Resin molded body and method for manufacturing the same
The methacrylic resin composition, enhanced with a fatty acid compound and optimized production conditions, addresses the issue of insufficient scratch resistance, resulting in a resin molded article with superior scratch resistance and transparency for various applications.
Patent Information
- Application Number
- JP2020571000
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2020-11-05
- Filing Date
- 2020-12-11
- Publication Date
- 2025-09-17
- Estimated Expiration
- 2040-12-11
AI Technical Summary
Methacrylic resin compositions in existing technologies have insufficient scratch resistance, which is a concern for applications where they come into contact with people or objects.
A methacrylic resin composition containing a (meth)acrylic polymer and a fatty acid compound, optimized with specific surface characteristics and production conditions, including a peak absorbance ratio P1/P2 of 0.0040 or more, a dynamic friction coefficient of 0.12 or less, and a water contact angle of 69.0 degrees or more, along with the use of saturated fatty acid amides like stearic acid amide and palmitic acid amide.
The resulting resin molded article exhibits excellent scratch resistance, maintaining transparency and weather resistance while being suitable for applications such as mobile phone components, bathroom fixtures, and vehicle parts.
Smart Images

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Abstract
Description
[Technical Field]
[0001] The present invention relates to a resin molded article and a method for manufacturing a resin molded article. This application claims priority based on Japanese Patent Application No. 2019-224164 filed in Japan on December 12, 2019, Japanese Patent Application No. 2020-044909 filed in Japan on March 16, 2020, Japanese Patent Application No. 2020-182982 filed in Japan on October 30, 2020, and Japanese Patent Application No. 2020-185151 filed in Japan on November 5, 2020, the contents of which are incorporated herein by reference. [Background technology]
[0002] Due to their excellent appearance, scratch resistance, and chemical resistance, methacrylic resins are widely used in many applications, including materials for residential facilities such as bathroom vanities, bathtubs, and flush toilets; building materials; and vehicle components such as interior and exterior materials for vehicles. When methacrylic resin products are used for the above-mentioned purposes, the products may be scratched by contact with people or objects. Therefore, there is a demand for resin molded articles made of methacrylic resin compositions that have better scratch resistance.
[0003] As a method for solving such problems, for example, Patent Document 1 discloses an acrylic resin composition containing a fatty acid amide. Patent Document 2 discloses an acrylic resin composition containing a fatty acid amide and an impact modifier. Patent Document 3 discloses an acrylic resin composition for vehicle exterior parts, which contains a fatty acid amide compound. [Prior art documents] [Patent documents]
[0004] [Patent Document 1] International Publication No. 2018-142164 [Patent Document 2] Japanese Patent Application Publication No. 2018-134801 [Patent Document 3] Japanese Patent Application Publication No. 2018-134854 Summary of the Invention [Problem to be solved by the invention]
[0005] However, the methacrylic resin compositions disclosed in Patent Documents 1 to 3 have insufficient scratch resistance.
[0006] An object of the present invention is to provide a resin molded article containing a methacrylic resin composition and having excellent scratch resistance. [Means for solving the problem]
[0007] The present invention has the following aspects. [1] A resin molded product containing a methacrylic resin composition, The methacrylic resin composition contains a (meth)acrylic polymer (A) and a fatty acid compound (B), On the surface of the resin molded body, a wave number of 1630 to 1650 cm was measured by a single reflection ATR surface reflection method using an infrared spectrophotometer. -1 The peak absorbance P1 in the range of 1710-1730 cm -1 The absorbance ratio P1 / P2 of the peak absorbance P2 in the range of 0.0040 or more. [2] The resin molded article according to [1], wherein the fatty acid compound (B) is represented by the following general formula (i): R-CONH2(i) (In the formula, R is a hydrocarbon group having 10 to 25 carbon atoms which may have a substituent.) [3] The resin molded product according to [1] or [2], wherein the coefficient of dynamic friction of the surface of the resin molded product is 0.12 or less. [4] The resin molded product according to any one of [1] to [3], wherein the surface of the resin molded product has a water contact angle of 69.0 degrees or more. [5] The resin molded article according to any one of [1] to [4], wherein the fatty acid compound (B) has a 10% weight loss temperature of 308° C. or lower. [6] The resin molded product according to any one of [1] to [5], wherein the fatty acid compound (B) has a melting point of 90° C. or higher. [7] The resin molded product according to any one of [1] to [6], wherein the fatty acid compound (B) is a fatty acid amide compound (B1). [8] The resin molded article according to [7], wherein the fatty acid amide compound (B1) is a saturated fatty acid amide compound. [9] The resin molded body according to [8], wherein the saturated fatty acid amide compound contains stearic acid amide and palmitic acid amide as main components.
[10] The resin molded product according to any one of [1] to [9], wherein the content of the fatty acid compound (B) is 0.01% by mass or more and 10% by mass or less, relative to 100% by mass of the total mass of the methacrylic resin composition.
[11] The compatibility parameter of the fatty acid compound (B) is 11.0 (cal / cm 3 ) 1 / 2 A resin molded product according to any one of [1] to
[10] below.
[12] The resin molded product according to any one of [1] to
[11] , wherein the content of repeating units derived from methyl methacrylate in the (meth)acrylic polymer (A) is 70% by mass or more.
[13] The resin molded product according to any one of [1] to
[12] , wherein the methacrylic resin composition does not contain a compound containing a fluorine atom.
[14] A resin molded product according to any one of [1] to
[13] , which is used as a raw material for a vehicle component or a mobile phone component.
[15] The resin molded article according to
[14] , which is used as a vehicle component, and the vehicle component is at least one selected from a tail lamp cover, a head lamp cover, and a meter panel.
[16] The resin molded article according to
[14] , which is used as a mobile phone component, the mobile phone component being a back panel of the mobile phone.
[17] A method for producing a resin molded product obtained by injection molding a methacrylic resin composition containing a (meth)acrylic polymer (A) and a fatty acid compound (B), comprising: The method for producing a resin molded article includes injecting the (meth)methacrylic resin composition into a mold from an injection molding machine having a cylinder temperature of 248°C or higher and 300°C or lower in the injection molding.
[18] The method for producing a resin molded article according to
[17] , wherein the cylinder temperature of the injection molding machine is 248°C or higher and 295°C or lower.
[19] The method for producing a resin molded article according to
[17] , wherein the cylinder temperature of the injection molding machine is 265°C or higher and 290°C or lower.
[20] The method for producing a resin molded article according to any one of
[17] to
[19] , wherein the resin is injected into the mold whose mold temperature has been preset to 35°C or higher and 90°C or lower.
[21] The method for producing a resin molded article according to any one of
[17] to
[19] , wherein the resin is injected into the mold whose mold temperature has been preset to 36°C or higher and 70°C or lower.
[22] The method for producing a resin molded article according to any one of
[17] to
[19] , wherein the resin is injected into the mold whose mold temperature has been preset to 37°C or higher and 50°C or lower.
[23] In the injection molding, the injection speed is 30 cm 3 The method for producing a resin molded article according to any one of
[17] to
[22] , wherein the resin molding speed is 1 / second or less.
[24] In the injection molding, the injection speed is 12 cm 3 The method for producing a resin molded article according to any one of
[17] to
[22] , wherein the resin molding speed is 1 / second or less.
[25] In the injection molding, the injection speed is 8 cm 3 The method for producing a resin molded article according to any one of
[17] to
[22] , wherein the resin molding speed is 1 / second or less.
[26] In the injection molding, the injection speed is 5 cm 3 The method for producing a resin molded article according to any one of
[17] to
[22] , wherein the resin molding speed is 1 / second or less.
[27] The method for producing a resin molded article according to any one of
[17] to
[26] , wherein the fatty acid compound (B) has a 10% weight loss temperature of 308°C or lower.
