance of the (meth) acrylic resin is not easily impaired, the copolymer weight of the methyl methacrylate unit in the polymer (A1) is 90% by mass or more. A coalescence or a homopolymer of methyl methacrylate is preferable, and a copolymer in which the content ratio of the methyl methacrylate unit in the polymer (A1) is 95% by mass or more or a homopolymer of methyl methacrylate is more preferable.

Examples of other monomers include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl (meth) acrylate. , Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate compounds other than methyl methacrylate, such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate; (meth) acrylic acid; (meth) acrylonitrile; (meth) acrylamide, N-dimethyl (meth) acrylamide, (Meta) acrylamide compounds such as N-diethyl (meth) acrylamide and methylenebis (meth) acrylamide; Aromatic vinyl compounds such as styrene and α-methylstyrene; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether Compounds: Vinyl carboxylic acid compounds such as vinyl acetate and vinyl butyrate; olefin compounds such as ethylene, propylene, butene and isobutene can be mentioned. These other monomers may be used alone or in combination of two or more.

Among these other monomers, (meth) acrylate compounds other than methyl methacrylate are preferable because they do not impair the original performance of the acrylic resin, and methyl acrylate, ethyl acrylate, etc. n-Butyl acrylate is more preferable, and methyl acrylate and ethyl acrylate are further preferable.

When the polymer (A1) contains other monomer units, the content ratio of the other monomer units in 100% by mass of the polymer (A1) does not easily impair the original performance of the (meth) acrylic resin. Therefore, it is preferably more than 0% by mass and 20% by mass or less, more preferably more than 0% by mass and 10% by mass or less, and further preferably more than 0% by mass and 5% by mass or less.

Examples of the method for producing the polymer (A1) include a massive polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. Among these polymerization methods, the bulk polymerization method and the suspension polymerization method are preferable, and the bulk polymerization is more preferable, because the productivity is excellent.

The mass average molecular weight of the polymer (A1) is preferably 20,000 to 200,000, more preferably 50,000 to 150,000. When the mass average molecular weight of the polymer (A1) is 20,000 or more, the mechanical properties of the molded product are excellent. Further, when the mass average molecular weight of the polymer (A1) is 200,000 or less, the fluidity at the time of melt molding is excellent.
In the present specification, the mass average molecular weight is a value measured by using standard polystyrene as a standard sample and using gel permeation chromatography.

The lower limit of the content ratio of the acrylic resin (A) in the total mass (100% by mass) of the methacrylic resin composition of the present invention is that the obtained resin molded product is an acrylic resin having transparency, heat resistance, weather resistance, etc. From the viewpoint of not impairing the original performance, 55% by mass or more is preferable. 70% by mass or more is more preferable, and 90% by mass or more is further preferable. The upper limit of the content ratio of the acrylic resin (A) is preferably 99% by mass or less from the viewpoint of excellent scratch resistance of the obtained resin molded product. 98% by mass or less is more preferable, and 97% by mass or less is further preferable.
The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, the content ratio of the acrylic resin (A) in the total mass (100% by mass) of the methacrylic resin composition of the present invention is preferably 55% by mass or more and 99% by mass or less, and 70% by mass or more and 98% by mass or less. More preferably, it is 90% by mass or more and 97% by mass or less.

<Polyester modified silicone (B)>
The polyester-modified silicone (B) is one of the constituents of the methacrylic resin composition of the present invention.

The polyester-modified silicone (B) in the present invention has a mass average molecular weight of 11,000 or more and 20,000 or less as measured by gel permeation chromatography.
The lower limit of the mass average molecular weight of the polyester-modified silicone (B) is 11,000 or more from the viewpoint of excellent scratch resistance of the obtained resin molded product. 12000 or more is preferable. On the other hand, the upper limit of the mass average molecular weight is 20000 or less from the viewpoint of excellent transparency of the obtained resin molded product. 16000 or less is preferable.
As a specific method for measuring the mass average molecular weight in the present specification, the method described in Examples can be adopted.

Since the polyester-modified silicone (B) has excellent compatibility with the acrylic resin (A), the obtained resin molded product has excellent scratch resistance.

The polyester-modified silicone (B) in the present invention is one in which a part of the side chain of a linear polymer composed of a siloxane bond is modified with polyester.
As the linear polymer composed of the above-mentioned siloxane bond, a part of the side chain is a methyl group, a part of the side chain is a methyl group, a part of the side chain is a phenyl group, and a side chain. A part of the side chain is a hydrogen-binding group, and a part of the side chain is a hydrogen atom. Further, examples of the linear polymer composed of the siloxane bond include those having both ends or one end having a methyl group or a hydrogen group.

The hydrogen-bonding group described above means a functional group capable of hydrogen-bonding with another functional group, and specifically, a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, an amide group, a phosphoric acid group and the like. Can be mentioned.

Various organic groups can be introduced into the polyester-modified silicone (B), if necessary, and various functions can be imparted to the obtained resin molded product depending on the type of the organic group. Examples of the organic group include an alkyl group, an aralkyl group, a hydroxyl group, an acryloyl group, a carboxyl group, a carbonyl group, a fluoro group, an amino group, an epoxy group and a thiol group.

［式（１ａ）中、ｍは１０〜３０であり、Ｙは、メチル基又は水素基である。］

［式（３）において、Ｘは、互いに無関係に、１〜４個の炭素原子を有するアルキル基、前記一般式（１）で表されるＲ_１基、又は１２〜３６個の炭素原子を有する炭化水素基である。式（２）及び式（３）において、ｎ／ｐ＝１．１〜５．８である。］ As a specific embodiment of the polyester-modified silicone (B), a structural unit derived from polycaprolactone represented by the following general formula (1) and dimethylsiloxane represented by the following general formula (2) are contained in one molecule. A structural unit derived from polycaprolactone, which contains a structural unit derived from it and a structural unit derived from dimethylsiloxane represented by the following general formula (3) and is contained in one molecule of the polyester-modified silicone (B). Examples thereof include polyester-modified silicone having a total of 10 to 30 repetitions m and n / p = 1.1 to 5.8.
When the total number of repetitions m of the structural unit derived from polycaprolactone is within the range of 10 to 30, it is preferable from the viewpoint of excellent scratch resistance and transparency of the obtained resin molded product. m = 12-18 is more preferable, and m = 14-16 is even more preferable.
When n / p is in the range of 1.1 to 5.8, it is preferable from the viewpoint of excellent scratch resistance and transparency of the obtained resin molded product. n / p = 1.2 to 4.0 is more preferable, and n / p = 1.2 to 3.0 is even more preferable.

[In the formula (1a), m is 10 to 30, and Y is a methyl group or a hydrogen group. ]

[In the formula (3), X is independently of each other, with an alkyl group, _{R 1} group represented by the general formula (1), or 12 to 36 carbon atoms having 1 to 4 carbon atoms It is a hydrocarbon group. In the formula (2) and the formula (3), n / p = 1.1 to 5.8. ]

［式（４）中、Ｘは、互いに無関係に、１〜４個の炭素原子を有するアルキル基、下記一般式（５）で表されるＲ_１基、又は１２〜３６個の炭素原子を有する炭化水素基である。ｎ／ｐ＝１．１〜５．８である。］

［式（５）中、ｍは１０〜３０であり、Ｙは、メチル基又は水素基である。］ Alternatively, as another specific embodiment of the polyester-modified silicone (B) in the present invention, a structural unit derived from polycaprolactone, a structural unit derived from dimethylsiloxane, and a structural unit derived from dimethylsiloxane, which are represented by the following general formula (4), and , The total number of repetitions m of the structural unit derived from polycaprolactone containing the structural unit derived from dimethylsiloxane and contained in one molecule of the polyester-modified silicone (B) is 10 to 30, and n / p = Examples thereof include polyester-modified silicones of 1.1 to 5.8.
When the total number of repetitions m of the structural unit derived from polycaprolactone is within the range of 10 to 30, it is preferable from the viewpoint of excellent scratch resistance and transparency of the obtained resin molded product. m = 12-18 is more preferable, and m = 14-16 is even more preferable.
When n / p is in the range of 1.1 to 5.8, it is preferable from the viewpoint of excellent scratch resistance and transparency of the obtained resin molded product. n / p = 1.2 to 4.0 is more preferable, and n / p = 1.2 to 3.0 is even more preferable.