[28] The method for producing a resin molded product according to any one of
[17] to
[27] , wherein the fatty acid compound (B) has a melting point of 90°C or higher.
[29] On the surface of a resin molded product, measured by single-reflection ATR surface reflection method using an infrared spectrophotometer, wavenumber 1630-1650 cm -1 The peak absorbance P1 in the range of 1710-1730 cm -1The method for producing a resin molded product according to any one of
[17] to
[28] , wherein the resin molded product is produced so that the absorbance ratio P1 / P2 to the peak absorbance P2 in the range of 1 / P1 is 0.0040 or more. [Effects of the Invention]
[0008] The resin molded article of the present invention has excellent scratch resistance. The methacrylic resin composition of the present invention provides a resin molded article obtained by molding the methacrylic resin composition of the present invention with excellent scratch resistance. Since the resin molded product of the present invention has excellent scratch resistance, it can be suitably used, for example, as a mobile phone component such as the back panel of a mobile phone; a material for housing facilities such as a washbasin, a bathtub, and a flush toilet; a building material; a vehicle component such as a vehicle interior / exterior material such as a tail lamp cover, a head lamp cover, and a meter panel; or as a raw material for these components. [Brief explanation of the drawings]
[0009] [Figure 1] FIG. 2 is a schematic diagram illustrating an outline of a scratch resistance test used to evaluate the resin molded article of the present invention. [Figure 2] 1 shows an infrared absorption spectrum at wave numbers of 1600 to 1680 cm −1 , measured for the surface of a resin molded product (molded product (A)) using a Fourier transform infrared spectrophotometer. [Figure 3] 1 shows an infrared absorption spectrum at a wave number of 1620 to 1800 cm −1 , measured for the surface of a resin molded product (molded product (A)) using a Fourier transform infrared spectrophotometer. DETAILED DESCRIPTION OF THE INVENTION
[0010] In this specification, "(meth)acrylate" means at least one selected from "acrylate" and "methacrylate", and "(meth)acrylic acid" means at least one selected from "acrylic acid" and "methacrylic acid". As used herein, the term "monomer" refers to an unpolymerized compound, and the term "repeating unit" refers to a unit derived from a monomer formed by polymerization of the monomer. The repeating unit may be a unit formed directly by a polymerization reaction, or may be a unit obtained by converting a portion of the unit into a different structure by treating the polymer. In this specification, "% by mass" indicates the content of a given component in a total amount of 100% by mass. In this specification, the term "resin molded article obtained" means a molded article obtained by molding the methacrylic resin composition of the present invention.
[0011] <Resin molded body> The resin molded article of the present invention is a resin molded article obtained by molding a methacrylic resin composition described below. The resin molded article of the present invention has a surface that exhibits a wavelength of 1630 to 1650 cm as measured by a single reflection ATR surface reflectance method using an infrared spectrophotometer. -1 The peak absorbance P1 in the range of 1710-1730 cm -1 The absorbance ratio P1 / P2 to the peak absorbance P2 in the range is 0.0040 or more. This provides the obtained resin molded article with extremely excellent scratch resistance. In the present invention, the peak absorbance refers to the absorbance at the peak top of a peak that includes a corresponding wavenumber.
[0012] The absorbance ratio P1 / P2 is an index representing the content of the fatty acid compound (B) on the surface of the resin molded body and in the vicinity of the surface. A larger P1 / P2 indicates a higher content of the fatty acid compound (B) on the surface of the resin molded body and in the vicinity of the surface.
[0013] When the lower limit of P1 / P2 is 0.0040 or more, the fatty acid compound (B) is present at a high content on the surface and near the surface of the resin molded article, resulting in a sufficiently low coefficient of friction on the surface of the resin molded article and excellent scratch resistance of the resin molded article. Furthermore, the scratch resistance of the resulting resin molded article can be improved without increasing the content of the fatty acid compound (B), so the inherent performance of the (meth)acrylic resin, including transparency, heat resistance, and weather resistance, is less likely to be impaired. P1 / P2 is preferably 0.0045 or more, more preferably 0.0060 or more. On the other hand, the upper limit of P1 / P2 is not particularly limited, but is preferably 0.02 or less. When P1 / P2 is 0.02 or less, the content of the fatty acid compound (B) on the surface and near the surface of the resin molded article is not too high, so the mechanical strength of the resin molded article is less likely to decrease, and the scratch resistance of the resin molded article can be sufficiently improved. The upper and lower limits of P1 / P2 can be arbitrarily combined. For example, the ratio is preferably 0.0040 or more and 0.02 or less, more preferably 0.0045 or more and 0.02 or less, and even more preferably 0.0060 or more and 0.02 or less. As a specific method for measuring P1 / P2 in this specification, the method described in the Examples can be adopted.
[0014] The value of P1 / P2 can be controlled by adjusting the conditions of the cylinder temperature, mold temperature, and injection speed of the injection molding machine during injection molding in the method for producing a resin molded article of the present invention, which will be described later. Specific methods will be described later.
[0015] The resin molded article of the present invention preferably has a surface with a dynamic friction coefficient of 0.12 or less. The dynamic friction coefficient of the surface of a resin molded body is an index representing the content of the fatty acid compound (B) on the surface of the resin molded body and in the vicinity of the surface. A smaller value of the dynamic friction coefficient indicates a higher content of the fatty acid compound (B) on the surface of the resin molded body and in the vicinity of the surface. If the upper limit of the dynamic friction coefficient is 0.12 or less, the resulting resin molded article will have excellent scratch resistance, and 0.10 or less is more preferable. There is no particular restriction on the lower limit of the dynamic friction coefficient, and the smaller the coefficient, the better the scratch resistance of the resulting resin molded article. As a specific method for measuring the dynamic friction coefficient of the resin molded article in this specification, the method described in the Examples can be adopted. The value of the dynamic friction coefficient can be controlled by adjusting the conditions of the cylinder temperature, mold temperature, and injection speed of the injection molding machine during injection molding in the method for producing a resin molded article of the present invention described below. Specific methods will be described later.
[0016] The resin molded article of the present invention preferably has a surface with a water contact angle of 69.0 degrees or more. The water contact angle on the surface of a resin molded body is an index representing the content of the fatty acid compound (B) on the surface of the resin molded body and in the vicinity of the surface. A larger water contact angle indicates a higher content of the fatty acid compound (B) on the surface of the resin molded body and in the vicinity of the surface. If the lower limit of the water contact angle is 69.0 degrees or more, the fatty acid compound (B) is present at a high content on the surface of the resin molded article and in the vicinity of the surface, and therefore the resulting resin molded article has excellent scratch resistance. A water contact angle of 72 degrees or more is more preferable, and 75 degrees or more is even more preferable. There is no particular upper limit for the water contact angle, and the larger the angle, the better the scratch resistance of the resulting resin molded article. As a specific method for measuring the water contact angle of the resin molded article in this specification, the method described in the Examples can be adopted. The water contact angle can be controlled by adjusting the conditions of the cylinder temperature, mold temperature, and injection speed of the injection molding machine during injection molding in the method for producing a resin molded article of the present invention, which will be described later. Specific methods will be described later.
[0017] In the resin molded article of the present invention, the methacrylic resin composition preferably does not contain a compound containing a fluorine atom. When the methacrylic resin composition does not contain a compound containing a fluorine atom, it is possible to avoid the fluorine atoms or hydrogen fluoride generated by thermal decomposition of the compound containing a fluorine atom when the cylinder temperature is raised during injection molding from causing discoloration or deterioration of the resulting resin molded product. Since the methacrylic resin composition does not contain a compound containing a fluorine atom, it is possible to suppress discoloration or deterioration of the resulting resin molded product. It is also preferable that the resin molded article of the present invention does not contain any compound containing a fluorine atom. Examples of the fluorine atom-containing compound include conventionally known olefin polymers containing fluorine atoms, such as a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer containing a repeating unit derived from a vinylidene fluoride monomer and a repeating unit derived from a monomer copolymerizable with vinylidene fluoride.