[In the formula (4), X has an alkyl group having 1 to 4 carbon atoms, _one R group represented by the following general formula (5), or 12 to 36 carbon atoms independently of each other. It is a hydrocarbon group. n / p = 1.1 to 5.8. ]

[In formula (5), m is 10 to 30, and Y is a methyl group or a hydrogen group. ]

In the above formula (4), _{the lower limit of the content ratio of Si atoms substituted with at least one R 1} group as X is the total mole of Si atoms from the viewpoint of excellent scratch resistance of the obtained resin composition. 2% or more is preferable with respect to the number (100%). 5% or more is more preferable, and 8% or more is further preferable. On the other hand, the upper limit of the content ratio of the Si atom is preferably 20% or less from the viewpoint that the obtained resin molded product does not impair the original performance of the acrylic resin. 17% or less is more preferable, and 14% or less is more preferable.
The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, in the above formula (4), _{the content ratio of Si atoms substituted with at least one R 1} group as X is 2% or more and 20% or less with respect to the total number of moles of Si atoms (100%). Is preferable. 5% or more and 17% or less are more preferable, and 8% or more and 14% or less are further preferable.

The existence of the above-mentioned structure of polyester-modified silicone is ¹ H-nuclear magnetic resonance spectroscopy ( ¹ H-NMR method), ¹³ C-nuclear magnetic resonance spectroscopy ( ¹³ C-NMR method), ²⁹ Si-nuclear magnetism. It can be confirmed by resonance spectroscopy ( ²⁹ Si-NMR method).
Further, as a specific measurement method, the method described in the examples can be adopted.

The compound represented by the general formula (1) is a method in which a corresponding hydrogen siloxane is reacted with an unsaturated hydrocarbon or a saturated alcohol and then a (poly) esterification reaction is continuously carried out, or an unsaturated polyester and hydrogen are used. It can be obtained by a method of directly reacting with siloxane. Such a reaction can be carried out by hydrosilylation or dehydrogenation hydrosilylation, as described in European Publication No. 1640418. The production of a polysiloxane having a polyester group is disclosed, for example, in European Patent Publication No. 0208734.

The difference between the refractive index n _A of the refractive index n _B and the acrylic resin (A) of the polyester-modified silicone (B), from the viewpoint of transparency of the resin molded article becomes good, preferably 0.05 or less, 0 It is more preferably 0.03 or less, and further preferably 0.02 or less.

As the polyester-modified silicone (B), for example, a commercially available product such as TEGOMER H-Si6444P manufactured by Evonik Industries, Inc. can be used.

The lower limit of the content of the polyester-modified silicone (B) contained in the methacrylic resin composition of the present invention is 100 parts by mass of the total mass of the acrylic resin (A) from the viewpoint of excellent scratch resistance of the obtained resin molded product. On the other hand, 0.1 part by mass or more is preferable. 0.2 parts by mass or more is more preferable. On the other hand, the upper limit of the content is such that the content of the polyester-modified silicone (B) is 100 parts by mass of the total mass of the acrylic resin (A) from the viewpoint that the obtained resin molded product does not impair the original performance of the acrylic resin. On the other hand, 10 parts by mass or less is preferable. More preferably, it is 8 parts by mass or less.
The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, the content of the polyester-modified silicone (B) contained in the methacrylic resin composition of the present invention is preferably 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total mass of the acrylic resin (A). , 0.2 parts by mass or more and 8 parts by mass or less is more preferable.

<Fatty acid amide compound (C)>

The methacrylic resin composition of the present invention can contain a fatty acid amide compound (C). By blending the fatty acid amide compound (C), the surface slipperiness of the resin molded product can be improved, and the scratch resistance of the resin molded product can be made more excellent.

Examples of the fatty acid amide compound include saturated fatty acid amide compounds, unsaturated fatty acid amide compounds, and bis fatty acid amide compounds. One of these fatty acid amide compounds may be used alone, or two or more thereof may be used in combination. Among these fatty acid amide compounds, an unsaturated fatty acid amide compound is preferable because it is excellent in scratch resistance of the molded product.

Examples of the saturated fatty acid amide compound include lauric acid amide, palmitate amide, stearic acid amide, behenic acid amide and the like. These saturated fatty acid amide compounds may be used alone or in combination of two or more. Among these unsaturated fatty acid amide compounds, at least one selected from erucic acid amide, stearic acid amide, palmitic acid amide, and behenic acid amide is preferable because it is excellent in scratch resistance of the molded product.

Examples of the unsaturated fatty acid amide include erucic acid amide, oleic acid amide, brassic acid amide, and elaidic acid amide. These unsaturated fatty acid amide compounds may be used alone or in combination of two or more. Among these unsaturated fatty acid amide compounds, erucic acid amide and oleic acid amide are preferable, and erucic acid amide is more preferable, because the molded product is excellent in scratch resistance.

Examples of the bis fatty acid amide compound include bis fatty acid amides such as methylene bisstearic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide; Be done. One of these bis fatty acid amide compounds may be used alone, or two or more thereof may be used in combination.

The lower limit of the number of carbon atoms of the fatty acid amide compound (C) is preferably 10 or more from the viewpoint of excellent compatibility with the (meth) acrylic polymer (A) and excellent scratch resistance of the obtained resin molded product. 15 or more is more preferable, and 17 or more is further preferable. On the other hand, the upper limit of the number of carbon atoms is 25 or less from the viewpoint that the dispersibility of the fatty acid amide compound (C) in the methacrylic resin composition is good and the scratch resistance of the obtained resin molded product can be well maintained. Is preferable. 24 or less is more preferable, and 23 or less is further preferable.
The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, the number of carbon atoms of the fatty acid amide compound (C) is preferably 10 to 25, more preferably 15 to 24, and more preferably 17 to 23, based on 100 parts by mass of the total mass of the (meth) acrylic polymer (A). preferable.

The lower limit of the content of the fatty acid amide compound (C) contained in the methacrylic resin composition of the present invention is 100 parts by mass of the total mass of the acrylic resin (A) from the viewpoint of excellent scratch resistance of the obtained resin molded product. On the other hand, 0.01 parts by mass or more is preferable. More preferably, it is 0.5 parts by mass or more. On the other hand, the upper limit of the content is such that the content of the fatty acid amide compound (C) is 100 parts by mass of the total mass of the acrylic resin (A) from the viewpoint that the obtained resin molded product does not impair the original performance of the acrylic resin. On the other hand, 5 parts by mass or less is preferable. 4 parts by mass is more preferable.
The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, the content of the polyester-modified silicone (B) contained in the methacrylic resin composition of the present invention is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the acrylic resin (A). , 0.5 parts by mass or more and 4 parts by mass or less is more preferable.

<Silicone oil (E)>

Silicone oil (E) can be added to the methacrylic resin composition of the present invention. By blending the silicone oil (E), the surface slipperiness of the obtained resin molded product can be improved, and the scratch resistance of the resin molded product can be made more excellent.

Examples of the silicone oil (E) include polymers having a linear structure having a bifunctional siloxane unit as a main skeleton (however, polyester-modified silicone (B) is excluded). A polymer having a molecular weight of 2000 or less is preferable for the silicone oil (E).
The silicone oil (E) may be an unmodified silicone oil or a modified silicone oil.

Examples of the unmodified silicone oil include dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone.
Examples of the modified silicone oil include organically modified silicone. Examples of the organically modified silicone include reactive organically modified silicones and non-reactive organically modified silicones.
Among these silicone oils, a silicone oil containing at least one selected from the group consisting of dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone because the obtained resin molded product tends to have excellent scratch resistance. Is preferable.

As the dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone, commercially available products can be used.

<Impact reinforcement (D)>
The impact reinforcing material (D) can be blended in the methacrylic resin composition of the present invention. By blending the impact reinforcing material (D), the impact resistance of the obtained resin molded product becomes good.

As the impact reinforcing material (D), a known impact resistance improving agent can be used. For example, the impact reinforcing material (D) disclosed in the specification of International Publication No. WO2018 / 016473 is used. can do.

<Carbon black (F)>
The methacrylic resin composition of the present invention can contain carbon black (F). By blending carbon black (F), the jet-blackness of the obtained resin molded product can be made more excellent, coupled with the feature that the methacrylic resin composition of the present invention has excellent transparency.
As the carbon black (F), for example, the compatibility with the acrylic resin (A) is improved to enhance the dispersibility of the carbon black (F) in the methacrylic resin composition, and the obtained resin molded product is obtained. From the viewpoint of exhibiting a deeper jet-blackness, carbon black coated with a surface coating agent is preferable.

The surface coating agent is not particularly limited, and is, for example, a group consisting of zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitate amide, methylene bisstearyl amide, and ethylene bisstearyl amide. One or more selected from the above is preferable. These surface coating agents may be used alone or in combination of two or more.

<Other additives>
The methacrylic resin composition of the present invention is other than the acrylic resin (A), the polyester-modified silicone (B), the fatty acid amide compound (C), the silicone oil (E), the impact reinforcing material (D), and the carbon black (F). However, other additives may be contained within the range of the blending amount that does not impair the performance of the resin molded product.