[0018] <Methacrylic resin composition> The methacrylic resin composition is a material for constituting the resin molded article of the present invention, and contains a (meth)acrylic polymer (A) described below and a fatty acid compound (B) described below.
[0019] Since the methacrylic resin composition contains the fatty acid compound (B), the resulting resin molded article has excellent scratch resistance. The methacrylic resin composition contains the (meth)acrylic polymer (A) and the fatty acid compound (B), and therefore the resin molded article of the present invention containing the methacrylic resin composition has excellent scratch resistance, and the transparency of the obtained resin molded article can be well maintained.
[0020] <(Meth)acrylic polymer (A)> The (meth)acrylic polymer (A) is one of the components of the methacrylic resin composition that constitutes the resin molded article of the present invention. By containing the (meth)acrylic polymer (A), the methacrylic resin composition can improve the transparency of the resulting resin molded article, suppress thermal decomposition of the resin molded article, and improve weather resistance and moldability.
[0021] The (meth)acrylic polymer (A) more preferably contains 70% by mass or more of repeating units derived from methyl methacrylate (hereinafter referred to as "methyl methacrylate units") relative to 100% by mass of the total mass of the (meth)acrylic polymer (A). Examples of the (meth)acrylic polymer (A) in the present invention include a homopolymer of methyl methacrylate and a methyl methacrylate copolymer in which the content of methyl methacrylate units in the (meth)acrylic polymer (A) is 70% by mass or more and less than 100% by mass (hereinafter, these are also collectively referred to as "polymer (A1)").
[0022] <Polymer (A1)> The polymer (A1) is a homopolymer of methyl methacrylate or a methyl methacrylate copolymer containing 70% by mass or more and less than 100% by mass of methyl methacrylate units and more than 0% by mass and 30% by mass or less of repeating units derived from other monomers copolymerizable with methyl methacrylate (hereinafter referred to as "other monomer units").
[0023] Among the polymers (A1), copolymers containing methyl methacrylate units in the polymer (A1) of 90% by mass or more but less than 100% by mass, or homopolymers of methyl methacrylate, are preferred, as they are less likely to impair the inherent performance of the (meth)acrylic resin, and copolymers containing methyl methacrylate units in the polymer (A1) of 95% by mass or more but less than 100% by mass, or homopolymers of methyl methacrylate, are more preferred.
[0024] Examples of other monomers include methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (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, and dicyclopentanyl Examples of the other monomers include (meth)acrylate compounds other than methyl methacrylate, such as (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; (meth)acrylic acid; (meth)acrylonitrile; (meth)acrylamide compounds such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and methylene bis(meth)acrylamide; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl ether compounds such as vinyl methyl ether, vinyl ethyl ether, and 2-hydroxyethyl vinyl ether; vinyl carboxylate compounds such as vinyl acetate and vinyl butyrate; and olefin compounds such as ethylene, propylene, butene, and isobutene. These other monomers may be used alone or in combination of two or more.
[0025] Among these other monomers, (meth)acrylate compounds other than methyl methacrylate are preferred because they do not impair the inherent performance of the acrylic resin, and methyl acrylate, ethyl acrylate, and n-butyl acrylate are more preferred because they provide excellent thermal decomposition resistance to the molded article, with methyl acrylate and ethyl acrylate being even more preferred.
[0026] When the polymer (A1) contains other monomer units, the content of the other monomer units in 100% by mass of the polymer (A1) is preferably more than 0% by mass and not more than 20% by mass, more preferably more than 0% by mass and not more than 10% by mass, and even more preferably more than 0% by mass and not more than 5% by mass, since this is unlikely to impair the inherent performance of the (meth)acrylic resin.
[0027] Examples of methods for producing the (meth)acrylic polymer (A) include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these polymerization methods, from the viewpoint of excellent productivity, the (meth)acrylic polymer (A) is preferably produced by bulk polymerization or suspension polymerization, and more preferably by bulk polymerization.
[0028] The mass average molecular weight of the (meth)acrylic polymer (A) is preferably from 20,000 to 200,000, more preferably from 50,000 to 150,000. When the mass average molecular weight of the (meth)acrylic polymer (A) is at least the lower limit, the mechanical properties of the resulting resin molded article tend to be excellent. When it is at most the upper limit, the fluidity during melt molding tends to be excellent. The lower limit of the mass average molecular weight of the (meth)acrylic polymer (A) is more preferably 50,000. Furthermore, the upper limit of the mass average molecular weight of the (meth)acrylic polymer (A) is more preferably 150,000.
[0029] In this specification, the mass average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample.
[0030] The lower limit of the content of the (meth)acrylic polymer (A) in the methacrylic resin composition is not particularly limited, but is preferably 55% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass (100% by mass) of the methacrylic resin composition. The upper limit of the content of the (meth)acrylic polymer (A) is not particularly limited, but is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, relative to the total mass (100% by mass) of the methacrylic resin composition. The upper and lower limits of the content of the (meth)acrylic polymer (A) in the methacrylic resin composition can be arbitrarily combined. For example, the content of the (meth)acrylic polymer (A) relative to the total mass (100 mass%) of the methacrylic resin composition is preferably 55 mass% or more and 99 mass% or less, more preferably 70 mass% or more and 98 mass% or less, and even more preferably 90 mass% or more and 97 mass% or less. When the content of the (meth)acrylic polymer (A) in the methacrylic resin composition is equal to or greater than the lower limit, the resulting resin molded article is less likely to lose the inherent properties of acrylic resin, such as transparency, heat resistance, and weather resistance.When the content is equal to or less than the upper limit, the resulting resin molded article tends to have excellent scratch resistance.
[0031] <Fatty acid compound (B)> The fatty acid compound (B) is one of the components of the methacrylic resin composition that constitutes the resin molded article of the present invention. Since the methacrylic resin composition contains the fatty acid compound (B) and the value of P1 / P2 on the surface of the obtained resin molded article is 0.0040 or more, the resin molded article of the present invention has excellent scratch resistance.
[0032] In the present invention, the fatty acid compound (B) is preferably a chain hydrocarbon compound having at least one carbonyl group or carboxyl group in the molecule, from the viewpoint of easily imparting excellent scratch resistance to the resulting resin molded article. A chain hydrocarbon compound having at least one carbonyl group or carboxyl group in the molecule means a compound in which the carbon atom to which the carbonyl group or carboxyl group is bonded is a constituent atom of the carbon chain. The carbon chain in the chain hydrocarbon compound having at least one carbonyl group or carboxyl group in the molecule may be saturated or unsaturated, and may be linear or branched.
[0033] Examples of such fatty acid compounds (B) include fatty acids and their derivatives as chain hydrocarbon compounds having a carboxyl group in the molecule, fatty acid amides and their derivatives as chain hydrocarbon compounds having an amide group in the molecule, and fatty acid alkyl esters and their derivatives, or fatty acid glycerides and their derivatives as chain hydrocarbon compounds having an ester group or a carbonyl group in the molecule.
[0034] The fatty acid derivatives, fatty acid amide derivatives, fatty acid alkyl ester derivatives, and fatty acid glyceride derivatives are compounds in which the hydrogen atoms or part or all of the side chains of a chain hydrocarbon compound are replaced with other organic groups. Examples of the organic group include polyether groups, polyalkyl groups, aralkyl groups, and polyester groups, which may be used alone or in combination of two or more. Furthermore, the derivative of fatty acid amide can be appropriately selected from various compounds such as monoamides and bisamides depending on the situation.
[0035] These fatty acid compounds (B) may be used alone or in combination of two or more.
[0036] The upper limit of the solubility parameter value of the fatty acid compound (B) is not particularly limited, but from the viewpoint of tending to have excellent compatibility with acrylic resins and maintaining good scratch resistance of the obtained resin molded article, the solubility parameter value of the fatty acid compound (B) is preferably 11.0 (cal / cm 3 ) 1 / 2 Less than 10.5 (cal / cm3 ) 1 / 2 Less than 10.0 (cal / cm 3 ) 1 / 2 The lower limit of the solubility parameter value of the fatty acid compound (B) is not particularly limited, but since the fatty acid compound (B) tends to have excellent compatibility with acrylic resins, the solubility parameter value of the fatty acid compound (B) is more preferably 9.0 (cal / cm 3 ) or less from the viewpoint of excellent scratch resistance of the resulting resin molded article. 3 ) 1 / 2 9.2 (cal / cm or more is preferable. 3 ) 1 / 2 More preferably, 9.4 (cal / cm 3 ) 1 / 2 The above is even more preferable.
[0037] The above upper and lower limits can be combined arbitrarily. For example, the solubility parameter value of the fatty acid compound (B) is 9.0 (cal / cm 3 ) 1 / 2 More than 11.0(cal / cm 3 ) 1 / 2 Preferably less than 9.2 (cal / cm 3 ) 1 / 2 More than 10.5(cal / cm 3 ) 1 / 2 Less than 9.4 (cal / cm 3 ) 1 / 2 More than 10.0(cal / cm 3 ) 1 / 2 The following is even more preferred:
[0038] The solubility parameter (SP value) is a measure of solubility. The larger the SP value, the higher the polarity, and conversely, the smaller the SP value, the lower the polarity. In the present invention, the SP value is calculated by the method proposed by Fedors et al. Specifically, the calculation can be performed with reference to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 147-154)."
[0039] The upper limit of the 10% weight loss temperature of the fatty acid compound (B) is not particularly limited, but is preferably 308°C or lower from the viewpoint of improving the scratch resistance of the resulting resin molded article. Although the reason for this is unclear, it is presumed that the lower the 10% weight loss temperature, the more likely it is that the fatty acid compound (B) contained in the methacrylic resin composition volatilizes in the mold during injection molding, adheres to the mold surface, liquefies, and condenses. The fatty acid compound (B) adhered to the mold surface then diffuses and migrates to the methacrylic resin composition injected into the mold later, resulting in a higher content of the fatty acid compound (B) on and near the surface of the resulting resin molded article. The 10% weight loss temperature of the fatty acid compound (B) is more preferably 280°C or lower, and even more preferably 260°C or lower. On the other hand, the lower limit of the 10% weight loss temperature of the fatty acid compound (B) is not particularly limited, but is preferably 190°C or higher from the viewpoint of improving the scratch resistance of the resulting resin molded article. Although the reason for this is not clear, it is presumed that if the 10% weight loss temperature is 190°C or higher, the fatty acid compound (B) will not thermally decompose during injection molding, and the effects of the fatty acid compound (B) can be fully exerted. The 10% weight loss temperature of the fatty acid compound (B) is more preferably 200°C or higher, and even more preferably 210°C or higher. The upper and lower limits of the 10% weight loss temperature of the fatty acid compound (B) can be arbitrarily combined. For example, the 10% weight loss temperature of the fatty acid compound (B) is preferably 190°C or higher and 308°C or lower, more preferably 200°C or higher and 280°C or lower, and even more preferably 210°C or higher and 260°C or lower.
[0040] The lower limit of the melting point of the fatty acid compound (B) is not particularly limited, but is preferably 90°C or higher from the viewpoint of improving the scratch resistance of the resulting resin molded article. Although the reason for this is unclear, it is presumed that a melting point of 90°C or higher shortens the time it takes for the fatty acid compound (B) contained in the methacrylic resin composition to volatilize in the mold during injection molding, adhere to the mold surface, liquefy, and condense. This prevents the amount of fatty acid compound (B) discharged as a gas from the gas vent and adhering to the mold surface from decreasing, resulting in a tendency for a high content of fatty acid compound (B) to be present on or near the surface of the resulting resin molded article. The melting point of the fatty acid compound (B) is more preferably 95°C or higher, and even more preferably 100°C or higher. On the other hand, the upper limit of the melting point of the fatty acid compound (B) is not particularly limited, but is preferably 150°C or lower from the viewpoint of improving the scratch resistance of the resulting resin molded article. Although the reason for this is not clear, it is believed that if the melting point of the fatty acid compound (B) is 150°C or lower, the fatty acid compound (B) contained in the methacrylic resin composition is sufficiently volatilized in the mold during injection molding, making it easier to obtain the above-mentioned functions and effects. The melting point of the fatty acid compound (B) is more preferably 130°C or lower, and even more preferably 120°C or lower. The upper and lower limits of the melting point of the fatty acid compound (B) can be arbitrarily combined. For example, the melting point of the fatty acid compound (B) is preferably 90°C or higher and 150°C or lower, more preferably 95°C or higher and 130°C or lower, and even more preferably 100°C or higher and 120°C or lower.
[0041] Among these fatty acid compounds (B), fatty acid amide compounds and derivatives thereof (hereinafter, these may be collectively referred to as "fatty acid amide compounds (B1)") are preferred.
[0042] As the fatty acid amide compound (B1), a compound represented by the following general formula (i) (hereinafter also referred to as "compound (i)") can be used. Compound (i) is preferred from the viewpoint that even when compounded in a small amount, the resulting resin molded article has excellent scratch resistance and the inherent performance of the (meth)acrylic resin is not easily impaired. R-CONH2(i) (In general formula (i), R is a hydrocarbon group having 10 to 25 carbon atoms which may have a substituent.)
[0043] The lower limit of the number of carbon atoms in R in formula (i) of the fatty acid amide compound (B1) is preferably 10 or more, more preferably 15 or more, and even more preferably 17 or more, from the viewpoints of excellent compatibility with the (meth)acrylic polymer (A) and excellent scratch resistance of the resulting resin molded article. The upper limit of the number of carbon atoms in R in formula (i) of the fatty acid amide compound (B1) is preferably 25 or less, more preferably 24 or less, and even more preferably 23 or less, from the viewpoints of excellent dispersibility of the fatty acid compound (B) in the methacrylic resin composition and maintaining good scratch resistance of the resulting resin molded article. The above preferred upper and lower limits can be combined in any combination. For example, the number of carbon atoms in R in formula (i) of the fatty acid amide compound is preferably 10 to 25, more preferably 15 to 24, and even more preferably 17 to 23.
[0044] The fatty acid amide compound (B1) is preferred because it tends to have excellent compatibility with the (meth)acrylic polymer (A), excellent fluidity of the methacrylic resin composition, and excellent scratch resistance of the resulting resin molded article.
[0045] Examples of the fatty acid amide compound (B1) include saturated fatty acid amide compounds, unsaturated fatty acid amide compounds, bisfatty acid amide compounds, and methylol fatty acid amide compounds. These fatty acid amide compounds may be used alone or in combination of two or more. Among these fatty acid amide compounds (B1), saturated fatty acid amide compounds are preferred because they provide superior scratch resistance to the resulting resin molded article.
[0046] Examples of saturated fatty acid amide compounds include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, and methylolstearic acid amide. These saturated fatty acid amide compounds may be used alone or in combination of two or more.
[0047] In order to provide a resin molded article with excellent scratch resistance, the saturated fatty acid amide compound preferably contains either stearic acid amide or palmitic acid amide, and the saturated fatty acid amide compound preferably contains stearic acid amide and palmitic acid amide as the main components. Here, "containing as the main components" means that the total mass of stearic acid amide and palmitic acid amide relative to the total mass (100% by mass) of the fatty acid amide compound is 85.0% by mass or more.