Other additives include, for example, UV absorbers, anti-aging agents, light stabilizers, plasticizers, light diffusing agents, matting agents, lubricants, mold release agents, antistatic agents, fluidity modifiers, sliding Examples thereof include sex-imparting agents and colorants such as pigments and dyes. These other additives may be used alone or in combination of two or more.

<Resin molded product>
The resin molded product of the present invention is a molded product (1) obtained by molding the methacrylic resin composition of the present invention.
Alternatively, a specific embodiment of the resin molded product of the present invention is a resin molded product made of a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B), and is a JIS K7125. The resin molded product (2) having a dynamic friction coefficient of 0.28 or less measured according to the above can be mentioned.
In the resin molded product (2), the above-mentioned methacrylic resin composition of the present invention can be used as the "methacrylic resin composition containing the acrylic resin (A) and the polyester-modified silicone (B)".

Further, if the upper limit of the dynamic friction coefficient of the resin molded product is 0.28 or less, the resin molded product can be used as a material for housing equipment such as a vanity, a bathtub, and a flush toilet; a building material; an interior / exterior material of a vehicle, etc. It is suitable because the product is not damaged by contact with people or objects when it is used for vehicle members and the like. More preferably, it is 0.25 or less. The lower limit of the kinetic (static) rubbing coefficient is not particularly limited, and the smaller the lower limit, the better the scratch resistance of the obtained resin molded product.
As a specific method for measuring the dynamic friction coefficient of the resin molded product in the present specification, the method described in the examples can be adopted.

Further, the resin molded product (2) of the present invention can have a haze value of 50% or less. If the haze value of the resin molded product is 50% or less, the resin molded product is particularly required to be transparent in applications such as the above-mentioned materials for housing equipment; building materials; vehicle interior / exterior materials and the like. It is suitable for the application to be used. As a method of controlling the haze value, for example, the difference between the refractive index n _B of the refractive index n _A of the acrylic resin (A) a polyester-modified silicone (B) so that 0.05 or less, an acrylic resin ( Examples thereof include a method of controlling the type or blending amount of A) and the polyester-modified silicone (B).
As a specific method for measuring the haze value of the resin molded product in the present specification, the method described in the examples can be adopted.

A resin molded product (2) comprising a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B) of the present invention, and having a dynamic friction coefficient of 0.28 or less measured according to JIS K7125. Is a resin molded product obtained for the first time by the production method of the present invention described later. Such a resin molded product can further have a haze value of 50% or less.

In the resin molded product (2) of the present invention, the mass average molecular weight of the polyester-modified silicone (B) measured by gel permeation chromatography is 11,000 or more for the reason described in the description of the methacrylic resin composition of the present invention. It is preferably 20000 or less.

<Manufacturing method of resin molded product>
Examples of the molding method for obtaining the resin molded product of the present invention include injection molding, extrusion molding, pressure molding and the like. Further, the obtained resin molded product may be further subjected to secondary molding such as compressed air molding or vacuum forming. Molding conditions such as molding temperature and molding pressure may be appropriately set.

A resin molded product (2) comprising a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B) of the present invention, and having a dynamic friction coefficient of 0.28 or less measured according to JIS K7125. Is a resin molded product obtained for the first time by the production method of the present invention.

The resin molded product (2) of the present invention sets the cylinder temperature of the extruder at 230 ° C. or higher when injection molding or extrusion molding of a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B). It can be obtained by melt-kneading within the range of 285 ° C. or lower and setting the mold temperature within the range of 70 ° C. or higher and 95 ° C. or lower.

The lower limit of the cylinder temperature of the extruder is 230 ° C. or higher from the viewpoint of improving the scratch resistance of the obtained resin molded product. 250 ° C. or higher is preferable. On the other hand, the upper limit of the cylinder temperature is 280 ° C. or lower from the viewpoint of maintaining good scratch resistance and transparency of the obtained resin molded product. It is preferably 270 ° C. or lower.

The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, when a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B) is injection-molded or extruded, the cylinder temperature of the extruder is 230 ° C. or higher and 285 ° C. or lower, and 250 ° C. or higher. It is preferably 270 ° C. or lower.

Further, the lower limit of the mold temperature is 70 ° C. or higher from the viewpoint of improving the scratch resistance of the obtained resin molded product. 80 ° C. or higher is preferable. On the other hand, the upper limit of the cylinder temperature is 95 ° C. or lower from the viewpoint of maintaining good scratch resistance and transparency of the obtained resin molded product. It is preferably 92 ° C. or lower.