[0048] Examples of unsaturated fatty acid amides include erucic acid amide, oleic acid amide, brassidic 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 preferred, and erucic acid amide is more preferred, since the resulting resin molded article is excellent in scratch resistance.
[0049] Examples of the bis-fatty acid amide compound include bis-fatty acid amides such as methylene bis-stearic acid amide, methylene bis-oleic acid amide, ethylene bis-stearic acid amide, and ethylene bis-oleic acid amide; stearyl stearic acid amide, stearyl erucic acid amide, and oleyl palmitic acid amide. These bisfatty acid amide compounds may be used alone or in combination of two or more.
[0050] The lower limit of the content of the fatty acid compound (B) contained in the methacrylic resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1.0% by mass or more, relative to 100% by mass of the total mass of the methacrylic resin composition, from the viewpoint of excellent scratch resistance of the obtained resin molded article. On the other hand, the upper limit of the content of the fatty acid compound (B) contained in the methacrylic resin composition is preferably 10% by mass or less, more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less, relative to 100% by mass of the total mass of the methacrylic resin composition, from the viewpoint of preventing the obtained resin molded article from impairing the inherent performance of the acrylic resin. The above-mentioned preferable upper and lower limits can be combined in any combination. For example, the content of the fatty acid compound (B) contained in the methacrylic resin composition is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5.0% by mass or less, and even more preferably 1.0% by mass or more and 3.0% by mass or less, relative to 100% by mass of the total mass of the methacrylic resin composition.
[0051] <Method of manufacturing resin molded body> The method for producing a resin molded article of the present invention is a method for producing a resin molded article obtained by injection molding a methacrylic resin composition containing the above-mentioned (meth)acrylic polymer (A) and the above-mentioned fatty acid compound (B). The resin molded article produced by the method for producing a resin molded article of the present invention preferably has the above-mentioned absorbance ratio P1 / P2 of 0.0040 or more. Such a resin molded article can be obtained, for example, by the production method described below.
[0052] As the injection molding used in the method for producing the resin molded article of the present invention, a known injection molding method can be used.
[0053] In particular, the method for producing a resin molded article of the present invention is characterized in that, when injection molding a methacrylic resin composition containing a (meth)acrylic polymer (A) and a fatty acid compound (B), the methacrylic resin composition is melt-kneaded under conditions where the cylinder temperature of the injection molding machine is 248°C or higher and 300°C or lower, and then injected into a mold.
[0054] When the lower limit of the cylinder temperature of the injection molding machine during injection molding is 248°C or higher, the resulting resin molded body tends to have good scratch resistance. The reason for this is unclear, but it is thought that if the cylinder temperature is 248°C or higher, the fatty acid compound (B) contained in the methacrylic resin composition tends to volatilize within the mold during injection molding, adhere to the mold surface, liquefy, and condense. The fatty acid compound (B) adhered to the mold surface then diffuses and migrates to the methacrylic resin composition injected into the mold later, resulting in a tendency for a high content of fatty acid compound (B) to be present on or near the surface of the resulting resin molded body. The cylinder temperature of the injection molding machine during injection molding is more preferably 265°C or higher. When the upper limit of the cylinder temperature of the injection molding machine during injection molding is 300°C or lower, the resulting resin molded body tends to maintain good scratch resistance and transparency. Although the reason for this is not clear, it is presumed that if the cylinder temperature of the injection molding machine is 300°C or less, thermal decomposition of the fatty acid compound (B) during injection molding is suppressed, making it easier to fully obtain the effects of the fatty acid compound (B). The cylinder temperature of the injection molding machine during injection molding is more preferably 295°C or less, and even more preferably 290°C or less.
[0055] The above-mentioned preferable upper and lower limits can be combined in any combination. For example, when the methacrylic resin composition containing the (meth)acrylic polymer (A) and the fatty acid compound (B) is injection-molded, the cylinder temperature of the injection molding machine is 248°C or higher and 300°C or lower, preferably 248°C or higher and 295°C or lower, and more preferably 265°C or higher and 290°C or lower.
[0056] In the method for producing a resin molded article of the present invention, the cylinder temperature of the injection molding machine refers to the highest temperature in the compression zone and lightweight zone of the cylinder of the injection molding machine. Specifically, the cylinder of an injection molding machine is typically heated by attaching multiple heaters to various locations on the barrel of the injection molding machine. For example, in the case of an eight-section (eight columns) barrel, eight heaters are attached to various locations on the barrel from the hopper inlet (resin supply section) to the injection molding machine outlet (resin discharge section, mold connection section), and the temperature of each column is measured using a thermocouple thermometer with a probe tip installed inside each heater. The highest temperature measured in the columns of the compression zone and lightweight zone of the cylinder of the injection molding machine is referred to as the cylinder temperature of the injection molding machine.
[0057] If the cylinder temperature of the injection molding machine during injection molding is set to less than 248°C and the content of the fatty acid compound (B) is increased to such an extent that the absorbance ratio P1 / P2 is 0.0040 or more, the fatty acid compound (B) itself acts as a plasticizer for the (meth)acrylic polymer (A) during injection molding, which significantly affects the molding stability, such as causing a fusion phenomenon due to plasticization of the (meth)acrylic polymer (A), making it difficult to easily obtain a resin molded product by melt kneading or injection molding.
[0058] During injection molding, the mold temperature of the mold is preferably set in advance to 35°C or higher and 90°C or lower. When the mold temperature during injection molding is 35°C or higher, the appearance of the resulting resin molded product is likely to be good. While the reason for this is unclear, it is believed that a mold temperature of 35°C or higher rapidly cools the methacrylic resin composition, which tends to reduce defects such as sink marks in the resin molded product obtained by injection molding. The mold temperature during injection molding is more preferably 36°C or higher, and even more preferably 37°C or higher. On the other hand, when the mold temperature during injection molding is 90°C or lower, the scratch resistance and transparency of the resulting resin molded product are likely to be maintained at a good level. While the reason for this is unclear, it is believed that a mold temperature of 90°C or lower shortens the time it takes for the fatty acid compound (B) contained in the methacrylic resin composition to adhere to the mold surface, liquefy, and condense. This prevents a decrease in the amount of fatty acid compound (B) discharged as a gas from the gas vent and adhering to the mold surface, making it easier to achieve the above-mentioned functions and effects. A mold temperature of 70°C or lower is more preferred, and 50°C or lower is even more preferred.
[0059] The above-mentioned preferable upper and lower limits can be combined in any combination. For example, when injection molding a methacrylic resin composition containing a (meth)acrylic polymer (A) and a fatty acid compound (B), the mold temperature is preferably set in advance to 35°C or higher and 90°C or lower, more preferably set in advance to 36°C or higher and 70°C or lower, and even more preferably set in advance to 37°C or higher and 50°C or lower. In the present invention, the mold temperature during injection molding refers to the surface temperature of the cavity portion of the mold used to form a predetermined shape, into which the methacrylic resin composition is filled, and can be measured using a contact surface thermometer.
[0060] In the method for producing a resin molded article of the present invention, the injection speed during injection molding is set to 30 cm 3 By setting the injection speed at 30 cm / sec or less, the scratch resistance of the obtained resin molded body is good. The reason for this is not clear, but it is 3It is presumed that if the injection speed is 12 cm / sec or less, the fatty acid compound (B) contained in the methacrylic resin composition is sufficiently volatilized in the mold during injection molding, and the fatty acid compound (B) is present at a high content on and near the surface of the obtained resin molded body. 3 / sec or less is preferable, 8cm 3 The injection speed during injection molding is 5 cm / sec or less. 3 It can also be set to less than / sec. In the present invention, the injection speed is expressed as the ratio of injected resin volume to resin filling time (unit: cm 3 The resin filling time is defined as the injection time at which no change in distance can be observed in response to an increase in injection time, when the distance from the screw to the nozzle is plotted with the injection time on the horizontal axis and the distance from the screw head to the nozzle head on the vertical axis.