The above preferred upper limit and preferred lower limit can be arbitrarily combined. For example, when a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B) is injection-molded or extruded, the mold temperature is 70 ° C. or higher and 95 ° C. or lower, and 80 ° C. or higher and 92 or lower. Is preferable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

<Scratch resistance test>
As an index of scratch resistance of the methacrylic resin composition, the difference in color tone (ΔL *) before and after the scratch resistance test was evaluated according to the following method.
The methacrylic resin composition obtained in Examples and Comparative Examples was supplied to an injection molding machine (model name "FAS-T100D", manufactured by FANUC Co., Ltd.), the molding temperature was set to 250 ° C., and the molded product (width 140 mm). , Length 140 mm, thickness 3 mm) was obtained.
The obtained resin molded body is installed on a flat table, and a friction element is used using a Gakushin type friction tester (dyeing friction fastness tester, model name "RT-200", manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). As a result, a scratch resistance test was conducted by using a stack of five Kanekura gauze (trade name, manufactured by Care Life Medical Supply Co., Ltd.) and reciprocating 200 mm at a distance of 100 mm under the condition of a load of 500 g. For the molded body before and after the scratch resistance test, a colorimeter (model name "Color Computer SM-T", manufactured by Suga Test Instruments Co., Ltd.) is used to emit light rays in a direction parallel to the direction in which the friction element is reciprocated. ΔE * ab (color difference in the L * a * b * color system) was measured under the condition that the incident light beam was incident and the incident light beam had a diameter of 15 mm.

<Total light transmittance, haze>
As an index of the transparency of the methacrylic resin composition, a haze meter (model name: NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the total light transmittance of the molded product (A) in accordance with ISO13468. .. In addition, the haze of the molded product (A) was measured according to ISO14782.

<Dynamic friction coefficient / static friction coefficient>
As an index of scratch resistance of the methacrylic resin composition, the coefficient of dynamic friction and the coefficient of static friction were evaluated according to the following methods.
Using a scratch tester (model name "KK01", manufactured by Kato Tech Co., Ltd.), a spherical indenter with a diameter of 1 mm is pressed against the surface of the test piece A in accordance with JIS K7316 to apply the horizontal load of the indenter. While keeping the constant (5.0 N), the moving speed of the indenter was 100 mm / sec, the moving distance of the indenter was 70 mm, and the vertical load (unit: N) when the test piece A was moved on the surface was measured. ..
The coefficient of dynamic friction was defined as the value obtained by dividing the horizontal load (5.0 N) by the average value of the vertical load measured in the section of 10 to 60 mm starting from the starting point of the moving distance (70 mm). Further, with respect to the value obtained by dividing the horizontal load (5.0 N) by the vertical load, the maximum value of the value measured immediately after the start of movement of the indenter was taken as the static friction coefficient.
Using the test piece A3 point, measurement was performed once for each test piece, the coefficient of dynamic friction and the coefficient of static friction were calculated, and the average value was used as the final coefficient of dynamic friction and the coefficient of static friction.

<Mass average molecular weight (Mw) of polyester-modified silicone>
The mass average molecular weight (Mw) of the polyester-modified silicone was measured by gel permeation chromatography (GPC) according to the following method.
First, 20 mg of polyester-modified silicone was dissolved in 10 ml of tetrahydrofuran (THF), and the mixture was allowed to stand overnight while being heated at 40 ° C. Then, as an internal standard, W400 (trade name, manufactured by Tokyo Chemical Industry Co., Ltd., 2-2'-methylenebis (4-methyl-6-t-butylphenol)) was added thereto, and the mixture was filtered through a 0.2 μm filter. The obtained solution was used as a sample for GPC measurement.
In GPC measurement, two separation columns (manufactured by Tosoh Co., Ltd., trade name: SUPER HM-H) are used in series on a high performance liquid chromatography measuring device (manufactured by Tosoh Corporation, model name: HLC-8320 type). did. A differential refractometer was used as the detector. The measurement was performed under the conditions of the separation column temperature: 40 ° C., the moving layer: THF, the flow rate of the moving layer: 0.6 ml / min, and the sample injection amount: 10 μl. Using several types of polystyrenes with known molecular weights (Mw: 340 to 1,950,000) as standard polymers, the molecular weight equivalent to the standard polymer was determined, and this was used as the mass average molecular weight of the polyester-modified silicone.

<Structure of polyester-modified silicone>
NMR apparatus (JEOL Ltd., device name: JNM-ECZ-500R) with ^using the nuclide of the ¹ H and ²⁹ Si, the composition of the polyester-modified silicone was measured by the following procedure.
First, the polyester-modified silicone was dissolved in deuterated chloroform for NMR measurement so that the solid content concentration was 5.0% by mass, and this was used as a sample for NMR measurement. Next, ¹ H-NMR was subjected to NMR measurement under the condition of 1024 times of integration and a measurement temperature of 25 ° C., and ²⁹ Si-NMR was performed under the condition of 2000 times of integration and a measurement temperature of 25 ° C.

From the obtained ²⁹ Si-NMR measurement results, for example, as shown in FIG. 1, the main peak on the high magnetic field side is the dimethylsiloxane unit in the polyester-modified silicone (B) of the general formula (6) in FIG. _{The area (I b} ) of the singlet peak derived from the Si atom (Si _{b ) contained in the above, and the Si atom (Si a} ) at both ends of the polyester-modified silicone (B) observed on the magnetic field side 30 ppm lower than _{I b.} The area of the singlet peak derived from (I _a ) and the total area (I) of the peak derived from the Si atom contained in the polyester-modified silicone (B) were measured.
Further, from the ¹ H-NMR measurement result, for example, as shown in FIG. 2, when the proton peak of the heavy chloroform solvent is 7.26 ppm, the polyester-modified silicone (B) represented by the general formula (8) in FIG. _{), The integrated value (I 1} ) of the singlet peak derived from the _{hydrogen atom (H f1} ) contained in the polyester-modified caprolactone terminal structure near 3.4 ppm, and the hydrogen contained in the polycaprolactone repeating structure near 4.0 ppm. The integrated value (I ₂ ) of the peak derived from the atom (H _{f2) was measured.}

Using the following formulas (I) and (II), the value of n / p in the formulas (2) and (3), the value of n / p in the formula (4), the formulas (1) and the formula (1) The value of m in 5) was calculated.
m = I ₁ / I ₂ ... (I)
n / p = I _b / (I-I _a- I _b ) ... (II)

(raw materials)
Acrylic resin (A-1): Acrypet VH (trade name, manufactured by Mitsubishi Chemical Corporation, acrylic resin containing 98% by mass of methyl methacrylate unit)
Silicone resin (B-1): TEGOMER H-Si6444P (trade name, manufactured by Ebonic, polyester-modified silicone resin having a mass average molecular weight of 13,000, m = 15 ± 1 in the above formula (1) or formula (5). Within the range of the above equations (2) and (3), or in the above equation (4), within the range of n / p = 1.6 ± 0.3)
Silicone resin (B'-1): TEGOMER H-Si6441P (trade name, manufactured by Ebonic, polyester-modified silicone resin having a mass average molecular weight of 10,000, m = 20 ± in the above formula (1) or formula (5). Within the range of 1. In the above equations (2) and (3), or in the above equation (4), within the range of n / p = 5.3 ± 0.3)
Fatty acid amide (C-1): Erucic acid amide (trade name: Diamid L-200, manufactured by Mitsubishi Chemical Corporation)

[Example 1]
A twin-screw extruder (model name "PCM45", manufactured by Ikegai Co., Ltd.) containing 100 parts by mass of acrylic resin (A-1), 3 parts by mass of silicone resin (B-1) and 1 part by mass of fatty acid amide (C-1). A pellet-shaped methacrylic resin composition was obtained by melt-kneading at a cylinder temperature of 250 ° C. of an extruder and setting a mold temperature of 80 ° C. at the time of injection molding.
The evaluation results of the obtained methacrylic resin composition are shown in Table 1.

[Comparative Examples 1-2]
An operation was carried out in the same manner as in Example 1 except that the formulations shown in Table 1 were used to obtain a pellet-shaped methacrylic resin composition.
The evaluation results of the obtained methacrylic resin composition are shown in Table 1.

Since the methacrylic resin composition obtained in Example 1 contains the polyester-modified silicone (B) as the polyester-modified silicone, the resin molded product has excellent scratch resistance. The transparency was also good.

The methacrylic resin composition obtained in Comparative Example 1 was inferior in scratch resistance of the resin molded product because the molecular weight of the polyester-modified silicone exceeded 2900. In addition, the transparency was insufficient.