[0061] In the method for producing a resin molded article of the present invention, the surface of the obtained resin molded article is subjected to the above-mentioned production conditions, and the wavelength of the wavelength of the obtained resin molded article is measured by a single reflection ATR surface reflection method using an infrared spectrophotometer. The wavelength of the obtained resin molded article is 1630 to 1650 cm -1 The peak absorbance P1 in the range of 1710-1730 cm -1 By manufacturing the resin molded article so that the absorbance ratio P1 / P2 to the peak absorbance P2 in this range is 0.0040 or more, it is possible to obtain a resin molded article having excellent scratch resistance. [Example]
[0062] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. Various measurements and evaluations in the examples and comparative examples were carried out by the following methods.
[0063] <Creating a molded body> The pellets of the methacrylic resin compositions obtained in the examples and comparative examples were dried with hot air at 80°C for about 4 hours, and then injection-molded using an injection molding machine (model name: EC75SX-III, manufactured by Toshiba Machine Co., Ltd.) under the specified conditions for cylinder temperature, mold temperature, and injection speed described below to obtain a molded body (A) (length 100 mm, width 100 mm, thickness 3 mm).
[0064] <Scratch resistance> As an index of the scratch resistance of the resin molded article, the haze value before and after the scratch resistance test and the difference therebetween (Δ haze) were measured according to the following method. The molded body (A) was placed on a flat table, and a friction tester (a friction tester for color fastness, Type S, modified from the friction tester Type II described in JIS L 0849, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. Five layers of gauze (trade name, Yamato Factory Medical Gauze, Chikyu Tombow, 100% cotton) were stacked on a flat friction tester (length 20 mm, width 20 mm) as a friction element. As shown in FIG. 1, the friction element was moved back and forth 50 times over a distance of 100 mm under a load of 1000 g so that the center 3 of the molded body (A) passed through at an angle of 45° from the position of the gate 4 during injection molding in both the MD direction (flow direction during molding) and the TD direction (direction perpendicular to the flow direction during molding). The friction and wear treatment 2 was formed on the surface of the molded body (A).
[0065] Next, for the test piece (molded body (A)) before and after the scratch resistance test, a haze meter (model name: NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze value of the molded body (A) in accordance with ISO 14782 by irradiating a light beam parallel to the direction of reciprocation of the friction element at the center 3 of the molded body (A) (for the test piece subjected to the scratch resistance test, the center of the surface where the friction wear treatment section 2 was formed). Three test pieces of molded body (A) were used, and one measurement was performed for each test piece, and the average value was taken as the haze value. The haze values before and after the scratch resistance test and the difference in haze values (Δ haze) were calculated.
[0066] <Absorbance ratio P1 / P2> The surface of the resin molded body was measured by a single-reflection ATR surface reflectance method using a Fourier transform infrared spectrophotometer (ATR: manufactured by Thermo Fisher Scientific, model: Nicolet iS10) at a wave number of 2000 to 1500 cm for the surface of the molded body (A). -1 The infrared absorption (IR) spectrum of the compound was measured. The measurement conditions for the single reflection ATR surface reflection method are as follows: Light source: Infrared light (IR) Detector: DTGS-KBr Beam splitter: KBr Resolution: 4cm -1 Accessory: Single-reflection horizontal ATR (Smart-iTR, Thermo Fisher Scientific) Prism: Diamond Incident angle: 45° Polarization: None The obtained IR spectrum is shown in Figure 2, where the wavenumber is 1650-1660 cm -1 The position where the peak in the range of 1-1 ) and a wave number of 1630 cm -1 Position (x 1-2 ) and draw a baseline between wavenumbers 1630 and 1650 cm -1 The absorbance P1 of the wavenumber showing the maximum absorbance of the peak in the range of 1770 cm was calculated. -1 Position (x 2-1 ) and a wave number of 1550 cm -1 Position (x 2-2 ) and draw a baseline between wavenumbers 1710 and 1730 cm -1 The absorbance P2 of the wavenumber at which the peak exhibited the maximum absorbance was calculated within this range. The absorbance ratio P1 / P2 was calculated by dividing P1 by P2.
[0067] <10% weight loss temperature> The 10% weight loss temperature of the fatty acid compound (B) was measured using a thermogravimetric analyzer (TGA) (manufactured by Seiko Instruments Inc., model: TG / DTA6200) according to the following method. While flowing dry nitrogen at 100 ml / min, the temperature was increased from 40°C to 500°C at a rate of 10°C / min, and the temperature at which the weight loss rate reached 10% (weight loss of 10% by mass) was measured.
[0068] <Melting point> The melting point of the fatty acid compound (B) was evaluated by the following method using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., model: DSC-6200). Approximately 10 mg of fatty acid compound (B) was placed in an aluminum sample container, heated to 200°C at a rate of 10°C / min and held for 5 minutes to melt it, then cooled to 0°C at 10°C / min, heated again at a rate of 10°C / min, held for 5 minutes, and cooled again at 10°C / min. The maximum point of the crystalline melting peak observed at this time was taken as the melting point of fatty acid compound (B).
[0069] <Fatty acid compound (B) content> The content of fatty acid compounds in the resin molded body was measured using a gas chromatography measuring device (GC device) (manufactured by Agilent Technologies, product name: Gas Chromatography GC7890B, column used: Agilent J&W HP-5, outer diameter 0.32 mm / film thickness 0.25 μm, length 30 m, detector: FID) according to the following method. A 0.2 g piece cut from the molded body (A) was dissolved in 5 ml of acetone and then dropped into 30 ml of methanol to obtain a precipitate. The precipitate was then removed using filter paper, and the resulting supernatant solution was used as a GC sample. 1.0 μl of the GC sample was injected into a GC system (injection port temperature: 280°C, detector temperature: 280°C, split ratio: 1 / 50, carrier gas: He), held at 80°C for 2 minutes, and then heated to 300°C at a heating rate of 10°C / min. The content (mass%) of fatty acid compounds in the molded body (A) (100 mass%) was calculated based on the peak area of the fatty acid compounds in the obtained gas chromatogram and a calibration curve prepared in advance using standard solutions of fatty acid compounds with known concentrations.
[0070] <Dynamic friction coefficient / Static friction coefficient> As an index of the friction and wear resistance of the resin molded article, the dynamic friction coefficient / static friction coefficient was measured according to the following method. Using a scratch tester KK01 (manufactured by Kato Tech Co., Ltd.), in accordance with ISO 19252, a spherical indenter with a diameter of 1 mm was pressed against the surface of the molded body (A), and while maintaining the horizontal load of the indenter constant (5.0 N), the indenter was moved over the surface of the molded body (A) at a moving speed of 100 mm / sec and a moving distance of 70 mm, and the vertical load (unit: N) was measured. The coefficient of dynamic friction was determined by dividing the horizontal load (5.0 N) by the average value of the vertical load measured in the section from 10 to 60 mm starting from the starting point of the travel distance (70 mm). In addition, the horizontal load (5.0 N) was divided by the vertical load, and the maximum value measured immediately after the indenter started to move was taken as the static friction coefficient. Using three pieces of molded body (A), one measurement was carried out for each test piece, and the dynamic friction coefficient and static friction coefficient were calculated, and the average values were taken as the final dynamic friction coefficient and static friction coefficient.
[0071] <Water contact angle> In an environment of 23°C and relative humidity of 50%, a drop of 0.2 μL of water was dropped onto the surface of molded body (A), and the contact angle of the surface of molded body (A) with water was measured using a portable contact angle meter (manufactured by Matsubo Corporation, product name: PG-X).
[0072] (raw materials) Acrylic resin (A-1): ACRYPET (registered trademark) VH (trade name, manufactured by Mitsubishi Chemical Corporation, acrylic resin containing 98% by mass of methyl methacrylate units) Fatty acid compound (B-1): A mixture of fatty acid amides containing stearic acid amide and palmitic acid amide as the main components (trade name: Fatty Acid Amide S, manufactured by Kao Corporation) Fatty acid compound (B-2): a mixture of fatty acid amides containing stearic acid amide and palmitic acid amide as the main components (trade name: IncroMax (registered trademark) PS, manufactured by CRODA) Fatty acid compound (B-3): a mixture of fatty acid amides containing stearic acid amide and palmitic acid amide as the main components (trade name: Amide AP-1, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-4): a mixture of fatty acid amides containing palmitic acid amide as the main component (trade name: Diamid (registered trademark) KP, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-5): a mixture of fatty acid amides containing methylol stearic acid amide as the main component (trade name: Methylolamide, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-6): a mixture of fatty acid amides containing methylene bisstearic acid amide as the main component (Bisamide LA, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-7): a mixture of fatty acid amides containing hydroxystearic acid amide as the main component (Diamid (registered trademark) KH, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-8): a mixture of fatty acid amides containing erucic acid amide as the main component (trade name: Diamid (registered trademark) L-200, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-9): a mixture of fatty acid amides containing stearyl stearic acid amide as the main component (Nikkaamide (registered trademark) S, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-10): a mixture of fatty acid amides containing stearyl oleic acid amide as the main component (trade name: Nikkaamide (registered trademark) SO, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-11): A mixture of fatty acid amides containing oleyl stearic acid amide as the main component (trade name: Nikkaamide (registered trademark) OS, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-12): a mixture of fatty acid amides containing ethylene bisstearic acid amide as the main component (trade name: Slipax (registered trademark) E, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-13): a mixture of fatty acid amides containing ethylene bisoleamide as the main component (trade name: Slipax (registered trademark) O, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-14): a mixture of fatty acid amides containing ethylenebiserucamide as the main component (trade name: Slipax (registered trademark) L, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-15): a mixture of fatty acid amides containing hexamethylenebisoleic acid amide as the main component (trade name: Slipax (registered trademark) ZHO, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-16): a mixture of fatty acid amides containing hexamethylene bisstearic acid amide as the main component (trade name: Slipax (registered trademark) ZHS, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-17): a mixture of fatty acid amides containing hexamethylene bishydroxystearic acid amide as the main component (trade name: Slipax (registered trademark) ZHH, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-18): a mixture of fatty acid amides containing lauric acid amide as the main component (trade name: Diamid (registered trademark) Y, manufactured by Mitsubishi Chemical Corporation) Fatty acid compound (B-19): a mixture of fatty acid amides containing oleic acid amide as the main component (trade name: Diamid (registered trademark) O-200, manufactured by Mitsubishi Chemical Corporation)
[0073] Here, in the fatty acid compounds (B-1) to (B-20), "contains as a main component" means that the target component is contained in an amount of 70 mass % or more relative to the total mass (100 mass %) of the fatty acid compound (B).
[0074] [Example 1] 100 parts by mass of acrylic resin (A-1) and 2 parts by mass of fatty acid compound (B-1) as fatty acid compound (B) were fed to a twin-screw extruder (model name "PCM30", manufactured by Ikegai Corporation), melt-kneaded at a cylinder temperature of 250°C, and then kneaded at a mold temperature of 60°C and an injection speed of 23.3 cm. 3 A pellet-shaped methacrylic resin composition was obtained at 1 / second. The evaluation results of the obtained methacrylic resin composition are shown in Table 2.
[0075] [Comparative Example 1] Except for not using the fatty acid compound (B), the same operation as in Example 1 was carried out to obtain a pellet-shaped methacrylic resin composition. The evaluation results of the obtained methacrylic resin composition are shown in Table 2.
[0076] [Examples 2 to 5, Comparative Examples 2 to 12] Pellet-shaped methacrylic resin compositions were obtained in the same manner as in Example 1, except that the type of fatty acid compound (B) was changed as shown in Table 1. The evaluation results of the obtained methacrylic resin compositions are shown in Table 2. The content of the fatty acid compound (B) in Table 2 indicates the content (% by mass) of the fatty acid compound (B) relative to the total mass (100% by mass) of the methacrylic resin composition.
[0077] Although the amount of fatty acid compound (B) in Table 1 is 2.0 parts by mass, the content (mass%) of fatty acid compound (B) in Table 2 differs among Examples because a portion of the fatty acid compound (B) was thermally decomposed or volatilized outside the mold when kneading with a twin-screw extruder or obtaining a resin molded product with an injection molding machine. The same applies to Tables 3, 4, 5, and 6.
[0078] [Table 1]
[0079] [Table 2]
[0080] The molded articles obtained in Examples 1 to 5 were made of a methacrylic resin composition containing a fatty acid compound (B) and had an absorbance ratio P1 / P2 of 0.0040 or more, and therefore had excellent scratch resistance.
[0081] The molded article obtained in Comparative Example 1 was poor in scratch resistance because it did not contain the fatty acid compound (B).
[0082] The molded articles obtained in Comparative Examples 2 to 12 had an absorbance ratio P1 / P2 of less than 0.0040, and therefore were significantly inferior in scratch resistance.
[0083] [Examples 6 to 11, Comparative Examples 13 to 14, and Comparative Examples 16 to 24] Pellet-shaped methacrylic resin compositions were obtained in the same manner as in Example 1, except that the cylinder temperature of the injection molding machine was set to 280°C, the mold temperature was set to 40°C, and the type of fatty acid compound (B) was set as shown in Table 3. The evaluation results of the obtained methacrylic resin compositions are shown in Table 4. The content of the fatty acid compound (B) in Table 4 indicates the content (% by mass) of the fatty acid compound (B) relative to the total mass (100% by mass) of the methacrylic resin composition.
[0084] [Table 3]
[0085] [Table 4]
[0086] The molded articles obtained in Examples 6 to 11 were excellent in scratch resistance of resin molded articles. In particular, compared to the molded bodies obtained in the corresponding Examples 1 to 5, the molded bodies obtained in Examples 6 to 10 had an increased absorbance ratio P1 / P2 value and better scratch resistance (ΔHaze) because the cylinder temperature of the injection molding machine was changed from 250°C to 280°C. The molded article obtained in Comparative Example 13 was poor in scratch resistance because it did not contain the fatty acid compound (B). The molded articles obtained in Comparative Examples 14 and 16 to 24 had poor scratch resistance because the absorbance ratio P1 / P2 was less than 0.0040 even when the cylinder temperature of the injection molding machine was changed from 250°C to 280°C.
[0087] [Examples 12 to 14, Comparative Examples 25 to 27] Pellet-shaped methacrylic resin compositions were obtained in the same manner as in Example 1, except that the cylinder temperature of the injection molding machine was set to 270°C, the mold temperature was set to 40°C, and the type of fatty acid compound (B) was set as shown in Table 5. The evaluation results of the obtained methacrylic resin compositions are shown in Table 6.
[0088] [Example 15] The injection speed of the injection molding machine is set to 3.9 cm 3 The same procedure as in Example 12 was carried out except that the heating time was changed to / second, thereby obtaining a pellet-shaped methacrylic resin composition. The evaluation results of the obtained methacrylic resin composition are shown in Table 6.