Since the methacrylic resin composition obtained in Comparative Example 2 did not contain the polyester-modified silicone, the scratch resistance of the resin molded product was significantly inferior.

Since the resin molded body obtained by molding the methacrylic resin composition of the present invention has excellent scratch resistance, for example, materials for housing equipment such as vanities, bathtubs, flush toilets; building materials; interior and exterior of vehicles. It is used for vehicle members such as materials, and is particularly suitable for vehicle members.
Examples of vehicle exterior materials include meter covers, door mirror housings, pillar covers (sash covers), licensed garnishes, front grilles, fog garnishes, emblems and the like.

Claims (19)

A methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B).
A methacrylic resin composition having a mass average molecular weight of the polyester-modified silicone (B) measured by gel permeation chromatography of 11,000 or more and 20,000 or less. The methacrylic resin composition according to claim 1, wherein the polyester-modified silicone (B) has a mass average molecular weight of 12,000 or more and 16,000 or less as measured by gel permeation chromatography. The polyester-modified silicone (B) contains, in one molecule, a structural unit derived from polycaprolactone represented by the following general formula (1), a structural unit derived from dimethylsiloxane represented by the following general formula (2), and The methacrylic resin composition according to claim 1 or 2, which contains a structural unit derived from dimethylsiloxane represented by the following general formula (3).

[In the formula (1), m is 10 to 30, and Y is a methyl group or a hydrogen group. ]

[In the formula (3), X is independently of each other, with an alkyl group, _{R 1} group represented by the general formula (1), or 12 to 36 carbon atoms having 1 to 4 carbon atoms It is a hydrocarbon group. In the formula (2) and the formula (3), n / p = 1.1 to 5.8. ] The methacrylic resin composition according to any one of claims 1 to 3, wherein the polyester-modified silicone (B) is represented by the following general formula (4).

[In the formula (4), X has an alkyl group having 1 to 4 carbon atoms, _one R group represented by the following general formula (5), or 12 to 36 carbon atoms independently of each other. It is a hydrocarbon group. n / p = 1.1 to 5.8. ]

[In formula (5), m is 10 to 30, and Y is a methyl group or a hydrogen group. ] Wherein is an acrylic resin difference between the refractive index n _B of the refractive index n _A polyester-modified silicone (B) of (A) is 0.05 or less, methacrylic according to any one of claims 1-4 Resin composition. Any one of claims 1 to 5, wherein the content of the polyester-modified silicone (B) is 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total mass of the acrylic resin (A). The methacrylic resin composition according to the section. The methacrylic resin composition according to any one of claims 1 to 6, further comprising a fatty acid amide compound (C). The methacrylic resin composition according to claim 7, wherein the fatty acid amide compound (C) is at least one selected from erucic acid amide, stearic acid amide, palmitic acid amide, and bechenic acid amide. The methacrylic resin composition according to any one of claims 1 to 8, further comprising the silicone oil (E). The methacrylic resin composition according to claim 9, wherein the silicone oil (E) contains at least one selected from the group consisting of dimethyl silicone, methyl phenyl silicone and methyl hydrogen silicone. The methacrylic resin composition according to any one of claims 1 to 10, further comprising an impact reinforcing material (D). The methacrylic resin composition according to any one of claims 1 to 11, further comprising carbon black (F). A resin molded product obtained by molding the methacrylic resin composition according to any one of claims 1 to 12. A resin molded product made of a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B).
A resin molded product having a dynamic friction coefficient of 0.28 or less measured according to JIS K7125. The resin molded product according to claim 14, wherein the haze value is 50% or less. The resin molded article according to claim 14 or 15, wherein the polyester-modified silicone (B) has a mass average molecular weight of 11,000 or more and 20,000 or less as measured by gel permeation chromatography. A method for producing a resin molded product obtained by injection molding or extrusion molding of a methacrylic resin composition containing an acrylic resin (A) and a polyester-modified silicone (B).
A method for producing a resin molded product, wherein the cylinder temperature of the extruder during injection molding or extrusion molding is within the range of 230 ° C. or higher and 285 ° C. or lower, and the mold temperature is within the range of 70 ° C. or higher and 95 ° C. or lower. The method for producing a resin molded product according to claim 17, wherein the cylinder temperature of the extruder is in the range of 250 ° C. or higher and 270 ° C. or lower. A vehicle member including the resin molded product according to any one of claims 13 to 16.

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