[0089] [Comparative Example 28] A pellet-shaped methacrylic resin composition was obtained in the same manner as in Example 2, except that the cylinder temperature of the injection molding machine was set to 230° C. and the mold temperature was set to 60° C. The evaluation results of the obtained methacrylic resin composition are shown in Table 6. The content of the fatty acid compound (B) in Table 6 indicates the content (% by mass) of the fatty acid compound (B) relative to the total mass (100% by mass) of the methacrylic resin composition.
[0090] [Table 5]
[0091] [Table 6]
[0092] The molded articles obtained in Examples 12 to 15 were excellent in scratch resistance.
[0093] In particular, when compared with the molded bodies obtained in Examples 3 to 5, the absorbance ratio P1 / P2 of each of the molded bodies obtained in Examples 12 to 14 increased because the cylinder temperature of the injection molding machine was changed from 250°C to 270°C. The molded article obtained in Example 15 was also excellent in scratch resistance. In particular, compared with the molded article obtained in Example 12, the injection speed of the injection molding machine was 23.3 cm / s. 3 / sec to 3.89cm 3 / sec, the absorbance ratio P1 / P2 increased, and the resulting molded body had excellent scratch resistance. On the other hand, when compared with the molded body obtained in Example 2, the molded body obtained in Comparative Example 28 had a reduced absorbance ratio P1 / P2 value and a reduced scratch resistance due to the change in the cylinder temperature of the injection molding machine from 250°C to 230°C.
[0094] The molded articles obtained in Comparative Examples 25 to 27 had poor scratch resistance because the absorbance ratio P1 / P2 was less than 0.0040 even when the cylinder temperature of the injection molding machine was changed from 250°C to 270°C. [Industrial Applicability]
[0095] The resin molded article of the present invention has excellent scratch resistance and is therefore suitable for use as, for example, materials for housing facilities such as washbasins, bathtubs, and flush toilets; building materials; and vehicle components such as interior and exterior materials for vehicles, and is particularly suitable for vehicle components. Examples of vehicle components include tail lamp covers, head lamp covers, meter panels, door mirror housings, pillar covers (sash covers), license garnishes, front grilles, fog garnishes, and emblems, and among these, tail lamp covers, head lamp covers, and meter panels are particularly preferred. Examples of mobile phone components include the back panel of a mobile phone and the front panel of a display, and among these, it is preferably used for the back panel of a mobile phone. [Explanation of symbols]
[0096] 1 test piece 2. Friction and wear treatment section 3 Center of the test piece 4 Gate
Claims
1. A resin molded product containing a methacrylic resin composition, The methacrylic resin composition contains a methacrylic polymer and a fatty acid compound (B), The fatty acid compound (B) is represented by the following general formula (i): R-CONH 2 (i) (wherein R is a hydrocarbon group having 10 to 25 carbon atoms which may have a substituent). the fatty acid compound (B) is a saturated fatty acid amide compound, the total mass of stearic acid amide and palmitic acid amide relative to the total mass (100% by mass) of the saturated fatty acid amide compounds is 85.0% by mass or more, On the surface of the resin molded body, a wave number of 1630 to 1650 cm was measured by a single reflection ATR surface reflection method using an infrared spectrophotometer. -1 and a peak absorbance P1 in the range of wavenumber 1710 to 1730 cm -1 The resin molded product has an absorbance ratio P1 / P2 of 0.0040 or more relative to the peak absorbance P2 in the range.
2. 2. The resin molded article according to claim 1, wherein the surface of the resin molded article has a dynamic friction coefficient of 0.12 or less.
3. The resin molded article according to claim 1 or 2, wherein the surface of the resin molded article has a water contact angle of 69.0 degrees or more.
4. The resin molded article according to any one of claims 1 to 3, wherein the fatty acid compound (B) has a 10% weight loss temperature of 308°C or lower.
5. The resin molded article according to any one of claims 1 to 4, wherein the fatty acid compound (B) has a melting point of 90°C or higher.
6. The content of the fatty acid compound (B) is 0.01% by mass or more and 10% by mass or less, relative to 100% by mass of the total mass of the methacrylic resin composition. The resin molded body according to any one of claims 1 to 5.
7. The solubility parameter of the fatty acid compound (B) calculated by the Fedors method is 11.0 (cal / cm 3 ) 1/2 The resin molded body according to any one of claims 1 to 6, wherein:
8. The resin molded article according to any one of claims 1 to 7, wherein the content of repeating units derived from methyl methacrylate in the methacrylic polymer is 70% by mass or more.
9. The resin molded article according to any one of claims 1 to 8, wherein the methacrylic resin composition does not contain a compound containing a fluorine atom.
10. The resin molded article according to any one of claims 1 to 9, which is used as a raw material for a vehicle member or a mobile phone member.
11. The resin molded article according to claim 10, which is used as a vehicle component, and the vehicle component is at least one selected from a tail lamp cover, a head lamp cover, and a meter panel.
12. The resin molded article according to claim 10, which is used as a mobile phone component, and the mobile phone component is a back panel of the mobile phone.
13. A method for producing a resin molded product obtained by injection molding a methacrylic resin composition containing a methacrylic polymer and a fatty acid compound (B), comprising: The fatty acid compound (B) is represented by the following general formula (i): R-CONH 2 (i) (wherein R is a hydrocarbon group having 10 to 25 carbon atoms which may have a substituent). the fatty acid compound (B) is a saturated fatty acid amide compound, the total mass of stearic acid amide and palmitic acid amide relative to the total mass (100% by mass) of the saturated fatty acid amide compounds is 85.0% by mass or more, The injection molding method includes injecting the methacrylic resin composition into a mold from an injection molding machine having a cylinder temperature of 248°C or higher and 300°C or lower, In the injection molding, the injection speed is 30 cm 3 / seconds or less.
14. The method for producing a resin molded article according to claim 13, wherein a cylinder temperature of the injection molding machine is 248°C or higher and 295°C or lower.
15. The method for producing a resin molded article according to claim 13, wherein a cylinder temperature of the injection molding machine is 265°C or higher and 290°C or lower.
16. The method for producing a resin molded article according to any one of claims 13 to 15, wherein the resin is injected into the mold whose mold temperature is set in advance to 35°C or higher and 90°C or lower.
17. The method for producing a resin molded article according to any one of claims 13 to 15, wherein the resin is injected into the mold whose mold temperature is set in advance to 36°C or higher and 70°C or lower.
18. The method for producing a resin molded article according to any one of claims 13 to 15, wherein the resin is injected into the mold whose mold temperature is set in advance to 37°C or higher and 50°C or lower.
19. In the injection molding, the injection speed is 12 cm 3 The method for producing a resin molded article according to any one of claims 13 to 18, wherein the elongation is 1 / second or less.
20. In the injection molding, the injection speed is 8 cm 3 The method for producing a resin molded article according to any one of claims 13 to 18, wherein the elongation is 1 / second or less.
21. In the injection molding, the injection speed is 5 cm 3 The method for producing a resin molded article according to any one of claims 13 to 18, wherein the elongation is 1 / second or less.
22. The method for producing a resin molded article according to any one of claims 13 to 21, wherein the fatty acid compound (B) has a 10% weight loss temperature of 308°C or lower.
23. The method for producing a resin molded product according to any one of claims 13 to 22, wherein the fatty acid compound (B) has a melting point of 90°C or higher.
24. On the surface of the resin molded body, a wave number of 1630 to 1650 cm was measured by a single reflection ATR surface reflection method using an infrared spectrophotometer. -1 and a peak absorbance P1 in the range of wavenumber 1710 to 1730 cm -1 The method for producing a resin molded product according to any one of claims 13 to 23, wherein the resin molded product is produced so that the absorbance ratio P1 / P2 to the peak absorbance P2 in the range is 0.0040 or more.
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